Introductiontochemicalengineeringthermodynamics 140911165411 Phpapp01 PDF

Introduction to
Chemical Engineering
Therrrtodynam.ics
SEVENTH E.D ITION
J.M. Smith
H. C. Van ess
M.M. Abbott
Contents
1 ~"TROD COO: 1
Ll ~ ~ of'The:JUJCM:l~, I 11 .._ r 4 t ' 1 .. a .... .. ._
l .Z Di.J2lt!n.siCll'1s aJlCI Un.irs . - ................ ~ ..... ... ................ ...... . . , ............. . ... . .. . 2
u ~or Amount or Si~ - - -- .. --. 2
L4 ~ .................... . . ................... . . .......... 3
1..5 T~m:fe' . . _ .. . . . . ... ........... - .. *" .... .. - ... .. . . . .. ............ - ........... - - ..... . ~ . ............ - _.._ ...... .. 5
1.6 ~ -~ .. ~--- - .._ . ..... ..... .... .. ..... ...... .. . ~--- 'l --- .. - 6
1.7 w~ .......... ,. ,. ......... , . -"' s ~ .... ~ !I . . . . ..,. .. 1 8
., , . . . . . . . . . . . . . . . . . . . lol .. . . . . 4 ' . . . . . . . li
1.1 'Enttg) 1
- ~
. . . . . . . . . . . ... - ....., - .. - t~ .. - - LO
.. 1 ,. .. t> 1 - "' t ' t r " 11 f'
I.J Hear .......... ~ . ~ ~

.6 . . . . . . . . . . . .. ~ ... _ ~ ~ . . ~ ~ l5
. . . . . . . . . . . . . . . . ., .. ... , . .. , .. . .. , " , ... '"
2 TBE ftRSTLAW NO otBD BASJC VO CEP1!8 21

2.1, Jouk"'s ~ ... 2L
a l't P a I e I t a I a. II a I I a I a a .. . . I. I&. .. I.,~ ~ iJ a .-1 a 4 .0.
u ~~- - - . ~ - ~~~ - .... "" -- . J/1~.1 ~ lf

2.3 "lbe A::rsJ l..aw" of~~ ................ ., , _, ...... , .... .. 22 1!!1 ,. . . . . . , ........ . . .
2.4 Energy Bala.nce ror Closed S)'!i'ttmS _ 23

l.S lbmnodyoamie Swe and Stale FUDCtioa~ .............. _. . _... - . . _. _ . . _~ 26
2.6 ~m.hm-um . ~ I a a a a a I 29
&. a .A. a a o a .- a ., a il -' "- ,. lo. .., o & a fl' '"" ., ., .,. .. .. It 1'"' !!; e ._
2,7 The- Jlt'ia.tie Rok . . , ................. , .............. ~ 29

....
4 ............ lol ..... _ .. _ .... __ .. _ .. _
2.8 The R~ible ~. _. . . . . ... . . .., .. ,. ~ ................................... . 31

2.9 COMIJinf- V and LtJIISt3:fil-P ~~ a 1 1 o a o o r a o a a ~ a a~ a 37
2 ...10 &tba_lpy' ......... .. .. "" ..... 38 t . . . . . . . . . . .t . ... . . . . . . . . . . . . . .. . . . . . . . . . . . . . - . . .. - .. 0 .... - ..... - ..
1.1 1 ~ Cs~lV .... ~ . . ... ., . 40 .1" ,. . . . . . . . . . . . . . . . . . . . .. " . . . . . "' - . . . . . . . . . "' .1" . . . ._ ;:J_ p
2. 11 t. and .Eoi:rgy Balances for ()pea Syac:ms _........ _. _. ____ . _.. . . _. _. _... _ 44
J VOLUME1BJC IPllOPE.RTIES OF PURER DS 64

!.J PVF Be-havior: of Pore Svbsumces ....... . "' . . . . . . . . . . . . . . . . . . . . . . . . . . . J/1 . . . . . .. M
3..1 Vtrial ~ uf State . . ...... . ... - .... ~ . ~ t - ... .. "' , ~. ..... , ...... ~ .. "' "" ... . ,...,. 'e !r -r , - .. ""' ... 10
33 1bc Jdeall Cia a.."'._ .. ..
a .., e: -.. ~ .... _. .... ii - 5o. il,. .. ,. ..... - .. "'"' .. !" .. :5. ~-- r 73
3.4 Application of k Vi..ri:al ~()liS ,_ ... _j ._ I I Jl . . . . . - " ~ . . . . ..._- - ~ .. n
3.5 Cnl:Jit- l&Juati~ ~ofStak T" .... .......... " , ... ~ ~~ ~ . . . . . . . . . . . . . , . . . . . . . . . . .... M
3.6 Oeneraliled C011elillinM for Gasc..i ...... . .... .. , ... . .... 99 p . . . . . . . . . . . . -- - ...
3.."1 Oenemlized Cotrelations fM Liquids ~ ~ . . _.. , ... _.. .. , . ..... T _ _ .. U:)Q
vii Obras pro egidas por d r itos de aut<

4 11&\T EFFECTS 12!
4.1 Sal_5ibk Htaa Eff~ ~2S
~ Lat ~m~~s ................... ... 4 .. .... A ~~ ........ ~ _ . - ... . . ... .... _ .. tl3
u S'~ Hat ol~ ... .. . .. . ... ~.- . . .... .. .. . . .- . ...... -~- .... l3S
..,"
r . . . . . . . . . . . ... - . . . . "" . 1:1
~_Heal of pmmati.(D_ ~ 136 11 ._. a. a a a a a a 111 " a a4 .._ La "to\ a
~H.eatof~.,. . .. ,. .. -~~~ ,. . !t 1!. ll9 !t ,. . . . . . !! . . . .. ..,. ,. ., t'..,
u 140
~.,
143
s
5J Stia11:11:1l\l10 orb SeteoM :l.aw LOO
52 u._... =--.
~ QJ~~ !l-" l !"" l' !' _ .., - .,. -. . , .....
a
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p
a I
'!' !' '! ..

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a 15. ,J
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.a ..

at

.-!
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ii if
- . , - " ' 11
....... .
11 e
.. .
~"'I!
.. 5
r ...
ii ...
'! 161
53 ~~.c::~tum~ "11!!1 . . . . . . . .. . , :"1.~11fl,. ........ . ... .. ~ 163
~ ~f ~ " . . . . ... .. ... ., ... "' jil .- t - ..... ,."' ~r '"'- ... t T "' - ..... - - r,.. 167
5.5 ~~~or an 'Ideal Gas . ~ ~;. i + 1 o " 0 T + ' r 4 rro
5.-6 MJitbeJDatieat Statemalt of~ SeaxJd U ~ ~ a a a r a a a a l7J & t L
5:1 61Juopy~fot()pemS~ .. .. . . ..... . . ........ .... ..... ......... . . . 176

u C81oa~ of -~~ .,.~._ 'am . .......... ...... ... . , ......... ,. ._ ........ t. . . . . . . . . . . . . . . . . 181
u ~ WQt.k- a ... !'a -. a a .- .. ., . . . . .
. 0 a a. a 1.. il i - liS
ii 11 &.. a a .. . a.-S IL!!I O. ie+ ~ "
5J.O TJm Third Law 4 ~ .... l88 T J
s.JJ Enttopy trmm tile ~ic V.ewpciJnt ... ~ . _ _. . . ........... .. _.. _.. _........ . 188
199
6.1. P:mperty llelatio.ns ror HOIIlOgell!e.OiliS Phases . .. ~ ... r' . . . . ..... .... ... ., . . . . . . _ .. _ __ . , . .. _ _ ,
l99
u L~~ ~-!!Til,. ~ e .,-~ - ~ r y~r" "
1'! !'! '"' "!" ... ,_ .. ., .. "1"till'~!'"'"!! r-"T't-""'1 .. !!'II !I: IIY 208
6..3 ~Ulual Properties by Bqwmoos 1o f Stare . . . . . . 21:5
6-A ~Sy~s ._ ...... ...... .... ..... . 1\ . ... ..... . a.~ a.._ . . . . "'- ..&.~ ....... ~ aaa;a._. _ _ .. DO
'-5 ~.:Jillal)lieDia~s ........... . ....... ~ . ., - -"'"" . ~ - - -"" -- . . - - ,. ... . ., ,. . . ,. .. "' . ..... --r . . . .. 22:5
tatJ:ta. of' ~-ylllilllic ~s ., 226
"6-1 Gcnemliud Propeny Com:.Ja.Wms for G~"' . .. . ...
a .- a a r II ::t W II '1' I! .- !II II If P II
J
II

II 11 1 "I a a
..... . . ... ..... 230

'C a a .., II I a a
7 254
~ ~ of ~es:sible Rnid:s .. II II II a I' W II II II a S II !II 'II a II . . . II ... a I II II a II :t.. a a & a 2:55
~ ~~~) a r a ~a II' ._ IS :61 a L a jl "' -. a a .._ a ... r: a 11 "'- a .._ lj co a ~ a ._. a .i. a .. "' .. 268
~~ft\~ 19" "1~ . . . . . . . . . . . . ., ,"' '!! '" ... . ,., . . . . .,_ ~"! "'r '"' '"'" ~"' '"'I"'
.. . . . . . . . . . ., . .. ,. .. "'' ......... , , !1-3
8
&1 De Stea:m Po:weJ- l'la:DI__.. a llf llf a t. II ow t a a a , tt e t: *t a 1 a t " ill .., " a t a 4 o 2911
IU ~amt.~moa., ~~ . '""" ......... . " .: . .~~~. _. ~~ 3.01 ii " ............ . ....... ....... . . . . . . . . . . . . . . . . . . . . . . . _ .
u Jet :EngiJJe:s; ROC'k.l ~ . -.. "..... -'" ........... ~ ...... .......... " ... .. ..... , . 310
317
,,l 'fJie: CIJ1lOt RdifJJ.aiiDf- ~ + "' ... ~ ~ 317
,.,
l. .. .. .... a 5 a il .. of oo1 . . . . "'! 1o i p _. .... o. of o. oi .. "' .. .- ... . . . .
ttl Tile v...-~m~ 'Cyele_.~ lP' . , t ~ r I .. II t a .! II rlle 11 . . . . . . .,. I' a 'I ., . J' 318
"TTie ctlcb of Re~t ., ... ~~ . . . . . .. . . . . . . . . . . . . . . . tl . . . . . . . . 61 . . . . . . . . .. 321
3l3
~
..\lis-~ ~ri.grtli<;tn 1 "'~ .ej . ~- ~ ~ ,. ... . . . . . -- ... .. 1 - ~ ... .... .. - t' ~. ~ ....... .,. - .. ~ "! - ..... "'J .. - - . . . ,. "'t
'~
9L6
TJie J:le:ILt "Ptl:riJp. ~ . - r
L_iq:"~Ji~!<~D ~
"' " .. "' ..
11 ... .. a .1. ~ 4 <

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w ~a a

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r " .. ., "'
Ill a.._ If a " ...

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a ~ a 327
-. 3:!6
Obras pro egidas por direitos de autc

10 VAPOR/LIQUID .EQ~I: INTROD Cl1
10. 1 The ~of !q'uilimlllll . "'. "L ..... r ..... . . ,.. . . . . . . . . . . . . . . . . . . . -- . . . . . . . . ... . -.. 33.8
t o.l The Pbae Rule. [)ubm~ 1bccaJ:em .................... , . . . . . 319
I 0~ VL.E: Qaali~ ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 1
t 0..4 Simple Models for ~ Equilibrium ......... _. . . . . . . . . . . . . . . . . 341
I 0~ VLE by Modifiecl Rat!ult" Law _... ..... . ..... . .. .... .......... - ... 9 358
10.6 VLE from K...VaJue Correlations . ..... . ....... .... . .. .. . ~ .......... 363
11 SOIFJ(). THERMODY~ICS: THI.WRl' 371

11.1 ~niDl ~y .Re.brioo ,. 'II .. II a ' ... t a t a a I! a a t a a a a a :t a -. a a a a . . . I II a m
11.:1 The Cbcmial! Potential and Phase EquilibriA .. . .. -- .. -.--.-.- .. . . -. 380
ll.l Piln:i.4Ll ~.e:s ~ t .. "t to' ., po ., "' - .381
'I# It ,., 'II Ill' ., 'II .. ' t a 1 P a P a ... a a ll a t .. . !Ill a a 1: a "' a a a
1:1A The Jdcal..(hs Mixwre M~ ........ . ...... . - . . . . . .. . . . . . . . . . 39.

1.1 .5 Fugali1y Wkl Fopdty Coe!tflcieot: Pure Species. .. . . . . . . . . . . . . . . . . . 394
ll.J6 f \Jpcity a:ad fugacity Coefficietn: Species in Solutioo ..... ~ ... .. ....... _.. 401
IL 7 Gmeraliz~ Cotrela.t:iom fot the Pug,ocit~ Codficimt ... .. ................... 4U1
11.8 The ldcaJ..Solutioo Model . . . .. ... ........... .. - .......... . . .. .. .. . 4l J
ItS ~~~- -- -- ~~-,.., . , ............. 413 t:
J2 SOLUTIO "THE.IlMODYNAMla : APPLICAnO

n1 Uquid-Pbase Propenies from '\'l..E D4.l1.a .. .... . ............... @ 43C
1.1.2 t.!~s for Lfle._ ~ ~ ~y ... . ,. . ..... ,. _, ....... .. .......... 1: 446
UJ Propeaty Changes of~ ..... . . .......................... .. ...... 449
1M Jieat EfrecG of M'OOD8 ~'e!I$CS ~ r e 456
Jl CHI:MIU\L.RXACTIO_ EQUJLIBRJA
IJ.I ~ ~it.nl C-mlrdi:ti:QI:t' - ...... -.. . - . "' ~ 4::84
0 - ,., .. .. - .. t - t .. 't ..... . . . . . " .... 0 II T " "t ""
W Appl icatioD of Eqllili'brium 'C riteria w ( .b emical ltmttiORS . . . . . . .. 418

J.U The SIWkllll'd Gibbs-Energy Cbaop and the fqml lbriom. Constmt 439 r
13A F.lfa:l of Tempcmtul1e an the EquiUbrimn Cooslant ...... . ......... . . ~ ~ . 492

13...5 Ewt~ion or Elvi lfbtium CAmstants ... -.... 496 H ... H - -. n H .. u H u
13-' hlation of Bquilibrium Coo5nm1S 1.0 O.mpositioo . . . . . . . . . . . . . . . . . . . . . . 498

U..7 Equilibrium Ccnvenions for Single Reactions ....... . ... _. . . . . . . . . . . . . . . 502
1.3.1 Phase RuJ~ and Duhl'lll's ~ fur Reacting S trm . . . . . . S14
119 Mu~ "Eq_uiJia:.i:J, . . ......... ... ......... 518 0 ...... ,. . . . . . . . . . . . . . . . . . . . . . . . . . . . .- ......
13..10 Fuel CeJ.Js . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S29
il4 TOPICS IN PHASE EQUILIBRIA

14.1l lbe ~ Fammlarim ofVLE ......... ... . .............. _. ~. S45 t t .
14-J VLE (101J1 Cuh.[c f~ of State , . . ~ .556 r .... 11 '' .- &. .._ ._ ... .._
14-' Equilibrium and Stability ~ .. ~ ............. . ................. ... ... ..... ~ . . 575
I l..iquidJI..iqWd Equilibium (U.EJ .. . . ............ ~.. . . . . . .. . . . 581
14..S Vapodl.iquidiL_iquid 'Equitimwn {VU...E) ...... .. . . _. . :590
l4A SolidiL1quid Equi.1iNillm ~SU!) ........ , . ... . . ~ . . . .... .. .... . .. . .... S91
14.7 :M,B~ Eqlli.libri.1J.m (SVB) ., 1'1 ~
... , ... r . . . . . . . ,. " .- .,. ill
I 4..8 PqoiJibTium Adsocption of ~Gases oo Solids ... ~ . . . . . . . . . . . . . . . . . . . . . . . 606

143 Cbmoti4; Equilibrium and Osmonr !Pressure . . . . . . .... - . . . . . . . . . . . . . 621
Ob asp o egtdas por dire os de autc

IS 111Elt_MOD~ A!tALYIIS Of1PllOV.BS5ES 635
ts.t 1bermod~ Amll.~ of Sli*l~ Flow ~ . ....... _.... . _.. 6.3S
16 INTRODUCilON TO MOLECULAR TH111140PYNAMICS
16:1 M~ ~i' tOf Flll.iJI$..,-- - . . . ....... . . . _. .... II ... . - . .......... . .a. . ll ... . - .... ~ .. - ...... - .l .. &:1-7
16.2 ~d~Coe:m.~~Potc.nl:ial~~e l! l'l fl' tre -11"' " re.,, _. ., r 6S-4
163 b:lemaltinm'gy of ldd C"sses: Miaoscopic v~ ~.. . .. ........ .. ...... ... 651
16.4 ,..~Oil~ .._nr.-i'l'~ ........
~~ ~7~
-....:....:,........ .. -~-....~:-- * .- - .. - - ...
~YJR4 ~
lill_.lll. ~LIIIFI!U ~~ -4 .o ....... .~ ~ .. -
~
IJI._N'
1"
!II' ,.,
Aydropn Bmldiug ad O...e-'Ji a~~ .. ~. u -- . u .. u 662

~ Beh:lvum~~ies: ..... .. .. .... 4l M:S
.iiii . ................ . .. . ..... .......
'16.1 Mdfulllr B~ for Ml)~ Bcbavmr __ . _. __ . _. . _.. ... _. _.. ~ . . .... . ..... _ 669
IU "YLJi.by ~~~ a. ~< ' ;~ &.aa .. .- a. ... a!&. a-"_...._. ,,..;,.'i. .. a;a,a.a..-5 ........ ... .. ~ .. 672-
A ~Fadunind Va.ldeoftiJeO..CuWnt 617

B ~ ofPilftSpedi!s
C a-t c.,.Idts and Props ty 0....:S vi FOIIIIIIUon,
Jl) ~~eoa.p.-~
ru ~ Fl.uidiDM . . _. _. _. _ _.... . ~-: _. .:.t:\ . .. _. ~. _ _. . ___ ~ _. _. _ 68&
IU Solution of ~e Ptoblcms by t.t~ . ....... ~ . ~ ..... -... . .. -. . ~ . -. . 691
E D.l.etiKalcr~n~ 69'S
7l2
21 1~121iml ....... ._ ... ... .- . " ~ ......... p ......... .. ' -. . . .. . ~ .. .. .. 712
G 'l'beNlod,aamk Dltpantt
H rr-NWAC lelbod
I N~t"Mdlod
lllll!eloda
...
SuhiN!I
- bMio
--
Obras proteg~das por direitos de autc

List of Symbols
A AFea
A Molar~ HoJmOOfttC~MQY .aU - TS
A ~. empidcaJ equati~ ~ Eq. r(4.4~ !q. (6.761 '15qj. (l2.14)
d ~~on
a Molar area. adsorbed phase
a ~er,. cubic tqnations iif Mate
ii1 Pania1 ~ a~;bic equations of Mate
8 'Second vUW coc:flid~nt, dens:iry Qp.!mlion
B ~.empirical~~ e_.g... Eq. (4.4~ Bq. (fi76), E.[. ( 12. 14)
~
B ~ ~vlrial co.dliciem. delinal by P.q. (3.62)

B' secooJ virWI~~ ~mc~'iioo
~.. BJ Flmcliou .poerahod ~ttitial~ wndmioo
ll'ij lnc~oo secmd virial eoelliciem
b ~. cubic ~ns of5t:a.,
i, Pani.al ~. (Ublc cqu of 5lBte
c Tb.i:rd vimJI eoel!fidem, density e.xpn&ion
c ~.. empirial ~e.g.. Eq. (4..4).. Eq. (6~76}, Eq. (12.14)
t R.ft.toocd third-vm:aJ ~i~ dtfincd ~ tea
C' Thi_lid viriaJ coeffiamt. ~ apanskm
CO., c 1 ~___5., FQC.ralized lhird-virial-c:ueftidatt c-orrefudoo
c,. MolV o:r specirfu: hem: capacit)'. c~t ps~
Cv Molar or ~rlic bat capacil)~ constimt volnm=
c~ Standa:rd-sute beat ~ty, ,cfQlilant ~~m
AC
- p~ Standud llmt~ chaege of readion
(Cp)n Mmn l1eDl mpa~ty~ enthalpy calmlttions
{Cp }s Mean belt ~rily. entropy eaJcubdions
(Cp}n Me:a_n Aaodud fa1 ~ty. maba)py ~
{Cpls Mean g,1nda1rd beat capacity. CfdrOPY Cl\lculatiom
c SpmJ of 501Ll\d
D lFourlb virial CX!eftidenlt demlty ~pamion
D Pamnt.tu. aupiriad cqualiom. e.g~ Eq. (4a4~ Eqa(6.71)
D' IFowth virial oodfidet1c. presst~tt ~pansioo
E1 &Dergy l~
E~ Kindk~
~~...J . ......... _,--:.a~
Ep \,(I U."II~-.,.ul.ld.l ~l!<o!i.- ~ ~
F ~to freedom. phase me
xi Ob as pr otegidas por d1 reitos de aut<

,. ~
F.arad~;5 amstmt
F
A ~.. PQJe~i
S~sm fugadty
Ii
~ Foguclty. species f in solllti
G llolaio:r ~<Db$~3N- rs
07 S~tue Gibbs eDIUJ)'. spedes i
G't ~~ Gibb! coqay, _s~ J 6t IOIW:iOIJ
o" lh~ Gibbs~ G- Gfil
o R~~~aG -G'
l!tG Oibbrs~ t:~ of mixinl
6a= Sm_udr Git.t~f!Y cban~t cllf ~on
46{ Standard~~ cbaDp af fonDalioo
a Local ~billion of g_rt\ity
8c ~~ OOP.Shmt!:! l2. 11~ft~)"'" 1 ~ )-2
&i Degtmeriiii:Y
1l M'Q)8tQr ~c mlblllpy Q + P V =
n, Henry':~ ooosta.n:t. species { In sabdio.n
Hi &andard~ <tntba_lpy, pine $(lit0its i

.B PmW elllhalpy. speeies i miUhJtioo
8Jtcess mdJatpy ~ H - atJ
BR. ~ em~W.py H - u
re)~. <e) EDIL~ &e~~p)l' rof1e,J3alOO
All Bntba11py clRQw: ("ha1t") Qf 01Wnx; llso. blalt be.at ofpl.mse wmsitioo
Ml Red of sa1Diioo
AJIO S'EIIildard
- . ...
......... I ar ~
,_,.,., dmnn:
iittllri1WI
AB3 Slmldard !beat: of reutton a1 ~ te.mpm.ture To

b.llj ~ ~y cha-nge wfommioo
h Plauck" OOJ!$fAPt
l RepreseDIE u integml, delioe~J. .e.g.. by~. (6.65)
! Fmiil ~on pomntfaJ
x, Equililfrium CODSRml. chemieaJ Jadicm j
K, Vaporn"tqUid ~ mtio_. ~ i S / i/Xt
k Bol1zma.nn ~s ron5Wl1
c MniM l*lim bf sy.sUm ll'tll . titfliid
I Len~
IIJ ti.quathm-of-.state intetac.lion parameb:t.. Eq. U4UO I)
I Madl~l
AI Mol:i1r nws (mulea:Jiar weigln)
M Molar~ ~~c. mmsiC ~ propaty
Mt m
flrtia) pnipctttJ. ~ISS ,f r.oJuciou
Jf =
~ prnpmy ld - ,\fUI
J41 ~pn~aM - M'
hM Pmpen:y change of IDL~
Ob as pr otegidas por d1 reitos de aut<

1m
!:.M~ Sbmdmd pmptm)l change of~
~14} Sl.lmdard pRJpe.tty dlange of fonnmm
Mass~
Number of chemical speci.~~ ph~ role
A\"Opdw' nDI'Jilbl:r
'N'umber mmotes
.Molar RM~rnte
ii MOles of solvem per mod'e o:f suture
Nwnber&f mot~~ i
1\hsotute~
Srm:ldard-..._~
- - ~~~
-~
p~ Critieal~
P; ~~_j'C
~, P) functions. ae:ue:ralized vaporr~ correi:Woo
lb ~~
Pi ~~specie!!- i
~ Saturali(ln \I'8P)r JPl't.~ species ;
Q Heat
Q' IRait of be$1: trausrcr
q Vob.unmi~ ~~~
q P.J:mmet~ ~ ~~ ~r~
q Elcc~dwp
ii PiiAia1 ~cubic! equation of :sr.am
lJDivcJnl ps wmwn (nd;k A.2J
,.R ~oo. rutio
r lntmoolecuhr sepo.mion
Nll.filbef of U.~~~ .;hemica1 reactiom. phase J'Die
s
~
~ Of speci:fi.c eotmpy
Si Parti~ C'ntropy~ ~e5 i msolution
$E i&<:~ ~Y s S- sM
s Remlua) elllftOpy E S -- st"
(Sxl! (SRt l F~ gear~~..entnlVJ~tion
Sc Bnlropy ~n per nnh ~mtt cf Hald
Sc Ralcof~~n
AS Emmpy dum:ge of mix_UIJ
(! Sllnda;rdl cntrop' ~ or~o.
ASf SlaOdanll erut(JJJY "ban&r of fortMlim.
r Absolom lempenl~ tel im ar ~
r,. Crt"ticaal '~
T NOODIIl~Jingepoinl temperature
T,. ~ u:mpcr.n1R
To R~bap::q~
Ta 1\bsolule te.mpwture of surrouruliritp
TsQt ~~~~~
Ob as protegtdas por dlteitos de autc

, T~ OC cx , - F}I
lime.
v ~ Gr speci'k inte:mal enet!J
u lukrDJQJoeuhlr -~ ~
It Velociry
v Molar (If specifie \"'luma.
l) ~~lion of S)l'Siem drill b Gpor
V.e Paniall vel~~ 1 mmlmim
'Vc Critieal wlumc
v, Redooed \'Ghune
yl:' Hxce~ wlume ~ V - v.z4
v v- v,
6V
Residual 'WJ!lmle ~
....Jiir-... - or. miim~
\ib'\JIQDIS:q~~~ a1-
""""
volume
-
...
--~
~~..fi of,...,.,
F- I~
...
..~ ~tan.C:~on
w " lor([
w \\brk m~ f)lO'Wcr)
o rldbl ldea1 work
~ hJAt..W()d . .
Wk!Q l..usl v."ittk
~ J...ost..~ol'k m~
w~ Sba1 wort for Bow process
w. Sbiif't power fur OiJW pJVee55
z~ ~lole fmction:. species f, liquid phase or genaal
x" Qual__b-y
)"~ )1oJe fnetioD.. ~ t., WJX1f ~
z Cc>m~lb3'1ily fJJDtm iii P VI RT
4 Orititai C:OIDJII85Sibility f~tol E P1! V,. /.1( 'fc
zO,. z 1 Pimcoons, gmaaliud ~"bility..factor comUJion
z PMllion ftmcliOIIJ
~ pha.w compiC5511ilily fmnr. Kfinol by Eq. (14.108)
-- EleY.diWJ ilbtwe a datum 16eJ

. r . . . -111 _ ...a. fi - .:..... . - 1.... ....ud - L .__
~
'V''Vt;;i~ M! I-IJ!Ae f'SC-o oc mi),HJ,? ... ~n ~n a I.IJ.!.' _ p~
~ ~Q:$$ ~JDamj(; I~)'

[)enoccs p.base II'BDSWoo1rmm adsoRed pbe tc po1
~ due fw ao ideal 50lvti
~ vaJoeo far an ideal gas
De~ liquid~
~ phase mmsirioo fmm Hquld 'I D "-apor
Dmuos ~ud tkrmodyJAmic- prq;lerty
~ solid pblse.
Tr"''...-...-~ nJ.w..-,.,.. .......,_, ,....., JI:d . .
! ..I
~~ ~ ItO ~L, IJI\11~ >UJI _
,_,.~&~~,&
tJU1$lbOQ
l'!>elldes alcGd value of;m ~""e th~ ~pmy
~ \utpof phase
Deftotes. a wbJe at inlin:ite dilution

a Pu:nctiQP_, wbit- equations of state (lhble l.l, p. 98)
'" Po~)'
,a.p A$. ~pts. i<kntify ~
~/j As supmaipt, ckouo:& ~ mm.'lilioo from phasr ~ 1U ~ IJ
fj VoluDte ~ity
/J Pammetet. ~ubk- tqunlioM of sm~e
ri ln1e,vation c~t
y Ratio i()f beat~ C p / Cr
~ Activity ,coetftcie111. ~ies i in sofuliDP
d ~flr'Opic ~~t
Coa&m~. cubic equa~ioos of sbife
f
f
f l)
\Veil dqJI'
El~ ~tlivlty of~
tntamotecn1N pote.mw riD'Iatoe\
E :R.eactioo ~
~~ me~eney
,1 ( ~ COIIJPia.limtily
n Spread~~~ adsotbed ptlase
n Osmotic pre~
7f. . umber ~~f phi~SiM,. pb$ rutr
p .fouldfbolllSOD f:l~Jefficleot
,i-, DipoJc, moment
Pi ~ pohmlial.. spcci~ i
v~ Sloichi~li number.. ~ i
tJ MOlar specilic dcJWty .... 1/ v
,Pr cno.ai dcMiry
Pr R~Cied densit)r
t1 OJMram. dlbic ~of !i~
u tol~-~ cli:amda-
t
4l,
=
1'empenamre l""dlio T I To flo Eq.. (6.77). T
Ratio offll:gae.i:ty ~defined by Eq~ (14.2)
=]-
T,.)
~ Fnpdl)' ~JU. pute pedes.;

~~ fugacily meflkren_tt ~~ in w~
~ .- Funetions, ~~~DtJifdatibn
., . g Ocm!i1Dnt5; cubic ~uatiliJM: o-f 5tlle
W' Amntric; factot
Notes
Ai a Slllbsaipt. denorcs a contml YOinme
As D ..... a.-~nl . A ..._ , .11:.-..~o- &II'
~'"" ~-"11 '""'me~
0 As 1 5ll.lperKJi.pL ~dena~ tbe scmdald tate
o.~ ~ apatt.iaJ P'OJJcttY
~t deuotes a IDI1e mle'
Om~ dc&Mt$ a propm)" msolulitJg
DiffcNDCe opentor
Obras pro eg1das por dire1tos de autc

Pr,eface
1'bmnod~t0ne oftbo centra1 subjects of ~T ,is~ onlawJ ofmn~ a,p--

pnmiJU,. 1'hc juti&ation fOF ~nting dJe 5nbjtct from a dlemim--enJioterinl 'riewpolnl
il oor ~oo that i1 is nl05t effec:till"ely ta11gbl i.n me ,a mt_en ,o f ~ disdptp,c or 8ttldt
oommi~
AJdJOIJi11 iJIJffXhWr)" ID I JWe. 1he owerial (l( WJ I - U'tm~Jd DO( 'be l.bouglu simp]:e.
~ ~ :d no way to make b $in'r,ple, and ll ~111- PeW co tr. ~ willlbxl d.w a
d~ task of,d isaMuy l:ie8 ahead. New coocep~L ~ mel symbols appear ru ~ bcwU-
dcrin:g I~ ;ami~ ~ plB)i$Q. paiL A r. _Jialer ~baikUp is 11 ~ to dt::w:hJp
a~ to ~iiSOtl and w apply d.~ l,llindpfa iD the mtution Gf ~ ~b-
le.m. Wln'le ~8 me rigor~ of 50UDd dlnm.oi)'illlll'flic ..o!i, 'e lave
~ ~'a)" eft'"vrt CD avvid ~ rnatbcrn:atH:al eomplelity. ~ ~
~g ~ wrillllg simple acm~,.._wicc. prescot~ ~~ We Cill bantb~ s..pp)J
dr ~ morifttion. bu-t our objedi.vc, illm ~n for .0 J)eriws ediliaJs. :is a bleallneDI
dt.:tt ngy be ~ClOd by any studeHt willing co ~~etclsedue d~~
' "'-. c-.
FiA1ri clJ_.., - f d..- 1....-..JL .,.. IL - ! - -'-~: ..II ~--J.-- of . ......._
I .fill; ~ "'"""' . --"'T'"~ 0 ~ ~ ~ ~...m;. ll.lll3lii!IUUI'l anUI a ''IKPT~~ IllS
finllaw. Cbtpten l and4 treat tbe~~mre fldlmoreflfidds.ad ~
be:iL e-1f~ ~ t:idy ~of die tml ln!r 1o tr.a~imc ~ 100 ~law
aDd some of ill applicatiom Ill ~ in Cbap. S. A ~of the 1hm:t:llldyrmnie
pmpel'fies of plfti fluids in reb 6 aJ:kJws genmd ,fiPPlicatLOD ofiM fim md~ ~ W
provW furs~ IMtltleQl of flow pwcsscs in Chip. 7. Chaptcn 8 and 9 deal with
pwa: prodactioo and ~em pmcesses. lbi: mnaillda'of~bld. COPCCnled Willi bid
~ ~ UJp1 mb unique domain ofck~ rlbmnod~ Chap-
b:n II .md 12 pJ'OVide a~ e.xpnsitiM Gf lbe Uleol')' .and applicrirlou uf sr~
IM1I!DOd)namiQs.. Chr:mi~ c:q11ib"'xiwn is (AJc;:Rd It ktllfh in Ch_ap. 11 Cbapcu 14
driJ$ -.};tbJ ~ [Jib equili- iJid~ M MW14ecJ ~: Gf rwporf)iqmd eqDiJlb-.
rivm. ;mel adsorption IJlfJ osmotic equili.bria. Chapter LS fJlaiS tlhe 'l.bermodyn.mc ..,.,. of
reUI ~ idfording a review of IDilCb ol' ~ ~ 5mbj:tce IIL_atta' ef tbmmJdymunic;s.

Tb.G lD'JattriaJI of~ t S cbapltti is Qltii\C> daD adcqoatt for an ~ymr under-
~ ~ iiind. ~ ~ by n content of olbet OOUl"Se&. :is teqoired i1l
lhe dmice of wbal. is- o~ 1k fin.t ll diaprm i:rJckJdt nwerial tboag.htt ~ as.
W.:.ff .Jan-
,_..., .~ ~ .,.,~rutt.illl.l o.su
,..a.,....,:..-.l Cfi. ~ 5--. cxbJ.....-t=mt.
I!!'PLI' Whi9!e illllV
-~ 0- ~ ......lb-:sel.t'iala'COODe
~-&" . lin cbemital-
a:~Jineering thmoodynmliCG - proide4 these lJ chapteu 111aJ re.preseo_t ~ Wllt
lh~ tau imJ pril\i:ipl-es of c~ ~~ do not d!epelld on. wry p~
mar.1et of rbe ~ .o f .m.mer;, lhey an: 1m of aiiJ ~ ~tioos. Howe-~L.
tbe tJebftior ubibited by ~r-... ~ lifplids.. aDd solid$- doc$ dqlcgd WI ~ pu;MicuS.
~ and mOttprer 16 ~ Ill ttlllnldactinn lD mo!ealhr d.rmoclynlll!llic . (i) which
~is- ndly ml!de in eadi:er efmpttrs..
'l'IWl ~ L& ~\"e~ tomab it a useful reference borhin grrulurue .~~
and for prales.siooBJ practice. ~. ~ CODsidmd:it"Jm mKe ~I prudent seJoc..
tivity. I ~-t.p do DOl mc1udQ mtai:a ~CJ 'W'(tlll!y of ~nti~ ~ of Q' specllilitcd t:ttdJtn'e_
1beJe iDo'lude ~to po1ymm.. eJcdrot~ .and biomamrials.
'Woate~lO~ ln~.wdc-, prof~ mri~ wbo bJce~
uibtlled in \'alia lli'a)"i w cDc quality of dm ~~ cditiOII!, ~~ ;md io~y.. thro~tgb
~liwl :md ~ ~ IUJd q:it~;~ln. over the 55~ and six ediliom of il$ cvojut!oo_
1b aD we SleDd WT 1hanb.
J.M. Smith
H. e. VimN~
M~ M~ Abboa

.....
_.
t;
ltlu
!b! '& =. !.
I B~~i~~~ '~]t ~~~~~1~
~ .. J; .~. r. I"' II- ~~ i EJ!
~ s. .. I- r ... . s. n. ! .i g
~~ I .;.: 1
. . ST. ~
.~. .. M =
. -
. -
I i~l~~~~~ ltlrlrtlil!~l~. - ~~~:il
~- ~ t ._] ~ f ~ ~ ,. ~ ~ ~ I il I .
~
m
I tr [ . !f ! sr "" J D
~
I , - , I e .=- ~1 ~
st~;&" li c. qc. . I '
e 9 . .;;r
it e' :~
., c.
... } ""'cr I ,; - , . ;a
I ~41'
a
m
~
-....
~I f ~- s~. .. f - ~. A~.. 8' :~- 1 ~. ~_A t' Jl.-. I I
-
: I '
1.,
I . e;.. fli' ' ~ ~ ~ W
I
6 . . ... 6 en:
;! ;:,
n
i-
' =' -
Cl!l
Si~ a"
~
....
-a
( iJ!
lit~~-. K _ ,..
~ ~
- . I
r
.
S &
=:,. ,
;:, - fil
=;, "X
~
a ,, ::r
~-j~ar
~ i! ~. - ~: i!.:. :iii~ ~ .~
1
s IJJ.-. ~;: i
1
0 ID
....
P"
; . 1 . . . . . a:l
CL
c
. " i ~~e.~ . I - ~ 1ilti ~~'I
1 ..
i. ; e.
~
i~ != !
~ I ~~ ~ 1I f. j" ~ f ~ .. ~ ~ : ~ s i Ji ~ : g
:1!. ~ ~ ~ ~ e . I CD
.
Sl
0-
0 I
0"
]- Jl..Jall
~ a 'I ' l~~
~ 1.
1
OJ
(f)
"C r ls-r
~ ~ -- "")
i.
- I. h .ai
1 ;t
_ r
lJBtllo
i. - ~ - :I
- '1
.. ~ it i .. a e1 ~ ~ i .s u, I!. I ~ i ~- ~~ ~
ft
"""' !!.. ~0 ~
= (
"
0 . ....,
,...... , II ~. iiiil I
CiD
1!1
J.s!i~ ill.t ~ ~~~~~~~ !Sf It 1
co
a.
Ji'ii 1.lill JiJ i:1ti_ tr!li_t!

ru
C/l
"0
I twa. ~t l~. _ ;]-. -._ ~~ l'... l t 1 a ~.~~

1 sr 1 i
0
~
0.
JrJa. rJj , f.,l ~J .. [ .. 1. ~~fit

t ~~ ~ l
~
-a.
(ti
0
C/l
' o
:i ' , D: & 1
CD
Ill
c
1.2 DIMENSICWS AND UNITS
~~ ltt~ am pttmlrJ"~-&:. ~ tbmugb our 5eDSOJl pacepeioos and
not definable iot tams of a:D}1bing simpla-. 'Ibm' \lSe:. ~. ~ cbe ck fiilirion (lf -
bi'tnvy ~ of measure.. divided inl:ol spedtlc umu of m.e.
Primary umts halo'e been let by
i~ ~ami ille axfdied as the~ SJ*m otUum (ab~llted SL
fur s.ystbnrl fntrmad(IDI)).
n. ~ ~~ me
S1J unit of~ 111e dwal:foo. of 9J~I92AJI.TIO ~ of
mcft21ion associ;rted witlb a specifiedJ ~tnnsition of the ~ attr.O:L 1'bc nu:~er. ~~ m.
is dm ~ Q$t oll:enpb~ de6Ded as fbe dlmcw;r Bsht tm\~ m.a vacuum ~
11299 m, ~of 3 semnd 1be kilogr.am~ symbol :t& i.s die IJ1aU of~ Platimnnfjridiu:m ~~
der kqtlll b .lntml3liooal Bumlllll of Wdjhtt and l!tm$Ute8 at SNres,. fto.nm:. The unit of
tmapt11U11re i:i -. ktdWI:L, S)mbol ~ etpWID 11213..16 of abe lhm:oodynamic -~ of
me l!riple point of W'ater. A detded disew_ on of ~etnptnl~ Ute ch.ara.cbrisllic dimcmioo
of ~namjcs, b si~"Ml i.m Sec. 1..5. 1bg mo/.11,. !)!mboJ moL is d'e iaed as tt.e amoum of
mbsmnee ~ by as maar e~ ~ti~ (t\'g., 0Iblecuk:5) d:Jr#: arc aJmS iD
O.Ot2 ta ,., ~~ll. ThL is eqtlftl~~tgl to me gam .il'Dflfle ~J ~by dlemi.ti~
Mu1tiJ*s and dedmaJ flaaians of Sl uniti ;e ,~fed by~. ~in wmmoo
c_.._,.tm T-.t.."
1JSO ..,_ .:o.&RU 'LAUIC 1 1 J~rL..:-
Jl,~ L I~
... ('1m
- timeau
- - - IP -- - 1 em
- ,~'~~ -- ~ 10-2 m..
I
-- and ...... lb-....,~
-- du~ ~w..........
as I q~ J~ g..
"JWJle L I; Pftfba for Sl nus

Multiple Prdx Symbol Multiple ~ Symbol
1cr=- ~ f IfF lb a'to h

to-n pko p I ()I kilo k
lo-' taaaO tl lo' m;ep
_,--
1\1
Jo-6 :mic.:t'() p. lo' ,gtp. G
m-J ~mi~m m E012 taD T
Jo- l om1i c 10 15 pt:ta p
Oilltfsy&UZM Q[ ~' sudi M tbe: !EngiM eflgtn~ ~ 1lSe oml$ ibal: aJJe related
to Sl units by lbcd oon-Rrsioo {actnn,. Thus,. t'k foot ( fl:) is ~ liS 0.)041m., the pound
maR (lbm) u 0.,.453S9237 kg~ and me pound mole (lb mol) as 453.59237 mot
1,.a, MEASURES OF AMOUNT OR SRE
Nu:moo ~or mol.es. n

~ ~IJI"CS fGT a~. ystctu we w~proportion ro one: anmber. Mass. a pfimi~iw
wimoo1 cfefi Ditim.. may be divided by dJe molar M, eOIDill.OOiy rCiliJed tbe rnolarul!!r

lA. &Ric l
11.1
rt-=-
M
TDUI wlttme. ~gtb $iR lJf a~ t" n ~~quaJ11il,. lf';m_ ~ 1lu1 ~a
c( three lengths. b may be ,dWidtJd by . - ~ or1fllml:rtt or SMles of die sysll1n ~o yield
'tfPerific or 111oiw lc'O(Wlte:
ur Y~';:;;mV
Mol~ \"'iume:
Sl*ifi or mol:lrdimsity 15 ~as die ma~ of~ molar rol11m11:: p v-t.

~ qc.antities (V 4Dd p) BRi ~nt o.f dJe size of a ~ mdl are ~.es
of intMSAY ~ wrilbJe:s~ 1bey - ~of .. .. ~~ P~'&ll~ and
~~of a s~m. a;kli~ ~ lbat .-o:e indlependlm1 of S)'IU9D ~
1"4 FORCE
n. Sl unit off~ is the tJrwtvr,. 5Jll}bol N, deJi,-ed from NeMDn" , seeood bw. wbldl a:-
~ force. F as .:be product of Dl3.;1S ~r-1 and QOC~~ a; dnts F = ma. Th.e ~
de'Jined as 1M fon:e wtllcb Vilhen ~to a mass 0f 1 kg ~!liD: ~tfilion of L m s-~
lhus the~ is lerh-'ell unit~ I kg m - !_
In the En8fidl ~ring 8Y~ ,o f uaiu, f~ i ~as an addiciomd iodqJeruknt
~on atoo; willllengtb. lime. &1'ld r~. The [pOUnd forar (\tbr) is defined as 1ltal fon:e
a,ilmb ~111tes 1 ~di ~P~r~iJ n~ 740 fed per second pu9Qmd ~ua".s ~aw IIII6t 'ben=
indudie a dimensional ~ cmn.1'lml fct ~ Vtitb ~bit deftnititto:"
I
F ,;;;;r -IIUI
8c
I 1
l(Ibt) - X l([h ) )( 32.17QfU( )-.-
Hi: .
and k ~ 3117400bm)(fll){lbrl .. 1 ~ >-:

Tbe.pound}{vt:t is equi\\'Die:nt it04A4822l6 N.
B~ force and llDIIS'8 aro- diffaem eouce,pu, a powxil f'"" and a pound rlltW are
CitTc:rent quantides.. and me1r lll'ti.l ~to UOt ~ QQe WH.KbeT.. ~ au equatioo ~ both
!mil$; Obf) gild Clbm.), the dimeD51ooa.t ~t ~ llliW also~ in the~ to Ut.'lb: it
dimemiooally correct.
Obras protegidas par d1reitos de autc

4
~,Jrt propc~ty mm 10 tbr f~ of grariiJ oa a body, and i.s cerreaiy ex-pressed in

newtt.iM c.r in poand!l flJT(}~. Unfoll'tUD&ely. SfiDdards of are often cllied. ~~ and
use of a bilar:a to ~ ~ is CIRDI! ~ilflinJ.." ~ one iiiiHist d~e~n wm abc:
Wllf.Ot -~~Of lml$S.
or--ant wbem "'Weiglnw is med .a casual infonnaJ way. m
Example 11.1
M astronaut~ 730 N in HOuston. T~ Vlhete the~ IIOeal8tX:Bieration of 9\\Yily
is 1 ;: 9.792 m s-i. What are ltte astrortauf$1!naS1 aru:l ~~on the~. where
r~ lmm~ s-~
SOlution 1..1
W'U&o :r , N~mn, taw is: F ~ m1. Whelme.
730
m ~~~ N ~ 14.55 N m-1 ~
1 9.192 rm 5.-l
~ dM oewton N luG the lilliH q JD s-2,
m -145Stg
11lit lflMI vf the llilroiDUJI. ~ of lOCation. ~ weighs dcp;nds on ~
~-~ ~c Tllm 00 me Oli}Qil the ~ams wejM>.t
'""-'"" ~ !jiiii!ILJ!!I \IU. o-"""" ...;y
................ ..............
'9 ""' ~
Ffmooo) -;:;;; M8,11'100D) = 14..:SS b x J.67 111 $ - l '

or f"fiiiO()O) = 12-4..5 q m s-2 ~ 124.5 N
Use of thE Bn.;!tisb CllJmeaing ystem of m ~uirrs ~- of'lbe s-

~s -eislll to flbc) zut the watum of gl CO (tlM:sl- 2 Wi~ I :N ~m oo
0.2l4809(fb,) 100 I m w 3.28Gl4(11):
Wetgbt of asb'ODa\d in HOJ.Moo .; ~ 64. 1(fbc)
Newtoo~s law then gives:

Fgc 164-Uib;) ~ 32. 17406b.m) (ft}(lbr)-1( .t-2
m = g =_ _.......--....---3-:-
~-~...,]-
(fl_)....;{s-.)_..,..2::"-....;.;.........;..._
m. ~ 164.3(lbm)
Tbus die .lt5k'Onauc':!i mass in (lbmJ m1 ,...~ m {fhiJ in Houston are ll.l:iiMntml:_-w
i.IIDD6.111be &3J.De, bml &n llbe: moon this is not tbe a.se;
mg( moon) (164.:J)(S.48) 'WI ill....
F( moon) = ~ - 32..1140 = -"0.-.,..q)

tf I(itr i
ce.
! S' J. -
!a IL:u.i i I{[;'I~ l
~~-~; B. a'~5
it: . rr ~ ~rc I
~! r ;'I ~ ~~
J~
~ . ~ ;,.
~ ~ gt l i"
f ~- lis !I:lil t
~ ~J
as a ~
~.ffll}. ~
I i ...
i.n lr"~
~
f~ i~ J
c
~ IR. ~ i ~ at:
I
t' ~ ~ tR t .J81
= .
~':1
J fI ~ 'i ~ :
li
i ,~ .~. ;- e. ~ ~ s 1.. ;.. ;;~ ~ ;; lt:1!. '... ,, , ~
~ i.:: ~ gn~ i 1
~I Js.e g~ ~ i ~ 1 ! : ~ g! I$, i I =
9 a :a
I SL:q li'
= .
a In ! 1
I
r 1f ;: ~: ~ ~ ~ ~
t!
Ill ~- ' tt ~ ' I" ~ e.~ - <!J Ill' '' < -
l!:
~ !
'
! ~ ~~ l !~ i.: Ii ~ ~ ! ~ i Iii l.fi. i!. ;I J. i :, ~ !.!
' i. j ~ -ut;.I
I.
:1
r
J.~ l~~r. IB~Q ~ Q~~. ~~E!,jlp.l. fl!! I~lrIJ

i;
I" s ( r- ~ ' ~ ~ ~I c.~ r .B') a. 9 ~ . ..f"
" .
:=l !I
;:
' I! . . =I f
0
...,
0"
tl)
CfJ
f 1: I ~ la..=a.~ J a~ J.P ~ . ;;i&~ ~ !ti i 1', -- :~r j aa. ,. 1:i.
.oil ; e.
!.
p
. 1 1

i , . . : B- '-.. ~

I
"
. ~ ~ I I
~
. ~ ~ .~ ,~. ~
~ ~ 11
5\.. (
I
"C
a ~ of. ~ a 1: s ~~ ~ l ~ ,C ~ .a .. ,f ~ ~ ril ~
i;
L . 0 C '
~ ~- I ~ ~- - . a. . . i iL s 8 il l e H ::c =c. "' S . w!i ~ . ~~ ~ , ~.. li
~B."'! ~!, : ~ =- ~ ~i' ~ ~~~ ~~: ~ r ,. 1 ~~ [~S:
ce
c.:
Ill
IA ,m c
(t)
l [
"0
...,
0 't:il J
w~.s.~ ~ fi! a~.. J~ iii ... J) tl ~rt!~ If :~ ~ ~
:!.IIJII~~~~rj :- JS.l'l .. i ~:; ~r:i,.,l 1 :ttl.
t1'fi~;ij liiJ.i~ ~
r lj
Cl. ''f' I!
ro p
s-
(/)
-
J fw I . r . t\($:g t . ...,
0.
CD
ru
c:
r'\
&aW!: directly related to die Kd'7in ale b)1:
T(R) ~m I .&T K
the .Fabnmb~St scale is relat:ed to me IR3Didne. sca1e b) an eqouio.n ID'Iai{)got.tS tu b Mm~on

~~the c~ms aDd Kdvm~
,r P> =TCRJ - 459.67

1b.us ribt kJ.."Cr .1imii of iltmpcR.toi!D ou die: ~ ~ -459,.6.7 F). 1'be 1rektioo
~ Fahmlbeit , Cf , : .
tffl =; 1.&~ + 32
~
.YI!;
..
~
nnritt ~ ,..~ M~. am ..s.._ ~-" *--i.liftb ftl!lrh,, ,.. .._.._
rv-_....,./l y~~!J~ ~~ ~ ~ - - IU_~ ~____llg '~1-eJt""-".ll.Y "IlL '!!'l"@;t
..., ~~.,~ ft."'\
IS -llla.'t.. ~ J.
1be Cehins depee :md lbe kelvin represent lhe wne lemperotb11e inlen.or:ll, as do the
fiifllttllleit ~ ~ ~ c:.. Tilt tebl.io ~ tk: {our tm~pcratuJie ~ an:
shown mFt,g. 1.1. In~ absom ~is implied b)! an uoquallfia:t
Rf~to~n..
1l!& IPRESSUR&
1be ~ P aft!td by A fluid OD lli smf!iiZ . definrd M ltJe nmma[ fun:~

by ~ ~
fluid! pu unit 11a of t'be mrfxe. If ftm:ei 8 ~ in N and area in m~.. tbe mtit is tbe
ne ~m per sq~ m~~ m !lli-~ _.w
thG ~. symbol h. tltt huie Sl: ~ ,of pra~
ln 1he Eogfish ~ system a aMJ~~~DJ unit is the pound)b1r.r pY rmatre .in&b ~).
'fbt; ~ ~ f'Of p~ Ul;bJ..tt<I6Dt ~ tbt dltad..w~ii#Jt puge in ~biro a
knt:Mn feme is, balanced hy .a tlu~ ~ ~ ,oa known ~~ Wbtooc P F1.4,. A =
siq)JG design 500Wn in Fig. 12. Tbe pis.toa is camUlly fined 10 Ole cylinder ,m itjng the

7
cJeamnce ~ 'WeiPJs are pl:ad on the: pm anJiliM JIN'$su:re. ofme oil whim tend! to mate
am pistml Jislt:! b ~ batmm! the ~ of gmv.ity on lhe phton .and an dmt h su~
Wlllh 1M form gl\'lm by NC"Wtnn IJI ~~ pres.surc of~~he oil b~
F lnR
1'- - - ---
A A
where m 1 t!Je. mas of the- pi51:m, piiii:. WMI ~ ~ .ii-lilx lucaJ ~kmlfDDI nf 10fltr. llltd
A is, ~ ~~liamtl a.m. III' lhr !PlsiDD!. Gauaa m~oo usr !1lk::b Boutt~oD pn~gcs.
are alibmted by COIIIpmi:son with rdemd :i@ht gm
llpNi2:
Dead~ illoiMY.,...
IBtcms.se a ~mcm oofull\fiof ,.,.~ tlwd llfidtrw loft~ of gntvil)"~ a~

at iU in dlMct ~n 1D its beiPL presswe b nlso ~ the apiwalil:Dl beilbt
of ftu:id atlumo. Thi~ i!i the' ~i~ fPr ~ ~ ~r ~ fur- PIPAII"C ~
C~ of beiJM iO ifOJCe per unit.cttea follow J1urn Newimn'i lllw applied lG If& :foree of
gmvity KtiJw DD the liii5S of lhdcl die tvlmnn. The' ~~~US. aha by: IPil = Allp., wlw:re A
l.bc ~~~ Jll'r.li or die mliW~~~t. b l iits b1~ llDd IJ 1s the ftoid dc!miry. 'J.bm:lot.:..
F' mg AhPI
p 1:Z "i ;.:;; A - A 1li:a ltpf
"lihe ~ ID which O'uid hriJ.hl ooCftSPOI1ds il. dctrnnial=d b thl:l den.eilty of die ffuid
wldch ,depeJJd.sm lu idt:nld) and ~~J ami~ focal~ of,ptv:.iry. 'lbus me
(lortl is the ~W't ~ilkut or I mil1imcf.a- uf IDCIWJY II (fC iDa~ ~
field. W H requd tD LJ:\.311 Pa
Aoolha wm or~~ is the Slmldald~ 1'r~~m~ llleappw.dnic ~ pii:I-
SUl'f! 9medilb)rlbe- ,earfb ~ 11 sea ~oaL ddinm 101,3"'...5 Pa, UJI~325 kPa.. IX'
0.10l32S Mh h ~ 1111SI IIIIi' ddiued Jo5 ~ . cqRI tofl98692l(mo).
MaY pte:ml1'e gauges give ~,.gs wbkb mre the ~ betv.'l:ell ihe pregrure of
intenN md dJc pn:m~re urn~~ The:sl: nadinp ;n kDawo . ~
pres.wres .md am be com~ co abmluu pn=siiiM !by .Witim ofi bc bmullmir ~
A~l'utt ~g'5must'br~d in~c~~
Ob as pro eg das po d e tos de au c

a
Eumple1.2
A dea(S..wergfn gauge wllh a t -ern-diameter piston fs ~used to meaaure ~pressures very
accurately. In a parllcular instance a Ji1US of a14 kg (ltldudng pl$ton and tpatil)
bfmgs il intO balance. If me local 'IOCl8lem1ion oC .,.;ry Is 9~82 m s- 1 what Is dle
gauge J1f8SSUf8 bertg tmeasured?' If lhe tbmuiJ;aetriG ~re is 748{10w)t wtlat is the
absolutJ s;tfe861Ue?
SOIUIIO:n 1.2
1'bt ~ defltd !)y &fiiVilY OD - pl&mnl J.mlt and w-ei..gJB ils;
F- mg = (6..1~){9.821 = (t0-295
F 60.295 1
04up ~~ ~ i ~ U/ 4 ) (11' ~(l)i = 16:n N cm-
"lbt ,absof~ ~ islbtrt~
I'~ 76.71+ 48.){(UiJo1333l) = 86.14 . ag- Z
,p =861.4 k.Pa
lxampla 1.3
~~ ar-o me maGing on a manometer filed wilh rnetCIM'J' is 60.5 em.. The klcaJ a.cr
cea.talJcn Df gravity Is 9.784 m s- 1 . To what pressure does this. tleight m r:rt8rCtiJy
Qf.lff&Sp)nd?
Solution 1.3
l ccaH ~equamioo mlhr p~W, 1~ P ~ hpg. All :r.- lhe dmsity rOt
mereuJY - I .53 1 cm- 3 "'l'kn.
P ~ fiO..S ~m. 13,..SJ g cm 3 M 9~714 m s- 2 :::;; 8,009 g, JlD s-l em~::
or P ~ 8.19 kg m -l cm-2 ...- 8.009 cm- 1 .80.09 kPa ~ 0.8009 baJ:
1.7 WORk
WOJt W . pGduouod w~r a r~ ~ ~a~ B.)'~ me qu:mtlty' of

~ i:s @ive.D by tbe equalimr.
dW = Fdl (t I )

1.1. Wc.rt 9
w11m: F is me~ or lm::e ~g along me fine of the~ dl. Wbm. inte-

lfllkd, " equadoo yidds lhe WOii m u fiDilc p1~ By miiVCIIIiun. \lt'Drk b ~ 11$
potiti\.~ 'Ailcn me dl&pl;w.ment ,i:l ill the .sm:m: ~ ,b 1M applied on:e and ocpDve w1b9l
they me in~ dbedioosk
The ~"DDl whidJ ~~ u ~ in \nJ~ of a ftuid o[ttJ!I ~lr.IDJ in
l!bmDodymLIIIfe~ A eommrm eumple ~ !be mmpreiiicm or s ,p AMim f a_ IMil in 1 q'futder
~ &om lhe DID'~lllm1 af a_~ "he f<Re cxm1al by 'd E pb(oo oo lk bid ~ equal
l01 dJc t;J(Cduct of~ pl$JDI1 ~ ,BJ:ld die )Xe~tt of dJt ftuid. Thr ~ uftbcpisum is
equrd w lbe total \'~dwl~~ ofltbe IDiil da\1hled hy the Mea c flhe pktorL Eqwmm ( ~ ~ )
lh:rd'orr~
(1.2)
Hqmd:ion u .l~ apresses the wort rdooe by 0 finite~ or upami:oo pmce:ss.7

f'~ 1.3 ~a pudt fDr ~ of a JB5 fmm pabill wid~~ \!D~Dmll! V{ at
prewn p, m point 2 with ~ Dllll! 1q - pmwae 1\. 1bi:& pam m1ata m.: p-ess~~~~: 11 my
pmr.. or ~be: P'~ ~~~ ~~ 'mJUDle- Tho WVfkrttqttbtd P sn b1 Eq. tm~J ;1Dd h pUflU'ioual
1D b ara l'llll!ler ltM curve or Fi~ I .J. 1'he Sl unit of"
1
die oewton..JildD cr jau:Je.
s~ J. In lhc En;liJb ~ ~the unhroftet~ LDI!d iS tJ. bll~ptWJndjiur? (ftlh,).
Obras pro gtdas por d1rer as d aut

10
1.8 IEHERGY
11llCl gmem1 ~e of c~n ,o f eneru was cstallhhed about lSSO. Tbc g_nni ,o f ltbi$
pnncipJt as it appJks ro mtelwriC$ W'l5 implidl bJ dw. "uk of Qalileo CI ~L64l} and ~~
N~ ([642-1726). -~ ' follQw& dkeal'from Newmo~~ seamcl Jaw of ow0on oocc
work k ddned os die p:mctm:t Of {mere and dispbrr.lanm..
Kln.l/1: En4lrW
Wbmabodyafmassm" acteduponbyaf(ft!C .F~isdi._~ _d~tl:l dulri11ga ditfrq:qriaJ
~ (lf~ .dt, dJe 'rOJt douc is gi\"'eD by E.q. (1.1). lncombin ioo b 'NewtOO~ssecond
111w meq, titm ~
dW = m~JdJ
~~is.~ Q duJdt .. where,. ~me wlodiy or me body~ ThU&.

du dl
tHV =WI-d!= rn-411
ill 4r
Beca~~Se ~ d'dlnitiCJo of 'Ciodry " 11 e dl/ dt'., 1be Q~ mwar ~
((.4)
Bad1 of the qumtJti ~m~ mEft. (1.4j j Q tladc eMTI.}... Q K'nn i:JlUIOdOI:ed by Lalrd
Kd'iin1 in l8S6_. Th by~
(I~)
EqUIItitJD n-4) ' l.bit tbe \\Qft( d-ooe m ~ hod) m~ it from an initt:al vetoci~
P:a to a fiJm.l ~ D:: is cquM e the ,c bmtc in~ C1JC1U of me bod)'. O!IO\t"c rdy, if
I m.nvm1 body ~by the actioo of 8 mlsbnl ~ ftlr work doot by the bod)' is
~~ ro if$~ im ki.oetic ~Y In lhe S1 iYili!m of uniiJ with mass in q ;md '"'clocity
iD m s= 1~ kineUe m1911 E r 1w ~tta; fJDits or kg ~ ~-1 B~. me newKm is .ne 4XJJDpO$ill!
unit lg QL -l. EK is~ mDS!IGD-Inelas Of joules. ln ~with Eq. U .4). tb_D il h
"t ,o f
'Thum.'JM (tli!~:Jgora. ill EQII3b pity - '-fl . . Gc'l:iDm pllysiN

10:1 ro-ec~~or~

1.8. F..oelgy
uem, ldn;ti~ cpeq,y is c:;~.~ itS fm.,2 lac-. "~ tr

rn lhe Euglisb ensiDCerin,s
has dJe w~ue J2 ~740 axt 111e lmib .fltJ.m)(ftJObf)-~( J-1 T~ms u.e tmit 01 kioetir ~aau m
.
lhl$ sy~em i~
PlJientlal EIIINfiY
If a body of .lUIS$ m iJ ~ from :an imlbtl d~ ~ 10 a final eie'V31ion z1. aa upward
force m le:lst equa11o 1bl: eigld of lbe body most be exermd' on it. and.Ibis fo.reo .1 m~,.-~
throu~ me ~ tl - : ~die ~jght of tbD body , dR' fofcc of~ on h1 tk
mi:tiimmo fatr.-e ~ is; ~ Illy ~1COB" -w:
w&ere g is thE m.I ~oo ofpality. The. minimum, wed Fell~ to ra die body
me prudlia ,of~ fmfre mc1 me ch.1n,ge in eiewtioo:
'W -= F (tl - :1 ;; mg(~ - ~t )
(t6)
We see from Eq. ( 1.6) ttw 9o1Jilt. woe on 1 ibod)1 iD ~ il is qual to rdle ~in dJe
qutmti.ty m:.g. Com~. it a !bod)' islowemt apimt a RSi.stin; fOI'Ce cqu;alto its \\~, lbc
wotit dt.rne tty ~ bod~ ~ ~ (0 Ole change In lbe qa:ntity mt,t Each ef lbe quantines m;,g
r
in LEq. U.6) is a~ .,uv~' 1hu by lklinitkm.

(1.7)
In the Sl ~ vf uniu -.i1h in Q.. dmtticm in ~ aDd die ~km of gnvity bt

m s-1 pxcmia.l ~rgy b die amiJS oftg JJil- s....1 This i!1 the ~or~ tba mtit
r4 wodt,.in a~ wilb F,;q. (1 .6).
In lk Eng)l en~~ system, ~rulal ~ is ~ as m:cgj g . Thus the
unit of potentia] ertef!Y in dris ys1em :
EnerfYCOII&rWitiOn
liD any euminlioa of~ ~ m ~ m*. ~to fi:od rtn ~ ~ts
hiM ttln3in coriSiaDI mprdloss of~~.- wbidl ~ One Slldl quantity.. em, recog,-
lm xd iu 1he dlevelopman of rnerd~a~Ue~ is rm:ass. The ~ miliry of the law or ~lioa.

12
of tw~SS su~ lbtil olhtr CV:J:JSr~OO p,ri_ndpks ~ bo of ~.j)le Yalrllf:. l,l.'ltb R~

~~ I.D rt~Eig)' obselve lbt q . ( 1.4) and ( l .:fi) .bceh iiHJw tba1 wgk Gone. 00 body .
equal to die dlange m a rquantity Vibich I~ ~ ~lioo1 of the body io ~ lo it$
wnwndinp. I~ ~~b ~ the W'OI1c petfDlilDCd can be ~ by ""arrying outJ the revene
process and lliUIJ1ling ~ .bally lo i . i:nitmJ emtditiOll~ . obcscr~-.tia . ~~ tmtlmtll:y tn ~
tboiJghl 'b it_. if b work dont em a~r' in u:cdmdill,git or i:o ~ i1 can be subsequendy
~ then the hod~ by virtue ,o f its ~~kM:ily or elewlioo CDIIlaW the ability or ca_paci ly
It\) <)o rt.b \\\~ 1\i:s ~ pto~d SO usdill in riJld~)' i~Dteluinics iblt the ezrpacit)' rO { ill
bod~ fm' doing wo1k .-as gi\'"ell lbe ll3lllle ~ ~ a vrordl deri'\"Bd fmm the G1eet w momirng
+-m woct~"" H~ the wort ~or &L'ftimttirtg a body produces a C'b:mp in it IUtetlc mu,gy:
and the wol'k c:Jimc on body in c~adn.g il ~a change iD t pll1otdiJJ.rM~~
. = 1-;:::: A(mzg)
1f a ~ ~ given magy wbeu it is eleva~ 1hC!D tbc body ou ~-cs w- ~ this
~ until h ,Wnrms ibe -~ of Wltidl it i.s m:pabf~ Ali *'1it~d body, or~ to man
freely. gain in kioetU: en191>~ ~ it lmei iu1potential G~DJY 50 that .. ty far dcing
vrotk ~ ~d For a frJy rumos. lxldy 11ns ~ dlac
Tht: ~idity oftbi$ rc quatim !w hem~ by~~ 1bw the deelllp-

mmd o1 the concept of enei'8Y led logir.ally to 1M tho principJe of GDC1'IY C'OG!ia\-ation Dl' all
JHQY!Iy ~flkpl ~t!B-. Ample CZJ~ilimental e\~ to JustifY ~ gene.mla1ion '\II
~18ined.
Olhr li of~. ~ 1~. ~and f~S\tita\lnnaJ ~mt,:t~ ~ me
possl'bleJ 1'1111= ~l ol:nious is potmtial aJa!Y ofcooiigu.ruioa.. Whm :1. ~ping Gml~
is dane lby ml atanal r~. ~ lhe ~ can 1~ l*f~ dlU. WCilk a~Jl$l
a ttSiwng [tlrC!e,. Ole spdna ~ ~~~cy far doin8 wmt. 11lis is porenti:d energy of
CODfipnlttoo. ~of the Jame form ~a:lm in a ~!d n~.t!Jbn band or in n baT of MeUtl
~f~ mlbe dasric region..
The~ aalit) \l' lbG priOO.:pl(! of f;octK'fYalion .(l(rpSt in ~ li$ iQg~ if Vlr!C
!look opmt M)dt itsdf as a Corm of~ 11bis is dearly pe:mi.ssilble. becanse 1bolh tinelic- and
pgt:mtial~ cbmg~ ~ GqUd :to the wOik ~ iP ~Ibm l[Eqs.. (J .4JIIttd (l.6)]A
JftJwe\'et'.. \\uk is energ lrt tmJUil and is cever ~pn:lcd as m.J.ding in a body. '\\'hc:n w-or\ is
a.'
dooc and don not appGar simubB~y wort ~bcre. it Q; ~ into anodlrt fnliltl
ofcaeqy.
Tbe :body m assembla~ em wbidl atl0tioo is f~d tWlcd ~ s,~l1!'frl. All 4lse iii
QJicd 1.111:: SJHro~. Wbm V~u.i i$ done., ii is~ !by me~ m tbr. ~ or
vice ~ arul la lei'IY ~ llrUSfetnd from tbt sua roundi~ to the 5}~~&. or die Fe\~. [L i

l3
onJy dwiJJg 1bis t:ri.UISt'tt that rthe fof:m ,of,~ kllewn watt eK<tS.. In cOMJust, ~ and
~ ~~ ~ v.ifh Ole sy.Nm.. 'l1IUr '~ ht:N.~ ~ ~ wb:b ~ce
to ![be swmundiD!5~i.e.! tmetic meliY ~ GD \~ wilbJ respect W roo mm:JIIlJll:tiBgs_
:md porentWJ-energy ~ an tlev.aoo willa 'f'CS~ 't o 8t daaJm kveD. t:~atms~$ m kiMCk
and. ~ eneJ'5:Y do oot depend on lhe5e reference conditions, Jmfl'idl:d IIIIey m:e de4
Examrp le 1.4
An eleWior Witn a. mass of 2.500 kQ rests ar a r~ 1o m abe'Ne me baSe or .an; ~e8-
tor shaft:. tt Is ralsed to 100 m abc.MJ the base 1of fie shaft, .t1ere lbe cable hOking it
breaks. The elevator ~atts treey ro lhe base of 'tt\e studt and S1fik8s a SU'Ong spring.
The,spring is designed to bmg the eiBvator to 1881 a~ by :maans al .a eateh 8J'fBf19&"
ment 10 hold the,e ENA~or at lhe posftfmr d mDimum sp(flg Qlfq)res&fon. Assuming
the emir& proce8S to be friefiOnJtss. and taJdng s : 9..8 rn s-:. oak:t_date:
(a) The pOtential enerw of Ul& elwator in its fnitia~ po8itiQn relative to the ba$e of
1
the shaft.
(b) The ViPOrk done 11 raising lhe rfJievatoT.
_ The- po
(c) ' - IBntisll '- . m
_ _ energy _ D.-. _ _ _ lin lits_hi,.,
....IMilor
,..., "' ........... pos
.,,v;!M - - ~n
!J!U [,_'I_.;ROII,.,.
...~_,. to_lth8_"'-~-~
~
of the shaft.
(d) The wlodty and u.etlc enetQri of lhe elevator Just before 1f1 strikes the ~g.
(e) The potenlial enar:gy of the compressed sprilng.
(t} 'The enetgY of tnt $)'$IMl oonsistlng of me e~ettarm and spnng (1) at \be swt
of 1M prt~C~A. ~ vtben the elevator reacM8 tt& mulmwn !h eight (3} just
beJore the eevatof strikes 1M spring, (4) der lbe elelialor has come to rest.
Solution 1..4
Let sub.saipt I ~ die ini~ ~ iUbsaipt l. oondiliom Whal dE
de\-amr is a1 j bfgbest pofiition~ and :mbsc'lip l. eomfitio.ns just before 1he el~
. - .......:t...-... ~ ~n
- ~ ~~ q.~ '"'If"" ""'"0'
fa) By Eq. t 1.7)._ E~ ;;; mt~8 ;:; (2..SOO){ ~0)r(9.8) ~ 245.000 J
(b) I) Eq. tl.l)~ W = 14 l~

F dl = lz:.
. ft
mg dl = mst:1 - ~~)
wheDce- lV = <1.100~(9..8.)(100' - iO) = UOSP I
(c) By J34 ( 1.71 Efil !!!'!! m ...U ~ (2.:500)(100)(9.8.)-= 2.4~0.001 J
CJC:e thai W =E~ - E.I'J ..

Obras proteg1das por direitos de autc
l4
(d) Fiom the priociple <d ~~energy. Oll!el may v.rrite lh;d
lk mor the ~Do- and:po~ r _ dwinl the proa:s:s fmru coo-
dibl:m llO 3 . 10! lhat is.
~r" E1 und EPJ. ~ l't:to,. ~-

B~j = E'z.-= 2.450.000 J
(d ~Cb ~ die~ tDCJRYOfh~~Jringmdl lhe kinetie JleQJY

of 'tile~ IIIDSI rum t& ~.
6E ,.,-,llfbW 4-B I' (~1U(If') ~ 0
1'b.c ~ J*l. en~ ~ ~ 5PriDJ llml the ki~ manr of tbe dor
mw are 7.ertY. ~ tile final fK*IXial ~mers' or the spring mm:t ~ ihe
!kindh= e:.-g of the dewalm _~ Wun: h ~ d. ipling. Thus die fuml po-
ltmtial I~ Clfme ~b. 2A!Q.000 J. 1
([) 1f ~and. OJcsprlDg m~~e tam tbe &)'5lem. the imaw enam'
of the ~ - " ~ p:ilential ~ of(bc~-r~at l4S~O:O ' Tbo loW~
of 1be sp;cem em dlanJ~e mlty if milk is tmlldeiT'ai !between it and me 'W.I!rOIIOd-
:iqs.. As the ~rm is rai~ wed i do on d1e ~m by the ~ ,
in. ~ lli:DOUIIt of l,lDS~IDl J. 1b.os lhe ~~ of~ sy~ when dE elewtar
tea:lbb IDKDnlDD hi1hf 245.D00 + 1205.000 ; !ASOJXIJ J, Sob ~
~~ oomr ~ndmy wilhfn lbr ~ widl.no od: lraDSfer bet~ lh~ ~
tan amismnnmdin~ Hooce ~ rotaJ magy u f lhe an remains amstmt~ at:
aAlO.axJJ. It merely dlm~ from pentW ~ ofpo:U'tloo (c~) oflibc
~ I lie mft'D of " elevator to ponmlid cmn;y of ~oo of

Ow;~
1bk eumpie :illuu:lles appJk:ltioo of dle law of c~on ()f ~

CDJJiYr ~ ~be ~ jpJ'GCa5 is UIJIOdi lo OCCUJ Mtbout :liiiidion; tbe
~ onainr.d 9.al,'l r.m~y r 5ndl ... Ktt:at._.. ~ ,.
t
Dmiog dle rperiod of devclopDMml .rtf lhe [law of ieQ~ of~ ~~ hea1
DOl gaxftlly ~ 85 a form of mern.tut Wti ~ an indestmctibfe ftwd
called .aJ1mlc. This a n . ftrmJy ~ Wid for my ~ no ~.oonrction w;as
n'Jadt lbctwun ~ ~~ from frit:tioo and lhe ~ fW~~IS of ~v. TEe- taw ,of
0)11~ or~ ~ lhttrtom Linnr>td ifi .apptic4tioft li) frict\iles.s ~~ ~
~~ .Nm ~h Jimitatim . ~ ... lik- wvrt ~ DOPi R:pJdcd as eneru m ft"anSL

1.9. Ileal
a ~epl thai gained ~ during lbe )"em 1~ IRS~ ~ on _at1C0U111. of 1M

dmic ~ of J. R Joule. These apcrimmds IK ~in ddait mClllp. 2.. but
~1~ ~~~of~~of~
1.9 H'EAT
We bow fmm apcricnce lhat a bot object bnJu.ph1 in GXMd. with a cold objeet. bocomc5
eooJer, wbeftas lhe cold object llecGmes warmer. A ~ view is dm ~iDS is
flnlll5fm:~l QUI lbe llot objc:ct to the ooldl ope.~ ud we ~] 1IYI1 som1liing be:i1 Q.10 1lJu ,..~
my tim heat always flows from a higher tempen1.1.Ure to alDift:l' one. 1bis Jea:b 10 ~.be ~pl
ol t~ as d dfh.ing force fw tbc tra.nsf'a el CDf1Y as lint. More [pneWdy., diD rate
ofM:ftt Q'HMC~r fro.m QD: 'bQtJy ro ~ ~ pupo~al ID l flc ~Pft~d"tffefcoec bcla'Cim
the PW ~ hen ~ is DO lempemllDe dift'~ dJa'e is DO Del tr.msle_-r af beat. Ill
tbc ~mic; ~ heal is~~~~ bcml 5turcd widdn 8 bodt~ Lib wort.
it exWs omly ti ~ in ttttmit rmm one body h) aftDtller. in ~ termioo~,
bd.~ a S)"Siem and it.~ ~~~- Wb~ en_ou in dte fuon olbta is addrd (()a 5)*111.
ilt is ~ u a~ !beat !bot as JdDebc imd tpoterlli:al ~ of lbe .attl!I'IW and mo~ rmking
up (be~
In spite of die ~1 n:i.tm'e of heat. 11 is Gfl~n Yin'IXI i.n rdalifm m its ~~ on tbe
')'5lem from ~bicll 01' to vdlic:b iit i5 lmD5ferired. As a matter of faa. ldil ahou1 l'900 the
ddbritioQS 1'1( bfiite. of ~t ~ bad em die: tfinpecfjlbfe ~ of .a unit ~ o! ~~
Thus me mlom wa~ long defined as 'tmu quanti~ of 11=11 wbidl wben1t.nmsltlft'd to CJ~Je pam
oi VI lffMslcd itS~ ooe ~ Cdsiu Li~ dlcBmfsh thrmltJJ ,utrfl~ or (Btu).
Wti defined i8 tile qumlity Of~~ ~ Yl1 ht:D ~Ci':fed m Vi'lt pound mau uf w~ r:;Died
its ~ ooc ~ ,~bm AJJtbgu_Jb lbe$e 4dulitiom povldl a "Yi.d" for tbc ~
of beat units.. they depend oo e~.pedmmm matk wfl.b wmer Wid are llru:s subject Ia c1111np IllS
me.asuremcuts ~ome men. IICCI.JI'8te. The calorie and fDI!U) arrc now ~ ,as lDlib of
eDeQY. and are Cfined !in relalion ro tbe jooJe;.. tbe Sl wm af enag,y .eqnJJ t:o, I N m. "'bis, is
~ ~ ~ ~ wbcn a~ of~ ~w ~ ~ 3 di5otftmc of OQiCl mc'ta.
All odzr energy writs an: defined as 1IIDiliples of' 1M joukl. 1bc foot-pound/tWA for e:amp.le,
is cquivakns to J.lSS8119 J. tk ad.OIW to 4.1840 l. and Uu= (Btu) t UW1M J~ 1ille Sl unit ol
power is lbe ~ gymbo1 W~ clefiJwJd as a e~ ma.e or cme joo1e ps secoodL
Table IlL l of App. A provides m a~ IMI of coll\'mOOn: fxtors for eDeJ:gY a wen
:U ~ Ol!lla' writs_
DDAB
r!n"V_ ~
~;u:a
1.1. Wlmt hi the ~taJuc tlf ~ llotld wtun lll1ll its units io a~ in wmdl 'ti:lc: ~ die Coot,
and abe pcund lftiJU me defined as in See. l.l. and rbe unit ,o f f'oree u the poo114rJ!.
~ m.IM f~:RXluind b.t Biw l(l.ba.) illi ~of Uftl(a)~1

16
1.2.. ~ 1.:1Um1T u me
tiandameut:d SI ,eJeeO'icld diDJm1io~ with ~/e (A) IS unit.
Drtmn~~ , for~f<Uow ~~ annbinlboosQf~aJS[uni
r.o, F.lectrrie po'li\-'er. (b) ~ Cbiif!~ (c~ El~c ~ ~
l:d'J lecoic rr&istBDt'e! (l'} Elecuie padrooee..
U .. Uquidl\':tpOr ~Oil~ :P i!i td'rm~al ~ arf'mlctic;m M' tc:mp:~

by an cqu.:Jtion o the fuJm:
b
~u, P / tb :M=o- ,r c+c
Here. ~rs tz.. b.. find care~~ cooamx. S~ it is~ m
~P by tbe~tcqUillion:
1J
IDP - /kPa=-A-
7
+C
Soow bow the ~m. in tile two equmo are ifldmd.
lA.. At '\la"MI! ~ nn: tanparatJ.D do the Ccl.sius .aoa ~ t~ scab giYe

l!be sr.un.e 1l&Dni!!iical va1UI:7 \\'b!i.t is lhe Wllu~~
L!. ~- upmlJD)I!rm"are~redwtlba.de:d--~~ 1bpWo9~

i~ 4 mm. 'W'tl.tf is the ;xppm::timate :nms in Jet of the ~lgms mqtdted?
1.6. lftssures.ifiJl lD JJIJO{ntm) are mc:LmJ'ed with a deadweig,ln gauge. The piSiiOn tfuun...
eta' O.l7'(in). Whtrl is abe ~luafe Ina! in (Ibm) of dlc wd~ ~
L1. 1."be Rmding em a nwcmy maoommr at ~~c loptn t:o lht a~ '1.1 one ft'ld)
S6 ~m. 1l1c ICJCa~aeediU'iltion of ~ravity 9.832 m - 1 ~ ~
is 101 .18 li.h. Wlud is lbe absoJ~ ~ mk:Pa beio_g ~' The~ of
mawry:u::!S . m13.534 gcm...3
1.8.. "f1li: reading on o merau:y mmometer ru._ 70(C'F) ( ()JJQJLQ die Mtfi-OS~ at....., end) d
JS.62(in~ The local ~ of gmvi~y l2,24l{ft)(~)-1 . AtmOspbaic: ~
29.86(m ~~l ~ JB,me absola~~ in <~> bcittg ~ The dtMfty
<11 matWi)' a1 7 J I 3.s43 g 001
1!.9~ liqoid ~hat bob t ~bth'cly tov. ~ are oftm 5ltll:1!d liquids IDlltb their
'-TIIpDr ~- wbicb 11 ~ temper.m:oe can be quite itmJe,. Th1.18. tH:IIwJ..Dt
Sl't.lmd as aliqukiiVGiPQI' syStel'n is at a ptrc::i51SUme ,c:lf2.58 bar for ~:c>~'tlmt of 300 L
~salle ~tom.ge {>so ml) or l llis kind is Rl~De~ doae in splw'rictlltmll:s. Sug-
FI.WO~wby.
1.10. 'The lim~ me~ .a fme p.ropemes of~~ ;ga_..es v.~ 1IDide by
E- H- A~t t:n F~ ~~w~ 18691Jld ~ 393, B~ devdoptq tbt ~gilt
~~ he: -urked in .31 lllioe sbaf~ wwJ used n:zmary manmmuer :foe-~~
of~ tu Qlt8t dan .wo bu.. ~the htiRIB or maoomem: requimL
Obras protegidas por direi os de aut

UL An~lbmeasured-=A~Xdemfin ,tl~tyon , - ~ofa311Jli:ng
fmmwbieb " ~a M'(l q.Alap oo artb~lb:~~~
t"ticn of ~\~ll D. 9.8 Lm -l. lbe 9j!1fiDg aren.b J .08 un. When lbe imiml:ment pildc
'~P ' lsod,cd oo M ~ it radi the informatioo ilba1 the ~ t ~ 0.40 em.
Wlmt ~the~~ ~ILI'rlotl of gm~it
LU. 1'be 1i'ari-adoo Dl Ouid ~ure ilh, beight - described by dJe differenttll equatioo~
,J p
-:o::::r-pg
tl:
HeR. p QXci& dlmiil)r and g is the local acceknrn011 of gr.J\ily. ror ao s'JI:<
gfl5, fJ :=: "l.( PfRT. \\;here .1~ is llllD1ar rr:rass and R i~ me onl"\~ ps CODXW11!..
Modeting lbc al.mO.sphae WI isodltml~ Q()Wmn,of idA1 11 EO~~ . ~
amhitnt _pres$lDit in ~"- v.i~He ~ = Uiilli!c) nwuh~ ro ~ i.ewl Fm' mr~ tate
1\.f c _ 9' g moa- ; \l'alues of R are gi\"eel in App.
t.u. A group ot eng:ioeen bas landed on 1he 1DDOIL and 01ey \\'isllto determine ~ .~MS<S
of some rodr;s. They have a Jlrill! $Calc calibctted 10 I'C'4lll pounds mau at a LDalW)o
~lee the .~ of gJllrit)r is l1. ~ 86(ft)h) :1. One of (be mooo lhu a
~ Gf' ~8-.76 Oil!~ St;.UC. Wba1 d iU ~EMS1 \\~tis it!!. ~~gbt run lhc momf?
Tan I '(IIKl!OO);;:: S.3l(ft}( }- l .
l .l4. A 70"\\-m ootdoof security 1i~ burns. oo ~ Ul booTS a da)1. A new bulb eos~
SS~OO. and the tlfetime is aboo1 l .tt,J) hoc~. 11 ~'lt_ricity ~ $0. Ul pa- t ~bolJI".
v..u is l..be ~- priec of "ieauity.... per li,pl:?
LISe A ~ i ~ in a 1..25(ft)~e. eylindet by a pisu:m. on whicb ~ \\ ltl!u.
Th~ mass of dJe pistoo ami weight ntpther is 250{lbm). The local L~CCC1a1lti Of'
gravity is :U.] 69(tt)fi)-2 and aimospbe.tic pressu:re is 31IJ.Ilfm Hg).
{a) '\\1ui1 i. the 11lne in flbtl ~on if.IJe: ~ by die ar~tt..lbe pt~A; atrd !the
w~ :asmming no friaioo ben\!'CeO the ~mn and cyliDtfer1
(lJ) wtm is the pres.snre ru me p ~a (psia)?
(c) If rtbt p in the ~~WHirr Iii hraiftlt im~ p.l!binJJ ~ pis.ton .alld ei&1n
UJJ9f-nrd. lf lhe pi;ston and ~'eigbt iU'G raised i. 7(ft" wtm 1ht ~m dons !by tk
gas in (f1 ~)? Wh:u. is r~ ~ i.m potmitllil ~nc~J-~ of the piisum aad v.-~igh1'1
U~ A .p . - coo.fined in a O.ot7..m~ ~ioda by g pi.stoo. oo WIDcb Ri u ~~

'The mti$S of lhe piston IJld ~ b)gtther' JSO kg,. 1bc I~ ilC:~ of gravicy
~ 9.1 ml m -~.mid ~beric pressure ~ 101.51 tPL
(a) WhUL is die fott.-e 'lrn oewmos.~I on the gil:'J.hy me .atftKll..~ dB: pmm. und
llhe \\>~t.. ~ no frielion bdlf,un dw piltwl .and eylinda"?
(b} Wba1 . (be preswre of the ps in tFa1'
(c} If rrbl! ga in me cyfmder ris ~ il ~ pos.bing the pisrm m1d weiP!
upwri lf (he pisron uDd wOP arc ~ Q.S) m.. \\<bat ~ lbe ~'Oft done b)t rthe
gas iD kJ7Wb:lt is me cb::mge in potcDlial enJJY at tbe pistao ami v.~gbt?

l:S
U& AD .mdmDObiJe lmimg a. lliJS! of 1.l501tg i:s ~diag 11. oM) m - . \Vhd is i:ts kinetic
~ mkJi1 How mud~ ~at. muss k cklot U.lltil 1\ to .a slop?
j.'lt~. The ti:IJ'hinM ma hydroeledric plml are fed by lWter' fulling lfmm 3
50--m baght
~ uminK 9'1~ em~ (Of"~ Qf)iiOitUIJld ~ ~d~ ~-~ Wid 8% b.%
of me mmlliD:g tP.CJWa' in tr.msm - wbat b the m ilowrate of water required m
fKM .. 20Q..'Walt ll;gt,l buHJ?
IJrh Bdmv is h of a~ oC.Wl'YeBioo &~ IIS!elol fM ~-o~~~

e.sti:ma~Es.. None ll'lnl i.i diet., but llbOst ~ ~ W witmn ~ l~Wi. U"Se
DIJJeA.l (App. .A) 10 establiSb abe .a ct coava~
~(ahli) ~ I hat
l(Bw}~IU
l(bp} ~ 0. ?l tW
1f mdQ ~ 25 em
1~) ~0.Skl
~(~) Ill& 1.6 hi
Uqpatn ~ 1 li1et
~(yald) ~ 1. m
Add yow- own items 10 1be .. "l'bc idea is l'O k=p the Q.lC\'-tnrioo racun si:mpk aud
easy co remembr:t.
L11.. Consider the: folkw.iDJ proposal (tw a decimal .calmd'K The funtlamemJJ runit is tile
rda;tmaJ )~ (Y~ eq\W 10 the t\DIIIba" of~ (SI) ~ requimd for die
earib to ~ a circ:uit of die sn__n. OdJu liUits are ~ in tbB table bdow.
~ wbt.re ~~ ~ ror~ tWimaJ mii!:N'b!runits ro oun~
ealenclar~. n pros and ews or lbe proposal
DimaJ ~ Uttll Symbol Deftmiicm
Smoad s~ l Y.r
~ MD ' Yr
Hour llr I 'ir
Day Dy I 3 Yr
\\'en Wk l trl Yr
Mondl Mo t,o-1 y,
Year Yli

1.11. :Enqy eusti nzy JR'IIly willt ertaD so~ eoaJ $1-S.C~Llmn, g;JSQliiJei a~
1
' 'tc -I'

pr1 ~ 11"\n(-m..l a~A c,llml 'cltv ,Q Ctft lii\AII1Jio'ft~L. ,......,.....,_;:~...~ ' ,' ~ a.., LO nrtf
U. ~~~~ _IOU -~ lfll ' .T 'IU" o&IU-II~AII'UII. '\.d,AI'n;JIMltULJIU Jllli!C'- _ 1:11 r-
daese.OD a common llwis ~~ ~g diem inS Gr (ARWtif6Jth is appm.Ummdy
1
a
lo6(Btu).] fUf lhi~ ~ ~ '' bGafi_og . ' of29 MJ q -libr ~and

37rG Jm- 1 fur~.
(a) lhmk oAicr dle du' ~flY~ with~ to atcQY cost iDS QJ- L.
(b) 6Jp1abl ~ f.~Qe ~1 j:q 1hr nmP~ fiESDlt$ 0( ftO (a). ~ IIQ ad 'Ill- 1
~ , nm1 disadvmttqes of me dlree. eDaJY 5lOUI'CCS.
Ln Otemictd,.,pkmt cqplipmtnt 005~ mety '~in pmpmtioo tome. ln ~ Wnplest ~

eGSt C 'iMC!S wbh sW.e S .~gtn die qJI(JIIIJ!Iric ~
c .e.. .~s~
Tbe ~ expoocDt ~ l)~yfbetween 0 and ~ . For wide mity ofequjpum11)'peS
it i& ttpptoi.itmil:dy 0.6~
(al ForO< /} < ~.~heR tb;,J ~ pe:rWJif.tl"re ~ ,.ittJ ~..DI ~ ~

~omy of Kale.""'l
(b) Comidc.J the case of 1 pberical stmrap hilt. 1lle 5iD is~-~ by
irfireniaJI voiDI.'fiC ~~ . S!bow dml fJ ~ 2/ 3. On wl'&ll ~ M ~ would
)fW expect ~ly G 10 dc:peud?
tt>C p RllfkPa .rr c p lk_Pa
~ &8.5 3.1 32~7 4t9

- 9.5 5.48 44.4 I 66.6
0"'
"""' P.4S S2-l 89.5
H.J 16.9 63.3 ll9.
2JJ 2&.2 1S.S UJ7.
Cofrclat& 1tbe d;iiD by fitting thtm to lh.e fultllliDc cqwti~

B
JnP~JkP'3eA - - - -
T{K +C
Th!U b. find iill~ \'AI~ ~ot ~ A. B~ .god C by aa ~rqtt lfeift'S5ion
~ ~ lhe comp:ni:Sall of CiOil'mlmd wbh ~ vaiiia. -wat h
..-..... ~
..-11..-. yt-h'::tiiiU
YIAi' - tv..:t:n.....
DOt- LI..MI -.r~M~~ pDIDt ...l.k:... ~ ~......:-'"'
VJ u_u;~ Qt.;~.
1.a (aJ bl IJJDPJEf 1970. b pl.lmp priQO of p5(1Jioc _ about $0.35(pJJ)"". ~ctn
I ~"0 and ~ lbe a\'eAge' mJ:e of mJlatjoo 108 about S~ per~ Wlml might
lr the ~peel~ pump pri.er in ~f 20001 Wbar rondD5ion rni,!IB roue~
fmm do e-akulaDon?

(b) A PhJ>.. mgi~ ~ bis ~in 1970 at a. &alar; of Sl6..600()'r)- 1_ reti.red
m at Allay of ~11)-~ . How "R:0 did . ~ keep up widl a_n
ildlaioo me of Sflt per )"~::at?
(..-) 1Uition i~ _ at :rt'm'jor ~ wm'lmfilius ~n tho UDinxl un ha~"C led mfb.~
on ruu;. b:y alnlt l4:t per )~ u~ lhi.s ~brul m wgest stm.~ rnr
~ tl:m fu1uit tWii.W (Q(' "child o pm"iUe unh~y. ~ no tinaocinl
4id., 80 Q1JJJ:oal m.llali<m me gf S~ p!r fi!m',. and a 'CUITI:OI tuiUoo of S25.0Cil()-71 .
Recnll the compmmdliDleJe51 formubc
C~(rl)
~;=;: l
1 + ,,
'111'
!! -
t
C(tl)
-httt! c c;m oo _ ~ -~ > ctr'T t mnnd h indL ~t t~- nod r is :a~ (inJiario~
~1:. *-)~as a clednwl.

Chapter2
The First Law and Other

Basic Concepts
The IDIJdem coocept of beal ~-elopa) Wllowiot aucial ~ ~ 0111 by IP.

1
~ ( 1118-1839), in lbe ~ offhl!s Dome q;ar ~., ~. dijtill,g@ ~
following E840.
lntbtir~~~oo1l:i ~~wm ml*~botbectJoik~
~to imure ~~ lo lhe IDfit ~famous, sefie! of rmtMlRJDeO~ be piJiZd kn:awn
-!1 ___. !.--1- .._..rl . d .. .,._( .....,_ ~id ...:.....
oiiD10Wll5 of wat. m~. wN JDC~elll)' m iDD rntMmaL..u ~___llllCI" &Ill apla~P~ u_~~;; uv_ _ p:g a
~~ ilbc ~ofwtll'td~ oa lbe a-nidiby me~ were ~)r ~
and dJe tclbpalbL~ ~ ur ~ llliJd ~ CllldQUy 'DOtaL He found fQf rl~Cb Duid lbaJ a
bed UIOUll1 ol wart ""~ requbed per unit ll13SS f~ ever)' degree of tempelilliD'e rise caused
!by lim ~tiffing, UK) rbat lk~al tnnpc~ranue orthe ftbid ccrutd be ~DRd by~ 1L~ or
heal tflrough Wnple ooot~ct with a cookr object. l1ms Joule demoastr.ned that .a~
~bJriomltip ~ ~ l'l'Oit and heat- tbtrd~-m.lbat lat . a rorrn (Jf CDeTIY
2..2 INTERNAL ENERGY

Ill ~ tiki: ~ o:f Joole.. cnagy adtkd 10 a 6JJU:I as "~ b lares uamf~I'Nd fm:m
Ebe ftuid as be.a_L Where .is this eoeJ1Y between l addi1iim to and e:r fmm me laid? A
~~~.-it b ~ witbiatbt ftui4 ill~ form.~~' ~j-
~~ mau of a~~ nildudocneqyfbill it m.1lf ~ ~a result
of~~ posttioD or~ Radler iil min m enetg oldlo ~ itemal
't o 'the 5~ Bec:a_JJSC' of ithelr tc~~Sel~ molion. d moleeub ~ ~ all!f11 o l
lrarlslatimt:; eseqn fM IDL'Jftll:omic ~ the.)' also pnssew tilldk: eDeJD' of mtallion and
.....~ mt-~
'lA ~ A~ . ..!'L.......:.-. "ft-.
,.-~V~,i!MWU. ~.:..-. Q 1
1 011!1 .uwuoJIJ _ ..
~ ~---- ~ '"'=- ~IIUY
~- ~0 I.~~-~ -a-..t...-. !l!II.M ~1
-:. IJi and
_
11b.=K; a:~ and rl kfl' ~ D ax~; of~.ll&lll.b ~ dc::Kribc:il bJ H 1 ~

~l"'aQJ,t~ .kwJ,flll!il * ~ ~. Nl!* ~ ftlf)lk;df ~ tm
21 Obras protegidas par d1reitos de autc
22
thus eu~ _- .o ~in iQ ink:mal ~- Wed dooe em tbe ~ cmn bLtve the s.tme.
eJiea, as was .dlown by Joul1).
Th_e imatild ennv nf u. liilbstaii.(Z also indlliks the pocm1ial magy ~ling from~
~ fon.'e!i (See. l16. l}~ On 1 sabmdleadar sca.le. eJEQJf i:;. a~ with u,e ckcimm
and nuclei of. aud wi1b bond ~coe:..gy ~IP& ~ lb: .~ Mlding at~, ~ a.\
IIDOlecalts. 1'bj Conn of enHD is ll3lllield inmnriJ 1D d.min,gukh i1 from the kinetic and potm-
llial c:n.CIJY DSSQCiated witb a 5Ub:stma heause of IIIBCliU.~ fa$llinn at moti:on. wtnd1
CD IJe tOOujiUJ ~~ t$. ~ ~of~.
lJttmW ~ has no CODCDe lhermodynamie delinili011. lt is a ~~ pril~Jr.
rit.lf~ h ~t be dbady mnsw;ed; ~ate 110 in~ meta& As a cesult. ~b:solll'h:
\."'"M~ ~ ~ Howeva, ~ H. DDii a disadw:mlap mthermodynamic :mal~ because
...,.,L,.,._,
onl:y ""'..,. l 'Jtd.
13u m mtaDIJ ~ ~ n:qun ~ _
2.3 THE FIRST LAW OF THERMODYNAMICS
~~~ .of .cmd' meq,y fonns ofC.DCQY .e a ~oo

ofl~ 1tnif til~OD of ~oi~ ~ f~. 1.3) m itll'lude ht.ilt nod mttmal ~
m addJtiOQ &'0wed: and aUI!In:tl [PW!IIitl aOO tinaic ~ lndrJed. 1he _gen:et~tioo eaD be:
still d.her farms. :sucb . ~ uf.ai;e tmrJJY, ~m ainlf, u4 UJ118,DC1k enau.
ex~~~nd'ed ID
~IJeJrning ~ Of tiJe V~idily Gf (bi$ gnmafhariao has raised.i~ SUI.liJM to a law of
na~ kJw!wa ~ 61$ll.aw of lkrmod)ffil~Diics.. One fomlal ~ i ;
Allbaugh ...., aaume manr tarma.. a. tom~ quantity of energy I

- -......,..,.. an
- d ;.A--. - gy ..--.....,...._ In -fOrm h aftftaaM abnu:l-
co.-."' JII'JII(I'II . . . ....-,..,...- !loft'... ...-..- - -
........., In ether tormait
In ~on of dD , ltN, tot 1)\~ ~ rile 5phm; of ittft~ of me ~ is
dirlded mto ~ padi. tM rtt:m and its S~HffiUJf40., Tht re;joo mwhXb lbt pMCe$$ oc-
r
- :s S:'1 ~ the - -+-

..._,. Ci - ~~ - - - itP""'II.Lo
C\~ "- w:jJh ~ tm AA'IiNft ~ ~ ~ ..............,..,.,.i,o ......,,
......., ....mg ""l'"~ - ~
A be .o f ~ its boll-ndaria may beRM or~~? rigid eT hJble.. :Fre-
qutl)tly a~ c~ ol a~ &Uhs~: illi ~olberasa i1 may be mmp~et. In nny evenL
tbt: e.qu:nicm of~ ;ue writKn wilb t~JJOttn a wdl~ ~~to
~ ~tiotl OD 1 tf.lc panicular p~ of~ Mid OD lfle <ecpli.ptnml mdllDWerii:a1 diredly
~ in. tbe ~ ~. tM 661 bw ..lies lO dlo . tm1 aJtJl its ~i n~ llCJit
lo the~ dnoe.. For any ~ 1he 1itrn Jaw requ:.i~:
4(8oergy ofd.e m)+ A~of mvnndinp) ~ (l.t)
wbue Ike di:ffmmce ~ * tJ.~ .qni lid ti:Dite ~es in lht qua:tdib tlldoscd in JlllreD.~
~. Tbe ~may ~~ in its iDimlal ~ m m po~a~D.al or kin~W eDUJY. and in
t~ poten1W or kineli tmeJXY of :i tmito- p!11'11-
lll tilt ~=~ of~~. brow and wut represerrt energy In rmmil .ac.m.u the
~dividing lhe ~' bm its sumJUDWDP, IDd ant~ ~(l)m/ or conlained in die
~ P~alt Jdnetit:'" lind ifilem2!J ,~)I em me Olber bam ~de wilh and ~ aoJ!ed
ntt mattu. riD pradice Eq. (21) ~ spedal lOJ!inS suittibk [~ ~ proc-tic~ tlPPli~
~ ~ devd~ of~ fOf'CfJS. mdliMir sub~ .upplkmion ~ tbe subjed of the
muainda" of Ibis dlllptA.

2.4 ENERGY BALANCE FOR CLOSED SYSTEMS
!If tM- boumllm)~ of a gysmm does Mil permit th~ lr.IMfer of IMf'tB' ktwft'D 1be ~ :mid
its surmumlinp, the ~ t8 Aid t& be dosrd. zmd i is ~ WWitlllt. The
~Of iba3k ~in rhttmod)~ hllidJ!Tmd b., il ~ elQllRuU100 of
d.~ ~ aDd fur ~ reJSOn they are ~ m <ktail t.re.. Far ~D~J~re impurtmt for
industrial pPll-'lice :are ~ in wbfcll nw= ~ lhe ~ bomKialy as SlR'aJm lba.t~
en.t9 ami leaw pl'OC!eSS equipmm1. Sucb.~.rm =:n .ullo be opm.. IDd 'lbeJ are ttead 1alef
in Jb:is. ~ olltt iM ~ fwndation m.utm.uJ bas t:.n ~nkd.
8osc oo SltC'atJtS enta or Jwe u closed $)'Stem. oo cotqy assodated wit.b matit.t is
~md acnm lhe boundary wbicb di\'ides, the system f rom hs sunol.IDdinp. AJ~ ene:gy
t~t ~a dosed ~SttmJ ,tod r-~~ mtD ~~ - bcalaod WGtt.. gd the
toW eneigY ebange of 1be sui'I'Ollltdings equals me. 11e11 et1e1gy ~ to or [tam it beat
.rw:t v;"Or.L The ~ ~ o Eq. (2.1) m:~y bact(g be~ tty
A(Eneqo1of~ ) e~ Q : W
Hem Q and 1A'IO'Ik W alway.s ~ m me sy-*Jn. mid me d.nice of sips USl:d wilb dlese
I}IDiBtil1ie$ ~Oil wtiitb ~oftn~ ~Mill~ 1D ~ ~ B ~
a-s positive. The moclem sip com-anion makes dte lll.lJDeDcal values bolbrqmmdties pomM
fer ~cr- iiUo the sys~ frorJ), the 5imt1Unding!.. Tk ~p$1itiD-S ~uamirb ~ wilb
Rrmmce (0' tiJc RIJT'Oimdinp. Q_.. and W!A;J[ hav~ dJe ~ "go.. :te_ QHIIT = - Q m1
w. - - 'W. With dril W'Jlk~:
A(Eoergyofsurmundings)-. Q + W~ ~:a ~Q ~ \1'
fquatjllQJ (1_ i) Dovr ~
A(E~ o fW ~ltm) == Q + W
11m. equaUon ~ 11m die total eMJX) dtmge of a closed ~ e1JU11i tbe net enmg
tnu1d'cm:d mto [1 g b.ait lWd wurl..
Oostd sy.srans uflr:o un~ p~
<luriQg wb_idl only lho miBifQl U~CI}0' of tbt
system ehmges. F~ sudt ~~ !q. (2.cl) reduce..\ m!
~ A Ut e "fia + w I (23)
wbeJ:e lP i.i lhc tmal intern.a1 ~of lbt symm. Bqwr1ion (2.3) '9pti to~ i:Jrlmly..
iqftnlu: ~es in die intamn eoqy cftbD y51m1,. Ft.- dilfunuitil ~
14fJ' =dQ +dW I (2.4 )
~~. OOMftltlliiD urd s ~by die ~iii (Jfl4ta oCf!cumMid ~tlirtiiim)t Jfcw,.
~ - ari m.
dKiic:c b . m- dlr: IODt IR4 in dr tim ofitlms elf IIIb lim '\I'D dtc ~11Ifk4
die i'i,Pt sidleof- (U) . '!lf1iftllll " - "~.

rr
ln ~ {2-3) .ud (l. *be I;YIDboJ! Q. w. and penam lo lhe entire ~ wltlcb Ilia)' IDe of
.my me and, elmrly dili!Rd. AIJ I
lbe 1 Rquirt ~on ID ~ Plk t.uefi)' uniq.. li n
dJO Sl ~ lbr umt6 dr joulfl Olb Ufihs in use Jlf'e lh.e [~ rhe: (ft U..)p and ~be (Bru.).
"'btal yotnme V' rmd Kdtll iman:tt ~energy U1 dcpmd ,on tbo quanticy af mute-Iial in a
~-and .~~ ,QJJlUi-.e J)Klpctid- In OOI)iJ;a$t. rtmpttatmc Wld ~n:;. t!ir prificipal
IMrmodynunic ~ for pure bomo~ duids. ;ee ~ut of che QUmUty of
matmaJ. and m: luwwo ~ iB1~5is!f! pn}pCdi~. R.lt: a. ~ ~~tt"m. am altd'D lti'Ye
filmfi$ of~ for tbe sren~ propertie.s, S'UCb as V 1 and u'. i
where lhe plain S)fmbels V 4.M.U JqJresent lhc \"O)lUDe and iottmal eDefJY of o u:trlt amount
of~~ D Wilt ilmJS QE" II Jm1e. 1bese ate respectively .qJi{JC or lftOitl.r pro~
and1lley are ~f ~ollbtqualityof~ ~y ~
AllbOugb V ' and IJ' 1ot a ~OfiiiMOUa w~am of Ditruy lim an

~ prDp1111e1.. apedtlc and molar volume V (or dlnlfty} and
specific and mDIIIr 1n1ama1energy v .,. ~.
Note ~ ~ill~~~ T liWL P bav,e Matensi\oe ~
For a clOSEd Sl'*DI n llliDks ll!q$- {l~ll ~md {2A) DIY D1JW ~ wrhltn~
I _A,( IIU) ::t n A ll c::: lJ + W I

(2.6)
.m 1bi !Qtltl,. 1f.hc5e eq,llltiOM slw esplicidy lbe ;woont of~ compri.iing the S) tem..
The eq or lba:modyDimi ve oftm ~ far a ~wi\"0 diU'I 4Dl'Kiiint nf
~ f'Lthtr mric lm!t!i or a l1'iOk. 'I'bm. ror n ::::::1 l ~ (l.S) taod (1.6) become~
All ~ Q + IV
1"be '~ fw Q and W ~ a.~:wap. U8plicdllbr fb:; mass or~~ -o l 01oms . ~ned with the
left silk af r.be. enacr equation.
F.quDoo (1.6~ is the olti:mate ~ of all p-1'f!JJUf1 ~ tha1 COOIJt'Ot the in1tna]
.-
~y (() Dm--..
_ ,tt...,-:o: .... Jt ~
-.-A..IC ~~)~
--~\UQUJ_ .
~I!
001 - r-- Oi "'ii>RIJlon
&H:.J I'U U
6f iorcnmJ 1.~l;:l.jl'
..,..,....,...,..1 tMre iS
noo~ does it lead 10 alt~ ~Jim 'the imemal IGDmJY. Wlm it prov.idcs is l~ ~
fur ~g dwJgr..f in ~~~- W!tbom it7 {be fim ~IIW of lbefmod)~ (uttrd nQ'I
'be formolmd.. Indeed~ the tint law~ prig~~ of lbe oxr~ of dJe iniCTMI
eoqylt die csselltiol ~of "'1dc'h is surnJl14fi2:edl '-n the ro~ing mom::
'lllel8 Rim a tDrm of~ ll muwn1as Internal enetgy U ,, wlllld1 Is
a.-n lntrfnaic propwly of .,......, functiondy relatad to the if MISUt
. _ coonlinatH which dtMidertle tile system-.. For e cfoeed ,. ,._
--~ *"In~~ in tiD~, AN tivert bJ ~ (2.5)
andf2.1).

Example 2..1
Water tiCMS <JV8r a waterfall 100 m ~ height Take t kg of lhe water as the sysreml
and assumerd1aJ it does not exchange:ern!lfg't wlU, ijts .surrvundngs.
(a} 'Nhat is the potential enerw of the water at fhe top Gt tha laDs with ~e$p8t -.,
the basero!'N1e fans?
(b) What is 'the kinetic energy of the wamr lust before H strikeS bottom?
(c) Mer the 1 kg ~o1 water etrtefS tile weam belOw 1M faJIS~ wtJat (lt\ange has
oooumJd ~n iits stBtB7
Solution 2~ 1
1llc l q; of ~r ~~no energy widJ ~ Sl,lrf(RJfldiiJP,. ~ fol' eacb p t
of me prroo E.q. (2. La ~ m:
A~ o tht: ~) = 4U + ~BK 6-E, : 0

() Frorn F.q. r I.7}. witll g equnJ to its ~ wiDe..
p ;;;:fffzg ~ I k ~ lOOm x- 9~m s- 1
kg ml
a 980.66 Si =s 980.66 N 1D c 980.66 J
(b) D-u:ri:111~ lhe free JaU oJtbe \\ ~ oo Dlhanlsln ~ forcon"\Uitlllofpu&eo-

tiul fit~ m~ into lni~ ~IH@Y Tho.~ AU mnSII be zero~
K /':.Ep ;: Ex. - gl + 11j- efi'J ~ 0

rm excdl~m a;ppm..'ti.uuuiCiiD. Is E ~;1 1'1 - 0. Tbet4
.-2 ~ Et:-1 .!: 9$0.66 J
~t') tbe ID q of "l~ bottom ;md ith adler ful1iQ \tltl1u ~v
fMn :i ~~be re.'lllirifi& rumulei!t.a: bas 1h d&ctl of~~ t.fnllLc tPeJU
into inkmal ~v. Duri:ng thi~ ~ A'Ep is e~lllia1Jy ro, and'&+ (:Ll)
beromes;
01'
~'e'v. lbc S~ramJ RIOt'iry ~-d mmiL ~g EK, D~=jligibk.. TIM.

A(l::::! E~e1 ~ '980.66 1
The mern.D result ofrtbe~ tstberom.'eBion of~ eoergyoffhe wa.a
LeT rnto mtarnd meqy of die . c.lunp . imemd C1X1U is~
b)l a L~lW"e m.e of me "wu. Because ~~~ mthe mnoom or 4. i 84 .11 q - l
~ ~ rot :1 t~l1lfi1Je ~ l1l ~ :~c mwara. the ~IDe ~ ii
980.661~.184 ~ ~o.u.a~c. aswmin M bE t~w Wl1lb tbc ~

2.5 THERMODYNAMIC STATE MID STATE FUNCTIONS
'1'bc DCitltion ttf Eqs. (2:.3) lfuwgb (2.._6) uge:sb that the iniamll-eomgy terms om ibe. ~ft
tit' ~ ifi ti:od fnHp dJt rquaoti1i,t5 OQ ik ~ ~ OD dle Jrj, refket ~~ in Jbe
th~k 5~oCIII!: 5)"5t.mm as reftc.ded by it5.llftui'litli(\'Mlftk p~~ amons Whi~b
-. ~~ ~ and density~ Fot bomo~ ~ substa~~CC W. toaw &om
exp:rimwe tba fixing of cKse properties abo liml all the~.. and tbus ~~oes i
1b~ Slate. For ~~ aitt:ogdl ps . ~~-of lOO K and a pressme
ot lo' tPl {I bar) has a fiBd sperJ& vaillrt'lle o.r dn$iiJ aDd a fiud molar inb:mal tnqy.
~ il b a eu:mpkm l5et of intJ:omjC5 lbermodymuiiE pm;pertieL rf lhis ga is ~ or
~eom~1 or~ and ~ben Jet~ 10 i mit:itJ ~and ~ure. i
~ propa:1ies ue rescored to lbeir iDiiial values. lbe)1 do DOll depend oo. the p;JSI .hf!;w_ry
of dJt ~ P.W oo Q 1n a.tJS by wb:idl it~ a ~~'~ .sba. They depmd onJy on
~~ ~reacbed Such quamm are 1mowo ~ smrl!/U11Cliolu. When ~v-"0
of lkW .ill rikd \111Jie$ fur 1 ~IKE ~. dJe ,JkmfDil)"'ff11llir lllk!
ofthe! ~ is fully ckl19'1DiJxd.. This meum that a stale ftaoctkn .BIK!h as sptd&: ~mal
~;,a .~ dw ~ ~ \~a may ~tonr t.: ~ matbe.rnalict\lly as
r11l\diou ,o f such e~ ~ :md pressure. or tem~ure and~. lind its
~~be idmulkd widJ poiors on a {mll).b.
On the other hmltlhe laiD uo die dfbt ~ M ~ (U) thmugb (26). RJI~tiol
badand work quantiUes.. ;:n not ~ lbey &'CIOWl1 for tbe eDa'@Y cbanFS that ~cnr
in tile ~ Tbey ~~ on ~ o:nore 0I ~~ ~ and may be a&saciatr!(.ll Wllth
8JICU nMhcr lhain poin on a ,..aph. ~ted by 1g,. J.3. l\ltbougb ilime is OOllll tl!Jiet1oo..
dymunk ~*~of~~ ~cabk w~va- ~II ~4mt.d or-.wk is
;t,)QI.....~
~,..__
'.il1'he ~ of a smre i'unl;;tioo ~s am i:ofinitcdm.d drmJ,.e in its '-:.lutt. [IQ-

Jftllim of 'Sl.lCb a dift'emmal ~t51 ma fimtc di1lmmec belween lWU of iQ "'31~. e.g.:
Tbe dilremmats or heal Wid wort mre DM ~a'+ bm DR inflnit~mal ~- WbcP intt:-
118led. tbt:se d1ff~dals jive :not finirle ebaogcs.., bll finite :nnnmt15.. Thus.,
I dW-. w
lfot a ~tcsed ~ uodersmiOB chc ~ cbmp in ~ b)' ~..~ processes. ~i.
meot sl:lo\vl 'lila~ the :tmoo:nu of bea1 and work Jeql)ired dllifer fur dille11e:m ~ bnt dm
the lllln' Q + W is the SQ11'JeforullJnTJCuses. Th___i$ i5J d~ b~ fur idmlifie.atJoo ofinlem.al en-
ergy fwlaioo. The same \'lhle of 4f11 u gk bJ Bq. (l.J) ~ or ~he prOCI!:.BS.
Pf(Widtd etnty t1w c~Aog-t; in t.be Q ~ dlc1 same initia.1J and Jimdi NU!i~
~t""'mc ~~ a perc ihci~-of aamfli=r~~ ~

~ iD UfdeJ: 'lo ~die *k' W 1k ~ gQy ~ lill'attill fr:oal l'ii."'\ 1'bc ~ ~ dcVrm~
c.e -~ U( Sa:. l-1.
27
Example2.2
A gas. ls oonllned in a cylinder by a 1piston. The Initial pre5Sl!re Gf the gas ls 7 bar.
and the volume Is 0.10 m1 . The,rpiStM i9. hetd rin ~ t)y ~Metes in til& cylindel vm11.
The whole appatalus is paced in a total vacuum. What Is 'the eneJSrl change ollhe
apparatus iJ tne, re.slndning latCheS rue ret1lOV'Jd so that tht;t QB$ $Udden1y ~~ ro
doubire its tnitial volume. 1he piston ;Sb1kina ether latches at 'lhe end of the pJOCeS$?
SoluUon2..2
Bo:-~ che quesdon ~t:m abe: emire appmlWS ~ sruem is men M lhe
ps. pistoot. and qiindeh o avdi [q dooo ~ ~ ~ bGcllU-W DO (OJ'QC"
enennd tu me symm ll!BWeS, and no heill is ~ llmmgb 1tbe \'.iiDntm sura
I'OUiiding dle appamtus. Hence Q and W ~re JCm, and 1th.c tabl energy of dlc-
Sy$ltlh r~>t-'5 nQIC dtan~ Witoout lll11bet [nf~ we qq 'SS)' notbillg alJ(Iut
me dimi'l:l.ltitm of energy aJJlOtlg the p;m,s of lthe sy5-tem. 1bi.5. IIJI};l)' felJ be diffa-
ent than dJ: wdal dbuiWoa
Example2.3
If the 1PJOCGSS de.scribedlln Ex. :2..2 1s repea!ed. na In a vawwr~ but irt air a1 atmo-
spt.Jic pressUJ8 Of 1011.3 kPa~ ~ ~ the energy change of tne appanttus? Assume
the rate ol .heat exchange between 1he apparatus and the surrounding air Is &taw
-~with the rateat Wliit:ft me pocess ClCCU$.
Solulaa 2..3
1be S)"SStm is chosen as t~fm\\, bu. ~ -woJt is f.koe. by d~ S)'$ttm till poShin g
bad lhe ~ It l8 ~111B21ed as ~te product of die f'Qit'iC of mnospheric
Jlf!e5.~te otL die back ~ of the p1 on F ;;;; PS;r. A _nd
tlu: di&pt~ of lht:
me ~
and A V' 15 the volume
pistml l)J -;;;; A V' j A. tkJe.. A . the mea of
~of ~he P."'- ~ i wur done by the ~m net ithC ~~ ~~~ i.._ a
negative quantity: dms.
Mt = - F Al ~ - Ptrtm A 'V';;;; - (UU .3)(0.2 - ttl) kPa.m3 ~ --10, 1 ~ itDJI

~v = -mO.J3 . m;;:;: -l0.13ll
Heat ~ bdwem the ~ aJXJI :m:n:v11..ndi:Dp aJw ~blo mtri.s ca.w...
bwlbe pmMem ~ wrmktd br me iosmm.af~ 111e ~has~ imi.1 befcre
~heat ~&r 1m had time to take~- Thus (l ills~ to be~
in Eq. (ll).. .giYiq
A(&ergy of lhe tiysiteml C! Q ' W !!:![ 0 - 10.1) :::!1
1 - 10.[3 kJ
1be tOlall ~of llbe system bas tk.cmul!d ib; an amount equal to lhe work done
oo tbc surroundinp.

Eumple2.4
'When a syatem IS laken fliOm state a'to Slate b In ~g. 2..1 aJong tpafJt acb. 100 J ol
heal 'Oows into the .s ystem and 1he :system does 40 J of WOik.
(a) How much haal llc:.ws into lhe syslem aiong pa1h aeb nOle WOfk done bv the
system Is 20 J?
(b) The system RmJmS from IJ to a aJong path l1da If the "WOI1it done on th9 system
is 30 J, does the te:m absorb o-r liberate heat? Holt much?
Solution 2.4
~
. ll.....t ........
HMJ;_
- . _.......... . nl i: - . ........ -~
U~ ~ ~._F$ 0~)' !Jilts gn~!AI.I ~ ~IIY ~ ~ ,~, IS
. ........ :~o.c...-<~ n... ,..,., ..,..
app!jeable. .For path Qd,, and 1hus. fm fLt:J" parb ~ mm am 11.
All" ~ Qb ..&. WQd ~ 100 - 40 -601
(a) :For path aeb.
AU!b - 60 = Cludo + U'all .! !!:! Clatb - .20

fb) FOr padl hd,
AU~ e - AU{w ~ - 60 ~ Qbtht + Wll1f.Q ~ QbriM + 30

2.1 EQUIUBRIUM
Equlffb.fillm ls B word deooliDg D .mule mefitiOIL (be ~e of dcmge.. JA ~es

;rl --~ ...... '
1!.~ ~~ 'Ll"
-Jv th
!{;Jgj.
...............~- ,n f ...t.an ~tit.._ ...~.;,.......... .~an~ ---~
_.,. ~ ""~ ~-'- F """' __!_~ ~~ 't;l,!; - - ~~ [!.&II'M!J~ ~,.. -- - ~
.._............. dim- on. a
~scale. Thu,s. a ~lao at arullibrium wm urdu contlijiQJ'tl aam mat !DO dwtp
1.n ~ am occur. Beatme any 1taldeocy tO!MIId c'banp- i~ am..liial b, a driving fDrc.e of ~
!kind or~ die a~ of :such:.~*~ .mdicates ~ tbc 1 -~of W~fdd\'ingf~~
H~ooe for :1 !i}~ at eqOOibrinm a.11 ~ ~ in at~Ct balmae:. Wbetber a cb2nge 8dl:Cilt)t
occu in ;,; ~ ltiJt at c;.quitibrium depmd~ mJ ~ u wdJJ as on ddmia; :f~. ln
many~ !tllbjoa (o ~ driv'ID8 fm.ws chm~ ~ G a egJilible ale.. beawe
Ute~ to change i RfY larp:.
~tllds. ..,,r ~ .................. Jtmd,..... bri- ~ about ..ea--1 -...:....-...... ~ r ~-
D:"&r:td
- Q.l <_ - Ill w ,a~Vlll& 1.011..~ - I!JII,I' -PI - Iiiii"""'- ~ 0 'IIP---~;a.. a- II"'UI
~ple. imbal~ uf UJeeb&nkal fon:es sucb presM'n oo a piaoo lmd to eMl5C ~

~as~ mnprrabm: dilf~ ~rod ~ caliSt b 6ow ofhr4t; ~ m~
:potential teo~~ to, ~~ e& be lransfarect from one ]Jiwe 10 iiDOtbm:. At equilibrium
1111 illltb_ ~ uc iD tiLaoee.
In fi'l!lll)' itppli.Qifions of !~)~ chemica] ~me of 110 ~ For e:lw
~a mixlm'e of~ aDd uygen at onlinary ~eOGdillom is 11'1otin,cbeuJ~equitibriwu.
lbcnmse of the 1~ driYLn.g ibJDilt (or the rwmatioo of 'W:Iltu.. Hcwe\"CT; C:~ ~11 u
i.\ Mt ~ lhis _xwn can exi:st iD lloog-tam thermaJ and lllii!C5hmiM1 equilihrium.. ODd
purd)' pbyftca!J ~may be analyzed without sg;ad to~ a.:mical ~D.
2.7 THE PHASE RULE

A~ indicated earlier.. tke tate of a pure .bo~s ftuid is tboll ~ two im:aww
~y~ propn'tie& are set II ~c v.~ Jn eQt:ID:Hl"' Wbal mv p!NS~CS 111'1. in eqru-. .
.li'b:riu.m. the ilate of die~ is fixed when .olll()' a ihlgle pmpeny u spocifi-ed. far c:umpk
El -......;~-
"" ~ -I-...- - ..I lia..:..t
_,P aftll.l -.~
w-
- .. iIQ
- ~-...:~
..,'I,ILIUUI~P .
"''2. ~o... Clilii. .......ri """"'v iL1 tnrw=:r
li1't. lOll -1'il' 'I U"'<II . . . - 'l\lJ&II VY Y.
[[ is ~DI.e w dmtge die tanperillm'e without al50 'cbanging tbc ~if vaporlliquid
tquilibriiJID i lO be Olaint~
For multi-phase tems at equilibriu~ lhe number of ind!epmden.t \ilriDbles tba.t IDIDl
~ arbitnlriily th~ co ~&b m iB/'QI5iJ~ "* . Ji~n by rllr ~cddl~ ~ ~ ,Df
J. Viillard Oillb ,., wbo deduced il by~~ in 18?5. h rils pre:seated bme without
proof in me form applicable lO DOOJ'eXIing sy.sttrm:'
where lf is. tbe numl1cf o1 pba! N , me o~ Of clcml~ ~ and F ~ mt

fk.gi'N'-$ r!iffmedom or fbe sysrem,
~~ ~ Gltti cll)9.rl903). Atia'!llilllt'aa ~IQI ~-
~ jnilltit:1tinm Ufibr ~ ~ ftXI jjJ1!~~ ~ bt jn"H to Sat_ ~ _. dll! ~ nm lot i.'Udi

li is~[D .,.

'!be i m.~'e state of a system ac equffibriDm esmbll&bed when its tmnpemtut~e. ~
11ft.. and 111m of d lfD - ~we lheldore If -Nir: vmiab~ but
tttey ~ IJO!idl ~dt'm.. 1be ~ fQle IP O.~Jllmbrref ~&om this~~ wbidl
mm1. J3e arbilnuily ~c:d to fb. :ill MnWDinJ ~lUte vuiables.. and dJm dJe inJ:emi.~
or ,
A phau ti' o hom~ ~ of maner. A _ or 3 mixture of gase.s.. a li.qnid ot a
liquid solutioiL and a ~IM tid .uo~ of A pb -- n~ lll!i be con~
~~lie oi ~$phases cue a P' di~ ~ bubbiGs iu a liquid~ a liquid dL~
as 4ltJpkb in ,zmolbu liquid Ill whim it b immiscible. :wd solid ~ pmcd in ciJtber
a p or ~uidl.- lD eacb case a ~ pilaR is~~ a~ .oonli'lWDil p.1:wi:.
AD Blnupt iD ~ ~ ~ ~at tbc-ibOundmy bet\\1:0 pbases. Vari~ phases
~ ~ !bat ltey mllfl fir in tqll.l"Dbnum tOr lhe phase ruie rto oppty_ An a~ of fl
~system l equili&rium " -~salt w!Won a1 :iis boiling pa:inl. wim
oct:SS ~ pe:sent 1.'he. ~ plwes(Jf =
Jt are CJ)f&t:illble sali,. tk ~aqueous
~DDt and wpn ~ ;n the baiJi1rs pHat. 1M two chankaJ species { -c l ) are \\"'fiier
aod F= l.
1be:~ '~moe immrtw ~ independe1u of the~ of ~he symm
.md of~&: imlividu phases. Thus~ [JJibaa mk li\ tdl HIDI'J iDfonuaaioo fw a Jaup em
~fur asmatl OM Md ifr ~ ~ am.ommi of .:be~ ~f.. mlj mdi\'liduaJ-
JPha.. fiXIDiposil:km 110 ~~ Yalblbks. Olraal or tvml ~ ~ 110t ~u. more
ftl;m ~ p)J:ue i& ~
~tid Pinln!n nnmbc:r of degtee of freedom ror att)' )"Sm'D i~ urn.. 'When F e 0~ the
s)'Sb:m ~ im"fU''J t; Eq. (2.1) beeorrm :tr l + N. nUs VAIIIB :J" is 1be maximmm nnmbel'
of 'Ph:tse"' 1\fch tm~ toe~isr m cqnilibnwn tbt a~~ N clJtnlical ~ Wh.t11
N =- J!. 1IUIIlbu ill, ~lie of a criple point (~ l. O. for eump1e. the llriple
pint of~. wble tiqldd "1l~ ~*he ooounon foPb of i1'e oWi ~ mCll[uilibri.um,
oecws 0.01 t.C nnd OJXJ6 ~ 1m. AD)' ~ fftJrn dJese ~COl'l1'.tilioM causes a1 ~ me pbase
1
lo ppm,
ExampleU
How many degJees ~or freedom ha ~eacll of the folowillg,systems?
(a) UQuid water in equilibrium 'NJ!h [ts vapOr.
(b) Liquid W'atef in equi1ibrtum With a t'Aixtme ot'N-ater vapor and rcinogen.
(c) A quid so1U11DI'I of alcohol fn wafEr rkn equl]bftum With b vapw.
Solutlonu
(o) 11Jt ~ cooblim ~ cblmi.ieaJ ~~ mstiDg ~ tao ph:a,1 (om=.
liquid :md one wpor). ~
F ~l-x+N -::2. - 2+~ :::-l

J1
1bi$ result i . m~m Widl ~ ~ 1IJat rw a gj\~ prc581Ufe ~ff bra but
ODe boiling: pliiU. Tempermt~re ~or~, but POt b<ltb.. may be ;peci.fi_. rer a.
tan~ ofwattr j_n cquili\lrium wnb . qpcr.
(b) In this case. two~ species are~ A,gWn 1bete are lw.~ pbrMes.
~ F=-2 - rr+ !V=l - 2:+2=2
Tbe additioo of an :i nM .c:&S to a sysznn of wa~M iB equilibrium with iu vapor
~ ttbe ~cs of the s,~m. Nm~r lemperalOI'e and pewn may be
ifide~tly oaried.. bot cmcc- tbry aR' .fb.cd the ~ystrtn ~'bed r-4ill mist m
equilibrium Oldy at a p:uticubir ~tion CJf ttbe vapor pbase. (If nitrogaJ ii
~ uegtigibh. soluble: in water. lhe Ltquid ~ i:s (JUJe ~.l
(c) Here N ;;; 2 and w ~ 2, ~nd
F = 1- 1r + N = 2-2 +2 = 2:
TM pba6e-Hlle YViabla arc mnpemwe, p,.sure.,, and dii:J ph;Lw cgmpo5itious.

l'b Q)mpositioo qtja)iks me i:lbm dr fii.8liS Of molt lf;iBciiom of mr ~ mlil
plmew ami (bey Dl1lit IWD. ro'1IIIRy fm each ptmse. "I1ms bing lbe mole fmcOm. of
the ~u m ~he liq~W ~ ~~ly ftu5.tbG mole ftaclioo of lk ~,
These two compositions cannot bor.b.lbe arbflrariiDy specified.
2.8 THE REVERSIBLE PROCESS
The r;krliclqp~D~:DI of tbmnodfOami(:S is TI!hili~ed by io~Jan of a ~d kJmt l)'f clo1id,-

Y&ltml ~ ~ M . rw~.-v:nibl~:
lleWJI81ble EJtPtjiWon of a Gas

The. l'WI.L\Ife of tcNY."rsibJe ~sn i$ il~ h)' the ,c ump e of a 511111pft expmsion of gas
ln I pmonlcylimer ammgemenl. 'fbe apparatw sOOWD ln Fig. 2..2 is imagined to cxW in
m ewruated ~- 1'bc IJH ~ped inskle dte ~ Ul m(WeDJ M the ~; oil eke is
the swro:undio~ Expamioo processes. R5Uh ~hen mass ~ ~ 1ium UK piRDn. :fo:r
simplidly, asotr~e mat the ptmm di.'da wilhiD the cyli.nder wilhaul fdr:iio.n and that a.e pWDo
and cytinda nc:idmu itbsorb OOJ ~t 1~ MoJW'Iri'Cf'. ~ tm.~ ol the ,8*5 in d1t
eyllimltu is kJw and !became Ute lDIJg of ps is m121L we .ignore tbe eft"~ of gmvil)' un lbe
~15 oftll c~inda. 1bis ~ tha11ntVi!ly~ ~~in~ p;.art very
sman ~lative to in prMSIII'e and (hat changes mpotmtial en_ergy of the ,filS me l'l.lipble in
complFisun "'ilb the ~ntiaHoe.rgy cbu_ges ol the pi'SUJO -assembly.

1k' piston in: fi!t- 2.2 ooofioes r:.t.e gas nu a pnmure jus' sulil'ii;ient to blllanl:e te weigbl
ef lbe. pi:ston and an lbal h Sllppot"t5. Thil k a -conditi~ of ~u.ilihritun for the .i.~m 'ba5
oo amdency to chwlg-e. Mass 1llU5t be mnovcd liam tbc: pistm~ if ic is to~ lmagj:ne first
dW 1 ma;ss tn mddenl)f did from th~ pi:&tDR m u shdf (at lh~ !mll1l: Ja-el ~ The pislOO
~)' t.t_elennes, upwud. reaclti:ng its .muimum \1docity n1 the point ~~ ~ upward
ron:e on thr pkiDD JUSl hobmccs il.S \\'rigbt. LIS .o:J.OmentWD mm
C&IJries it ro a lbigher le~4
wbele lit re'l.~ diredion. If dte ,Omn Vi~:rr bold ia lhis position m
ID!Jximum clrwtioo.,
il5 pormnm~.gy ~ would ~ neat~)' equal lbe \\'OJ'k dbne by tbe gas duril\g me
nidal AroU. l:toweva-. whoP IQliOn.~~ lhr: pRtoo mscmbJ)' m&illotcs. Y~~rilh ~~
mnpfitarlc;, ol~ilM.tdy t',mning 10 NKt .at a m=w equifibriwn position :a: liM!! ~ iiS initWl
positiOIL
The ~Mioo.s ,o f lhe. piston ~ly .are damped out because me viscous ooture of the
gas gradually ~ gJ'05.S din:ctcd liXIC:ioo of the-~~ brl:Q cW.illtic lODkcnla:r JDIJiion,.
111i tiimpatn"f!ptres!. b:DDSfnflll'aosomc ,ofm~ workinitJaD,- done by IMps to mise me pimlEll
bact into illtema:l Cf1e1iY of the g;w. Once die proecss i iniU.ated. no mforitNim_al change in
~ Cl.lDIIfi~cnn ~il:li<~ ~~is urn:~~lf.
AJ1 pmr;esses cmied o ut in fim~ dm. wi1h ~ ~hshmcrs. ~ nreDmpanied i:n ~
~by d.impllli~ie dfec~ of Dfte' tmd VI'~~ and nll.ill'e dtiwfore i.rre\'el'&ble. Howe,rer,
oneeon imQg_itl~ iP-rocesse- tbln me f1ree. of dissipalhrc df:ls.. Far- lhc ~pmmon pruce&S of
m
Fi.g_ 24 sud! ~~ blt\.'C their tiOgin the :SUddm ~of a ftni:ee ~ fi'om lbe pNOII.
"l1H: JleSUbing ~ ru ron:.u 3CiiD,g oo lfx: piston CBil:.!lCS its aacb:noo~ and leads W1
ims wbseqnMl osclllmion. 'Ibe s-u_dd\eu rem&\"31 Of smaller .mass iocremems fedvce-s, tvt does.
mat elhninate.lhi~ dksip:lfhre effect. E~ ~~ ~"31 of nn infinitr3ii:nm11JU15.-. L~.ads t o pistcm
as;ciDilliotllt cr i afinil~iD]lll amplituck 4tld a consequenl diL.~pa1ive effec~ HoWte:YCr". nne may
lifJJDgi~ ~ ,..1KKID small mass lQCJtuznJ."'me. 110Dfi1t~d one arm-~~ (if:itle sud:l:
~ ll1nr pt&toRtS ritte is oonlinunm.~ with minllte ticiDHilioo only at dJe end ohhe pmoe~'-.

33
~ limiting ~ of Jelll()\!a) of o s~m of in:Onitesimal ma from dlie pistun .,

~maled wM-o die OIJSSe:!i .m in fi1. U are replaDed b)' a pi& of paw~ b~ll io u _,.
fine ~ !rom the pmo& Dmifig lltis ~ lbe pl!too rises m a Wltform 1M very aw
~ mx1 tbe powder c:oJ.Jeas in torap u e"w hQber leve.b.. The ~Y~ i-tl ~ PJOlie tbao
diffcRu.tially dis:pJ~ fmru intcma~ ettuilibriom or from ectoillbrium wttb its SUJ"J:DUndinpJ
If m.: ~-wt of powttu from tbe pW011 is Mopped and die dim:tmo of INDSf.u of'~ m
~ .&...-.
l~'P~, u_-.;: ~
_.,..~ - - .cA~-L-.
J!t'h,~- andJ
"'lD~ _ _ ~
~
i'8fd! ~~ ;lr..,
_ _ -.1......
__ 1Hc;t-LU41 ._ih
--''iii'f--.-1
.._.. '!1, 'D nd.
~~ puu.1
~be sysrem aod i summndinp am uftimab:ly ~ 10 'rinuaUy mar mihal c.wldilio The
original p100e approadN:s m...-
nibillry.
Wttbx!;t lhct umptio11 of o &Wtionles.s ~D. 'We canool i.tmt.giue li ~s.'bl~ ~
![f tilt ~ sticks~ of ffifticR.,a bite lti1IS$ mO'.St ~ re~ before dE pWom breaks
fJOO.. Thus tbe oquilibrium condition nee~ 'lD ibi'ljty is ~ ~O''(:'f.
frk:tit.llq bet~ l'ft'O $llitil\@; pa:tu1 is ~ ~ fur the c!Mjilioo tit mecbaniall enm'IY wo
jmemaJ iJi ugy.
Tbi~~oo bas ~on a~ cl~..,stempt~ lhco~of '~ m
o cylin&r~ ~ oppo:sitc pnx~. ("()!llpmssiOD of a p ina ~cylinder~ is ~bed in eu.aly the
Sllllle \\faY~ Tba'e aJle.. howe\-er. maiD)' ~ whim .IDe d.rivtm by dx in.lba_lafa <rr force5
odtcr dlan ~ ~ For~~ liar flow oecuns \dim a l(ftn~ dlllereooe
a.im. ~tedritity ftows 't mtlrr me influence of an el:ee~-e force, ami dlmricaJ re.2101ions
oc:cur bee& sea chnnical potalti.aJ mWts. ln ~L.a ~is~~ wlaJ lht 18 ft [Ol'Ci:
~g ~~ i:s onty diff~ial in ~- ~ beat is lfilMfemd .rewntib'ly wl'leiL it lmw from ;1
finite object at ~ure T 1:o ;mother sucb old~'l am remperatute T .-.. df_
Tilt ~Jill ut a a-ettible dltmkal ~oo is Ut~ted by the ~omposi'tlim of 4'31t:imn

curbortltc.. whmll wben beatld f-onm caki1n:n oxide and c~ diaide gas. At equilibrium.
this yiiem ens a ~~tcltk ~itiov ~ ~ COJ for~ ~"'en ~mp:.n:~. WbtP
ltftc- ~~ore falls beb)W Lhi$ '"'llt~ CoC03 dec~ AS!tlllnc lhut a cylinder is. fi~ wilb
m
a frictionless pisUm ami cootai CnOO,J.. CaO,. Wid CO! equ;ilihriwn. II ils isnnmcd iD a
~~urc balh. fk'twn jg fi&- 2-3? ~ ~ 'l;\l.f~ ~ tqUj.fi.ty of
~ ~~re with 11m of lhe h1dL 1llit tempe~ is adjr11Ste.d ~a ~:due sudJ tlat
w
die ~tiuo ~ juS-1 sufficient to ba!~ lht \\~igb& on tb:c paton. o ro_adlfron
of liiicdi~l eqWiibtiWIL 1be ~I reaaioo held in bdcmce (to ~rium) 1J.)' the 1
JPRL~ of the C<>!. /my c~ of coaditions, ~~(! :&tight. aqR ~ eq'lfilibttmn Wid
~.li lbe ~ali b.l ~din ~lot diredi:Oo ct ~ othct.
Er me ~t is d~~ iDcre~ me~ pre~!iUre nses clifren:onany"' and CO:
eCJIIllrines Mtb eao
to lfonn eaco~. ~.l1uwinp llha ~ lO &11 do.ly. 1bc beat ~~ . .
b i..bis tertfKm .raises dw: ~ in the cyiimjer, ad beat Oows to the bath. ~
1bc weigbl di:f:MralliaBy ~IS oft the opposil~ .eba.m of~ Thil same ~am obWtrdi if
Ultl re~mm .o f the b:tth i~ ~or~ If abe tempa.alwe of~ batfl is reed d'"tlfer
eo.tiaDy. beat flews mm tbe cylmder and cdaum aubooatt ~ 1lJe; ~ ~
~- ~ 1.0 rise ~Ill!~*/~ wfrid1 iD tum roi! tM [JMI.oD and weighL nli~ OOD;oo
liJmes wd die OIOOJ is eomple.tcly deeompnsed. The~ .. ~vmibk. (W id lc ;ystem h
IX\'W mor;e ~ din~~ ~ from equitihrinm, and only a di:fft~eniia'l IO'Verim;g of
~ te~ of' ~bath ~s die .100:1 ~ t~e~Uta tn its initial ~-

Same mem.h:aJ reamon am 1:1= eanitd out in m ~)li.C edl. m'ld in dill, mse they
~ be hdd inrbahmm by am applied poumlial di:lf:ercn_ce. If stK:b a cell roomts of rwo elec-
trodes.. one of zinc anddJe ~ ofphJiia~ i~ WI~ 1;dllilltm ofbydmdi!an&m
lidd~ the Raai90 'l im (I{>WJ~ k
11:Je ~u j hl1d llJider Bud c_onditions or~ Wid pces:s.w-e. and me .d eanXJes QR c:uo,.
m:dal aWJmOy ro ~ If 1he eledm:IDD(.i\fc fOKC produced by d~e cen i"' ~
bu1anced by ~ porrntl:d dlffb~ or ~ porcnti~er~ l.'be reaa.itm i:g beld iB equilibrium..
1llr: RtiCiian may be made m proceed mdl fOl'VtVd dhce&ion by a stigln. ~ in the op-
posi.~!ll dirtr~. ODd L1 may be~ by~~~ in l.be poumilial
Iliff~ a.bo\'C lhe- emf ef 1lbe cell.
BummiiiJ Rflllfllrb on llfwelslf)le Processes

M\-asibk ~:
b ikliooit~
b IE\'a' 'IIJDI'C lhatiJ dlllm:uJi.aU)! f91()\'ed film) equ.lh1mDm.
TJID."e~ '5Df.Xle-s5iW uf equilibrium s.t:ates.
b dri\~n by fo:~ wtlu.se imtw~~ru:e I. ditferenlill 1n tmt.iD flude..
O m be ~ Ql m)! palm bj diffammd dYp.ge in e.(~ oondiliQDS..
Who ~ ~\ it.11 f~ pa:lflt, 8Dd ~ ~ iDiiW 5~ of }' J!DJ .mal

~
An eqwlic.-. derived in SaL J.1 ~iRs lie \WGfk or 41X!mpe&Sion or u:pansion o'f u g
C'mlsed by lbe cfifk:muiiJ ~ f:J( D pi$tnn i n l:lcylincfrr:
dW' ~-l'd\1 1
Ob as pro eg das po d e tos de au c

lS
1be w.-'Oit. dOne ~aD lbt systan is given by lhis eqwlll:oo ooJy when cenain ~dbame~ of
~ ~.mible iOCbS ~ rta__li?Al. Tho li:r$1 m(t~lflcDl ts tb;It tk' ~f't\1tl ~ PI} ~ lltan
i.nfitl~y dkplaced Imm ~ stm of immml eq1litlibrium. ~ by IIIIDarmity of
~and~ 1'bo ~ thm alwap .m idmtih.bkkt f~, iQclvd...
mJ ~ P. The seoood ~e~~.~ is lN1 tk ~ t~r; oo ~~~DR man infmit~y
~J~Kedl Jimm,'IMdwiica) equilibrium 'Wi1b its 8Wilr0Ulldmp. In dJis ~t. the ~~
1
~ P n., ~ ~ 1hafi Jnii)ur~l)' tRit of ballltliX" "'-Jib 'tile ~ ibroc, Mid we JruiY lfifite
~:be mbscirotian F PA dJat ttmsfom~& Eq, (1.1)- inlD Eq. ( 1.2). ~fer wbicb these
~ arc mtf ve wd to be TJUdtCUiic411)i ~fflble, mid 4. t 1.2) fN)' be ioltgti)ted::
II:'
W: - l-~:. PdV' r( L])
r
The re asibJe. process is idleal in~ it prod~ lht best pos_ible ~ ~~ ~t& a
limitao D pd'mn:mcr of ~actual p~ bot l5 Qe~"Cf" fully realizol An mitial ~atall.nion
of \\'UI't. is often made for a revemible ~s. l~ the dloke is ool\CCD sud!l :a ~taloul:dion
_... oo a~
iB.JN -1ati""'"' _ s1!H1 rn..
..,..~ .at .... rntetR:lb
, L.ID _ - ~..--~.
"" ~,,.. - lhc U
.w.. - _ - - w!l"'-
',mll"IIJllJ
_ _ -- li"' .......
_........ 01 .ol.... ru.p.p ;v with :m
W!l!" ~mll.-:""'~~
~ ~dfidnu~ to yield n ~ iiippm:xlmatron m me rfllt t.d an ac:ttra1 ~-
Exampla2,6
A horirmnt.al tpi:sfOOicyQnde~ ammgeroom is placed in a ,oon_S1ant-tempemture baltl,
The pistol1 slides mthe cylinder fth negligible f~ and an external towe ~ n
;.,., m.,.;; ... -~a.+. .:..,:a.;.,.l -
~~~P~ ~ '""""&IhunrGig&Spress..._."' .
- - - . of 14 ~o..-~-: Til.. ... i1i1i1iaJ
.._,,, n~ - \101
_ gas . UDJe . 0 3 W .. The
~. is 0.,
extemaJ bee on the ptGton Is reduced gradualy, and ~M~ gas expands isothermally
as its ~ doubles.. (j' me ~uma of fhe gas is remredrro its pmssute so dwtt 'lhe
p~ PV' !s CCiiRSta!d. what is the work done by lhe gas in moving the external
~1
How much work l'IOUid be done tUl the ~IIJWlternal force Mf9 sl!Kklenly fied'uoed to
half El$ initial \r.8lue instead of being gradually redueedr?
w= -41-..000inl ~ - 29 112J

The fina1 ~'i$WC i$
' k 42-CIKJ
pl = V.' -- 0 06 = 700~tm h Of 7 lbat
%
Jo Lhe second~ rcduaioo of the "Llia_l ~by i.~ ~ lby wddro
~ or lk p ~ ~t fOI're equi'Wlatt m a pressure of 7 tm..
E mroally, be:rt transfer remms the systrm to the~ final eqvilibtiUin h:! ~
in the: re'VOS11dc ~ 1b.1s. 6 V' fs the ~ a Wore. btll the \\'Oft occotn-
plWitd ncr gmm by Bq.. ( 1.3). btbm. the mk ~dome agairm the exlemll fon:e
equal~ the equivalent extmlal ~ lbn__cs die voiiiJDle ~cblnge;
W ~fl x l0S)(Ct06 -0.0ll_, - 21.00CUI

1bi$ ~ U; dcittly nm'cllSibie. and cmn.parea with 'ibe Jl'e\'efiible ~ u
said to have an ~iency et
2 1..000129.112 ~ 0.721 tOt' 72.[~
Example2.7
Thep]staveylnder au:angement st1own In Fig. 2.4 cootaJns ,Jbogen gas lrapped !be-
law the pislon at a presswe or 7 bar.. The: IPfstOO ij:s held tn plac-e by latdles. The
's pac8 above the piston Is ,lf!lACuated. A pan Is attached to the piston rod and :a mass
m of 45 kg! is fastened to U1e pan. The piSton, piS.tOn rod. and pan ogether tlave a
maas Df 23 kg. The latches lhotclng fh& piston are released" allowing the pistm to
riSe rapdy runtDI it Sbikes the IIJP of the cylinder. The distance IOO!Jed by ftile 1pis(on is
O.S 1m , The local oooelemtfon of gravity I& 9.8 m s- :z. Disc:uss too energy changes that,
cmcur !because of nus proous.
37
Solution 2.7
This~~ lht limit~ ca~ of~~ fw~ at
~"em-.. oondow ~ Let gas llolte be me
~tan. 8)' ~ basic me
f
d~Ibmion. wolk daDe by b- gu Gn the smciUIIdiDp ~ f'l dll' . whae P
4
is me ~ ~em:d b)" 1he p oo me pi&l.Otl. Beawse lhe ~ u ttert

1
rapid, ~ ~DIS ~lil mlbc p.-5. md odi_hc.T JP OOI' 1J1e iotJ:gr.aJ I be

evalmted. Ho-we\w. a re~urn 10 Eq. C2.1) avoids. me cak.~ af work 1"be
tn.eiD ~ IJf ~ &ysmn ~the gas) is Au# rm ~ fl.1l1QQIId'inJ,s die 15f ~
rod. pm. .md maz m manp lo potemial e~' iiUWIIM (HUD, ~and cy~
dYmp in mtaml mJY. l'VicbrQ = "' Eq. 1(2-l) ~ writtm~:
A f.J'~ -L (AU_k,. + AEr mt) = 0
wMft AEp ~ (43 + 23H9LB )(OS ~n3.2Nm
2..9~ CONSTANT V ~D CONSY~P PROCESSES
Far n mol~ of a homogeneous ftmd aJO-r.Uoedi in a dosed IJilem the. enaJY bcitaru:e ~
d'(nU) == dQ + dW (16)
where Q aod lV alliW!ys ~nt Klltll beat aDd wo~ wbale'w tbe. value of n. 1M wcrk fur
a mtmnicdty m+el&ibk c1~!)'~ ~ h Sivt:fl lay Bq.. (l..2). bt'M v.rtit~
dW = - P'd ("V)
(U)
ThiS! Cll.CTg}T ~is gcDa'al fgr- ll moles ofbomoge:DEOUS ftuid ma closed ~m WKlCIJoinf
.a ID!Cl;.'iwU,caDy m'mi4Die pr:oce~
ConstJtnt.Volums PtotJtlss
lf the. pmee:ss fiCCIII'S at mWWt raW vo~ db! WO'fl & urn~ M~ lot dosed~
the la:st tt:fffl ot Eq. ('2JI.~ i; a_lso ~ bo:::w~ n .md V ate botb (D~ ~
dtJ ~ d( Rfll {cms11 V\ ('2.9)
~ Jklcb; Q = ra lJ.U (WAS1. V) fl.lCJ)
11nls the hem 11'aD5femd ill a mecbmica.Uy ~b1;e.. cons1i:~JH..vol:uJDe:. dDSed~ process
eqoab rtE intt.rn.DI-c~ Cltafigt of the system.

CtJnstsnt.PiflaU,.,PI'Ot:eU
Soh'Cd rordQ'~ f4 (U) ~
iiQ' =,d(II'JUl i- P d(n V)
Far a eooslilld ..~ Cl1Jaop,

dQ -=d(ntl) +d(RP) - d[iRi(U + P\')]
1'b; 3fpeii411QC (If (be ,I:J'lP U + ,V., boili IH:ie ldJd in ~ appHamoM. ~ W def~
blitii!JO fm' aonmtimae ,o f a new~~- 11lw.. 'the 111albmmlka1 (and. vnly~
delifioa ,o f c:nlb.1lpy (~dgl' ~; if~
(2.. 11)
~ R, U, md V am molar or llllk-nm:s '~The ~g ~ b~ ~'r now be

~
dQ ;;:d(nH) C~ P) (2..12)
Q == n 1l. H (MlHtl P) (l.JJ}
2.10 ENTHALPY
The~ ottbe cmhalpy u td by~ (2.12) and (2-!J)_ 11 ruso ~ 1n mqy

~ fCIII tmw ~ ap-pfied to :txa_t ~ ~ cfisci:1btion cot~
puDQJ$, cam bbiJ _ ~ en;,., fur ealmb.lien fJl bea mj wo:rk.
ne tabob1ioB orvaloes. of fl aDd tv fN the infini~ :anay of pom"'bbe pmc:tsses rimpos...
~ 1k ~ ~tate functions.~. $Deb as ~iiic ~ ~ti~ inmnDI tfttllY~
....~ MtbaJw~ are ~ rnperties of mder. Once O..mninod a ~m' sub- ror
~ tnmr wlucs for liquid :nd wpor ~ ~ be tal:>arlt~ flil.-tioPs ofT iUld P fQII'
ftlN~ ~ ifi me mlroltllioo ,o[ Q and 1V fe_r any ~ ilw~ring Ibid ~ubsnmce. The deter-
mimtioo I ~ values tor~~ rwcti(m and rhnt COO'clmian :md US& am~
mtaw~
AUltm"ms :ofEq. ~I I' D11LW be~p;E,~ jp 1fiC ADJG~ ~pod~ P V ~urn~ Q
tDCIIIY pf IJVJ~ Of [peJ" ~ ~ as; diDes u~ merefm'e 1:1 also 11M IIInl~ of energ per mole or
per unit ~ In lbe Stq~~ the h6e 011ilt nf ptr~ b l.h:e ~al ~ N rn -~ Wid,. fm tl'Ktillr
'A 'ViOid bp IEL ~ Dutdl - " w1JO b .~ bdiv LQ . ~~ m.

i:1 1
pc:m:alueliMii'J m19U. ud ~ ~ ~ fwpfl}"~iill'il ! (58: ~ ~ rJm fll)llt:w}
L:&te~ I ~ tr! ~ :110. 109. p. 3. fooaMn 2. l9(11),)

2.10.. .Emflalpy
'ltOI~ ~ mor 1 1111: P II J'll'l'ldUellhen bas lbe Dlli$s. m mo.l- 1 or J IDOI- 1.. to dE. English
lineailfig s)'Sttm a ~ llbi1 fer (lie , v pfr\dacl 'the (ft lbt~-~ .. wbicll an__ses
when~ ls i:il (lbr) ft)-2 Witb volwiJc ln1{fAr(lb; )- 1 Thi rremlt b IHWill)' ~ed tO
{Bm)(Jbm}- t ~ flWWODI by 778..16 for . in Eq.tl.llk lwwrst bWJillm)D .En:~r
mperiDg uni1 for U and H i !be (Dtu)(l.bc.J-~ .
lBecanse U., P. and V me aH ~ fiuoct~ H as clebJJed by Eq. (2. 1 I) - a so a
!li.1B'tc' fimmgg. l.ike V :mel V ~ H is 1m in~'l; propa1}' of ~ 'Jibe; d~ fvml
of IEq. { :t 11 ) :
dH =dV + d (P V} (2.14)
This equation applies wbtmcwrcr a diR'cn:mtial ~ oct!UJ'I mdie em. Upon ioll!~
h be~ m ~ for a 6nitt dwige in w sysae~ZC
Exarnpre 2.8
C8ladale Au and AH for 1 kg ot water when it ts vaporl2ed at the constant mmpera~
tJJTtt or 110~ and the c:onatant pressurre of 1101.33 kPa.. Trhe spedfio wWrne$ of iquid
and~~ at lhft$e colldilior.s are 0 .100104 and 1.673 m3 kg"" L. iF 1his change.1
heat in the amoont of 4258,9 kJ ts added to,the water.

1
Solutlon~a
We tate me l k@ of water M ~ sy te:m.. ~it alone is ofinliftiL and ilmagiae

it ~ m a cylind by a ftiaillntcss pisn)n \\frldilt act~S u. ~Dtsnm ptes.'Stttl:
oft U)J .:33 kPa. '" bear is addett.lbe water eva~ ~g from loiDW
ro its fttmd w!umt. !qualion (2. J3) ~ writt~ ft'Jr1bc I..kg SJ5(em is:
AU - tiH- 1\(PV) IAH- P A V
P av !!!: 101.3'3 t:JPa x ( 1.613 - 0.001) m1

1
= 169.4 klP~un3 = 1.4 tN m-~ M 3 ~ 169.4 kJ

2.11 HEAT CAPACITY
1IJOdem ~-or btal 8$ ~ m wo ~ bf be: itb dllll tt tJJy bPs A
t:apxhy for hea. 1be smaller the tempnatm:e. dlmp in a body Cl.USed by the ~or a
fi' -o qua;wBy of beat. die ~ its ~Y~ ~. i& '-1 ~~, ~!~liP be ~ a.\
u
c d(lfdT .. 1'bedmicuJ&y~itb this dw il m:lkes C. lib Q. a proces~quanticy
radJcr llm a sac fimt1ion. HQ- ~n. iit dOes JJ me ~ ot two quiDritiJ "'rim tbis
OUIOIDded a:une that~ in~ smre ftlnmoDS,. DDalDbi~ refaled to adler stale .fmtdiom.~
Heat Clpaolty Ill Consllmt M:tlume

~CftiSt#nt'WIIII:in& llrar ~) nf a.~ Is ,d tflant
Cy (~)
ar . 11' (l. l6)
1his defmitkm ~ both lhe molar beat~'Y and lbe ~ b&!m aparity (usu-
ally adW ~ btat).. dcp;ndiDJ whtlbcr rJ is tlw ~billa or spoci& ~ ~
A1-~ . . deJinidoD " DO rdem~ 10 .my ~. b niliam in an espedWJ~ simple
wayto, aCOIISUIDt-whlmc [~ in .adostdsyge~ flilrwhi~l!q. (2:.16) rooy br~
dU ~c ...tlT 1(\ons~ V) (111)
(2.18)
1'bd mw1'l: ifh Hq. r{ l. IO) far a mvJct cuticaJty renniblt~ COMWitvoh:lme ~; ~:
Q= 11 4.1J ==, J.n

T,
Cy tiT (~ V) ( 2.19}
If llJe \'tllmDe \Wies ckiDns lbe ~ !but returns at abe aid .of the prote ~ to i initial
ue, ~be ~ ~ ri,gJub' !be Mkd ~ of ~swot ~ ~ r~jb ''2 = v. iilfJd
A V : J 0. ~~ cbanges in !U.fe f11Det.iaas me mdeperuleru of pmh. aDd may dlercfore
be c:~ by tquab(DIS fQr il tmly mtlStatit-WIIwnc ~ witb the &aliJC Urltial W"ld lind
~ Equati (2. 18) tbeo tti AtJ = f ,c,,
dT. beai1!1A U" Cv. and T ;eo aD run
r~~. ()Q lbe Qlhcy bmid. Q aDd w ~[ 00 ~ alld Eq. (~~9} is. i1 vulid ex~on
Q. and W is iD ~ XIQ, only for a ~~lr.o/JilfW ~ . Thi.s is the reasoo for
IDe &tinc~Wn bet'W'CCI " f-\lDCiiom and Q and W~ 1ifle prin~ple lhal ~ fuol;tions an:
i'.ndGpcodsm of the PI~ is an O'n~ IIPd o~ul ~
F-or 1M alrdldon of ~ chanpa1 an II1ChJal proceu. map be
f'IP'M'id'IJI lftJ' Olber pmctSSwtdcl!l :aooampll....,tbe santeChange
lnS~ata.
Suda au aiJmlaliif\~ f'I'OCCSS IDiiJ be~ lw ex~ bef:.aa.w ,o f i: si.mPfkity.

4[
_ (8H)
c,. !!! . ~ '
3T p.
(:U0)
APDT~ dllt1ilion ~ both ~~ Qd ~ b;3l c-a~des, depM,Jing on

~ H is the IIDD1ar o.- ~pedfie e-ntbatpy.
This beat ca..,my ~data in an esped:a_Uy iimpiC
way oo,. tS~-~ d~ .:t'~ p~ rw ~ eq_ a.lO) d ~ll}" d1 'Wtlfaeo.:
dH;;::;: c,. dT (cons&P ) {UJ)
wllen:ee AH :;;;;r { f", C,. dT ~UWL~ Pl (1..1'2)

Jrl
for a. mcdlanicau:y mvcrsilde. COH.ii~ ,p pxvc=ss. dlis rc.sull ~ be~ with Set~ (l. J3}~
(2.23)
lkca.use H~ C rr. 3mli f ~*i:e fimdions. Sq. (l.2l) ,applie.smany pmce forw~b ~ Ci1l Pt
wbedler or DOt it is .ctually Cllllied eu1 all constant ~ H(Milft-V. ,only for- lhl: IIIIDdlia-
~, ~II*. ~~-ure ~ QA ~!tea~ .and wort be ca.k1Jlalttd by me eq-ions
Q- n all. Q _, nf CtdT. and LV:;;;;; -PnAV.
example 2.9
Air at 1 bar andl298.15 K (~0) is ~fiSed 10 5 bar and 298..15 K by two dtfleMM
mechanicaly rewrsible processes:
C&1cu&ale lhe ltteat and work ~eq~Jiranents and Au and. li.l l of the .a ir lot eacbpath.
Defollowfng heat ~mea ror aJr may be assumed Independent of ~
C~ ~20.18
Assume also for air lbai PvJT ~s a constant. reaardtess of the changes rt undergoes.
At 298.., s K anc11 oar the rnoaar VQiumie or air 1s 0.02479 ~ mQf- _

42
Solutton2.1
1o ~ ~ 1a:te 1he ~ as 1 mo1 or
40 ~onWkd m am imagm.aty pis-
tnrkyliodllr ~ Beause the ~ awideral aro m~:t!y
I'C\~11.\ 1M pi " imqkted to ~ iTh lbc cylinder wi:thow Erict!GD. The
.tiDal "\110
~ "" v. ~ ""ll.O'J.t19 H) =Q.0049B ml

(a) Oming the fim srep Cbe air t8 c-ookd 'die eonstam pressure af I bar 'UIII1il the
liD.al \-d..~ of0~0049S8 ml " ~ ~ lQt(~ Of die ldr at rlbt:- tDJ of
lhis aJOiiDg *P k
_,
t
v..,. . (0~)
- Ti ~ :: 298~ tS . . ~ m .>~ K: J 7. QJ
V1 0.02479
1
Q =All ~ Ct dT ~ (19.:10)(59..63 .... 29SS5) ~ ....6.941 J

AU = AH - A rV}1= Alf ..... I' 4 V
I!Z --6.941 - ( I x J@)(tl004958.-.Q()I!..4i!J) ~ -4.958 J
Dmm.g l.1JD senmd 51:ep rb : votnme: is held C(m$'bllt1 ar V::! while: tk uht II he-filed
10 ib ~ uae. Oy &J. {2.19).
6-U ;:;; Q-- C.,f AT (2{178)(191. 1S- 59.63) - USI J
1\l:kt COIIIJ!kte proce ~~ d:w: wm of iu $1~1>$- R~
At} ==- -4-;9:JS I 4 .~58, ~ 0

Ute~ 1bc a.w a-pplit$ tOdiiO ~ ~, AU e: Q + W. imd lkrefan:.
if);;: - 1,.983 + w
!'4~ (1151 AH ~ A U+ ~.( P V). aht>appms iD the entire~~ Bm

:rc;;:;; r~. Wid lhcmf'al'e, PI v, = ~Y2~ ~ 6CI'Vl:; o~ ~
t.H~A1J;::;;0
(b) T~ dilfatut 5tep5 ,are U5N in dUs ~to teadllhl .arnr 6il;:d StU~ of the air. .
1n the first step them
is hi9ed at a~ wJwne equal to its inWal \ , . un1iJ
die~ ~rat of s bar m~ba!The o:it temper.dllle aJ lhe end of this step 8:
T' =:! T1 ~ - l98.1S (I) e 1,490.15 K

43
All this --ttp lhe vel~ u \XJRSWit. iUd

Q J;; AU-==- Cv IJ.T ~ (20.78)11.~7:5 -298. 1:5).:;; 2A.18!J
In lhe second .step the air is coukm m P a ~ bar m its inal ~Cue:
Q ~ AH ~Cta ll 'T - C29.J0}(29&.1S - 1.490.75) ~ - 34.7mJ

till e AH - A ( P'Ll ) ~ AH- P dV
= -34.103 = (S x 1~){(tll)(9S ,..... 0.0~4-79) = - 24.l8S J
For the MCJ S~eps combined..
Q 2t788 ~ 34,703;;; ~9.9,,SJ
~
dfJ = 24.788 - 24,188 = 0

w = 4 V ~a;:: o ~ t-9.9lSl:: 9Jts ~
AH;; AV .;;;;l)
The~ dlanges ~u and d H ~~for me given chaqe in~ are

lhe ~ for botb J*b$.. On lbc adler b1Wl 1be &mlwt:IB 10 pU (a) and ~(b)
dw: Q d \l' ~ OD the path.
Examp e 2-.10
Celt._ llhe in~ern8l,.nef9Y ,9Jld enlhq)y cha:nges lhal oecur When air is changed
from an ._ "lial state ol ~~ and 10(atm). where its mOJar YDiwne fs 36..49(ft?{lb
mOfe)- 1 to a ti\81 Slate at 140 F) and 1 (&'ltR)AAssmne i Jr aif thai P v JT is eortStam
Mef thar c v:. sand c ,.;;; 7(81u)(b more)-l r rF)- l .
SOlution 2.11
B~ property~ u:v ~Pdmt of dJo ~ IbM lwiPp lkiP otJopt,
mlk!llnliom may be basc.d on a {\\1)--gep._ m~ ~ibleproce_ssm ~
1(lb mole) of llir iB (o) ~~ :ill comta_nt volume to b finD) ~ :wd l6)
bcaled at~ ~ 1:0 rhe 0:na1 ~ ~ ~htw ~
l!ft ue OPJ ~ R1VLtio 5QJe.:
BeatDSe P V = i T, die .rmia T JP i.s i."Qm.tlllll far step, (<~). The inmtlllCdi ~
tempendllre between me two ~ps Is lbeJ!efore-~
r = (499.61)( ~/ ~0> .::=t "''"'fR>
and b IEmpel'ULm: "1:wJga f(B' the I 'WU SliCJIS ~~
a. Ta = 49.97- 499.61 = -449J'O(R)
A:T~ ~ 599.61 - 49.97 - S4,.70(R.)

rw swp 'W~ by E'4$.. (2.18) and a. l5)
JiUfl ._ C'V oT4 ;.- (Sl(--449~70) =- -1.248..StBtu~
.AHQ m AU~ + V 6 P11
;;; - 2J43.S T- ~ 36A9) (I -- 10){1.7195) = - 3, lJ ~ .6(8nu
1
~ ~r 2.l ~ 9S C(IIJVmti. * P l' pmtluct from (liiM)!(fl)j~ ~1't:tch ils an~

IIDiL into I(B lU).
fOr., (b). lM \>-qlum: f>f ~ .~if~
v,"' v. ~~ = 36.4!1 ( ~) (:~) .. 4l1.93(fi)

1
BJ &p. (2..Zl} LlMI r- ~ S1

6Ht, - c, Alb;; (7J(S49.70) = 3.847T9(Dtu)
AV.~ =ll~ ..... P a'Vh
= 3.847.9 ~ 0J(4)7.93 =- 3Q;49)rf2.7l9S) = '!t756.2(lku.)i
for die 11\\in step$ l()Jether.
llfJ = -U4B.S +11563: =S00.7(BtuJ
llH = =-3J4Lt5~ + 3.847..9;;;;;;; 706.3(B.tu}
:2-.12 MASS AND ENERGY BALANCES FOR OPEN SYB-TEMS
Altbuugb 1bc {oeQs of llxl Pl~l ~- ~ oo ~ ~ cbc ~-PtS ~

~find iJr ~ ~ pliariQIL 1M laws ofll'll:tS.t! and eJm1Y ~00 ~y ID
Q/1 Jm .m open tll tOe:Joxd;sy .eros.. ~ dleopro ysrem includes~ clo
$~ a ~;al ~ '111IK .temllllinderrOftlm o.er H lbftefore ~ to dle ueatmeotof
cpen and fJnD to the dsvelopnmt tA ~of wkt appt"~bi!ity.
Velocity, u
mc: Ma

(U.IIJ) l
The a:na fOJ 1:lffl.l A ~ lbe a~seaiomd i.d'ea of a eoodUit und p - ~.ific DliJlal'
tbsit)t ltboug_h \'doclty is _ l"tddr ~u,? its ~ maym1d u i ~ ~ lbr
u'"~ ~ nf a streWD iD tba diredWo normal to A. flowrale"i m. r4 al:l:d q ~~
~m.'l1f'C8 or ,g;md'Y Jib' oml of lime. Vdooity u is ,quicc ~1 lo n:z;r.urrej #$ it ~ nbt
~ ibe m~of flow. Ne\mbde:s it is am impmtont design~-
Example 2.11
Liquid no-hexane ftOw.s at a rate, of m :;: : ; 0..75 kg s-1 tn a pipe. wrth inside <lamete:r
D = .5 em. Wl'lat am q, h. and u? What wo~ 1hese quanti1ias be for me :same ;, if
D .. 2 em?' Assume mrlfquld ~thai p - 659 kg1m-'.
SOiutlOJI 2..11
\\.~ h;poe
0 75 1-"" s- 1
q -- ~ ~ -- u, A 001 J4 m) -
6 59tg m- .;1
,; - (0.73 kg -l)t(I&J gq-l) =8.70lm.DIJ -J

811.117 & mo~-
Ga ~ m, m~ quamit~. am i~ or D.
1lie \orlocily~ how~ de-
pemhi oo dia~r l.'llJ'vqb ~ ~ q A -'. w'llele. for ciiaJbr ~on. A ;;;
(n / 4)Jil-. ft1r D , e S em.
Simi! ly.. for D - 2 em.
Q.00l14 I
u :::;. 0.0Xlll4 :;: : ; 3..63 DJ
1be region Qr ~ idenrlfied for wwly - of opeD q5{ems is Qilled ~ 1:0/:wi:Jr. it b

~ iMm in SIIJ'1'0Utldiop by a t(ur~ ~- "ftte fluid within llbt annrol ~ tome

fJ,p:ft 2.5: ~Iql~tllioo of a
mdJDI I
b die thrrmod~ 5J!itml &It w~ l1.1'laS$ and. ~ b.lilnnc-:ti 8Jir. wrimm. The cnolrOl
'~shown Ktwmarlca~Jy m F~ 2.S ii panned fmm its~ by an, ~te
eoDIIDJ ~. 1W:o ~ \\lirb ftaw niles Pili~ I!!Dd nil .-e !Sbown diKeed into the comrol
'IMJunJe. md one fi.hmm ttb IJow miBiiil is d~Jeaed ODt. BecJ.me ~ .iis ~Ox rare
dJanp of - .;mm lb: c0111tlll W)ltmw... lhn~tw/dl. equals tba Dd ratE ,o f flooA of mass
Into lhe conllml vOillll'l!e.. The am'elltion b tbal flow i positive n di:leaed lrtto lht COIIIJol
votumcud~--e wbt11 dircerdw1. The~~ ii ~~r by.
(2.25)
Mre 1t1e second renn for lbe ,oonrro;~ wt~~:me of~- :.5 _
t6(ri~ = m1 = du = ~
'n. dift"eoco ~ "'"A~ :l'.ltm p:it}ts thQ: diffe~ bctv.t~ oxil aod mmmce ft W~dl
die subscrlpt ~" iDdicdes that the term .applies to til! llowing &tJ"ea.rM.
Wbcn ~ ma.u ftOVt'f&te mk aiveo hf Eq. (2~h !4 (US>bcto~:
dilleY
T" + 6(pvA)& ;;; '0 ~c2.26)
In dJis form 1he ~fm~S-.bal.aoce ~~~ i8 ofre.n caiiJed abe CDttriJWfl)1 UjUtJtitmA
The ow~ dtanc1mted ~ mte is an ~ specW for wbicb
amdit"UlllS \\ilbin the com:ml WlUllU; do IDOl e_bange wilb lime.. 'inle rorun1l Vt)lum~ IDea 0~
~aim a ~~L IJ1ISS offt~ lmd b ftrslor~on 1mB of B ' q. ,p )$) u ~ mducing:.
&j.(2~6)UK
A(DPA)rs :;;;; 0
1bc emu ""steady mtc... ~ noc ~Y iu.lp)J tbac ~ ~e ~ DlCJidy dm the:

inllow of t~U~S.S i!\,aaaly matdled by mbe omBow of m:as&
Whe:n then is hut a .single e~ and a 5iPJ,le wt
~ lhc JruliS ftgy.-rate i:s me. m
same (OJ ib otb meams;, lben.

47
,., lltA 1 ll2Al uA

m::: - ~ - = ~ (2!7)
Vt 1 V
Beamse enagy.lib Jm~SS 1 ~ comcn~C.d, the rate ofcbange of enc:r" "Writhin thr concrnt \'clu~
oqu the Bet ~of~ transfu mto lbc ooadtOJ ~- StteaniS 00\\in: intO and ow of
the mmrol \'OJWDe baw: ~d Mtb them energy in i~ i.mmmL ~- and tindic
f~ d aD comribute 10 tbG ~~ chatJp of tb~ .5ysttm~ Eatb Uni~ ~ of ~m:.mt
~ltO'lics illllla mtal ~ f) + j ..2 + ~,. where u is me a~~ \'elocity of be SU'e'arn. <: i.s
its efe\'l.tion al:Kwe a datum ~et and 1 is ~be local aca:l:eratioo of ~vity. Thus... eacb sb"eml
~ enmgy a d'le nne (IJ + ~ u~ + !I )tir. 1be. oet ellei!Y nnsported inu; me system
by tt.llowiD,g ~ is lhcrd(lfe - a [ {u + ~.w + Z&) m~ .- .. whtte ~ rilr:cr of ~be minus
..m,gn wdh,
.
~ ' . ad.- ) -
A ID ma__b. tbe tenD re__ m - tn4. 1'he r:aJ~ ~.. ccmnula.tion
- - l . - . - . -~ttJe
wtdrin -
(OIUltJI \>oUmte ifi{:f~ mis qpamlt)' iD addi'lioo ID lbe hea.lrran.sfer me Q and work nne.:
1 ~
cf(mlJ)c
dr =- l!i
[(
U + ~u + ~) m. ] II+ Q + wrrkrate
Conarol
vol:ume
n~ W'OCt mte may inc;lade: WPfk (If 5e'\.~ ttJ111'18. r~ ~ is ~ with .-mviPs
dJe !Dowmg streams lbrough ealmlees and was. The fluid at all)' eucr.mee or e.m ~ a 5d of
U'-e:~ ~I'~ v, u, H.~~. ~ cllall a -~~ of Qui<~ with IIH:s:e ~

exms at m ~emra:oee or ,~ u 5bown in Fig. 2 6 (ll the entr~~~~Ce). This lliDit mass of ftuid is
~ted a.P(D by additielltdl ftu:id. hac ttpl~ by pist;oo wbieb 0,~ the ~_nt ~e-
p. "'i''C work done, by this phmo tn IDLlViPg the UQit ~gh abe emr.tnce i I' V. and ~
~ tP 1')11\. ~ aiA"' de~ tb1 kt"'-ceo nit.a d ~ q~~
the nt1t v.'Odt done na the !ryunt whtll all eu.tna:r~m and ait -~me tllren inm ~ is
~A[~ PV)ti)rs.
ADolll.er fonD of 'WUit. tbe shaft wflll i~ iP fiB. 2.6 by mtt: Qf~. In additiw
wor:k IIIIa)' be aiSOCiated wiJh ~ or <lltndion of b co1Jiro1 volume and there may
be~, a~ ~ rorrns of . . mo ,an indod~ hi a m~ ~an ~md by w. lbt=
pn:oecflng equation may notV be written;
d(m:~. ~ . . 6 [ ( U+ j14'l +t&)II]& + Q... 4m,(PV)m1 + W

~ o1a'ms in accmd wi1h the dc6nitioo of ~py. H - lJ + Pv ~ ~to:
d(JDd~n ~ - A j[(11 -to ~.,: +:g),;.] + Q+ W

~. usn11y !Ji~
j d(m.J~ + 6 ( ( H + ~ ,.1 + tg),.)]r. "' Q+ W

~ wdocby ll i:n lbe e~ tams of eoeJiiY ~ illhe lbulkwme.a.n \'docll)'
dtfi""" 'by~ tVIIim.. tt : 1/4/pA.. Raids H.owilJ8 itt pipd 01bibit a vd'ority profilo_ as
shown in,Fig. 2A which~ &mn zero at~ wdl t(lhe no-slip amditiDill) to a maxi.nmm at
lflt ~of~ pipe:. ~ kintfit ~nCJ&Y of :II IJuid iJJ ft pipe de~ 0tJ itJ ~ pn:dik..
P.or ~ c~U~t or~ ft(Jw1o tbe pmfile ~ ~~ and ~lOB ~ the pipe~
dill diD~~ sbouid p-mpedy b: Ul. li1 fUlly ~d ltDI'bulallftaw, ~ 11101e
ICmllDIOO G1Se io pm.ctiee. the 'Rlocdy acmss the majllf poRion of abe pipe - nal far from
OI11L and ~~ ~lA as USEd :m (he~ ~wttim.~ i8 ~ nrarlry (;~
M1hmgh Eq. (221} is an1energy balanoe of ~le geoer;WI). it has limiliDiom..
1nJ _pad-~ it d~ tJb .t-.. ~ lhallhe ~of m or the C<JOtJol \~ ~
st:dimgry. Thos .11m !lim1ls for tinedc- and ~ c~ of tbe flu-id in thi: control
~am 18clodffl. f<rr vittoaJly .n applbllons of i~ m ~ ~~- Eq. (USl
is~ For y (but 001 aiiJ -.plie;loons. ki.nm~ md potr:utiai~JD c~ in lbe
8(1Wi(ag stJa:rnS - also n~ilble. and Eq, (2.23) lflim nmplides to:
Jc~;~ + tJ.{Hm ){J; ~ Q + t:i' (1.l9>
Examp-e 2.12
Show lhat ~ (2.21) 1l9duces to EQ~ (2..3) b Ule case oJ a closed system.

49
SO.u11on ~12
the .-m
'fbe 5CCODd ram of Eqy (2.29) \s omitted i_n me absence of llowin,gl5tre~ El.tld
~ mulllp~W b) tJ1:
tl(m U)~ = ,( ldl + Wilt
or
Eqvalioa (2.29) may be Upplied IQ a ~y or pt'OCCS.Ile!S of. IJ;Ilnlicnl -~ U! u~~

miied in me mllO'Illi.oJ eamples
Examp e2.13
An evacuated tank is filed with gas from a conscan.t-pmssure Rne. What is tt.e rrelalion
~ ll'le enthalpy of the ga$ in the~ liJW and Ute ~nal e~ Qf the gas
ln tl'le tank? NegJec1 f\1ea't 1raMteJ between the gas and tile tank.
Solution 2.13,
1'he Galik 'wirtb j 5ingle m~ :saves as the cmru:ol ~'Olumtr &cl~ dMre is
.-o e;;p)n$im ~ ~ ~ t;tt sb.:ilft ~'Ork~ W =0. If ~kinetic and potauiaJ.
eaergy changes am ~1*. Eq. f2..29) becoma:
dlt~~ U)tmk
~~~-
H' m:;;
.., O
dt
~ 'die prtime (") idarti10es; ibe enrnnce: ~and die mimiS is reqpimd
boall.l:SC it is m CDI:allcc sucam" The ~ balme1- i5:
H dm
;nr ;;;:::: -~
dt
C.o~nbin:ins ~ rwo bat~ ~us yield$:

MWtipl)fing by Jt ;md intqnniDg 0\19' time (Dcxing tim H ' is OOMtam ~:
At~mf/ -- H' Amr.at == 0
w11ere subscripts L rand .l denote inmat and fim1l ~ i n lhc limk.

B~ tJe -- m the lank wdaH)i u. ~ m 1 ;: o, tbrm.
a~tSUlt biovriDg lhltm abe~ Ma! ttmffutbe ~~ ofl:be gas eooW.De.dl

wMin l!be cmk. 81 lbe eDd of the-~ ~ 10 tt. tnthaf_py of die gtg. !Kldcd.
r
Example~14
An Insulated. etedrreaDy healed lank tor hot water contains 100 kg ot liquid wate~ at
art: wnan a povyer outage ~ If wafetf is wilhdmwn fmm tfi& tank at a steady
rata of liJ ;;;;;;: 02 kg s"' 1 herR long Will it take for the lempetalOre oflhe walef in me tank
to dAlJ) from 60 ro ~C? ~ ~cold . - ~tets me tank at U'FC, and neg~e
heat lo&ses '"'"'the c,.
tank.. For lquld waletl' lei C ;;;::; c, independent ot 1' and P.
SCIIutlon 2.14
~ Q~ W = 0. AddilioDIJIIJ:. ~~~mixing of lhe ~of the
tJ au-s implies ow the propert:ies of the wam rem~ die c-ant are ~ of die
-mthl!- um'k. With the JMSS ftownte m10 the Wlk eq'Ud to the m ft.owra~e
out. me... is amstan~ moreovu. lhediffenmces !between in'l:el: imd omtletldoelk aDd
~ COr!fJI ~ bc.~a1. Bquaaioo (2..19) i$1ha-.Ca:e writtac
Jll ,.. H
m- +
tlt m(H . - 1t~o
whve om;~ quamirms rert:r 10 tbe cuntdll! of lhe taol wul Jla is the
spccifi~ mlhalpy 0f diG ~ mkriag the lank. \V"Jth c,. ;; c,. ;;; c 1
dU ;:: CdT EIPd H- tim ;;; C(T - T1 )

dl dJ
~~~then be(&~ on nraQ":Ul.getlltUt,
ill c:---- m tiT

ni 1' - Ti
lnlcpation from r - owtJere r - T.Ql to arnitl'i&ry ~ t yieldS:
111 ID
la - -
m
(-T-Tt)
To-n
51
SumliluJjon ui ~ ~ inm dti~cqumioo gi~~ for diJ: t'mlditioru fill.&

problml..
-- I ....(J)- 10)
,.....,-._.Ill , L .J;L
iili:::lLL.,l
-
_.
0~ 60-10
l'ha~ it ~~ oona I 1 fl'llljJJJO rot Lbe wall'.l' ttm~ mthe auk fa d:m.Pfrofn
wru JS""C.
Enetgy &M~H:H fw S~te Flow Prf:H;ess

~ f'ar \\ilkh the aecumul inn tenn Eq. ('2..211. d(,.. U JC'\,/ Jf. i' 7ao aN Qid ro
oaur Deady 5ll.l.le. , tti!.c~ v.'idl respect co tbr m fm.iame. tllis IJICilm tbal dE ;mnss
o( lhe ~m wilbin lb: rW nlrOJ IUJt"Oe is constant: il a'lso ~ ~ no ~ occur ~lb
tin~ in I:!Jt ~ of lhc= fluid! wdibin l.be L:ODIIDI l'Ubom: DD at lib enll:iiiKet .lllld eML"L
~an ~ cmb'Ol ,. ~ ri ~'ible nl'lider tlxse cin:u.tmtm 1be ml)' w of the-
~ i :draft Vwutk:. LUld lhr: FnrmJ ~n~ balun~ Eltrt2.18). hecmncs~
AllbrAJ:jb U~)' Sla1J - does no& ~y imply U\llead~~ flow~" lbe usual upplictunn I !
dtis mp~lllilin ~ m stmd)-'Sl3le. ~y-flow ~~. hn;~~ liUCh ~ rc-pN-~ lht
indusaritd norm.
A r~ Jl"'blh.Ation multYi wkn ~ contrnl "' :woe b WI DPC.
alt. The ~~ rmtem lbcn_nppl.ies ambadi ~nat~ eq. (l..lGJ~ to:
"'ilrR: !!_ulm:d:pl ~rr &n ~Mm~ mn.inrd in this ~ ,mse J1lld ~a ~ ~~ from
mt1111JJt"e 1D c.'"iL Di - ion ~ ,;1 givcs:
Abl
+ -:;- K A~ = (} + Will
1111'
-
111m nmlfromtk-4!11 ~~sioo of tb: lim hlw b .m_ ~~ ~-D_ovr
ThO. c:cp.ation IIi
~be[ ~ cme ~and~ e.UL AU~~~ per unit uu~ a Oaid.

lD ut1 the ctJCfiY"~ cquatiul'li so &r wri!tm, the energy unit ~ pruiUBied UJ be the
~ in nml wUb tbe S] S)' em Gf units... for lhr Eng;lish m~,-r~ ')'SkiD Dlliu., abe
-~~~.0~} ~lb:Jit~o~-..~J!Rw i I ~ W " - aow 11R

H.lidl) b)' . IDlbf !I'Dt ui1Di llft1lb.la liD lba ll!lfiJ!D'blllia ~ ~ CtWI.1;Jftl
Obras pr oteg1das por dwertos de autc

Sl
""
kineni:- DDd pcxentlai-cnagy 1le~ ~~w lbe,y JIPIX'I[-. Tell~ 6isin by Idle dimensional
CQIIl!QD1 &- f$cle&- 1.4 ud 1.8), Ia ~l Eq. (1lla}r or ~~p1~., ib Wrilk~
1
Hal:. tile mua1 mnil for II md Q ~die (Bnl); kineai~ ~.. potcntiaJ e~Xflf,. md vik are
~ p~, M {rtlbt . l'beftfan! me fKmr 778.Jfiffl l:br)(Bm)-l rmm 'be-HSCdl wim ~
apptupiiale t.mns to pull tbrm all in ~m~ unbs ul7 dlba- ~l I lbr tor (Btu~
En DWI.f applicadllla. ~('-and :pm~ ac:nns: ~ cmiu~ lx:c~ tbq Bl't
~iBible ~with otheJr k1mL~ For~ ~~ IEip. (:!..lh) ond (LUo) mduce to:
'1lrl!t aptaSion atlbe fiAt 1J1w Cm a-.iy- eadJ-fllWl -is a1Wogous UJ Eq. U.ll
(CK nonl)gw proc tkrtl'tYef., mJ:batpy -.oo- tJwi i~ mttJY hi k ~)'BanDt
~yo(~.
A FltWI ~c.lorlnteler tor EltiiJltiPJ lfeastmmJIIIIfs

'l1r ppl-cntioo uf~. C.2....'~21 u.J (1.33) lO lbe mlm fpmdiad pmblimn. ~eo
liWpy \.~. Ba.-ruJI'Se N b: ~ fuottioo. '15 \ul~~t!i ~ r!JJOly on pmnl coodbi~ tmtlC'
dcifnmrned. they DAY be ~~ (or~ ae for .tic~~ of canditiom. Th I~
- Bqa (133)1 ~ beJIPPiied In ilabomJoly ~ desi!ned ror enthalpy illlmmn:tlllm
Setilrln 1
I
~, J
A simple Bm~. calorim:el is UlllSt.nlled scbe:amdial.U) iiD fir,. 2.1. lA ~essential ieatwe
i5 au~ ckctlk ~~ h~ l.ounef"Kd m OutAt'io-~ ~tl "l1lc ~p prmide!. fur m trniiUII

SJ
velodiy 3lld elewi.tion damg.es fmm :sectiom 1 m sedion 2. m:Wns lklillme- ad polienlial-
cuetgy dbaoac:s 'If tk Ouid oeglrgible. Widl 110 5lla6 WOit enwin; lbe ~ Bet- (2-ll)
led~ to A N -. fla ._. H 1 ;;;; Q. 1"be rate of heal trmifer 10 the fluid is deten:nined fmm1the
~ tflbe h-... {lad tlle o,1mn~ ~g lbJooBh it. ln ~~a ~ar~i& ~
~ bm in prlodple the opaaDoo of tbe flow a1ori:nm is simple. Meawmomts of the
beat rat~ and :t1mv ~allOw tal~ ottbc dlao~ a H ~ 5CfOOns 1 ad 2.
For ~.:rmpte, ~ af bulb liquid aDd wpor lllO me tadily ~ ~
C~Jmtant~am:e ba1b D. 6l1ed "W~.nb a mixtw-e of~ i" ud ~r to IDIIia.T:aio .a tem-
~ of PC. Liquid Wllmr is supplmd LO the app:tr-dftls. and lbe mil th3t. c.!WiiC!'S it dmJugb
the coosnun..temper.IIIHe b:dh i3 ton, enougb to hrioj il to an esil ~ of ~Y
G"C. Tbe: t;m~ and~ lltCiinn 2 ~~~by 5ui~ i~. val~
ar lihe eruhalpy of H:O fm varims -conditions at 8el(\lfDD 2 are gh-el'l by~
ll1.;;;; H, +Q
wht.n"J Q q dJc' lnt ~ p:r unit m of ~ ftowiltJ.
1'be ~varies f1'01D ron to ~ Ibm .in lbe runge marllDfl:fed hffe il kt..11 a Defl.'~gib1~
effect ou dl!c. entbalpy of Cbe ~ wa1~. ud for palCiica1 ~ ll1 a ccmsta_nt AJ)so,.
gu_~ ~ trf,ettthalpy.. .lite absftlll~ "JUU~ of~ ell~. are ~r-11.. An amit nny \'alue
may ~be _:_ iped ro H~ as dJG:Nsb for alitOllw ~1'1 ~ SdbJj Ha = 0 for
fiquid WllKJ at o:'C maL~
~ ;; n. + Q ~ o+ Q' ;;;; Q
iF.mhal.P)l ~ may be ra.bolmd ror lhl:- ~m!i mid ~re t:llilifil at. sa;-(too 2
fur Q L1lp llmJiba of niDSw In addition. ~fio.\".DIWK ~ ll1i1Hie foe lhc5e Mme
Mlditiws may be ilddcdl tQ tbe uhk. dons \\l"ilh ~~-~ ~ vf fbi; ~ ~
~ by Eq.. 1~ 1 .I ). ,f l = H - PY. lin drls way Jables .lilf damnodynatnie pmpem~ i.il'e
~f:4 o~ dac a~te vsdul ~ of cooditi~ Th~ lDfJ5I widdy ~sum ttaiNI~ion is
for- H20 Wld 15 kfimll11. us die~ tuhkt. 10
The mdtalpy may be t*:n zau for soroc ether 5fatc dm;g liquid a1 (J 'The c:_~ is
mbirrmy. 1i"tlt equatioot uf IIH:nnod~ ~~~ ~ 154~ (2--32)1and (131), i1J1P1Y to dlmrp.s
of date. fo:r wbidl1he en.tbalpy tlf/f~ .are independent of 1M l~n a the um paint.
~--.- ..........,.,. Qn adJr
...__, .,..,....,., ..... , ~
lii!!li'ioi
. J..,. . ......;....(
~"""- , sdccf~d
. ~ u4
1'1:11!..
I.C r ..u QD Ufb~t'i'iDNdtQI-.
&mib;a]mt ~~ be
__ . ~-J . ~--II"'R
made ror
the internal enagy. ~ause 'Ole iDtemal maJXY em bG calcvl.lbd bum dX c:mbalpy
by Eq. (2. LJ ,,
Example 2.15
For ...._ ...__ Jo ' . ii il H:!!t dj - n il A. fnla-.m-. Anm *""1.....- ~ a.-
. . . .- ~~~:~~ .I\.PII!r C 8 if1Jh8l8r ,.,-, _ ~ u8 ~"'~ Qcl. _ 8f8 l~l n JU W8.~ as UIIQ
HI' IDr
lest ftuid:
tO ~~ ~~ in ~ f- T~ tsx~ ~ ~ ~ ~ lti ~~ ~ A, ~ ~
~~ iii~ ptrupf:i'bt . ~ Cll3p.. 6.

Rate of heat edditfon rrom resislance heater a 12t140 w
The water i9 ~rJetefY ~zecl in 11'18 p~Utrt$S. Cabdate the enthaJpy of steam at
aoo~c ar.d 3 bar based .on II = 0 lor iqukl water a_t IYC.
Wutlon a11
K 4.z tmd 6u~ me tqli_gihtc IIDd if W$ mtd Hl tit 1ZIO.. then H-: - (}. :md
1"' 1
' 40J -ll
Ill ~ ..... == 3,010 J - l
4.1S g :s- 1 g
Solution 2-1&
Benlt5e the air retlUJ'ns. o :i lnirutl eoodlti()ftj ofT urul P. me ove:rulll ~:s
p~ no ~ in en1halpy oflbe IDr. Mnrco~ 1M ~lentld~ d)anp
of 0. ah i_s. pmuiiEd nqtipllk ~also the DUtia1 kinefi~ ~ of 1he
~ we Wi'ire FAJ- (2323) H:
1'be kine~ term i& ~~ #:1 tbiOWS!

& ]( . l J
2~ = 2 ~600-) = 1 ~7
a; kj
~ ~SO.ot'X) -:;- -
r
180.{0) N m kg- 1
tg
!!!: = 180 U :tg- 1
Then Q - 180 - 240 ::::l -'0 tJ ~~c~c'
.Hem in the amoom: of M u rmm be removed per tuosrnm of m:r [)~
bampe2.117
water at 200 F) Is pwnped from a storage tank a1 the rrate ot SO(gaf)(rmn)-[. The
I'J1Dfol a lhe pgnp ~- wotk at 1h8 tala ,o f 2ti'W- The water goes thiGJgh a
hea1' e.xQha.nger. givlng1up heat at 'lherate of 40,.100D(Btu)(m n) . . . 1 , and mdeliv&fed to a
$8COJ1tl SlOJttl& tank at an elevatiOn 5Q(H) above me,first bull_. Wbat is the temperature
ofr the water delivemd to the second Rlflk?

ss
Solution 2.17
This U! a stcady~1c. :t.eady~ftow proedS fer wbidJ Sq.. (232b) ~. 1b
Utitim and find ,-efoci~ or to rbc ~ Wib ~ ~ .and Ilk
~ tJ.u"l{l:g~ may be om:ined. The remaining 1aiiB an= ~ m lmih of
(Btulfib.o)- 1 ~b ~ cl apprqpri_au; aJD~~ ~ At 2CJOrPl IlK- &D-
sity ofw-d.(a' d 60.1(lbns){f1)- J r amll(ft~ i.socqoivalenl 10 7.48{;giQ; ltHJs the mass
lown.teis:
150)(60.Jf1.48) r:::: 40~~)(min)- 1
(l;;; -.40.CKID/ 402;:;;; -99...50{Btu)(lbm)- 1
lflbe locaJ wlueof g Is taken :IS 'lhe stamlrud wb. 32114(ft}(s)-:. the pcamial
~ tctm bGcom$;
l1.114{ft)(5)- l SO(ft)
....... A"" - ~-____.. ..........................__,_....,..
Jc _ ._ - 32..J14((bmJ{ft}Clbr)- 1t ~,- ::!
,;:;: OJ06(BcuJ(lbill)- 1
~ (2.3Zb} DOW yiekb All:
l.iH ~ Q + Ws ~ .!..Az. .= -~.50 + 0.21 - 0..06 - -'99.3S(Bto)(Jb.)-l

8
The ~Le value. fer llhe emhalP.)' of liquid watu m2fl*lrf) is:
Ha ,_ ]68.09(11to)Ol\n)-t
Thus. IJ.Ii - lh - H, - Hl - tQ.JB - ~99.1.,-
aod 112 = 168..Q9 - 99.35 :!!:!!: 68.14(Bm.( - - t
In this.e1ample W: 4nd {R/ 1t:).A.z :ue ~mall Wmpared wDb Q.. md for p.mdicd
~tbey~b.c~

PROBlEMS
2J!. A ~ ~ g ~tr til.kd wkh 2S q of wattt at 211'C ' fttttd widJ a~~
w .mis ~e to mm by ~IIY ading oo wdgm.of mass. 15 kg. 1"be weigm falls
ly ~ 3 dWaueo of s m iD drlvmg tbe mnu. Assmnin~. lhll aJt l\~rk. d~
OJl the. weigbl Is ~ [I) dtc: water WJd dlat lhe I~ ~let"dlion cf gnrl'it)' is
~.1m s;-Z.. e:
(a) 'l'tle anJOtttll of\\\~ d ,- re lht: u~
tb) 1bc ~-cncJ'l.S' ~e oflbe. ~r:
1(c) Thetimtl ~of1he . nw.fur men Cp = 4.JsU ~ - ~
(.d) 'l'be amount of beat that lnOISl bt- ~val from die walt~ ro return i~ to its initial
pemhlre.
(d 11bc IDt*l ~ ,e~mnae of the~ betllnse of ( i) dMl ~ pf'l nwmrtg tM
!Wight-. (2} 1be process oli ding the Ware~' btl~ ro RS iDhi.aJ .empemmre"' &lid C3)
boch~roplkr.
U lt~k ~lb. 2, I for IUl insUlated~ 11Jat ~JC$ in ~rnl~~tt 41-cmg wilb k
RR't' and has, a ~beat t~ ~qni\"illem to 5 kg of wate:t wart ~~ pK!bfcm ~
(#') ~ ~ gdi ~~ lk 5J5)~, (ft)"'lJe ~ ailone ~die~
U AD en.. iltiliaJJy ;n 1R.St, u dr~l orno a~~ &Wf~ 311dJ breaks. Jlh the eu
tttaf.cd as the 5)'1 -m.
(a) Wbal is lhe sip of W?
(b) . t~ ~p of ,~,
1(c) 'Whal b A.r?
(4) Wbar R All'?
(e) What is the 5ip of Q?
!ln.~ lthls p~i assume me pass:age m wm len~ time for mr brobli egg m
mum to irs initial ~ Wba is dJe origi:D of the hr.aJ. ~11111$fer o f put ( ~)'?
U ADd::Dc illOlM ltfidcr :~ lmd dfaw.s g.1 ~~ 41 ] 10 \"Dl~X. ~~ I J;S(bpt

of~~~ What ii b l:'&t"e of Ileac transfer from the mawr,. in kW?
2.& OBc ~of p;s. in ad~~~ a four-S't\q) ~_,ynllmic ~le. Ust"

~be dam gh"eD in the followiag table 10, delmmiae ~ \'3 fOf IDe miuin8
q m
. - i.e... U die
I Step A.U'fi QJJ ~V/1
I! -lOO 1 -6.b>
23 't' -lJmO ?
l4 7 ~BOO 300
41 4JOO ? .
')t
il~U 1 1 -l.400

51
.16. Cotm~~~mt on the ~i~Jility of coofiog JOW' kildHm in die 5U1DIIlCr IJ)' ~~dOOr
~ the electrkally powcmd rcfrigeratO.
2.1. ~[~~quadrupte.-pulmeoo.'tlii~ ofi(U Mbumd l4.11'

for fU1J.r1Jilase equilibrium ofollOcropic miid fOii'IDS oflhe ~ c:~JcmXaJ,S-r:niannone.
Bv.aln~ tbt dtmn
m
U i A closedL ~e ~tem eontnns. sp.~ I 3Dd 2 wapodliquid equilibrium..
S~ 2 is a \19'f li&flt @ia. ~DJ.iidly irosolullre In the lli'PJid fit- 'iJbe Vi1ptY ph
cmt~-ns both ~ i and 2. Soome additkJDaJ moles; of~ 2 ac added ~ die
'JMml,. \\itiro i& ~ ~ 10 its mil.hll T a.nd P. As .111 re:sWlt of tille: pracess. dots
the lwl numb,er of moles of liqnidl inaetu:. decmlse. or- moain ~~
u, A ~mr compriw.t "' cht~ J,4-(li~ and~ dltafiol ~ -s a ~~~

\~&lpOI'iliquid sysrem a
YPC and 55 kPa lt is fc:Jmld. after ~be addition of some pure
dlimoL tiJ:d die an c.1n be RIW1Rd 'l u ~~~urn B1 U. iniWd T BfidJ
~ . ID "'n:u. ~1m~~ changed~ and mwbat ~bas umH chaqaed?
2.10. For lbe sy5lml ~bed ill Pb. 2.9~

(a) How 1m1DJ ]Jb~e ~k:s in 3ddiLio:n w T ~ P ~ lbc~ Sl'J''*' 1t0 b
me ~i'OOM of bcxb plufses?
(b) lflbt~nmaod~~metore-tnai:Pihccsane_, m~thc d\~~~
of lhe 8}'5tem be cbmged (by adding or removinJ material) widxJut ~the
mmpus:itkins of the liquid Wid npor ~?
1.1 L A rmnk aJIItDiniog lO kg of ,.~r at 2a>c is fitted v;idl a :s.tirr.a dial r.Sr.diven \\~ to
* 'Uier.
the WB..Jiu at tbr rst.r of 0..25 k,W. Hwr l'OOJ does it
m rise ro Joc if M Ileal is r~ tmm l.be water1 P{lf
fot cbt ltlt\pmllute of lbc , Cf
Cp ;;; 4.1 lk.l .q-1 I
2.11. HG4t io the amtJUnl ol 1.5 kJ is ~ to a closed ~.., wbilc ~ io~ cnerv
~ 'blf 12 tl~ How nDlb Me.Q)I is tr.11Werred as wort? Por process caumtg
the 5IDle rd'ump d ~ 'buJ for which* t..L-ork ~ ~ l.tovl modi~ is~
2.13. A steel eding weiplog 2 ~ bas an iniliat teAlpmdlll'e of ~ 40, kg of WUia'

initially at 2SC1: b coolainrd in a pafctdy in..~trd 5tftl tant ~& S lJ. The
e:rsting is JJmne&wd in k wah:r and tbe ~ aUuwcdJ to miiiO llD cquih1witmL
Wb21 its linaJ ~~? ~ rcc:c of ,~ or c~ UDd :USWnC
eDMtam specme beati ot 4.18 kJ tg-1 K- t for wuter and! 0.!0 kl t,- 1 K-l foi s.r.ee.l
:Z..It. AD ifib'()fi"JjB~iMe
11Did (p ~ ~) is ~I in a ilb"lilil.ud ~ylinda' fined
with a frii~ piswn. Can mergy -,1Xt be~ lO cbc IU:J? ' tis me
dmop miJ!Jitat'131 ~cAme ftaid wM8 me ~dt'e ~ i.ncn:ased :t:tcm P. pt1
l-15. One k8 <Jiliq\lid 'V~ fill 2S1C:

(ol ~cs a ....pc:ramre ~of l K.. Wlmt is AU'.. mkft

(b) ~~# ~q.e In elewtioo ~ 1be ch~ in poten~W eng,Y llEp i lbe
s;une ll.Vc for put (a). W'hal - .6z. iin ~~Et~'5?
(c) k ~~ t'Fom re Ill fiD:d w1ocit 11. The dtmge ill kinelk eDell) AE i8
the arne A:Ui. fgr pm (a). Wb__at is MJ mm -I?
~ - di.@ Ike MSWrs ~(be~ p~ ~
%-..16. Am elewU: JDOIOT runs "1wtu uodCJ load. owio,g to ioa.:ro.il ~'UI"libill~ It ~
~ mat tbe ~ !energy be minimked b}l lbermany Wulil.ling the
mawr L'USinJ. ComrDI!tlt ailiei1ly ou this ~-
2..17. lbydmturbU!e ~ 111 a ll=:ad of 50 m of go 1. klfd and oWJe;t CI..IDduiti a1\!
2m mdiamdJ.. ~~die~ l(!liN"tl d~elapat lby die. fulbific for all Qot:fd
~doci1y of s II) -i-
1lL Liquid"'.,- EU J80-C and J CKQ.7 kPa has QJI ~energy (01.11an utbill"fll'Y s~aJe)
o762.0 tJ tg~ 1 mid a~ 0111011! o 1.128 c ~- ~.
(u) WfKn u ib mtb:llpy?
(b) 1l!te wamJ' ~ tmmghl ID dle \!apot" Sblte at ~C and 1.5()() ~ 'Where iiS internal
enCJIY 1.184-.4 kJ tg- 1 a:.Dd it$ .';(ttt;ifitHolnme 1:$169..7 cmJ ~-JJ. Cabllatt 6U
and l1H for lhe ~
119.. A.~llil boUy .111 itrlrud ~e~~~~ To iJ 1i~ in a bam of water m initiW te~
atiiFe t . Heat is IDmf'~;.~loJi from ~ dd 1o th: water~ ;. mre (/ = J{ - (T, - f ~,.
wbrft: X a commm and 7: mcll T ore ms~u val~ of the rempentures m
ttm wmt and did ~ an ~ f T as 3 flmlltlon of tbJDe r _ Cla:k
)lOUT , b. f~ dlc ldoiliftg ~ 1r m 0 and f ;;:;: oc. lgDQre dreeu of ~ W
~ IU1d iJit ~lh.: beats fm lbom WDtcl' :tru!l s:olitl
l.24L A 6it of eGOUill)D mail operatiom ~
ud SLnate.pip; bclil ~chrm~r: 1(lt) [)ouble-pipe heal-~ (d Pump:

(d)l 0:15 . (t) CAs~ fl) ~~ (g) oal~
Dcvtklp e simpfitkd fM'rJ cf tbe ~ Steady-~ ~ balance upproprb~ f-M

am opema.ioo. SJme ca.many, and justifJ. _, .ass:umpUoas y<JU make
.2.21., Ihe Reyookts number ~ dimm~ ~ \Yhich c~ the i:m~~-fa.y

of thl . Far large R~ :1 tlow il mtlbolent:. for small b, iii: is laminar. Pew ptpe ftow,
IRes upD/14 w~ D is piped~ and fl. ~ d)tnnm1c ~ty~
(s) If D Wld 11 ure fiMcL v.-IW Iii me elfcecl of~ mass fi~T.IIe mon Rc1
(h) If mJiDd p. aR fiHd.. wh:il is !be~ uf iru:rea~ D on lte?
1.11. M i:neooitpi'6~b1t (/J, ~ ~J Uqnid flows stmttily lbroogh ~Udul1 of ciradar

cmss-seetioo and ~ng dilmecer. At localio11 ~. lbe db_meter is. 2J em and lbe
vclomy lllil s-l; siOC'OdiXIl 1, w dimueseris S4}_m.
Ob as pr otegidas por d1 reitos de aut<

S9
(tJ)W1m ~ lbe \~ allocation 2'1

(b) Wbat - d.c kineti~y ctanae (l kJ- 11) or die ftuid betw~ locations I lWd l ?
l.%3... A ~~ of W'IIID Vi'lta" is piO!doocd iD a ~,.ftOW" mixm~ pn~.ess by coolbioiDJ

I .0 kg s- I of ooot wa.ter WI n iJ,C with OJ lts - 1 of bDti \dtft m1:5~C Durin_g ntixiPs.
beat is lost to the :sunuundinp at the ra1e of 30 ld 5-I . Wbat i5 the b:.mpemtlll'e or tbe
watm-W3ltt'~? ~me1bc~IW li'Btofwi'Wl~Qoo$tJBlf 4.J8 1kl l:.B- 1 K- 1
124. Gas is bled fmm a tank. ~ beat ma:oder belween the pB and the lnnk. ~
lhlt tmd aag ~produce tbeditrmmti:d ~
diJ dm
--"'= ;;-
.H '- U m
Here. U md m refer 10 tim gas remaining in lhe taok; H ' lhe ~~caftwpy of dt~
p ~in~ lha taDk. Under wb:n ~ndioms rean Oil! amJIIlCl H' ..... H'!
12S. W3rer a1 WC .HOM! in a t!b'aigll.t oo.rizoom pipe in wmm ~ is oo ~ or

ntOO ba~C .:.- work with tbe S\mWildiop. [ velOcity ts 14 m - in a pipe with
em i.ntemal 6\~ of 1~5 emrumil it ftD\w iruo il secdoD \l!llae. me pipe. diameter
~pdy me~s- Wihat is 8le ~ cbmge of dl: ~ if the down_~
dWne:ler is 3.8 em? If i1 b 1..5 cmj? \VIm i ax ~mum lempemlm'e dtmge ror an
--*~-
RUiUpme. m .m......... Jlpe
lo(JJ;
. ....
2.26.. YtfiJ 150) tmol pa- bour af air is c~~ rmm P1 ~ 1.2 hat to ~
6.0 bar tn ~
a :steady-tlow ~- Detl!\~ rneebmicaJ powu l 91.8 kW. Tempera.tures and
wloeili~ at:
T1 ~lOOK T"J=520K
lflel ::e: 10m - I ..
"" ; l.S ms- 1
&imate lbl: ra1e of llem: rn er fmm lh: ~ Assuaae for air dial Cp = ~ R
3llld rbat ~mhalpy b ~ uf~
:U7i0 Jtrogm ~tit steady tft ~gh . ~ insuJMed pipe: with mside dJiarneter
,o f lj(tp}. A ~ dfop l'l!$1llttt fmm ll\lW lbmu&b 1 ~ ~ liW~ Jug
upmemn fnim1lbc vai~ ~he p:essmtl is IOl(psia). lhc rtr.oqx:cll\!lni. is 120 lllld
lhe aRnge ~ocity i:s :20(ftt(sr 1. ll1he pressure jD&t down.~~rem~ fmm (he\~
is X>tpsiaJ. wba1 " me ~, ~ kl ~ lbal P vf T coMtm1..
Cv = (S/2}R.U1d C, ;: fff!) R~ (Val~ fQr Rare givRJ in PPr A.)
l.JL Wamr flows t:hrougb haril.mtal coil heated &om die oo_t!k.ie by hiibm~ ltoe
~ AS it ~ tbraup rfbe Olil lbG -.-r ~ from liquid II :!U)t kPa
iWd SIJ1C tu YaJXK' at ~00 tPa and ~25 C ben~ doo'ty is :J m .. - I .:d.)d its -.it
~~Y is 200m s'"''. ~ the bAt mmsfm:'cd ~ ~ cW1 pe:r Wid RmS of
WD9'.. E.nJbaipjj of lbe inkl and OUlkt 1m11m am~
lllfee 334.9 tl g-1 ; Ollifel: 2..726.5 tJ tg- 1

l.D~ s~ IteM!! ~t ~1 ~ lb~ 4 con~g.. in ~ ~t', lS em luna :md
wil:b an inlet diame of S em. Allbe ~ (~ 1). the. ~re WH1
~ ~ )2>50C ,apd 100~ gdJ tbe ~icy it 30m s-,
A!tlhe mutt~ t
l). tbe steam mmpemme md pressum ~ 2WC and 3:50 ~ Propmy vnlw:s are:
lie = 1.112.5 .kJ _q-l v~ ;;;;; 38&6~ err ,-
H-! .. 2:.945.1 kJ g-l v1 .. 661.1S err ,-
Wbl; is fbe \~ Gf the steam ar 1he ll!i'JUl) exit, md what is the exit c.fiameter1
(.o) T1mx lBO~ , of niamgen 8l C., MIIIILind in ~ -..usaL is heated tfi11S('JP'C.

llow muCh ~ rs mq-~ If lh: ~ u ~lig!Dlc !Deal ~? If tht"
Vlii1Lti:D1I. wellbs 1 a
100 kg ud ba,. o.s
ca:p:acity of u tg-l oc--.
bow much ~1
~~~uirorl
(b) Foar odes or n.i:trogal at 2rxt~c is COiltained i.n a ~llinder mrnngement
How lmJdJ kat liiUSl be et~ ~ w.bkh bpt at amtant
from 1bis
~ lfD .CXJOI it to we it dle beiit cu~y of d.e p8lfm Wid q~:Hm.ao:- is oc-
,.~tl
l.JL. In ~he foBti\lring ~ Crv = 3 .m Cp ::= 7(&u rQ!IO)c)-L - ~ for ni:trO;en ps:
(R) "l"bnx pound lliDI.c:.s of niiio.gcn 11 M m

), CODtmoedl II dajd ~. ~ ~ to
J~FJ__ How lfilldJ beat~ ~teqllllRd ifh \~bas .. ~le.heM epaily?1f
il '_ . , l00tlbm)md ~b ~) of0.12f8tul)(l"-J..... ,...... bcrw OIIIdl
lbeilll$~7
(b) 'Fa:u' pmmd mo of ailm at F) is eoota:ined in :t prwnlcy.l.i.mfl1:r :m-ang_e-
JDmt.. l!f'!M mucb hCid m~ I); cnr.u:--ttd :fiirQIQ ~hi$ ~~ whidJ ~ kq;Ml at wq-
~ to cool ir to 1150 if me Ileal ' city m ~ pisu>n :u.dl cyl.indcr
- ~td ?
2.J!., Font llheeq-Uillkm fnr the. wad cf m"ee8iblle:. ~~ c~ of l ~ of gu

u
in Ill piMoo(eyt:ind 51mlbly tbo mobgwlumt d tt. ps is~ by
II:T
V==-p+b
131 Stmn m2txl(p$a} ad (J(X)f'.F} (5t* JJ, m1~ a turbme lhrovP a )..inch..~
pt~ ith o ~ of IO(ft)(s)-1 1"hh! ob:anSt Dtm the ftlrbiDr b c.mkd through a
1CModb-diameli9"pQ:Ie md mat S{j)Ma) zmd ~ lsmte l:J. \Vh:l.t is the power output
of 11be r~?
H1 == LJ22.,l(BUIH )-~, V] s 3tMS(ft)3 (1bm)-L

IQ_ -1.J48.6(Bto)~)-~ V1 ~ 7S"'W4(f'lj3 (lbm)- 1

61
2...K. O:i:dKm di~ ~ - dlll!IS:. ~-<x.ded OJIDpt~ at e(ID(litious PJ IS(pM) and =

Tt ~ 5()(9f\ aad is disdl~ B1 ctll.\dili , _ .Pi, ~ SlC(~ aadJ T2 ~ ZCJ(){~f).
1b.e tnlMng CO:! How5 Olmogb a .a...~ta pipe wilfl a -.ekJclty of20(tl)(sl- 11
and i:s dib1ifld ~ ~ 1-incb-<1~ ~ 1bc aft wwt supplied - die
cmnp~r lis 5.JMI(Btu)(mr)])-i . Wka1 is the ~..uansfer m.tt from llle com~
in (Bm)(hr)- 1?
Ht ; 307(8tu)(lbia)- 1 ~v~ ;: !t2S(A)~(lb,J - 1
Ill - 330(8tu)(lb.)-l "~~ :: O.l80l) 1 CU\nl .... 1
by.
Q!::il.H - I VtJP
2;.J6. OD: kilogram of air is ~Olld revenaibb at con:S&a.m ~m from Ill ini:WII stare a
3M K and l bar Wltili m \'01umr: tri~ CaleoJ.m; W ., Q. AU"' lllDI1I AH for lhe
~ As.swne f rur lllat PV/ T::: 8JJ4 UQ mo~.-~ IC.-1 and C,- 19 J
J'llOJ_, x- ~ ~
2.38.. (n) An ~ fluid 1tp ~ ~amsmm} flows ~ a pipe of amstmt cmss.-

~iond Mea. u lht now is __.y. $bcwt mac ~locitr u ,and - ~ ~-ute
q ame oonsmnt
(h) A d~miw~y re.acti\-e g~ Sll'f:mlt How!li s:uadlly rrbmngb a pip: of ~or~
~ ma T~ and pm.sum vaey with pipe 'LmldL \Vbicb of the
lollowm:g.,q:uDI:ilRs ~ ~'I oon:swtt .n .11. q. s1
139. '1"'le muJranical~rv bakmc~ prmidas .a b ror ~esti~ prcssuiC drop owiq
tB :Urietion in ftnid llow. For i'Ceady low of m me~'ble ftnid iDa borimmJ.l pipe
o ~~r aos- sccti<JMJ ~ it may ~ Viritam.
AP ? ~ . .2
ll.L + gf;ppu - 0
where /F ls lbe Famringfriail.mjhemr. QurdDLI 11 gi\"e'S die fdll09riDg ~ for

I f1 for rorlrulent do.:

Hie. Re is die Re)'DDL~ mDJlbu (see Ph 2.21~ and / D is the ~ontess pipe
~ Tumkllmt How~ for Re > l~.
l.'l:l9s.tat_rl dit ftovl of liquid wazu , C. For QDC of dtr: seu of t~ditioos ,gi\-en
-liD!". ~ m(in q - I) ad API A L (iD kl?a m- 1). As.mme I D 1a O.fXXH.
fQE' liqul4 ~a( 25-~ p c 996 q m- 1, and fl. :::! 9.0 x lor' kg m- - .. ~
tbat die llmv w1nrbole:At.
~(a) D 2 em. u:::: i m s-1
tg
(bJ D - S ~ u = I (0 s- 1
( c) D ~ 2 em.. u ;:; ;: S m - I
1
(d) = :Sga ~s m-s-t
2.AL Sil. ~ ~t m
~ p1~ sia~~ m~ ~~ ,e~roleum lf'rac ...
limlation tem: medml~ ~ ~ i~ n-bllf~ and n~ A
~ biR:I of t&csc- ~ in '"li;JIOfltiq~d GQQifibrium ~n 1 ~ '~t On~-
~y plmse-rule variables in addilioo to T and P do the: oompos:itions of tl:Je ~-s
~
If T and Pare m ~n die same. ~ l.ba'e. any way rube ~tioo oftbe t~ Qtm-.
w1be.. eao be - pel (h) adding or reJilD\!iq ~) witbmd &\ff'~
mt.~ ofitr ?
24 lEiby1me a turbine 10 bar and 4SO IK-. aDd ~ Ql l { :atml) and l l:S ~ ~
m1!:! 4.5 kg ~-I ~ fbt, r.;Usl c ofi'~ mtbinc. Stmc fillY ~um )'00 fl:lake_
i
Dma: Ht = 7' 1.1 ll:l ~ 536.9' kJ .t~ 1 C/i =U S~~ :!OO)(Ilfl/ k\V'to_m
2A1 ~ hca:tin1 olahGID!: 10 ~ i& ~m~III__~!e must b.lli\Qdekd. ~lUI open ~

~ .apaD.Sion or the ~. air m. etmm~DJ. ~ results in leabg.e of :atr
w dJO out.doc>J~ J\ umin& ~bot tJJC molar pr~~ of air lwing the ~ arc ~
eme ~ ~bose c l.be air in me ~ ibow mat ~ .Wld itOOle ~ )fieM the
followmg di:tfa-cntia~ GJUlion;
Q=
-
~PV~+
dJ
~~
41
~ a 1IIm~ we of brat Uiln!fer lD lh:. air :in~ hllnc. and r is time. Quantilies p .
v" n:. and (j refer ro [~ m ioldie~.
1.44.. ((J) Wattr How ~ ~~M-IIOU!e ut o pn.:U bose. Filllil u ~ ror min ~I'Jru.,
of fine ~J\t /'1. !DDRml ~ Pl.. ~ b;n;e d!t~ D1 ~ d POUlc

61
CUtkt di~ 8}. ~ $teady ftw~ WM1 ~ ~IPric ~ 1\Jr

liquid .l et mndded tm m1.-om~ luicl, Hz_- R t := (~- Pi)Jp (\'W'
~ I[~Qf't,
{b)1 llfi ~ me 1t1uw canntJI ~ imly i~ we ~~ T1 > 7i, owm.g to 1DI.tid

liictioo. Hence. 8 1 - H1 _. C(T2 ~ Td + (P2 ~ Pt )/p, where C is. the specific
hc;nuf~ ~DilaU!yi bow~ ir:dusiQnof~~don~
lhe \<1liue wlit as found mPan (4)?
1

Volumetric Properties of
Pure Fluids
~ - -
'f&L,qunilijcs ,o f bait and woO. nco~ to emy ouL industrial proces am cal~ &om
1
~goof~~ic ~~a5 i(:fitemal ~and er~tbQtpy. r-ur Otri~ 1~

~um o1knew!aataifmm1~nts ofmolm' "'UimneAS funaloooftempwwre
iPdpn:s )fidd~Jlg~u~urc {PVJ') ~ wbicb may be~
nvtbeJrunicall:y as tlJiM1fioitt of Jtme. fhe. letit-eompl& ~ P V e: RT. f.d'OV:Idb. the:
simpk:sl mdl~ lDIJdl:d of' Ovid lbdlarior.. ~ of hnr ~ at~ for tbe ll'leterint i
6 gd tbo qliq oJ ~b ~ pipdrrw;s.
Jn lhb drttptn we lfiHt ~ dk! ~ lliltllff; of llic. P \l T bclmviot of putt. 6.ul~.
ThcJ:c lfolfows a dd~L1ed ~of dJe idtal ps.. Altcntion Ibm hii:DS ID more~ io."QYa:-
tions ar we. tJkb pro 'ide me fooDd:dlon mr qwmJitaU\'e' desaiptioo \lf ma.T-Ifukl bet.a\ or.
FiMDY~ ~ cont!larion.s ~tlld thin tJk;w ,redicti!illl Qflht f'VT ~or of
ftoids for wbi~ e:xperimeDml dam ar;e lacking.
3.1 PVT BEHAVIOR OF PURE SUBSTANCES
Une:s m..7 md 2..C of Fig. 3.1 ~ b 1 p;!I'e ~bmmf:e cunditioos of ~ure and tem
~ at~iridl Mllkll Uild llqtiid ~~in cqliiJiihODm with v.apor ~- 1llc~ V6[1(H'
p~ . ~ r e~~~ ~aiDe 12J am~ liquid/\':lp(ll" Cline 2-n
~ rebtiomhlps. The sel:idJ1iqnld eq-uifiibritdp ~p ~ repr:eseon,d by line 2-l.
The. lhmc ~ display OtlOditioos. of P mdl T at wtDdJ two pbasa may coexist. and ~~ "de
{he dragmm iniD ~~ regit~DS. Line l a2. m~: 8ub.ii11it1Jion cril\\~t~ sepatab:s tiE M)(idJ
md ~ ~ liDc b), rbt ~ t'JjfR', ~ ~ svlid ,and liquid n:gi(Lns~ line 2C~
the ~b.M cflr".:~. sep:ua~~ lbe liquid and g3S ~1 Poim C i tmwD 3.\1 the critU:t:IJ
fJO'inr. , ~ Pr ~d J:- B lbt big__hc:stJ prmiUN Q.fld hi~ tanpen,ture ~ -.bkb aJ
1
pore dlemleal ~ i& .~ w ~in ~d eqlli.lii:Jtblm. The ~lin~ .m:r-~ at

tho triple~ ~ tk; ~ ~ ~ majuitibrimn. Acrording h) U1tz ptw.e
Bq. (%.71 tilt: plpie poi:m is ~~ (F e 0). If me sy&t:.m e xtm along auy of Lbc t\lto"'-piw
lLD5 d fig.. 11. it uni~ (F ~ n.
~ iD dle tiD~~~ rqi~ it is dh'3fi_;mt
(F !!!Ill).

t'lumg~ or
Stille ~tnay ~~ll:d by 1m _ QQ ~ PT dn.gu_IP: ;g iw~IID:al eb!wp
by a \~ fine: 4D isolwi:-c ebaDge b)l a ~ tine. When sud1 a lf:De aos.ses '~ pba5e
~~ 411 ullm:pt cbm&e in~ of d:m 6Did ou:ttrs at ~ T aDd P'; e.@-, ~--apor..
izaljoo f-.:w die trammlltl from liquid to l"apory
I
I
.Ill - t- fiukll..pJA
.~
.P, - l"""lll.ill.-nirr!'iJ
~ rr,.._ . 1'I
c . ------
~ ill
I :1
\l'lpod~ : /'
,., ,r:
I
FilpN3.1: PT
ctic~p~~m for ,a. Pft
Gl!l~
I
~
'W'MiK ':
~ i

I
I
I
W~t 1~ 8;1) QPtli nut its I~ IIi~ mre()~ ~I g ~wid~. If

lhe Hn.a is sealed and cbe m is pumped or. w..ver w~ 10 ~~ 1be .air:. Wid H10 fills
lho ta ThOG;gta tht ~ in the ilia iJ JIIUdl rab:ed, ~ appcus I.IDICianJtd.
1be li'qllid w:uter resides at lhe ballam or fbc Huk ~ iH tlcmi.l!y ~ muCh~~ ~ban uw
of water' por '~:mel the LlnJ ~ ue in ~ailibrium at eondiliom. m~ by~
potm OG am.--e 2-c 31 Fig. l . I* 'J'bc! properties o f Liqoid and~- \""e.1Y dift'cas. ~~
if the tmlpmllll~ is ~ so that die eqtrltibrium sta1e pmpsses rupwardl along 2-C,
the ~h=s of the two 111~ ~ IDI:iJe and 1 1lfife oemty l\l.ib: at poill1 C 1Uley baxime
ldrl1tieall IPd tht: ~ 4'~ One~ . tba tr:msilio from liquid to
vapx may oemr nkmg paw mat do Dot mxs the~ mn.~ 2..C., ~. fmm .4 to B ..
The traJWtion frqp llquid ~ J.8.$ls thco 1.-ua!. and does oot iodude a ~ step.
1bt rqiw emliDJ ~--*and ~ pcatu dJan 1e and p( 6 ruarktd aJr
by damed fines i:n fig. :l .. l ; l!hese do t10t represem pmase ~ but nuha- iR limits 6.uxS
by die~--~ k \\.YJ~ ~id ~ ps- A pb;lso is ~__lty ~~d a Jiqllid
if wporiza'fion resuJB fmm ~llR. ndndlm .u ~ leiii(Cfmtt:e.. A pll:lsr b ~
a ps if co.llll:kmatiOD rnmd fmm temperatw"e l'edOcfum II con!StiiU pra.snre. Sin:ce mitla
~am lb.e i:nitfatol iQ ibe f!C!il)l) ~IlK:. da.~ ~- it c.tlbl dlc/bdd ~~
Tk ps. rq:ioo iJ .~ dhil.kd mw two ~ &S ~ted by 1be cbled ~

line ol F;ig,. 3. I. A gas ~o the left of tbii liDr.; whim c:.m be~ dt:b:eir !by ~oo at
~ 1e~ or by ei)Q_lm.i at cuo:snm:t ~ called' 111 vapor. A fluid ~ Ill a
te:tnperature ~d than T~ is Aid to be- ~~ri1it:uL An uemmple ~ muorspbaic air.

PV'Dl~~gn~m
~pre J, 1 dues ilat pnl\'ide any ill.fvnDatiOD illbom \"~ il maeiy di!pl~}ts.lbc ~ 'bo\md-
flties ona PT ~ On.a P\+' ddpam [Fig. 3.2(") 1~ tJounda.ria io mm become rrglo~~.~
where two pbaSies- solidlliqoitt. solidl~por. and liquklfapor- ~till )Uiiibrillil1 ~
~am~ by hwndJng t:~W"l Lhd ~t iin~e ~. 1k rebdi\-c .WJi0Uilt5 of
whim ~ me moW' cor spedlic) '~~lil~ m ~~ JXIi:ttn- "'l1lr; i:ripk. p>mt of
: . 3.1 btte ~a~ line.~ tbe~ ~~at a iin~ empenmue
and~
v..
v
(a)
ftpn. U IV ~ for a ~ ~ 61) ov.riug, :501idl. liquid, ;;aM "'P . (b) ' ov.riag
.&q,lid.l - pat. - \'apOf -- - '4!.ilb ISOI!llzmiS.
Fl~ l.l{b) tti ucpJid, li~ md vapor regiom of me PY diagm.m.~im

ruur ~ ~- ~ oo Fi.Jl- ) . 1 ~"~fin= and ~
pn:ta 1llwl Tc do not c~ a ph3...~ boundary. On Fig. ] ..2(b) It' iiolherm labe1ed T > T~ is
Ibe,refore ~
~ iliges bbded. T1 aDd T2 :ue for iUhcribQ] 1mnpen.twes. and Clllltiist of lhree seg-
mems. The lxirizonlal segme01. ~ot eatb is0lberm ~ .iJO possa.'ble. ~of liquid Wid
~ iD equitibri1llD. magi.QI from J IKplid the ldt eudlO 1001, wpor me rig)n end.
'Tbe llocws of lbe~ end polm.!S i!l me dfime-sbaped trur\'e hbelc:d BC fJ. the left filJf of wtri@
(frmn /J w C)~ ingie.~ l.iquKb ar dmir vuporization (boilliDB) ~ Wldl
me dght ft3Ir (from C w IJ ~~ V"apUU:i ut thEir~ t~ Liquids
and ~~ by BCD ;n iaid to be Aiatmtd.. and eoexi.Btin1 ~ ~ conoeaed
b1 ~ ~ sejtneJil of rhc :butbe (it rbe ~ ~ ~tk to dlt: i c:rm-
AJsc called lhe '~ ~~ it ~"CUI b-:r ~J pvHrt un Pi~. Ji.J where an isomerm ~
Jine)1~a wporimlioD C~Un~e.
Tbc ~ liqui~ ll=Fna . un*r dcnm; BCIJ; 1b.e ~IJ:..Uqr~~d regioo
lies m tbe Lefr cf the ~tf.d..ti.qpid eunre BC.. and ibe ~~..WJ:pt)r 1rcgkln li. to

61
ri.,&bl of the :sidiirulied-'!'lfD' CID'\<e CD. Su_~ tiquid exists au lempelilliiJ'es bttlow. and
~ vapor~ &t t~ .a/Jmre 1
dlc bo.iliq rpoiln b" the pvtn ~~. bocbmm
an ~ ~,.lfqnid Mgio:n ore "~ s;reep. becansr.liqoid wdumes change illle witb liuge
cbanpsin~
~ ~ ~ . of the i~berrtl$ ' .... (~~(!base region~ pro~~y
5bmter at higher ~ being wlim~Jy reduced m a poinl aa: C. Th~ the erilical
~GriOh llabeled fn elblbil$ ~ ~tQJ infl~-,wq ~ the ~ polfil C at fbt wp of rthe
dome.. \\Mre the liquid and l'aJJOI' ,hat;es become~~
Crlllt:aiSeltllvlor
lmlpt inJa tbe more of tbe crtt'ical pcim is ~ from n clescriptiiOo of the changes lbU
~ wbcn;) P!Jft sob$tatlm L't ~in~~ ~pi&fll ~-~can~ mllitiiiC'~ 'Tbe. &b1ed
\wtidl fma of F~ l.l(bJ indicate sueb processes. They may also ~ ~need o.o tbe PT
dillfiDD of Pilr 3.3. wbeR' the solid line is the '-~ OlL~ (iF'.,_ 3.1). and the dGbed
lines w-e c:tmtwU-\-olume pam in the single-ph-ase~ It lhe 'bil.be i Jill:ed vtd:l1 o'1ber
,liquid OT "'11f301 lbe ~~ process produces cbmges whim lie atw1 tbG ~ tina.~
1
by die ~lwlge fmm E ro F ( mMiootfd.tiquid} and by llhe chqe (rom ,G to H (~

vapor). 1he corresporuling '"~ imes on fil'. J.2tb) are not dtUJWD. bu1 L~ w llbe !left and
rijbtofBCDm~~-
~~ PTdt~l lfO'ta~ftmd
~mc ~~~ ~mfl
~t..~gme ill:lles in~~~
tepom.
If tile tube is only partially li1led with liquid (tbe emaiada being \~ m aplibrium
1
wim the tiqukl) beating ar :l itll ~ <ibatl - ~~~ 'bJ d'ie vapot..~ ~ (:solid.
liM} of .Flg.l.l~ For 1he ~ iDdlatted by 6ne J Q on }*lg. 3.2(bJ. tbt menisaD is,initially
~ur tbe top of the tube (pailttl J ), tiDd lhe !Squid ~ m0ic,irn11y upon llmting !o 61J me
tube Cpomt fl)J On~ J,.31be-process trKeS a p:db1from {.I. K) to Q. omd ith furlber bemng
dr;jrail$ ~ abe '-1'{JO(-pcrs~ cwve 11iktJta k lint: of e~ moliu" ~U~nr Vi.
1be pmcess ~ by line K _ oo F~ l~bJ 8t1ni wilh aJ IOwa' meoiseus ~~ iD
the: rnbe C,point K ), mxt~~e.atms wpwtr~ Liquid row a~C.ot ttqu 1M meni~ r~g; 110 ~

bottom of tile mbe (!poin_1 If)'. On ~ 3.3 the process ftill:ei a path fmm (I. K) m N . Wltb
funb:r ~ a ~lh ,CQ ocs. die: of - ~ant molar Tr'Oiu ~ V7
foradltiq filling~Jffm rube. wid~ .a pudwlarm~t~ ~iStDS leve~ tbGheating
~ f~ a vetticaJ liDe on ~ J.l(b) lhw _p;mes lbrt!Qgh dJe crioc:td point c. Fb~canr.
ta:m g ~ DOl ~ mueb ~ mthe l~l of Ole - dJe critical point I!
~ lbe rnmi~ ~ indis.mct. !Ibm ha:t}'. and 6na1ly di~ Oil ~g. J.3
the p:Dh fiDI rDiklwN me ~ all'\'e. ~ fnmi point (J. K) to dte aittcaJ
p:ri.JJJ C, re i1 CftWJ, 1M m.&-~ fluid region, nd foDO\VS Yc. 'tbt: tint of Q;tJqsrnpl
moi:lr \Vbune . . . n.lhe c:ritim vrlDme the 8uid.
1
or
Single-Pita R-.Jon
F or
rqkms die di~ What 3 ~ ~- Fig. J.l(bJ itnpticos a Jd~oo COO
~.dag P., V. and T .. ~ ~lka.D.J, f(P , V. T) ~ 0.. sum mmiml i_ :knm\11 as
.a PVT efJIIJ.lllua of sulfL h d ~ IIK'd!ar ,ecilk '9dhrrnc. aodileiDpel'aiU.-JO fur a.
pwe ~ li\lid. ia ~qp:itibrittnl itaf~ '1b.e ~-cts ~M of~ PV JlT. bas =
3pp10~ wlidit)1 rfcr the lCJ~tJP~ gas megim Dt Fi,g ..l.l(b), ;md is ~ in -~
iDSe..3.3.
~ of 5ta~C may be .so1ed for atJY t.mr of~ dm:c ~ p_ l". w T ~
a 6mc'lim mme adler I Far eump~ lif v is cou9dered a function of T and p. men
V :;;;; YCT. P). ~
dV
- = (~)
BT , dT + aP (!!) T
tiP 13.1)
..,.....,.,._ ~ti;\.-e:5l in Uri$ equarioq bu.~ dd:trite ~ ~ and are rrlmed to [wu
~ mmroonly t~ for liqw -' a_nd delnedl as foltowi ;
~,.. ~~~"'~ ,~ ..
U ; a j j - ail'li!il....,oiiAHtv
p iii.!.(~) CLl)
V BT 1'
Ka-yl aP (av) T
b1 amiJmaticm Equatio fl.U ~ (3..3 t )llcki:
~ = fJ,dT ~ ~Jp
The tsot.bemti for lhe liquid~ ou abe left tide of fig. l .leb) are vary~ a:nd
dosd.Y ~ nws botb lal';aT)p and (a v/8 Pl r and bent;~ bolb tJ :~.nd I[ are smun.
'ifhis e.lw!a~ bebavi uf li~ (oul.side the mtialJ lt'egion) ~~ an ide.Wz.aaioo.
comlDOilt~Yanpkl]~ in llid ~ ~ ~nd tooMJ dJe ~FeMible~ for 'fth:A:h both
1J and c ate zao~ No teid ftuid is uuly mcumpresxihl'e. but me ~ is usefuL beemJse
it prn~"OO al5d'ici~!ldy 11:aJAti lllOdcl of liquid ~ior for IIIIWY ~cal ~ . o
eqrnWtm o.f tate exi5aa; ro:r an Jta:om~Je :llold, beea~ Y is indeperulem of T und P .
Air J,fquilk jJ ~ almo5l aJway posim~ ('liqakt ~ bdweP:o ~o~ and 4QC i:.s an ~cep
tion~ and.- ~Y pushi\'c. .Ac c;unclitions noT dm:e to me aitk:al pol:nt,. JJ and ~

wrnk fo:nakm ~or rmn,pm~ 8Jld JR$8UM.. 'l1ws fnf small~ in T and P tittle error is
i~~ if lhe.y are asSUO'I< OODStanl lm~ of E'q. ().4) thai yidds:
"2
In i; = IJ(T~ =- Tt) - .r~l'? - P1)
Thi~ b g bs ~cliw ap~l(m$1doo man lhe ~all Gf.u illt'(IIDpressible IIUIII..
Examp-e3.1
For lqUid aoeiQI!le at20GC and 1 bat~
{J ~ 1.4$1 x UJ;-l ee -l 'k = fi2 ]g-& bar 1
Fo:r acetone; finct
(B) The value of (a/J JaT)v at ~c and 1 bar.
{b) The lPfes&UJI8 genera1ed by lheat1ng a1 constant v ffCitl 21rC afld1 D8f to
~c.
(c) The ~change in WJWme fotr a change tmm 20 -c andl1 bat mOOC and 10 bar.
SOlution 3.1
(o) The deri\vl-vc (8 P taT)v is~ JJ, apJilUeattoolof Eq. c1.4) tO me~
1
fur wt:Dcb V is mm.limt and dV - 0:

IJdT -~e ,tll' !!!!!!:0 (~ V)
p ;; ~.481 )( 1o- ;;;;: 24 '1m' ~C"''

3
( aP) -;; ;
aT ,, ~: fi,2 :x Jo
~b)1r JJ a.J .: ~ - ---~ ~in the 10~ tan~ Hncnal, mm a

eq_utK!o derived in (a) may be wriueo (I' :;;; eon~t):
li.P!!!!!!: !A1'
... ~ (1-4)(10) ~ !40 bar
(~)~ Dindl sn~nq into Eq1- ()..S' gn~
In~ :o (1 .481 x IO~l),(-lO)- (fil x 10""'~(9) .- --OiJ tl(Jj
v;v.._ = 0.9102
-
~ v~
-
= (0.9702:J(1.281) ~
- . l
1~4'9 ~m- 8-
I
'lheo. AV .- ~ - Va;; 1.249-- i.m;;; -o.033 ar ~- I

70
a.2 VIAIAL EQUATIONS OF STATe

lsalbe.nm for gases and wpon. lying abo\"e and to 1be fl;ht of CD in Fig. J..l(b). ~ mla-
tivdy . lc r~ far wmch Y ~. f ~ fkie. lhe ~ Pll for- giYeo
T ~ be- Ollldl ID.Die neaty eoosmn man eiJiber o ill meu~ber&. and benre JHOr1:' easily
~tal ~Y a a flmd_km of P . sv~ ~ PV flX an i5Cilben:n by a
powm- . ia P:
If b ;a ull';. c aC'-r etc~ lhM1.;

PV ~ af~ +lfP + C'l'z + lY ~ + - --J (.16)
~ a. tY~ C'.. ~.,arc e~ fw a ghreo ~and a p~ ellmli.eal species.

lrt pqoo~ lht right l5ii.1it of fq .. (3i6) i~ ro:t l11finife it"~ flolliyel-u~ iP pr~K.-1ice ~ finito
l1\1lllba' of~ ~ ~ In &et~ P v T dati_~ lhat at low~ b1meatioo aftu tv.!Q
(B\IJ}S oflt:4 proridls S3tisfi ~lmy r au!t
lilltiiJ.GlM TentperaiUres; UnJNttllll Gas COIJSiant

ParameteJs 8'.. C'. .en:.._ in Eq. 4S.6) are ~ depeadem :md futldiom or tm1~rature. 1!1u1
~tf (l iS tbo.nd bf ~ 110 be tdJe Still1e fUOCd iQ of ~COJ~ fgr a.0 Q'hemiw)
speriK "Ibis by IDI!lb'lll'le:m.et~B or \"'lllme
~ ~ll a runeoon.o f P for van~ ~ ru
~ l~ Fi~ 3.4. :for~~ i:s a plor ~ PV \1l. P for COW'~ at !he
tripfe.pcial ~ of 1lle fimi~g \'alue at P'V a fJ ~ 0 .is tbc S3IDO' fer ll1l of
~ -, ~ ~l(de~bytlm . ).Eq.(3.6)~
cPV) :;;;; a ;::;: /(n
:f1pn 1.4: (PV) * . me

lllmib:n1 ~ of P V
P _. 0\. t.~ ~or dli:
i8 p
This [IJNPCRY ofga_~ M ltbe basis lw e:smbtasbing an absdw ~salle.. All lb:ll
Iii ~uiffd ' llle wbi.nafY "-gntillefil af the; f~al ~ip ftT) and lht uss~t
of a ~ wb.Je m n. single point on lhe saUl:. The ~ proeed~ the lllm ~
ialcmalioaall~ 10' ddioe drb Kd '"ia St1iJe (Sec. 1.5)~

(PV) -aRT
Jill tbe "-roue: 113Jt6 K 10 lhe crDipMlflU'e of me triple point of warn (tbolft.l by
subsaip rl~
(3.8)
Divi~"reo of !q. {'3 ,'7 ) by Sq. (3,8) ~;
_....;....
( PI')* _ ........,..;.,..,_
1'/K
(Pill; ZJ3, J6 K
or
qn.ation (1.9) estabi~ me kelvin temperalm'e seale dmJugtlllul me ~ r.mre far

~Tbicb. l1\1Qf;S of (Pv are ~cnwly ~&e.
Tbc 5t41CI of a ps the: lbnhins coodil:ion \!\~ P __.. 0 ~ di -- on. ~
~ mati~ up a p become. 11101e and more: widel)f sepanted as prewn is deaased.
d ,me: 't'Ol'IDDC ot1t. ~ ~msel' ~iDe!j .. S"JDalb Mill, u.er f~ til c11e total
vo.IWI"W! ~by me gas.. ~ tbe forces cl atD'aCtim lletwem molecu.li=s lleeome
~~ sma0 ~~or dliC iucrmm1 ~ ~ mcm (Sec.. t6J). m1be timit.
,P ...,. c. 1De molead.a are ~ by iminite c.fiswlces. Their~ bceome ~
~ aliih 1bo b)l8) ''01\Unc ofUie ~ Blld d1C' imenno!ceular fon_-cs approadl ~ ~
condtlions defiJJe an UIMJ_.gtl.l Jftlk. and Eq. (3.9) ~shes tbe idetllgs ~~ mle.
Tht ~~ ~r tl in Eq. tl.7) il ~ lbe ~ gtD ,C (JRSfllnL lB ~
va1oe h delermlned by meam. of:&~,. c:ts) from ~:Unellllll PV '1' dam:
( P'V)~
R ;;;; 273.16 i
~ I'VT ~tl ~ iP Act be ~ II :zero pS1iUfllZ.. daJ.a takt.u II r.e p ate

a:tmpohlted 1o 1be :er;o-pressun: ita~ .b:tamincd ~by Fig. 3.4, llhc ~ l'llut
,n f PV); is ~7 L1.8 ~ bar mo~~ 1 ~l ro tllte ~iDS wt:ue of R:1
em? bar mo~- ;;. o-.,..

R = 22:1 U.S
.!73.~~6 K
.eM ,11,.,.
7 anJ '---
11 ....,
--t-1 K-1
v. tlii.UI '
T!l.rougb te use o ~moo facbm., R. 1111y be~~ in vanw' 1ltlib.. CommoQI) ~

..,-...rues i11'e given in Table A..2 el App. A.

I Za~
PV
(3.l0)
RT
TlM dimmsionks.'li ratio is calbed ~ c~ility fot:tor. With lhU drfinilion WKI with
a o RT [Eq. (3.7)].. Eq. 1(3;6) ~~
I z = t + B' , +(.."'P1 + o-1') + ... i (). I
D
~+ (J.[1)
Vl
84tb o:f ~ .,qllil.ti()(ls ~ kfiuwn M rirlHJ ~Jtt, afiiJiltc F.urtcl~ 8 C'; ', de-, and
B. C. ,D. etc~ Me ea1led 1rilli rot1Jirinu. P:mmtlden .tr and JJ are SNJDI!d viriail coef&~:
e and c are third virilll (!~~ ttc. For a P'm ~ mr: viria:J ~are [unctioos
,,.r ~urn amy.
The mwo ~of li(Jdlkfcilts in [f3'.q&. (3. [nand (1. 11) am ml~ mt foll(lft.s:
IJ
(3. ~31)
c- IJ?.
IY:
D ~ 3BC + 2.11''
1Y=- Cf= (3d3bJ r3.UcJ
liT (RTt~ tRT~
10 &m~ ~ nUI.il.lPS. v~ 5d z ~ P v1RT me.q. (3.t a1 and ~"0 fOf P. "Prb n~ dim-
ination of P oa the ri,ght of Eq. (3. J1).. 'Tbc ~ eqaation adUca to a powu SleOO in JI Y
wbiclt may~~ ~ lb-y ki'm "tbh Eq. fJ. ~2) to ~ tbt ,g.l.\'ell n:latinn:L 1ltey .hoW
eudly on1y rm lbe il ;o \irW ~mion a infinini series.- are ~pb,ble ~pwmn~
f01r'bc ~ f~ u:sed ;[ n ptanice.
~fml}l ~ ~cquat:ioni of ~ ~ bmJ. ~ for psa, tut the \irial eqgatioJis P
fk ~ 00~ futnly ~on ~;cat In'~ Vrhidl ~ides.~ signiti~ ro
u virlaJ coe:fficimts. l'llm. for the ~ in I J Y. 1be tenn BI V arias oo ~t m
itdr~OM twn~cn pain. of mQLecu.Ies {See. 162): me cI v) term. 00 OOOOWII of lhree..:bod)l
.inr&wrti~ etc.. Bemuse 1 v,'"()Jbody ima---rloo ate miB)l times ntore common than tbr'eo-
bx:ly he~ and ~y ~())QS :u:e tl'llriiiY ~ 1JJIOf1l nume.rou& dAD four-body
~a'fit.iDS.. r.t- m:e oomn~ to Z of ~- e'd) bigber~ ramm cfecrea:se
mpidly.

3J. ~ ldtalGas
3o~3 THE IDEAL GAS
83use ~ rmm 1JI V.. CJ V~ . ~ of die vhml ~ ~Eq. t:1J 2)~ arise w axxunt of
mo~GcWv In~ the: virm cosffioe~ats. ' " C. ttc-. Vt'tlll1d lM ~ ~ m> mcb ifih!fJIC-
~ tu cxH.t, Wid me vitla.l upaMion 'Gold ~ M:
Z -11 PV=RT
Mol~ i~~do in faa nisi!~ tmdififl~lhe~rwd ~rof mal~

As~ is. red'ueed,;d eom:mnttem;per.U.l~Rl. v
inaA50! and abe ~"bvtiom. o{'lllc ~~
2 1
B/ V. C/ V , D/ V ... mf4.
(3J2). ~- Fot P .-..a
Z ~ nniry~ noU:~eroose
of any dlaDge iD lbEI virial coefliclems~ bW ~ " hecomc:,s, ~ Thgs in tilt: l1mh 45.
P -+ 1. 1M equatiOJJ (l!f ~te ftid~ to t.&e ~ ~i~ form as tor llbe lbypillbetical mse or
B =C - - O~ i.e....
or pv ...... RT
w~bow fl&'OJD tbe ,phase rule that lbe internal energy of a re:ai gas is ~ Jlll'lCtkm of
~ a'\ "-ell as Df ~ 1bi5 ~ dtpmdr,n~ resoJts, ftomJ fOIUS be~~
lht mol~ If suciJ f~ did DOlt:~~. no c~ would be ~ rn ida l.be ~
Jntermolecular distma.t. aDd dlm:vfo.re oo enagy wouJd be rcqWK:d mbt:ing about ~
~urc:~m aJlSat~~~mpnarll~ -~ lbDliQ~ .~ofiDIIIKulu
~ons. 'lbe in1eroaJ eoe~gY Gf .a. p dependS oa ~only. 'The.se ~darDQm
of the lbdtavror of ~ ps tll wbidJ DO iJlmJIDt)(a.'IL_Jar ~~ ,p;.. aOO'of I~ -
m~~ limJf Q:i ~ .,~ ~ro lead mm, cte1inloon of an ideal gas as Qlle .-bose
~'VP~ bch3Yior . ~~by:
(3.15)
,f mpllfld Property Relllflotls for an ldttsl Go:

The ~fiDitiM of hem .c a,pxhy at ~ \~ Eq. (2.161. Bids for a ldcaJ ps to the
~CUI'IdtJSioo that Cv i.l :) funQino of~ QJdr-
Cv =(aU) ~dU(T)
iT v '::' ttT :;: c."en
TbrJ detlniog cqlllltJon for emhalJY~ fq. Q..l J1~ ~lied w i*4l . ICJUb to die~
llw H mn a a f~n ar rem~ only:
11 ~ U + PV= U(TI +llT= HCI')> (3.17)

The ~t capacity
~OJJII}l:.
(3.18~
A msefui .~ut~m~~ befw~ c,. l1.ld c.,~ fm lU1 itt~~~ fimi diffmoruwull of Eq. t3.17t.
= JT + R = c,.+ R
dH 4U
C, ,d T t( 3.19)
1'1dt tqUation CIOa not lmpiJ thll c, and Cv .__.............. gon-

stanl tDr am ldiNd ps1 but 1a nly that they wry with tempew ature In
sur:h a way that U1elr dlllerence II eqt... loR..
F<w any change of te of ttn 1idtal Pl Eq$_ (3- ~~()) Md (J_ ~ ) I$JJ 0):
I d!J - Cv d1 \ 3.2!tJ) AU- j C"rdT ().10b~
dH: C1dT i3..2L) 6H = I C,p dT {3.ZibJ
Beclll'Se 1Kim me ~ ~ ~ C\ of tm itltal gas are ~ns ot ~

ml)~. AU fcx Wl ~ tdttr ~'\til \ry Sq. ~3.20b~, rv~ of 1be .kind of IPI'
ronsm me~ ~ is detmnstfilted in Fig. JS. \\'htm bows a graph of rnrenw ~
b G ifit!I)CiliOD of mobT \'Ol'ume wbh ~e~Dpr!n!_tme as~~- ~ lJ ~of V.
~ pfot f U vs. v WI ~ l.etiiJ.'IeCdW1i'E b: a llori~tal fiDe. For dlfffRIH IC8lpe~ U
bas di!fkren1 Y:LlUcs. ~idla. ~ IJDe f'or ~b ta~~pem~ Thoo 5DCb lines~~ io
Flg. 3.5. Mte fof ~ 1'1 mKI one for il bi,gber tempemtnre T1. The dMbed line ~con:nut-
ing poun5 a aad b ~a e~~'\-alumc ~ fur whidl tb: tetli]HUIIWO ~
fmm r , to T:z i'DI1 die intmna1 eDCIIY changes by Afi : fJz - u,.
11Jis; change in intema1
~ i$ ~~ by Eq. t3..30b} 1
f
U = Cl~ dT. ~ d~ tifteS ~.Wg jll}in CJ ami c
;md points a and d repn=sent other~ 001 ocauriBg ~ ~eol'I:Stml \!olwne kd wtrlcb also
lmd ftmn a milW ~ T1 to a ftfi2i ~ ~~ ~ u-dph &bm\.-s lhar t~ man.ge
in U lw ~ is lbe arne as for die ~\'Obne ~and ii is ~
given by fbi: Si11fic ~ rni~D~:'Iyj AU ~ J Cv fiT. ~"\Wei, t!U ~ Jwt equ~d U> Q fll

3..3. The lde.al Gat 1S
~ ~j ~~ Q ckpeMJ 1D Oll1y on T1 m:l T2 but also onltbe p~b of~ p.mceg.

An aRi:J:'el,y analcJow discusil:on awlie:s to lire erOalpy H of an_ ideaJ ~ cSec Sec. 2.Il.)
The ide:t1l gas is a nwld ftnid ~ by :simple prt1pf'11J rtkdlms, wllidJ =n fe..
~dy 8(JOd ~io:R$ wbm applied 10 ~ psr In~ t.'ltlt!IJiaJitnu. , - m
pressures up' 10 a few bars m:&f dho be ~~ ideaL and simple equoaiom dJwl apply.
EquIIDns for Procas C~ for lrleal Gasss

~~provide '\\.'Ut and he-.n ~ 1be wort of:.. mecb:micatly mwsible
c~rcm t~OCCM ~ &iveo b) Eq. ( J.l~ ~R writt~ for~ \mil or,_ OJOle-;
dW~ - PdV
fGt an i.aJ p.s ia .lift)! d~ysrem pltll.~ . . fi.tsllaw as ~ b)l

1
Elt (2.6) Wl'imm fer 3
unit mass tOr Ill molt=. may be eambined 'ilh Eq. (3.20a) ~o 3itr.
Su~tioo for dW and ttQillliDQ r.x IQ yields Jll Jd$dOO ~tl tor ... idca1 gas in my
l:l'lecb.mia.Uy Mt'eftibJe e~~tem [JIIOCCM:
dQ ~ CvdT + PdV
This ~equatim COGIIains die ,!ariab'Jes, P. V. and T. oo)f c.n of .tlxb me inde~
WotkUJJ eqnabon$ for dQ and d W ~ oo wbidl paif M' lhese wriaM is selected ~
~dent 'Le., rt.q)OO wbidl ~ i diminaled by Eq. (3..l4J.. VlidJ P ; RTI It.
(3.22) I dV
dW~ - RTV
,f iJI
drQ- ~ C;dT- R'T-p (1.24) dW.!!!!! - 11. dT lt.T!f (l.25J
With T !SI P V I R,. me \W'Oft is simply t1 W ~ P'dV .. and "lUiJh C'v .given api:n by IBq. (l.. l ~
Cv Cr
dQ~ RVdP + RPdV ( 3.26}
Tl:mr tqmlOOoj may br: ~a1 fm i tb] ~ ID WJit,mt kinds of~ llS. . . .
scribed, in what iofll~. 1he ammJpti.ens implidl if_n the-ir dni\11ticm ~ 1hll the iY!*JD .
do~ ,ODd lhe pi'(JCeSS u
mecbaDlc:aU)I, ~

16
By tp. (3.20b)and (:Ulb),
-
By &J -(3..'22)1and (3.2-4)~ l'2
Q- MTbl ~;;;;:~niT - -~
ib - m
v1 P1
8)' -" (3.23) and {3.15) W =-ItT ln ~ - IT b1 ~
Nee 111at D. r --W~ a rm111 trun mo ton rmm Eq. (2..3i 'fhadj~
lsobaJic Proeess
By Eq- fl..ZU,).and (J.2lb),
.6r.J ~ JCvJ1 AH~ fc,dT

cuxJ ~ lkp. (3..24) and (].25)_
a- j c,rtr
Na~e lfW Q :.- A H ~ a mwll also gjm. by Eq. (213). Tlaefore.
I a=- tiN =I CrtlT (~ P) I (128)
lsOcbOtie (Constant V) ~~mcasa

Equ rns (l.21lb) ilfld Q.2 lf.l} ~ app~y:
.All; JCvdT and aH e I c,cJr

By: Eq. (3.22) and a&c lmic cquatioa far ,.v:rk,
Q--JcvdT end W==--/PdV=O
Note dl:l1J Q' ;;;; 4lJ. tt resuk abo p~ ;y ~ 11 U)). 1b:tdore,
I
Q"' IJ.U"' JCvdl (, a V) I {l-29)

Adiabatic Process; Constant Heat Capacities
An adia.baJi.G pnxess is one foJ- ~trldt Ume is beat tnmsfer be1wecm the ~ mci it&
DO
M~ITOWJCiirlp; L~~ d 1( ] - 0. Eam of Eq (3.22)'. (3.24), aDd 0.-26) ll1af tbeie'fore be _~l
~zero. huegnU]on llh Cv and Cp .~dim y~ sinlple rebtians allllJO.! de wriables.
r. p .aDJ,t v. vaDd rfl) ~~y reversible ildiaba11e rem~nil tV ~1'1 of ideaJJ
pses. fer eumple,. F.q. (3.22) bec:omes
dT R dV
T =- Cv V
Silni.bdyl l!q_;i. (l.24JImild Or26) l!!ad 10~
!! ~ (!l)~fi./C, aDd
Tl Pt,
1bese equaaiom rmt~ also be c;xpres5ed
r~n -1 =~ (3.30a) T pU -rl !~ : cons_t. {~.JOb} p V)' :: t"''ni:SL O.llk>
(331)
EqUIItiOM (8.38) ara Nstrictld In appllealion IQ, ro.l '91JM'o with c.o.u-
atant heat capaclliea undergoing rnedtan.icaQy reveiSibte c
expalllSIDil or compression.
= tl.fJ =Car AT
W f3.Jl)1
Altmlr.Mh-e fQmls of EQ. '3 32) r~t if t:v it dkntnattd in ra\~(1( of the ~-c;;ilp~ nn{o y:
y 5 c, Cr + R _ I + !!:__ m C~~ R
C.,- Cy Cu y -1
3trCt aodCJi ~~L y h.~1 Fu. i.lll iJbl

illlt ~ lho:a ilbl: br.1t ~l:ltl ~ u:
CD 'lbb.l.!l
aim:~~ C,. - Cy = ll crt11 ~ ~ mr moaamrli:: , Cp Cy ~IIIJ
~ VFJII't ~ll::ct.ltler=l.oy i.l ~ ~-eiO~ ~ l]Jeo~ ~~~
Obras proteg das por dn eitos de auto

W c: c, AT ~ yR. .....AT'
-
~
~ RTa PI V1 and RT1 ~ h. V:z. tbi1- ~on m_ay be writtr:o:

w ~ 12 - R1l ;;; P,~ ... ,...,~
y-~ y-i
Bqoa1km ~.J2~ and (3~:3) am ~raJ for ooiabatir ~Mel~~
055as ma e1osu~ ~ ~ ~ u oot. ixcau5C f .. v. and T IJ'e ~ tUDC-
u ". ~ of path. Howe.~ ~ _ Vi aJe usually Ufikoowm. Elfmmation ~~ "1
~mat eq. p.:u, bl' Eq. ~(J.D:l. '\lUiid Ollly tor meebaniicatty re\~ proe~ ~ w me
~ .
Wc P1 Vt
y- 1
[
- (!1){1-ll/f
~
_~]- 0
[(!!1)(y-W'
RTt
y-1 ~
r- ~]
1he SliDe remit is obt111:'kldi wbe.n l.be rek1ioo belween P and V giwn by Bq. (3~) is ~
far tbe inl~ W ; - f P dV ~ Equa~ (3.34) is ll'al1d only fm ideal wilbamstant
~w:a~~. m,Rdiabalie. med'wlically ~ e~ ~
Whm apptit to JQJ &p. O..JCJ)t ~ 0.34) often yield~ ;appmx
i~ poov'"l((~ ~ ~ t1om idtalll.)' ~ ~ ~ty ~11. For~~~
;Y - 161; ~ ~ of y are lA for dmtnmic ~ 9."Qd J..) far tri:m;ple po)yaro~Dic;
[QSti wdi ~. SG.l. NH aDd C&
Polytruplc Procasa
Becmse pDiytmpfu' Da:Ooi "''.nming m:t.my ways~n plit}"lRJpic p1i)C'tW W~ II mudd M ~
"~ \\lith~ a~~ it ~~a~ ~ted i~Jy tbc em~ cq_wdioo:
I p 'V i =t'OmiMt I (3.J5a)
Pot~ .~ ~ticm; ~$ m lPAp~ (3.lflfi,l ~ 3.30b) ~ ~iJ~ derived~
Irvf- 1
= COOitum (-..lSb> I!: p fl ~'' = romwu (3..35c) I
'Vbe:n the relalion between P &md V is ~'~ ~ Bq. 1(-J.JSat evalualioo off P dV )ttl:lds
Eq. (3.34) wm r ~P - by &; -
w~ 2.'. [(~)~'~~' -I] (3.J6)
Moreu~ for amstmn ben ~hies. die first b.w sol~'ld mr f2 yields:
Q
e (1 ..... y)llT~
(1-1 (y-- l)
[(!2)---l~fl
I Pt
- l ]-r {).3'"T'i
~,

19
'fbi;t ~ described i.D b seclion ~ lo rhe four p:Dm4 mown 00 Mg. 3..6 for
1
spectliC \~Of6:
~~ ~ B) Eq.U..l~ ). ! = 0.
t l5otbmnal ~: B) Bq. {l.JSb). & 1,

Adidlatic- ~; " = .
~proem: By E4 (3.35a). dV /dP ~ v 1Pd; '"" COQ$blJ'It V 1 8 e!!
~J.(( ~CIIpol)~
~~by
~ c. Ql'-
1IJTeYerslble Process
Ml ~de\ eloped in this seaion ba\~ been dmiw for medwlicamy l'e\~ dosed-
system PI~ for ideal pses. H~w, dKtse equatio~ whicb give fJlfJPUfY dttlnge
dU ~ d II, .aU. and 6 H- are \'ah'd fm" iideal g rega:nt~ess, ol t:he ~ They !appfy
equally to ra"'GmNe mdl ~le JM~ io both doied uod tp1m , btawse
c~ in properties dqx-nd ~oldy 01l dJe initial And final SUit~ of ~he.~~ On lbe olbtr
~ an eqotUioa, for Q or 'W. ~ .it is equal to a pr"'O)ee1y dcmge. - uhjcet w the rastrio-
iiomo of detiiwtioo.
The.l\"'Ot of an ~'1Kt pf(IC1::S$ 1$ ~~la!lcd by a ~re. :Fifit, W :btwo-_,
~ fwa mccb:mically !It\~~ lhal ~ tbtsmx e~ o ~
lk :a.mW ~ ~ ~ tbis iliMUb is tmlbi;plied ordi\idcd hy an ellidftlt)l
to live tbe actual wor If tbe pwcess produtc51 wor~ the absolute value for tile mrmJ~
~ ~:s mq.~:mF aru1 rmust t.e nwltipticd by m~J ~ 1r me~ ~ wodr-. me
value fo:r l:Jlc ~11Je process is too MmlJ and mus.t be dividr:d &y an rdf:iamey.
Applic:i11iCJttS. or lk tC\'ii.tifqlfSi and equadOM.m fbi& 8eCiiM ~ IDMrr-..mt'l iA mt; e2.a~f~Ples
mmn follow. In (WtJtiU'. the work ~of i~~"blc proo~, is ~ in Ex~ 3. _

Example3.2
Nr is ~ from an Initial Slide of 1 bar and ~c to a final stale of 5 bar and
~--c by tftr8e diffefGnt medilanieaOy 11JVersh)le prvceSMI in a dosl3d systarre
(a) Heal1ng at constant ~ume tiJowed by oooling a1 constant pmssum.

(b) rsothemlal compresslen.
(C) Adtabatle~ressian follawed by QJdlog at conscan~ YOJUIQQ.
ASsume air 1o be an ideal gas wlth the ,constant heat eapadtiee. c. :;; CS/Z)R and
Cp c (7{2)R. CBic*le the, l'IOJk reqdred, hea1 lnlnsferred. and the changes in
intema1 energy ,Bf'd enthalpf of the u tor eadlrprocess.
-
e
~
:S o1vHonU
~ tlte S)$ltiU U$ l moll of air. !Pot R == tt3 ~4 J mo~- K-~.
Obras protegidas por dkeitos de auto

J.J. 1be JdnJ G:JS 81
(t") The btitl:l] step of ~c ~QD ~ llhe .!lit It to lu Wial \'Ot~ of

0.()0495:8 m', By Eq, r3.Xkl)'.lhe tempeli'atllm at this poim ~
W = C" AT= ~ 20.185)(S67..57- 298. 1 ~ = '~(JO() J
(J- 4U = Cv (Tt - T') = -.5~600 l
ThWi for pmc (c).
Q =-5IJ()OJ1
Altboogb the pro;peny cha:ngeg A~U aod1 A II are uro for ~ ~ Q
lJDdl I~' aN p:nb,.dopmdent, bUI beJe Q :;; - W. P:"~ 3,1 s1KJws each ~
on a P v diagrum. kitlliSC' ~ wmt f-or cadi of ~ fiedlam'CGH)' tcver&~:"ll*
p~ ~'ell ~ lV .=. -- j' P d V. the WOI'k for each prneess is propaniomtl
to the ltOt1d ~ bdi)Vf die paths 00 die , v diQnm fftii1J 1to 2. The ~\"e mes
of I~~. correspond ( D d:~~e n~ wl~~e5 01 W.
Example 3.3
An ldeal gas undergoes.the fDIIowJng sequence of ~Y ~~ processes
in a closed sys.tem:
(a) from an initial raaae <A 7(JJC and 1 'baf~ it is~ adabatica1ly tc~ 1~0.
(b) It is then eooed fiOM 1SO 10 70, C Ill cont18nt pressure~
(c) FinaDr. rt Is &xpar.tded Isothermally to its origioal smta
CakBate w,. (!. A fJ, and A H for each of Ole dtree processes and for lhea re cycle.
lake Cl :; CJ/l)R and c,
= (Sfl)R.
p
'
Solution 3.S
l'OF R;;; &.3~4 J mol- 1 K- .
Cv = 12..471
The cycle is lii1:wwo oo PV diagram in F'~g. 3.8. Tam as a baDs I mol of ps..
(ci) for~ ~I ;88 OlldJetJOtag adfabalic ~0011 Q = 0: w,bence
AU ~ if'' = Cy AT ;::;;; (12A1l)( 1!4 - 70) ~ 998 J
bll == Cr liT=: 1(20.78S)(I!O --10) ~ t663 J

~-urc Pa is fooud from Bet+C.3.30b);
P., !::
Tl)yJ(Y- U
P1 ( ....._ e t E~
(150 +Z/l,IS)u ~ 1.6$9 bar
- Till 70 + 273.13
(b)Forlhhl ~ ~-,
Q ~ !iH!!!!!!! Cp aT~ (20.185)(70 - I~) ~ -1.,663 1
All== C~ ~7 ~ (12.471)(10 .... JSO) ~ .-..CJ9S J
w ... lltl - Q - -99'8 - ( -1.,663) - M..'i J

(c) For ideal p:se5 I.Didagai.og an OOt.bmuJ ,process. AU and AH are~
Eq. (3.21) yic-~
I') ~ 1.689
Q ~ -W ~ R.Tbl - ~ RTm - C!:r ti.J14)(34l.l5)m ----- ~ 1.4951
Pi ~. ~

Q co- 1.663 + 1'+495, c -Mi ll
A. c 99 + 665 - IA9S c !68 J
JiU z:: 998 - 998 + () a::::a 0
AH o 1.663- L.fiM + 0 ~ 0
'fbi: propeny ~ b. fJ and 4 H both ere MIO for tbe enme q"C]e. benuKe the
:lnitial and finat snlt~ aM ickllJ.fJc:d. 1ote 11&o 111m Q
follows from Jhe lir.si bw with l1t. U :: 0 .
W for tbt \!]de. 11m =-
ExampJe3~4
lU' the ~8:) ,o f Ex_ 3.3 Pte cJ)Iftiedrout JtJBWttf$it1/y lbut SO 88 to a(l(l(lmplish aaetty
!the same Chafl{J(IS ol stat~ Ula same d'langes in :P, T. u. and 1,~ ~hs:n dilf&ren
vah.Ms of Q and W res _ Qdcuf~ Q and 1V if eadh 5tep1is caJ'fled out t an
e#Hcklncy of~-
Solutlon 3A
If the ~dmnf:S of w:c .~ im E.t 33 ore~ ottt by ~~lc ~
~ prope1~ clwl~ for IIi~ ~ an: idtmical hb ~ of 3. Ho-V~ii.,~.
die values Of Q n:d W clumge..
(d) For ~i~JJ:wt.lcully re..'efiitJI'r-, Jiilliibl!itic rompn:&lioo.. ft' =: m J. If die p ~
80% efficle:nt com~ witb 1his1 W .a 998/0.80 ~=n J.:148 J. Tbh. smp CiDOtlt
bert be adiB~. B)t d~ fu"\t law,
Q ~ !AU ...... l = 998 ..... 11.248 = - 2SO J
1
(b) l1E work 'for tbc ~ l'C\'U&ibk cwtin,g l}fiJCI:5S IS 665 J. fo:r b
~ siDle~ Wcr6M/0. 8D::::~~Il. md
(J ;;;;: AU- W r;;;; -998-831 ~ I.A29J
(c) A$ "-lifk is .:lmx by lhe i)i'ittm i.D this~ lhe ~'a'Sible ~~.~ in 4l ilute
...alue is I~ tbtm dJe Je\."CQ:iblr wotk of .-.1,495 J:
"'' - {1),80)(= 1,495) ~ - l.l96J

Q ~AU ... W ~o tl96~ t,l96J
Fo:r lhc en.tiJe ~1e. 41.ll m1i A II are. za'Q~ witb
Q = - :ZSO- 1.829 + l.l96 ;;;;' -8&.1 J
~v =LJ4
J +D~- J.,l96:
A summary of mese ~and 'tllmJ.e for EL 3.3 ii gnm In me fo11uwiQ.s ~
\'tt!lno.,~ ..:tl'r in j(JUJI!S..

84
1!1.3.3 ~bk;., lb.l.4

4U 6H Q' w 4fl 6.11 Q w
(d)
h)
998
- 991
~,.fi&l
-1,663 -JJ)61
0 998
fj&5
_,..
998
~
- I.(Al
- 25'0
-L~
f ,24
831
(C") 0 I) 1?-195 -1.495 0 0 1.196 .......[
0 0 - J 1611 e 0 ~
n. rCJ"~ . ~ ~~~\\'Oft ,llPd ~ an equal~ of fqt_

1he S1rikinJ f\'e.:dllre of 1fJe comparison siHJmn in the tlbte i:s (bat the lDtBI womt
nquiml Wben me C)-de of~ ~1*. mort~ 'five times
tbe tUaJ W'Oit m[uimd wJ:ieD the sm;p$ me meeh:m.irolly ~~ e\l'ftl lhooJh
eacll ~ sbp is ,1S511Jbad 81Xi cflitlcml.
ExampteS.S
A quanmy of nitfogen gas is confined in a venia)) cylinder by e ~ pis~
Ther top of lhe piston IS open 10r the ~ lite walght of the piston makes
Ole pr8Sa.lre Ol me nitttogen 0.35 bar nttter than Ul8J of me sunul.d.ling attnosphefe*
Whtlt i9 at 1 bar aJKJ Z'PC. lhus the niU'ogen is~ at a pmssufe of 1..35 bar~
and iS 1in meet1anical end thermal eq-Uilibrium Wih tts surroundngs.
The piSton Is
forced into Ute cytfnder ,SQJas 10 compass the' nlnogen to a pre5Sur8 rof 2. 7 bal. The
nilmgen at Itt& Pf8-S1Ure is albw8d1to ccme to 1he/rtf8i equiliDl'fwn with the surr(JUI'dng
aimospherB ar DOC. AI this point the piston: rs lodcl!d m1place by laldles.
The~are ~~the piston fmm ~and the 8pp8.18luS in
time mtums to mechalcal .anti them!1al equi~Grtumr .. ... ts SUJJrOt.fOQl~ DlscuJ&s 'the
application of thermodynamies to this Pf008SS~ Assume 1ritrogen at D1ese conditions
is an ldeal gas.
SOlution a.s
WhM ~ I~ lh ol-; he frietioldess piJ :; n rcmo~,.e.t h piston HlO\l
rap:idbr upwml. and owm;;
IU ~ ~ ~ hoywJd its ~OOWD pgsitk-1.
1b ~ upaniioa ~a mrasibk~ ~ proeess. bea lit-
tle~~ Rsul from sirtgit tJi$ of dlo ~ aod bc:~se hott t.nlJlskr
I
b m.m~'ft)' slow. ~ die so.bseqoent osdUmion of die piston ~

im.wrsibilby a RW!'t of ~tinio1 and rurbukDL"e in 1xJlb the ps and 1he UfniU..
~- 1l!is ~ t_oest 1m filii a cai8i~ 'lime durio.g whidl be - ~Jier
oeeur5 iD an~ 5UftkieDt ~0 ~~m (be mUOJCnr to its i~l ~ of
~ 1111 ~~!Of 1..3) bar.
k . 001 ~illte ~o ~ 1tbc patb of an ~k PI~" and dd$ ~
impossih lb~ ~wlation al ei~ Q or W. lJnHte be3JIiUHI wcxk. tbe :propeny
d lmges of tbG systmJ ezm beelladatcd, ~they dq)e:nJI ~on the init_.al
amJ finaJ st~s. aod lhesc are knov.'fiL 8mb AU orul t.ll rm the up=ms!u11 ~

are zao. becavcSe dm imtiaJ aruJ fimd te~ ~ 17' C. The tim law a~
rn ~ Wi \\i'CU ~10 ~le ~ 4:Qd iJ~;
Q=-W
Allhoogh Dtitt.:r Q oor W c=m he ,._~cu~ tbirlr abso1~ 'V".iilu are. the ~
1br: pcocess ~ i:o ell:l-DIMI of the prstoo1and d~e allllDSp~ and a compen
sadog dea'ase in dx :iotanaJJ mn-gy of abe ;urmuudiu.g El.tmOSfJbcnt..
Example3.6
Nr nows at a :steady r8te ~~a hort~ntal pipe 101a panty dosed valve. The
pipe leaving the valve is enough mger lbu 1he ermance pipe 11\at the kineti04nergy
change1of lhe aJr as nflows 1hrr.M.Jgh1fhe V8M ls negDgille. The valve and ccnneding
PiP8S are _. lrlsulated~ The conditions of tns1a ir .up$tre&rn f'Rlm the 'vaNe are 20~c
and 6 bar, and ~he d'oMrnRrea:m pressure Is 3 bar. If alr is regaJde(:ll as an idHJ gas.
What Is the tempetature of h atr some distance ~downStream from the velve't
Flow fbrough a JliD1I)' clded vaiNC ~known o rhmrdtng pmc~. 'iJbe syscnn is
in..~~ rmating Q nePifbl~ ~. tfhe~eougy kiDelic~
dmn&es are uegtigibk. ~PO. haft wort is dompl . ~ ~ ~ w, o.
Eq_ (1.3'2) ~ f{)e 4 H tO. "'Ji1m&. for 1112 ideal~
The RSillh mat AH .., 0 - genera] f a ~~ pnxc:ss, ~ lbe assump-

tions of atg1igUJ1~ beat ~er aPd pOtelltW~ and tmtii~ ~ -- usu,'-
all)l vaM. If me ftllid is m ide gas~ tf10 tempera1W"e clulnge CJCCai'.S. '1'lte 1.bnltding
I
poous is itLha:mdy ~le. D ~~ u Hnrmueri_a] 10 the ealeulalkm, benJbO

liq. {J.llb) b.~ ror an ideal gas. whatnw m ~
Exampla3.7
win Ex~ ~e the trow nne of lhe al1r is 1 rna s- 1 and if both upstream and dowM'Iream
pipes lla\J8 an inner ciameteT of s ~an. what is lhe Jdnatir::..anergy change of the .air and
what is its 18111)eratvre cl1arwge? For air, C, ~~ Gfl) I( and M = l9 Q mor-'"

Sotldloa3.7
a av
;;;:;;;;;;;~;;;;;;;;;;~
.'\p A
A~ ! l}t =; (!.) (S X 1o- = l ..ti4 ;c 10,..3' J

4 4
H the ao.r~ ~mpaac-ure is lliUle ~ fMm the ~m reruper.mm:,

lhmtoapld~
nw. rae ot dlap inti~~ ' ~bctd"m:
~ tt.(!ti2 ) -. tHV A (!r )
'!!!!!! u )( 29 )( ;}10-J) c~r)sl- 2~) ~ Or.l 86 J -I

1
In die absena: of heal uwW'u-.1 wort.. tbr: energy balaace, Eq. (2.31 )~ ~
11(H + ~ rlm ~ ,;,_ tJ.N' +m4(~u1) ;: o

-
-~6T +.m4(l~r!) ~ fiC.r 6T +m~( ~ 2J ~o
-
~ ~
(l)(i{2){lt3 14) AT = _,. .4 (i~J = - 0.186
AT ~ -o.0064 K
Cl~ *~or ~ible bnptmtu~c c:hzqe ~ dtc Yallwc ts

jlwUied. liven fmo an upstream preSSIII'e of lO bar ud a ~ ~
or 1 bat mid c. me 5U au. lite:. the 1m1pCnt1lllB change is ooJry - 0.076 JL
'We~ ihaL aeep~ far 1t ry umtsual c~ion~ dH = 0 is a. ~
eneqy ~ fw a tlln;lntin; proc:as..

3A APPUCAnON OF THE VIAIAL EQUATIONS
11te: two farms of the ririal expm.~ gken by P.qs.. (3. ~ I) and (3.12) are i:nlb:Ute ~. Far
en~~ dlmli!3C is pra-tal cxdy ~eoll\c~e ~ '~ n~pid.. Cibat is, wberr
('0 ormme tenm wffree f ~ty close upjiltil:ut\tioos to me w.lt~~:S of1fle. ~ Thfi
is ra'lired fw ~and vaplfS all<M' 10 modem p~
fi;pft l.t; Cuq:wm:ihilily-!a~aDr

jmpbfOJ~
.Figtm" 3.9YM:Nt ~p~bili~~ractor gmp~~ f~ Vlluesof~oom~biJ.

ity fttcn;Jr z (OS C41mlated .rro.n p v T ~ rOii rntlbu_oe 1Jy thr: defining eqwnion z == , vIRn
Me potted y- ~for various corur.tmn ~~ Thc~g i.odlemJs, ~ grapa.
:imby "'1tat the viriDil ~ in p is inlenfkd I[D ~ IP3l)'tica1Jy. AJll Uolbr:fD1.1J ~
na1e at me \-aloe z ... 1 ror .P = o. and tbe isotbmm .are ~.Y nmgJn tint!s. mlaw 'PftiSIII"eS.
Th _ d~e ll!lnPlt oo an ~r:nn ,mt 11 = 0 b a &ODd appRlwnadoo.of dH- i Oibctm ftiotD P .--. 0
to some linit,e ~ DiffG'e11tWileo of Eq. (3.11) ror a~ (empemture ~RS:
(8:Z)
-
tJP
I
1'
!!:!
"' . .,.,.P+l0'' I'
B ~
l
+
Th~ U'Je equllioo oo

We mngenf lline ti Z ~ I + B~ P. a reM.lll ilL~ g.r"\."efl by ~
Eq~ (.t l l)tot'\110~
A :mere common fi1rm ~of this eqontion leMdb from ~ Wtotion for If by tiq. fJ.Ila):
z = PY = 1 + Bt
RT RT
n . equmoo -~ I . ~ p.mporDooality ~D z .;md P. mid ~ o!Wn applied t;Q
vapor~ at Slllbcrikal temperanm~tt up o meir sammt\oo ~P~ ru higher ~tmes

it ~ .a ~~1e apptoxlmatii.lt' for~ up ItO DJ ~ r'Jf satenl ~ w.hh tht
pras&11e lrmp increasiDg asme
cempmume ~
Equati.Oil O-l2) ~~may k ~to il\'0 fOr application a_t law ~=
PV 8
z= RT = I V (3.39)
HOWC\ttt. E4 (3.38) ts more oon~m in itpplJcatioo Mdl b ~~Drmally u lea$t as accurate as

&q. (139J. TbDs hm IlK 'Yirm1 equam u lnllla1tal to lWO ~mni,. F.q. o..38~ is pretmea.
1be ,second \liRa~ ~ B substanA:C ckpe:odan IDd funetion of canpmttun:.
~ wlue ate ~e for.tl1111Dber of~5 M~"' ~of ~d
viriall ~is 1J10Sit'ble ~ 110 d;b ~DC amiable. as d~twed in See. J.6_
For~~ ~ ~or qppraWAli\y or Eq. O.JSJ but bci<M the critk-at pre:
sure, me 'llilU] eqi.mti&D liU~ 10 three JmD!I, often pnntldts g~ ~ In this ~
&,. (3.12~ 1be ~on in 1/ V ~ 15 far ~llpaior ro,Eq. (3. LI). Thus ,.,iJeo We vDiaJ equmoo
is~ to 1 tree tet~:m.. me: ~tt= ftmn as::
PV 8 C
z n
!1!11 .;.._, =: ' + -1t + --=
v~
{l.40)
lbi$ ~ can be sol~ .OJmCdy for ~ bur i ~ iD vatu~ Soluliuo ror v~

madily ~lisbcd by an itcratke ~I!D!e~ as ih~ In E1. .l.8.
~DOQ
--"'~-----~ 2J000
Jiiplel..Jt Vl.Nl
efJt.fl~
m Band C
(~ lliJroFD.
---~~~~~~~~~~~~
0 100 200 300 1(1)
nK
V;al;11e~ of C.
lib those of B. dCpcad on ilhe gas and oo le:mpemUR.. lto\rewr. mudll~
i~ l.1iDwD aboo11hin1 virial ~ tbm a.hom ~ODd viDal ~~ lhotlp data tbr
ifJIUb1a of gBSQ uc fowxJ:m,the~ BEaD~SC virial codlkielll~ be)ood the. tlbinJ ~~n:
nmy blown and ~w,t;anse tlr \lrial ~ widJ mtft rh:m fh1ft tmM ~~MY~
its we i5 un.CGDDDCn

FJgure 3.10 iHuslmta ihe dred of rwnperatUI'e oo ttbe ~ ~mclenl B uod C for
~ .abhoogb ~ values are diffenmt b IMber~ the m:nds am s.imilat.. The
cum of Fl-a. 3. to suggesl$ dJaJ B inciOf.StS mcmotOiliaiUy wkh T: now~..-er+ atll~~
miiCb hlgba' than shown B nadx:il a :max.imwn and tbe_n slowly .~ The ~
~of c I'I'X1K dilieuJt ~o establish ~JDnltally.. bvt main fen , aRclaro c
is ~v~ -r kMf ~J.W'et!\ ~ diJoogb a matimum at a ~re near die '1i1ia~l
md t~er decreases J1o"t\lly with WcreasiDg 1 .
A class of cqua:lions inspirM hy Eq. r(3.1l>.r ~as Ollf4ed virial equati~ is iUu~
traled.by the .~'ebb/Rubin eqwmon:6
RT BoRT - At! - C.,/ i 2 bRT -a

p.;;:..V + Vl + Vl
.au c
+ V~ + Vl Tl l +
( r) -y
yl exp Vl
wi'L~ Aot Bo~ Co, a.. b. t . urul f ue WJ em.~ fm a Civcn fluid.. 11liis ~n umJ ~
m~mJ despite rlbe:ir amtplexity. are used in lfle. petmleum and~ indu.._qrles
for li.pt h~ g jla &w odJef~ ~l~o~xm~ered ~
example3.8
Reported wlues for ihe 1riaJ coetflcien1s ol isopropan011 vapor at 2(WC are:
C81Ctdate v and zfor iso~ Yai)OJ at 200"C and 10 bar~

r(S} The idaaJ-ga$ ecp.aatioa; (b) ~A (3.$8}; (c) &tpr~iotl r(3.40).
SOlution 3.8
The lute ~~:pmiiW'e is T 473.l.S K. and 1he approptriate \'lttue of me ps
coo~ is R;;;;; 83.14a:n' bar ma~- 1 K- 1
(a) For 1111 ideal! ~ Z = I. and

II ; ; ; R: =
1
(13.14) ~ . 15) ~ 3934 eJ1i3 moJ- 1
(b) S~"ing Eq. O.JB) for V gi~
. RT .
V~p + B == 3'"934 - JSB ~ 3;546~ 1.1l!Cd1

90
PV V ~' _
Z:!!:; RT e! lrl'/ P - 33M ~G.90l4
v, ~ p RT( t + v; + Y.ic)
11
y -0
bm'e V'(l s:z J~ lhe ideal-p alae. INumerieal!ly.
vl e 3$34 [t- 338

)9]4
- ~ 000
~] ~ 3~39
1(3~- I'
~ ~ ilmdioa <kpett(l$ Oil Ibis r esnJt
V}~ -
RT ( I +""C'"'
B
p v.
lhmttioo amDm.ies umillhe: ditf~ 'VI+i ~ V1 k iMignifiean~ and leads. attn
five i~ totbe final ml~,1
JT ~ l418 cmll'.llOl-l
from .bj 0..18fi6. In OOmprarUOB \Vdh 1Jhis ~ the idcuips: value is.
Z ::01 1
M mo bish md 84 (3,3fJ Bi~ a w!ue l_7iJ7 too Wah.
U CUBIC EQUATIONS OF STATlE
II m eqw.tioa of sate ib b.1 ~ lhe P VT ~ ,ot bodlliquids and \'apoi'S.. i1 mJ.ISt

~a wido: I'Aj-e or~ and~~ Yet it IJW1l DO( k w ~~~to
~t sc;essive IIUJDelical or u:dytka1 diffh."Utlie_s in applieanr.m. Pol)mamial teqnmans Ibm
aFC cubic iD mollar voJUllle offer a compconrl btt-.'"CltO poeralhy and Mmp!Jcity dJat is mitaho
m' m.:my ~ Cnhk ~are tn faa llle ~ Lequatiom ~It:~~
botbrfi4uid and vapot behJi\.iot

JJ. O:rbk Bqualioos ofSWe 91
The n der Waals Equation ol SIBle

The. fir.st pradieal cubic eoqwtioo of~ 'WM proposed by J. D. \"AD dcr Wuli* ill 1813;
RT a
P ::c V- b - 'l'-l
Hwe. a Uld IJ ~ posith coll5b.JI&.; ll!.oixo they :e ~ ~ i<Dlps cquaboo ~

Gi\"'Co mllei9 oft1 and b for a JW'&~m ffnfd. one an miCidue P a:s a fODI:(aon of V fur
~values ,o f T . figure ). I J i8 a, scbe1111Btie P V diqnun ~ ~ "!J!Cb ~liD
Su;pai.m~ ~ --mme" tepesenlin,;Wlti:S of~ liqnidl mKI ~ 'Vapor. For
the isotham t e > Tr: .. pressure is a moooumica1ty de~ function wUb ~ IIIObr
;.'OIIDJlt, The~~ ~~d Tc) reonf4i-ps tbeb~ tifilm(tOH crt C ~e
ot Jtbe Mikal. point. Fer l.be H81htmn T~ < r~. the pressme ~ m;pidlJ in die subcooJed-
ilq,Uiid ~011 witb i:Dcm~Sing If; a'ta ~~lh~ ~,.fiqv]d line. if 101!S through D mitJj..
mAim. rises lQ a m~i mlill\ ~(!ben da.'ft:~ ~ing dJc u~\liiJPOT liite ~nd QOO!m'tling
downward into tbe ~\lapel' regimt.
~ iS()(hcrms do 001 e.xbimt dri;S &mOOih rAmir:ion from saJ.I.UI1ated liquid to
.satumrd ~ I'Utber, tllcy eomain a hOri_zomaJ ~ with.in the: ~ R!p~ wbr~
s:atn:rmed liqtrid .md ~d \~pot ~] in. varying pmporti aJi me ~ina ar wpor
~ 1lli5 ~r2 5tl0wn hy (Do~ lint in FiS- 3. 11-.l~ M~)'tic. utd we ~J.II
as ~-i.mhle ihe unJieillistie ~:Mer of eguatim!l of state in the. two"ffl:.se regicn.
Actual~.. , tbb i' V ~or ji(Cdidtd in dtl ~em by pro:J~Cf cubic equations of smre is
not ~Dy ficrliious. If pressure is decreased on a sal~ ltQUid tkvuid of~
sit~ iDa carefully ,ooutm.11lcd ape~~ does ontOt-carTIUld liquid persis:b a!mr
to~ well ~ow its wpa!f pn:ssum. Similarly. raising Ole pressure on a Sidllmfed Dp'
in a smtnbleaperimestt does nm cameamdeos~and vapm-~ ~ w~ well
,~IYT~<u
.............. ~btl ~p~-
rr n ! Tiih m:rit~~ , IDI!'bl!""'-lli.le --~ .n f ~--.~t:.n..u arul
~ non
~~-~tulnOI" --~ - -- _ '""~~--- ._
subooolecl v-J,po_r (lte ~ IJy lhose portions ,o f tbe Pl' Uotham wbieh lie in the lWo-
pllase region ad."j4taU RJ tbc ~ of ~ tiquid aSld s:ill!lrar~ YUpli:-
CuhiC' eqlWions of~ b:we tliie.e \iUUme mots.. o[ Wltich tvro,may be ~compkx. !Pby:s-
icaDy n:teauingful \'0111~ of 'V an= ra~ ~L positive, and grentc'f dian roMtam b_ Rn- m
isadJerm at T > Tr,. ~to Fig. 3.1 ~ ~ lhat solution (or V aJ any ~ value. of
'P yjdd$ ml)i Dille i.1dl rtJOI- For ~ aitiml ~nm (T : T.,. t m ol!lo ~ eseept m
lbc! ~ ~ Q.~ ~ :m: thn ~ a_D ~].to Yc. f ~:lit T ~ fc,.
lbe eq:uatitm may emitm one or line mal ii'OOIS, d~n@. on dte ~ A1.tboQJb ~
roots are CCZIJ and po$iti\.'e, lbcy are oot ph)'-sh.'a.ll)' sm'bk: ~ foe lht:: ponioo ,o f an isc:Jdta1l1
I.J.inf belween S3IID"atcdi tiqufd and smunled vapgr (UDd!l' me -"dbme~ Only {(W the YIJII)r (1(
SQnut;Jfif}fn lftl$$~ p w ~ dJt ~ Vm(liq) and V~f~1ip), sJ:ablt Wtes,l}~ lit lhe ends of
lhe tuizolDI portico of 1he true isotfJemL foJ olfxr ~s '( . indicated by dm IKBiz.olilll
~~on Fig. 3~ l l :dxn,~ .mdt bdQw 'P a~).. ~he mctOcst ~ k f.kruid ,u r "tiquirl-~
vokuDe.. :tnd me ~est Is il wpt>J 01' ""wporal.flueq 'IOlWJIIe. The lhird NGt.l}rinJ between tb
. . . ~ ~ qffJO !iignifi~

l'llm't l.IJ.; .u
!1--~-cn by a cubit: ti)idiiofi of
sm. 1bc .iDtradu.aioo of t.M:

da Vlub.eqQI.tioo. uvaal hUDC!IM cutric ~8 of
\\1111) rtD
hM beeP~- AQ are~~ of abe~
p:::. llT - ______ 81V - ........
"""=""' 9) _ _
V - b (V ..... f,)(Vl +rV + 1)
UM. b., 9, It. ~ hir::b .i n seaera:J ~ OD. lempamule and ( far mix--
ond I'] ue p;uameten
tures)~ Allhough this cqdioo IJlPUl'S .0 ~ ~ ih:xibilil)'~ illm mheralt
~tNitm ~ ofrils cubic loop, 10 It ~to~~ diN w.t..s ~loq wJmQ JJ =b.,
e-a.and -1-o~
An imponam dw of cubic eqlHIIi~ mw.lb fn.HP the ~(d!DJ equ:ltiora \\!irb 1hc a,_
' ;RniDI!IIts.:
6 =a(f)
M.. ~ AIC1dll... ,w.. 19. pp.. ~ll . 1m,At~G. d! C~Ba. Snid Jn_ K. c. 01i6 s R.. 1... ~
Jr.. .l1J'. 41-'10. AIL D.C... 19?9.

RT a(T)
p:::::!! .....,_,..... (3.42}
v .... b ( \' + .;b)(l' + O"tb )
1\?r o ~ ~ ti and u are pure 1na.mbas..tbe -il.l'lle fur aU ~~ w~ ~
aers a{T) and b m-e~ dtpendmt. 1k ~~~nee ofo(71 i - ~e
elcll equa_lioo of~~ For the 9iDn del Wub ~ a(T) ~a is a~
~dod.~=' t:1 = 0.
"'*"""Illation tJf E(JUalltJIM)f..stafe ~

'Jbt 01JIIStml5 is WI Glq~D of 5late- fw a_ -pulieular may 1Je il\ ~ by a m lD
availab1e P V T diwt.. ~For mbk equations of ~ bo'lAoe\at. a.uitiblc ~~ we U$\lally
~ fivm ~fur tbc eritiad amstu T,. ;md Pc. 'Bce.ause lbe:rcri1ical ~ exbihit.s a.
bwizoomJ inleeaion a me crilim poinL ~-e nm)' im~ me ~m~ rolllliliom;.
.aP)
(.av
.... -o
r~ -
Vt1tae me ~pt Htr demot~ t1x mtiGd poinL OOT~n1huicm et Eq. (142) Jidds ~
sioos ror both da'il-'nfn which mil)~ be eqwttedlo za'!O for p ~ "~~ T ~ ~ .. WUI v ~ Vr- .
I
'l'bc' cqwnfou of ~ rpay it~lf be rittm fnr dJt; critieal coodi1~ Th dJrlM ~c
commfure~mts~ Pr~ V. ~ T4!'. . r~~(1t-)i< :md ,b . Oftbc~ "Wa) UJtmd lht!lile~itfon
u- Q:r
dlt QJ05t ~! dimi__na.tion Vc (II yic:Jd ~ rcl.atiq ll(1'c} tmd b ro Pc Wid ~.
The ~ I& drat Pt rmd Tc ;n: USillllly more accUJroml)r krl~ than Ycv-
AJJ equiVDkot. but li1'ICIDli migbdOf'ili'anL ~ .is :il1.muated ror the van dar Waab
=
v v for- mdJ gf abe l.im= ~at die critb;aJl point.
equatlott. Becatlse
4V ~ Vc)'J - 0
01 ~:,l - 3Vc- V1 + l l-';v- vel._ 0 (A.)

IEqWt.tioo (3.41)_. WJilmll for r( T' ~ Tt .. P P.. } and a;~ in ~l)nODlial fa~ hmtot11i6:
lVt=b+-
MTc
I{C} 3Vi = ,!.. ( D) vJ =ab
(' -
- (8)
Pc Pc ft.
Sot~ Eq. (D) rora.. -~ die RMlll with &f- ()"' mil l"iq forb Bi
1
a= lP,.V,-' b~ 3""
Substilutiao for' b-in Eq. (C) allows solutio ror v~ ldc.b UD! then be. eliminated &om the
~us. fOf a iDJd b:
V.. = ! RT~ a== !!~ b::.! RT{'

.. 8 Pe: . 6-1 ~t. 8 Pc
AllbmJg.lllhese ~~ taa)' not )4eld me beJtl. ~e. ~ ~tey pnwJde n:-:mm:hl -.';d-
ucs wbidJ elk~ alnlo$t __Lhrtq bt ~ ~ ~ ~s, od ~ (in
~ m wmsiw P VT diim.)riR- o:far:n ~Of~~ fdb.tdly ~~~
$Ubsdbdinn fur ~ r,a fhe equaticm r. lfle, ailfa.1 ~'hill:ty &c:IDI' recluces it im-
i&tdy to:
7
~Iii RTc = i3
' " " ('
A L~w.JD$ frcr ~, aJIIPbcable a.Jde to all ~. res-vlts wfr_never abe purtJ.t:Mr~rs of a

llftl.i~ ~ of _ a arc fnd by itnpositim ,of~ critial ~ Dnrem~t
Yalucs 11e fmmd far d" ~of , as iDdicned in Table l .JJ. p.. 98. Unfm:uuately.
the wJ:ues so~ doDD( in ammJ ~ hb dJost ~ rwom. ~nml wJ
of 'fc .Pr., :md v~~ eaCh c:hemiealripedes ln fact bas bs fi1l value of z,. ).ltRm'a', lht: r.il
pveo ill TMble D~l ut App. B for ~1111obs ~ are almost aJJIsroalllt tbm ;my f the I
equ.atian ues gi'\ret~ in T.lb1e :t J .

An a.D ~ apptim to dx pncric cubic. 1:4 OAl:)~ )lidds e-~om for
~~~(~)r aqdiJ. Pof rtbtf~
.ll~T;
a (T(") = 1 1 -
PG-
1lti$1itSUlt b td lmdcd II) eiJlptlaltnr:s .odltfr man ~be- m~ by i.ollrodutliod a d.imte~
fnndioD tt(Tr ) 11m bemmes mtity allbe critical~ 111.m
.a( T) = 'f#a(T;)~T}
Prr;
Fnnaim ~a-(J;.) b. an empirirBJ ~. speciic lD a partirolar -~tim of I tare r(Thl)it 3.l ).
~ b - ai,~n b)':
In g artd .P .m pun IHIIIIben... ~of

pmim1ar ftP11"ion of SlUle tom ifbr ~
1 ,ll5$],.,
In~ ~ r1.
The moda:o dc:vdopmm1 of eubi~ ~uaJkms of ~tr; ~ iaililted in 1949 by public:aOou
of lbl: Rod[Ldl!Kw...S QUO~~~
I'' :;;;;; RT ~ Q~t T )
'l f - b 'Ill'' + b)
wliet'ea(T) is fl\~ IJJ f4- ~(3.4S) witba(T,) = Tr- lf.!.

95
~tal obs:c:rvation shows dw oompressihil.i:ry faaors Z ftll' diftman fluidS exhibit simi-
lar" behmor w hm coneb1cd as a funaioo of' nuiJJd rmlf"ITillll? T, ad rriil:IC< pru.swe Pr;
by ddllli~
1 p
Tra- Mid Pr=-
T Pc
"~'here dimen&iooless thennodyruunic ooordinares ~de lfle bam ror me simplest {onn
of thrz tlaeoRm ofCOT'J'UfffJ'IltWig SlmU:
All ftuilil. WftH eompanild 81 tiMt ume Nd~ tam.pera~ure and r.
rd uced lpt'ieHUn!l~ have.~ ....... compreuftlmty ractor.,
and .au dwiate frDtn ldHJ.pa bettftiat to abOutlfta same cs.g.-.
C. tt;Sf~D4dln~-~Uli (Dffelari~ of Z ba~ on ~t' lbtu~ill mt caUttt .w.-o-~n- rotl'c-
lmon~a..
bet'al:R they Jeqllire use .o f lbe 'tWO reducing parameters Tt and P~- A!tboogb these
cm:cbtions. ue. '"C'lf oeady ..~ for lite! simple .fluids (argw. ~. and ~) 5) tma1ic
~me o~ f:Dt llltlft oo~ JJuilk. Appret(ahle ~ l:fiUI.s fr--om imi:o-
duction of 3 tbinJ COIR'SipOI]diog-stata pcuW':DSicr (m addition to 4 :md Pe-l. c~ of
mo~lar ~~ die: ID(ISI popular such pa.mmNer is the aamric faavr lllt introd~Jtm by
K. S. Pitter md oowerbls.. 12
The ~t_ri~;: t\d:or for aJ pgre d:lemle.a.ll specltS is defined ilh ref~ to its "1ipor
rp~~ ~~ die lopridrm Qf IDe vapor~ of :a pure Ooidlls; i!ppt01Ci maroly Hfie.M
in the re:ci:proatof ~ ~.
dlogP/~.t. ~
...........~..,:,.......,~0
d'~(~ / T,.
wbere P/~JJ is 1be reduced vapor p~ Tr 18 lhe redu,oed tanpemmre., and S i:s the lope (lf
a plo-t of log P/',. Y.s.. lfl;.. Nole lbaJ '1og... deool5 a logaritbm to (he: b:rse tO.
If lbc t,.~_. ~of ~oding ~ wae pmully vUdllbe ope
S wauld be 1UE mme far .all pure Ololitb. lbu b obtaw:d oot robe lf\lle~ eacb fluid Ius itS
owe dmraclfti~ wJue af s. wbidJ could io princip}e sen as. a 1hird OOI'I'CSp(IOdmc~~
~ H~ Pitlu ncmd lhm ml "~pal"'"'~ dam ror ~simple Ooids (Ar.. Kr.
Xe) lie oo tbe moe 1iDe v.ilen plotted as log P,. 1ft. ~ tbm lbe line ~ ~gb
log Pr,;.u = - 1.0 M 7;. !!::!: 0.7. This is iii~Utr3l~ .in Fig. ] .,a_ Data fi1t Olhe:r il lui& define
tOtber lines whost: 1~ Ci1n be fixed itt relalloo 1[ 0 me line for lk Miple Huids (SF) by lhe
d~;
log P,i\l!I(SF) ..... log p~W
The iliCielltt:ic tttctor i.8 defined n& this diifa-ence eYZilwlled al T" c:::r 0.7 ~
[m iii -1.0 ..... Log(.P~mht:::4.1 ) (:3.48)
lberd'M w can be cktan:Ulltd foi any fluid from f.r, Pc.. aD! asiu.gk vapot~ .m~
meru. made at T, ~ 0.7. 'Values of tEJ and lihe t'riti~ ~ Tc P~, :md V.: for~ numheJr of
fJ.uids II'E listed iD App. B.
Obras proteg das por dir eitos de auto

iFII.Urt l.ll~ A~
tafillCI2UIR~ Of
tbel!td~
~ l
I
-2
'a
I
1 1
-
~..
- - 1A3,.
TJic..dt:futbion of M> maJcm iii. wlue 2l'O for qa.~ 'b:ypton. a:ndl :~-eoon.:md ~I
data yield bilby fadun r.. a1tJ chR!e ftums that am ~~ &y the same ear-
wllcft z ~Pft'd - a~ of r,. ami Pr- Thii is die basic~ 1)1' abe rollowiQg
.dr~r.ptDURiffl UttfJrelll of-ror~g SUIR'.S.
u nu1dl ha'vtnlllile ume value of c., Whllll1 campued ill 'he ume T,.
lllld r#'. hiYIIiboUI:.,. ..,.. 'llllue af z, and au devlilde tran. klllll~
... bllulviGf 10 ..,.,........ d!grae..
V8pw & ~LID Roots ot the Genstte CWk &,llfJtloll ~at State
Altholagli Mt rna)~ t ~tly tbf . dJrtt I:O(JU. ~}w ~DCftc oubic ~D of~
F.q. ~ 4l~ in JDCiice fM ll\Oft: ~Y mlved by tcer-dlfi-e ~u Con~
protitlllS tiC 'IDiiiA Jikdy 3~~ ~~~oiJcn tbet:quaBoiJ ~ ~ W ~ fwm RUt~ (O lbe !iOJu-
rum :f.t.lJ' ;1. parricular ll'OOL. For the ~ ~ ~ ~ vapor or v~llike ~l.tlllle. Eq. ().42}1ii
~ ~
mu1h.i.l'i.rl v 1 (V
~V\ol~~ ""' li.. I RT
. ~ ""J :- - ..,
caD~
ti..-...... IL-. Wlltlttn.
ll,l!lli'
-
\"';;;;; RT +b-- a(1) V- b (l.49)

P I' tV+ E"bj(\.' +ob)
Solution ror V may be by trial; iitemdon~ with me sol'"~ ~ of n ~ p.1 ~- AD
i:nitial~Y~~inJate fw v i111 lhe idea4:-ps 'i'alue 1ri1P. For rc~ dns lJ alue is :5D.bsritu1ed on
Ulo rilbt .., of Eq. (3.49). The mWiiDM ~of 'V " 'a lbc ldl tt.-n mumed to the right
side. amt 11m~ coruimles Wltil ~ ~Jwtge mv - saitlbliy sm:(H.
AIDi equroinn for Z equiwlem rto :Eq. (3.49) lsi ~med by ts.Ub!titmiil!l V - ZRT/ P _In
~ dJt ~()0 oft 'tl difDCMi . S,(~Ua~~Lidcs Jtadoi k) ~ 1bm..
u ~ lliZl bibtltnm CDiDfiUitr ~ ~ rnr ~~ t:a'I~~Do- ~~oae

r.-IJiialq , " b" I\:' QJ H II:~ ;kmr._ Jlpft ~ [~~
!be a>U.~~f wlxt.-

\Vflh.~ ~Ml(Jq$ aq_ (3-49) ~~
z-p
z = l +I$ -qp (Z +EIJ)(.Z +o-Jl)
Equatir!XIS fl..SO) a_nd. (J..S l )1in ~OtPtrinatioo \\iYJ Eq . (3.45) Wld (3.46) ~d:
_
~3.53) q = '*'QafT,.t
T,
kaatiw solution of' F.AJ1. (3.52) il:ani "'-ilb the value Z ;::;; I substituted 011 lbc rig)rt side..
~mtrula.md mur of.Z is mumed to~ rigmsideandtbe ~ rotu:in~~o~
The liiW 't'aiue: of l yiecb the rolume root mrougb v o::o Z RTI I' .
Uquld & Llqukf.Uke Roots 111 the Generic Cubk: Equation of Sflile
Sqwuioo (3.49) may be. solved for die V in~ oumaumt' of llle fumJ traaion to p'e:
V~lt +(V+dJ)(V+ab) [
ItT + bP - V
- o'T)
P]
TJtis. tqnaMP v.ieh n ~n~~ting ~ue: (}f V = b oD lht right &lilt move18f:S uptm li~Cioo 1ti a
liquid o r 6quid-fte 'I'OOt.
AlP Q&\laUDP fur 2 oqoi'ralc.nt tO Eq. O..SS) i.s obtained wht:n Bq. (3--52) il ~1wd f'oc U.C
Z in me numernror of the final tmction:
(3.56)
Par lwation a 5UU'tiog value of Z ;;;; ~ is ~utcd oD 100 right side. Onoe Z i blown. lbe
\UUDliH't)ol is v = l liTI P.
~ons of state w.bi.cb espress Z as ~ funaioo of 4 and P,- :m:: Aid m be: g;t:t~c ~
~of ~ir jaJcnl .appLi-cability w ~J .s~ 8.Dd liquitb.. A.IIIY ~~ioll s_~ ~ ~ or
put :into ubis. form liJ pro.\ide l1i genernliz:ed c:onelaDon for me~ of ft . This ;dlow
ak ~:nioo w~ ,,.,~~ fmm "'rJY li:min=d infuli'llUII!iOo.. ~of~ SIKb as
~ vuo dli4 WW,s and ltedlkbil"wmg eq~o~ wmch ~ . Z a~ funtJiic'IOS. of 1,. and
P, only, yiekl ~ corresponding ~ oorrelatioos. The ~d/Kwoo.g
(SRI() equ:aoon14 aodllbe ftmg/Robinson (PR) equation." i01 wmcb tbc:i aemtric raetuT cntn'S
lhrou.Jh fW'Imoo a' T,: {l)) a~ ilD add:itiQmil par~l'd'~ ~ thtc-p,3F~ ~l'il"
&t3ites oomllations. The numerical :m:~prneldS far paramd~ ,f .. a. 0. and ~ both for lh'*
L
~eqwmom and for lhe y.m der \\~ and Rtdli:di/K~ equiiliom. a11e ~"en lll Tllb!e l. L.
~aN also gJval for a(T,.: ~) for the: SRK mid Pit.~

T-81*11: Paramtta- ~ r. Bqluu~nos til~
rFior use wltb f.q~. (3.49) lb-rougb (3.56)
~ ofSm~ f:f(f,.) (J f 9 Z,.

vd~ (18731 1 0 0 118
"'
21164 l/8
RK l949J r,-n I 0 0.08664 1.42141 i/3
SRK (1972) SH.(Tr~ c;)t I 0 0.08664 t,.4Z1 113
PR ~ 1916) arRtTt ; ~;~ ]+J'2 ~-Ji o.omo 0.4S724 Ct30140
r
1
1msn{ T,.; m) ~ [I + ~0.480 + LS74 Qi - 0.. ~16~) ( t - T1 n)

t aPR(Tr: m) ~ [I + (0.3'7464 + l.54'226,r>- 0.26992wl) ( l - T~r-) t
Example3~9
'flivl.m that the vapor pressure oll1-butane at 350 K is 9 ..4573 bar. flllld the~ molar
'V01umes of (a) saftmlted..wpo~ and (b) satu~qlid ~e, at ~se oonditions
as gM3n by the~ RedlicWKwong equation.
Sot:uUon 3.8
~ of 4 und Pc for rr-butant- &om App. B )lidd:
Po = 9.4S13 = 0-249 ,
r 37.96 ~ "
P"'..u:uuett:r q i si-w:en by Eq. {3.54) witb n, ~ , and a ( 1'r} fm tlr RK tqmttion from
11tble J. l ~
f ~
+r;.-l /l ~
. , T.-
"""' r
rz = 0.42-741 (O .,.,.,J,- sn 6 A.ota
.DL,.,. 'J = . UIHO
QT, o Ou08ti64
Pammeter fJ is found fmm E.q. (3S3):
fJ ~a!! ~ ~(o.o:s664)(0.23 I J !!!!!! o.D26ll 4

T,. 0.81ll
lQ) 1\11: the ~m ~.. write dJo RX Curm of Eq. (3.52) w~h mut c;~pcm
or
suhstinuieo uppi"'Jlriate \~ for f and (J fmm 1Dible .l l :
(Z ~ jl')
Z- I + jJ - qJJ Z CZ + ~)

v ~ ~!!!!.- (0.831)5)(S3.14)~ 331) ~ ac-.:5 cniJ mo~ -11
1' 9.4573 -..~~ .
H ~ \~ i:h 2.~11 cmJ moJ - l_
fb) FM tbesalllta1fXIliquid. npp3ry Eq~ (3.56) io its.ltK !Dtilll:
Z :; " ~ ZmZ + JJ) ( +tl- Z)

1
qfj .
01
- o ~-~? I
l .....u:w..:.ll-1 +
z,..(z + 0 .o26-l4l
., ( t .o~2~4 - Z )
&60o18 (OOlQ
( .. )1 ~ ' 14)
'The: inmaJ *P ~ sub.stitwion uf Z = P oo ~be right side of lhi:s cquadoo. lterntin

bds fU wtn-asc~ OP ~ ~ l = 0~043) I. \~.
u l = ZRT .: ~0. l D(83J 4)t3S0) ~ 1 ~'1 1 _ 3 , t -1
~ p ~~l ~- c~~l
AD cxperimelibd ~II is ~ I '..0 .._~ fOOl ~t ,

Ru com~a.. m~ oi v ~ md v1 ~for lbe 1Dt1llic:m ofEL 3.9 by WI tom
of ~be'~ ~___tiom of~ (;Qmida,r;d ~ ;goe mJillm~ foDow -
votc,ml mo)- 1 ''fan, mm-~
&p. vd\\f RK SRK PR E:t;p. ""'w R.K SRK P.R.
~482 2..667 ~j,S 2.$20 ~~86 1 J~to 191.0 '33.3 l27.8 l fli6
1
The s ~l\'DI'!~ and lbe ~Rmf!Robimca ~were d.~'eloped spedlie11Dy for

.lifmium
wpuflli:q--u:id
Roat;s equanom m
of
a.4k~JiamiwJ1 (S~- 14.21.
~ are llwt'il! ~il)l
fatmd wilb a snfrwa:re package udl m
l~ or MBPie,. iD which itamioo is an intcgnd .,. af abe eqmuion..sobing IOlltine.
Sturtin~ vaiue1 ~ bounds may be R~~Q.um,d~ - lllllN be awrupri m till: partkaJI:r ~ of
in~ A M~ ~for $0l~ng Ex. J.9 i given in App-. D..!.
3~6 GENERALIZED CORRELAnCJNS FOR GASES
~ ~livn5 fbl_d ~use. Mflli.t (Kif.JQ_JQr ~re COITidmnm of 1be lt ind1rde-

"-eloped by Pitzer and~ ror
the rtom~Miity fitd z mid ror the &:omd \illial
codli~B.1l6
16St;c- ~- up. dl.

'Tk! oomlatioo rw Z 15: Z ~ zO+ mZ L ( 3~7)t
whele zO a.nd Z I are fundkm of tdb 7;. ami P~. Whim m = 0. ~is abe e:a~ for~ simpTe
a~ abe~ ~rm~ nnd Z0 ~ ldtt~~~l widl z. "Th1:b.g~'lizcd~
lation far l as tt funmon ro f T,. and P, bn;d on c:lata forjl;L~ .q on. byploo, ,I DJ xmon J;Jm\ides
~ fdDt~ocshi_p Z0 - ~(T,. P,). By~. Ibis mpraadS a~ ~pood~
COI'IdaD for- Z. Because the~ ttnn off.q~ {3r..f1) b a ~lath"dy small~
roth" ~L on. & amt~ dorcs Dtll i~uce laJF~~ and o condiilioo rm 1Jl Qi:ll.y be
csedi lkme tirquick lbal1ess accurate 1estima1J:s of Z bin are obtained from a d'lree-parameter
~
Eq-uation (357) a simp lillearrr:tlilioo ~D Z and m for p-'Cil wine oi T,. uod
P., . &peri1Dellta1 rd ata fm Z for DCJOSimple fluids plotted . 6> at ~stmd Tr and P,. do
iftdeed yldd appminwely SUii~f! b Wid dleir ~ rp!IOYade \U)oes ror Z 1 from whicb
the.~ function z ll - ~ tfT~~ P,.) can be comtmcfedl
. tu:_IIWI!I ~.:..,. .-._:f...LI - L ...,_... ~--~ L r Y ........._ ~ V- _jl.1 '---
Of I.U!i.l
.&..o. l!i:-
n~ " l la- Jl!n r& WDS i:l"111!.i1Qtt;. "lY!IQ ~ ~~ V<Y ~ o!IDY ~~ L~

14iU
fowd ~~ fawor. AUboop iu developman is. IJB:sed oo 111 modifHd fonD of ~ 8cJloc:..
dJClfWcbbiR.uhin cquatioo of~ it tt1ks tbc foon of~ ~ilidl ~t '~ of ZO and
z 1 as tuar:lims ofT, WM1 P,.. 1.'besl! .are gi-...eo iB App. E as 'Dbld E. I l.broogb 1!..4. USc of
U1c5r~ofu:q requires i~'" "flJcb u ~ a1 bei'inninlof Ap-,. ,F. T&e ~
m~ oormlaOOo ~~ indicated by Hg. J. ll .. a plm.ef 7!J w . rif' farm i S01hemi!L
The:~ c:otrc~Mian ~ rdliable msnlts for gesa v.iJidl ere nOl'qlOI:.w or ooly
mghtlty poiar: for tbese.. emn of no rowe OJan l OJ J pe.rcem are indiC2leel WileD applied w
t,gnly polu ~ ar 1n gases that ~~w., ~ OI"CJft can be expe.clld
1be quantum ~ {e.~ bydmge& t.limn. and nmn) do not .conform 1:0 1M !i3me
~-~ b:fmti as do~ o~l !fl~ Thir~~ by 'IM ~ ~lioB$ .
somelimes~dby useof mllllFam~m.~fir.ecrlti~ ~lm. 1 For
~ tbe quutuiJil p:s , commonly found; :in cbmriad ~'the~
equat:ions~
43.6
Tt/K !!!! I ~ 1 1.8 (l-58)
+ 2.016.,.
2{).5
P~Jtmc 44.2 (l59j
1
+ 2.016T
V.c / '-'"!~ -"""''- =
.......J IIIJI,:It -
__ S-=1.5~-
.fJ:I9
I- 2.016T
wbtRJ T a,ab-4\0iute tanpem~~~re iD bbios. Use of 1heso el/eaif't criti.all :pmmtetQS for lly
~ re[lliMs !be f'1lrlller Siflt~ lhar Gl :=: o.
1be ebubr oafiHe or lbe gmemllzed oompt::aoitity...;fErotal~Rbrlun Ui. ... dboul~,. ld

!be eomp_Je.lit~ 10f the f~ zt' W 2 t pedudes dJeir iklCUJE ~ntali:OG by simple
eqnadoos. Howewer,. we aU'I pve ~e a&;LJ~ ~ 1ro tba fdooUoo:s for a
~ m1P of prasun:s. 1be basis f tdris iB Eq. (1..38), rtbe ~pies( form or the iria1
eqnattoo:
BP -I',
z~ E+ - -= t+B- (l.(il)
RT T,.
~ J. Pt1. ~ 1t. N.. Lidlrenl'kla .a E. G. de ~ Mdu ~ o{l'f1liiJ-PlriHt! qliiilib-

f14 3d til..i'fl~ 11]2,..111 fft~ ilanP1rH.. C"*"$dll! Rl\Q'. Nll.
flr999.

Th~ ~and m ~proposed a~ ~tloo... \lhidl )lcllh v:a1 fu,- B:
B~ If'+ wB' (l-6ll
Comp:arlson of equatioo wilb Sq. .5J) pro\-'idi:s . - f~1ll8 idmLiliC3tiom:

1
z0: 1 + B()~:
tmd z ~ =:~ B 1 !!.

1,.
Second iriruJ ~ ~ f~ O(rtlUIQJerann QIJ)\. ;md mniJm1y IJ0 mJO 8 I Me f11.11r ..
00 ef ~ tem~ Gilly. Thq, 1lle ~, wen ~ted by the fotkJ inA
equ:mous.= l9-
0.422
II' =0. - ""f! ( .661
T
The ~~ rarm flbe "1lliriW oq .on bJ \1lfidit)' Ol'lfy ru lcJv,. (0 DXM~enu:e pmr.sum~
~ l ~in p~ 1k ~.diua ~odfiriaot~loom ' lbwdore ~
tml~ whe:~e z0 ODd Z L lire ,:&I .. I 4ppro:th-naldy IIDeilll' f\LDCOOM of MdoliU ~ Fig
~ 3,]4 - , lilk:u ~ of z<' tv tP,. Jil'A by Eqs. ().64) (3.65) witb -\~Ues
of z!J from lhe ~o-~i.l.ity-f.aanr ce~ Thhb H. I u:nd EJ. The tl~-o oor-
Kmti crnrer by lhm N in &be re~n above idle d;ubed line of dlt figure. Par reduced
tr:lilper.t . - ~ tb4m T,. ~ tllefe - _ oo be DO limi.w:ioo (Ill dlt ~re.. f l'<M--a
2
llDhles of t, b: lie pre.ssurt mng,e decmas \\ilb rl~ ~ A rpoim -

~e:d~ ~.. d 'f, ~ 0.1 v.~ dJe pl'tS'5ure ll"aJJP is limited b'"" the satumtioo ~mrc.3)
'1bh. v i:ndicated bJ tJ& I'Mr~ ~ uflhe.das~ ltnm. The mhmrco~ of ztao
the: cotre . ~ ~ ln \it-w ofte ~I)'~ \llitb :JD) ~
~ ~ af no rnme 1bDn 2 Lfi zO are not sigaikii.D.'L.
"''bt rdfiti'fw"e :impljf'ity ofthe ~___tad~l...iiri4_~t cwrtWitm ~mud~
tiD J"eM~nmend it. ~w, ~~mprrdll.lMS and ~ of many ~micalp~~ up..
.mmtiom e witbiu -qinu ~1lcrc it1 ~ oe dn~ 'by IP I UIJKIUill frwn the
~ ~~ t..Ue abe parmt IXJt.l'd\ation. i1.b DiiOS( xt;ill'llt'efnr ~hir
i)XCi mx1 ammHe for mghly po1nr and usociming motecuJes.

lQ]
f,~prt: 11.;t ~or~ fgt r'. Tin: \lltiato<ucflidcm ~uo i5 ~ h)'lht

'itr'.O@!IllincJ; d:IC UcJK.nk:r oon:daUm. by k points. fn the: rrcpon above fbc. ~ linr 1br tWD
~t'ionis diffu by b$ tba;n ~q,
A.ceura~e vinru C'(lef-

d:ua fo_r dlird \!"uial ax91ieieniS we far l~ C6miDOD dimn for a-cmd
~ ~~~ ~~~ ~m ffJ],' dLU:dl '\oiliial I~ do appe3f mdx
llib.Vtttwe.
EqmttiOIJ t3 ,40) 11J3Y be wl'imm:
0.61)
(3.68)
where me~ seoo~ "irbd ~~ j i$ dcfind by Eq. (3.62)"" ad tbc ~ 1iJiJd

virial ~ocffi~ ~ de6Ded :
c CP'j
c
JifT!
A Pi~~ com;lalio.n b C i5 rl'ittm:
{3.69)

0.0031]
7.W..f
r
Eqwnioo (3.68 is ruhi~ iD Z .. ond annut be: a~ iu Lbr form of Eq. (3.:S?l. Wilh
T, rmd P, ~~ snimloo t4 r z ~ by uer-llllion. An initial~ ~ of z - [ 001me right side
10 Eq. t 3.6ti) ~rnmlly kuds lll rapid ~ro~,mcc.
CIHtdlllons ot Appmrlmats Vslldlly oiiiJa lllesi-Gss Equtlllon

1
"1'h:! qutSI.ino often ~ as I'D wletl lfle idc:td-g~ ~ may be used .3S a ta.SOnab~ ap-
J'IIllxincdicm t o milil) fi1JII't 3. 15 QD ~ "'ti ~ guid~
tD
. ,
.............
.........
'I
I ~
~ -1 ~
'---
J
/
JilipR ~15: RqiDn ~ zlll~ l'r D. ~
~~ aa
~ 0.98 MJd ' -~. and d~
~~ , ~nn ~~~ ~~1e
,ltp,pmdmmioo..
,I
I
~~
0..101
(lJ 1 3
Obras pro egrdas po di ef os de au

Exarnple 3.10
Detennlne the molar'V'Jfume of n-butane at 510 Kand 2 5 bar by each ot U1e ~:
(a, The Ideal~ equation.
(b) The rg &nenlliled eompresstmity..faetor eoti181iati0n.
(C) Equa ~ (3.81 ). With rhe generalized correldon far B.
(d) Equatioo (3.68)1 witt; lhe ~ ~~for iJ and t.
SOIIdlbn 3 ..1Gr
(a) By tbe ~J..p equation.
RT (R.l14)(510) .LIY._ l ~,~1

v -p - -
2S = t~.J em JUI.."IJ
fb) Prom 1tbe valtt~ of f c: ;md P( ~eo in Table B.l of Af.Jp. 8 .
T. :: .31{)- -
" 4l5J - t200
lnJeqJDladup in~ E. ~ aDIJ R.l dim provlde5:
zO ; 0.8615 z l :;::;; 0.038
Tttus. by Eq. (.lS1) wi111 Ul = o.~
z EJ + C'l ~ == 0.865 + (0310)(0.038) ~ 0.81:3
:=
If' z 1~ tho. Kamd~ aam. is ~ z. - zo ~ o~~~ 'Tm,s ~~IE

!;Oln~lfms"saams c:orrela:boo ylekl8 V 1,467.1 ~m~ mol-~~ wbkb 11:, tbaA
1% 1ol\'er manlbe ~ue .gjveo lb y lhe duee:-plmml:eUI' e~
((') Values j)f afl ~ B 1 .ue gi\'CD lb )1 ~ (3.65) and (3.~
B 1 IK! 0.059
~ {3.63~ wtd (UI) ~hen yiekk
j = lfJ + MJ1 ~ -().232 + (0.2(1.))(0.059) ;e -Q,l2Q

. 0.~,
Z = I + (-0.2211)- ~ U.819
l-2()0
from iit'bicb V ;;;; 1..489.1 ~ mo51-l ~ a wJoe less d:tm J ~ higher th:m that 11\-en
by the ~ility-fanor (;O~!Af~

106
cfJ- O.Q339 c = 0.0)67
BqaruHm 1(3.~!); Ibm yietds:
C a c!l + w C 11 = 0.0Jl9 (0.2.00)(R0067) ~ (UJlSl
Wilh Ibis \\~of i:. and lbe value of B t-rom fP311 (tJ, Bqj. (3..68) ~me$,,
z ~t ( ()J..z!O) ( IQ,659 )
~ .200Z
+ (0L(W2) ( Q_6S9
il.lQOZ
)2
, O.l2 1 0.0106
Z c~. -- + ---
Z zl
z ;;;; 0.876 and
T"be vatw:; of \1 ditfco &om tbatJ af pad (c) by abxd 0.2"1P. AD ~arud
\atue for Vi~ J.,.;l8():7 ~mol-l. Sigpiiimodyr the~ of~ (b)~ (cit~
td' tl1'e in1~ agree1nenL Mumal ~~ m lhese mntfllions is~
by :H~. 3. ~~-
Example 3~1'1
VJnat pr$$5Ur~J rs generated wher\ 1( mol) or 'm ethPit c$ ~ ma ~Unte oJ 2(ff)l
at 122r F)? Base ~cafculatiof'ls Ofl each of a. ~ng:
1(a) lhe ide~ eqlJmion~
1(b) The RedDchiKlNOOgl equatkm.
(c)A~c~.
Solution 111
fa) By dJe ~ru~lr-'& eq~
n
.. r::::::l
RT
~ = (0.7302) l2'2 + 4j9.67} c
, '
lJl.-.(aim
)
v 2
(b) ~ pre.~~~ gi~a11 by the RniJkbiK\\K'mgequatkm is;
P;;;; RT _ a(T~ CJ.41)
v ..... b V(V+b.,

107
Valllet ofa(T) i\Jld b come &om Bqs. {).43l aDd ().46).. ,.bae a(T,) c T,-JJr- in
Sqr (}.45)~ With values of fr ail1:d P~ from 'Tasbk 8.1 ~ 10 (R) and (mml..
T,. = !._ = :531..67 ~ l b91

t;. 341.1
(J.695}~Ul(O~Tl02}~(J4.1~1) 1 c:l '"' ) ft~ 6

4S.~ ... 11:.:1 ~mm t )
b ~ O.OS6M tiJ.?.3H2 )(.34J.I) = 0.-47 "HftY

45.4
Substlturloo of~ wlues inm ~ R~WCDJ c:Ql.Wicn now )idd :
(0,1.102)(581.61) 4,3.94
p c::. - - UJ1.49(imDI
2 - 0.4711 (2)(2 + 0.47&1)
(C'J' ~ the ~__xe iheR is ~ liu: ~ COID,PRiSilibiti\y.J~ COJ'I-

Iation is the proper cb rice. In tlht' absmce of .a kncn\'D value mr P,. m i~
potedure is based on the fioUowing ~~
ZR T
Pc.- ~
Z(0.1300t(SSL67)
~a
J
l ,.t
z
v :2
keamc P ... P~ P' t:=a 4:5.4 P~. dDs equmioo
0t1e now~ u ~ Yttlue. Jw Z, say Z e t 1.ibi$ gi\~ Pr ! : 4~~ ti1ld

alf~'l a DCW value- gf Z [D be colalhned b)' Eq~ (3 37) from -values in~
1
~ nb~ E3 and &-t ill tile redtntct ~ orr, =

i..69S. ~'ilh ~ ocw
' -'illle o Z, I ~r '-~U-e ,(llf P, ~and de: pmcedw'e ~ 00
:&igtifl~ ~~(ltt fmm oot stqJ to dm ~ 1'bt! bat \':l<fue or z fuund
iis 0.8.00 .P, -. 4. 14. This may be aJilfirnled b)' su.bstiwtim into 64 (3..571
of uc:~ b 1}1 ~ Z 1 from Tabks 6.3 and B.4 interp;jamd at P1 ;:; 4.14 and
T, ~ ~ . 695. \Vdha>w0.012.
z = zO +wz = cum-7 + (0.012)(0.258) :c 0.8'90

p ~ ~ e (0.890)(1'.7.302)(SlU.b1' = 1 u _ftfa.tml
~lf 2 7~ - J
Bec:mtse abe ac.entri~; fllnnr is .tmall the~ mx1 ~pat;amr;tct tv~l

h)'~ Jndations In' litde dilf&eut. Bath me 'RedfichiK\\"001 eqDiUion alld
lbe ~ oom~biliityfactmr ~give ~CIS dose10 lhc e.'q*~
i1:JICfltll ~dur- of 185(Btm). ThLt i<bl...p~ equatioo yi.eld5 a. remit that is high ~J'
14~~

108
Eumpte3..12
A mass or 1500 g of gaseous anmD\la Is comained In a 00.~ vesset immersed
in a constan!-tenrpei'91We bath a1 6611C. Celeula1e 1he pressure of the gas~
(S} The ideal-gas equatiolil; (b) A geooraimd oorrela.tiofl,
Solution &12
V .. -
v r-ll -
V'
;u
~(XX)
;;;;;: W ~021.2cm' mol- 1
n m/ M st.I0/ 17.02
(lJ) B)" dJa i.de:LJap equation.
p. = ~ = ( 3.l4)::l;;'J,~ 15l =27.53 bar
(b) Becao&e the Iedooed preswte ls low r( P, ~ Z7~]1ll2JI 0.244),. dirt .8Ftiet-
~ ~t:nl oondoo ~k151.rf6~ 'Vat:ur:.s of 8 a.lld B ~ &(\'eJI
by 0 .6S) . (3.66), with T,;:;;: 3JSJSJ4~.1;;:; 0.834:
~ into Bq~ (].61) with tW;;; 0.253 ~
B- -(lA82 + r( O.l$3)(-0.232) - - 0.54L
U(8li4)(405.7} ::: ~ .
B
= Bltlc ; - (0
P~ 112.8
_ l
8 an mo
1-1
16 1
Scd\"e Eq. {3..13) for P :
p !;; R1 .; {13. l4){331..1S} ; _ baJ

23 76
v- lll 1~021, .2 + 161.8 -
An ite:rW'IIl! soiudoo is nlW I"K'!CeSSMJr becmse B irs ~1 of~ "'.be
~~ P ~nd toi~PI~oiPr ;; 23.76/112.8 == 0.2lL
Ret~ to Fag. 3.14 conflnns.rlbe > suimbiJiiy mlbe.~~ \iria~~
~
~ data indicn~ ttw ~br ~urr i 23Jl2 bar 11t tbet givm oond'i-
tioa& Thus tim ideal--gas equtioo yie:lds an Wlb-wm bigb by aboo.I I~. wbe_re.as
die' \ifid~~nt~ca p
iim ~in ~:shlmial ~ vri1b ~
~ ~ 1hwgh,munania is _a [pOlzr moleenle.

109
3.7 GENERALIZED~ CORRELATIONS FOR IUQUIOS~
Allhougb llhe II!IOlar \"{}IWJ~CS of liquids. e&D be ~~ by me:ms of ge~ cubic cqUia~
bn~ of Sitale~ rifle ~ 1ft aJitm JJ01 of mp W:CUGICJ'. ~. diS ~~~T ~
iD:J~ dab for ~l!d rytui&. and Fis. 3.1 J illllm'alt.s curres ror both liqbidi m1 pses..
Wl.oe8 for ibofb phases 3ft pnwided in TnbJes. E.l duoogb E.~t KeaJIL oo '\W. that this
co~Oil :i tn(Xt\l ~~e f<K ~unpor~ a:nd ~li;htl)' plbt H~ .
lo ilddili011. g~d e om are available lfar lhe esUrnaft~ of molar 'r~ d
~~The~ ~m. ~'CI by lR:.cbn.n iB an eunrplt_:
\.'im ;;; V.r zil- T,~ (~.72)
Analt~ fmmoltm~ ~Q.Seml:
z;QI == ~zH+d - r,~:n (3.i3J

Tr ~
1lie only dsa. required are me cruicat oo~timtS.. .fJ\"eti lin T::tblt B. i _~ts ue ~ acru-
natoI or~ ..
Ly~ ~~nod H~n da'elop;dl a twi)-~ ~ir ~
ror
ooJMbrioo estimatioo of liqWd volumei. lt p:rol4du a ~oo of~ density p., as
a runetil)n o1 ~ ttm~~~t Md ~~ B~ definition.
P vi('
p, e .,. . . ,. -. ....... (3.74)
h \'
wbe.re h is lhe ~ky illlbe trlllad palm. The~ ~oicm ~ hown by Fig. 3.Jo6_
'Tii.!- ~- . 11- __ ___. A:.- b... b L 1 '74) ~
.IliA- tu.e~ may~~ or.ru.~-"'' ~'1.11 llilllli c... .. ~.or .c-._:...-; -~ 1-W...:.Ar __ L..-.,;.., ~lit he
~~~~~u.MtOO Vl w ....~ ~.J!f~" DL
wme ar mt cnlical ro~ ~~ rfmowo_ A berre1 ~ is. to mate- me of o ~ lnawn
li~d ~Jume (sta.te J) by the i&olily.
V2: = Vm p,.l rfl.7S)

p~
vl;;; lleq11iml volume

V1 ;:: ~'11 1r.Vhunc
~ IJr: ~ ~ <kn$iti6 fQd ({Q(QJ ,..,, ~-16
Thk method gi\te& pod res.ufis mdl ~ onf}1 e.'tpeti.ioent:d dQm t1mt are uwal.l~ .a\~le.
FiJurJt 3.16 m*o dc:lr rd~ iocrea&ing e~ ol bcJtll ~ure ami prasure on liqgW ~
my the crilia:~ point . approached.
c~ btlle moW dmdri~ as fll.fiOtlOM or~ tfJit &ft-,m for Dia.fi}' pdR
liql[icb by D3nben mdl CJm'iorkm..M
:Utt. G. ~!. a-. ~Dew.. ~'-. W. s4-SIL'1, 197Ct

"FFt. n. pp.. - 19'1t. ret 111 ~ 4'1f 2'1 . . .~
n ,A.Il... ~ A.~~ o . ~Jm. ~ lbcrrnlld~ ~ufPIR FfiOO~

u~ "~ t"-tlf..~ .s.. ~ <~. J9ss..
14-r. E.lbvhcn. R P. ~ H. !!.,, Sibil d C. C. Silcbbi:m. ~ ~ ~ P~ u/ I'Wr.
Qmai~ &!fa r(~.'fH)'b & ~!IDs:ml, P/t. t:mM JWS.

ExamP~ 3.13
For a.rnmoma 81 310 ~ estimate!the density of.:
(a) The satul'818d liqukt. (b)~ The liquid a1100 bar.
SOiut1on 3"13
~G)AppJy Eq. ().72) _JUte :~i ~ fr == 3~0/40.5-7:;;; 0,764L \\1t(b 1
Vr -11.41 orul Zr =0.:242 (&om Tiible B. I).

~ ~ Vt"~I -Trlf' e 02A-1)(U.242)~,!/' ~28.lJcor' mo~-t
For-.;~ die ~rimenlal \-.dl:le B 29.14 c-~ mo'Jr 1" a 1 "'I! di~c.
100
f, : 0, 764 P,. :;;:; ll2.B : o..881
~ilnt!P,g !he ~ p,. = .1.38 (Jimw Rg. l, 16)., ~ Vc mtOEq. (3. 74) gh-es;
v<' 72.41 __1
v = -Pr = -
l-.JS
= .10.45 mo~.-
Q.'l'f""
1

lll
In comparison with the experimental value o.f28.6 em' mm - 1.11m JOUh is ~

by6..S~r
If~ l$tlll1 wiW td J; ejq~triDIn.tal ,.~of 2.9. 14 ~ mof"' 1 'f or ~IIJB1td] liquid
at 310 K. ftl. (3.75) ma.y be ad. For me ~ liquid t :r, ~ o~ 764~ p,.. ~
2.34 (from Fl~o 3.16). Submtutioo of known values into~ (3.1.5) gi~:
Y1 ~ V1:: "'(29. 10 (~:) "'2!1.1\S r:nrl mol- l
'11M~~~ is in~ ~t wid~ fhe ~~td wluc.

Dit'eQ ~ ormr.- ~lei'' oomliJilm w.m 'W.hle.s or zC ad zt m.
feiJJOialed from Tables E. I iUid E.2 leu k) ;a, Q'l of 33.81 ~ i'l\01- l., ,.mcb is
si~Jt io e:mw.. DO<loobl ov.'int ro lbe bigblr ~ ~re of aml'Dtlftia.
PROBLEMS
l.l. ~ fhe valume- upwRv.ity and dte isotbemW ~ililf ~ ol
dEmit) p and il$. putial drri\;athu. for wattt at ~(yC ilD() I b3r, ~ ~ 44. 18 K 1r
bar- 1 To what pressure m~ wMef' be ~ m Slf'C to dwlgr ilt5 ~by
1tAt? " _ il)e ~ ,r : ~o~ or r
~
J.l. ~lb:. YQJIBlJC ~\il); jJ apr) i~ t't'bll~lilf K &pend on. T mid

p . P'rove ~bat
wf.lefe V ' molilf or ~ ~lume. Yo lbe h~l molu Ql" lpedlk \-'Cia
tUlle u m:o pressme, Qnd A and 8 pusilive ~ F'md an expnsioo for dle
i.wlbe~ cxmqJmsilnlity ~with tbU ~
<C
il c: ~ .................
V ( P +b)
~ r :md It :we fimcQ(lBii flf tempe~ oa.Jy. If I ka ~~ ~ ~

i!Oibennr&lly and revenibly fmm J to 500 bar at PC__ how nmcb wudc is n:qoin:d1
as
At. 6fPC b ~ 2., 100 bar ll!ld c ~ 0 . cm3 s-w.

H2
16. f1ie ti~ .0( Jbrllid ~ ~blod. ~a rnccbtbl;' _n:y fC\-ersiblt. ISO-
~ dwlge. of 51atE: at 1. !bar duriftg wbicb dJ8 flmlpel'llure erumges fmn1 o~c m Jo!i'c .
~ ~ v~ . w~ a.
llll' ~ :md ~rr. ~~-a fOlliqWda_rboc ~emtebbide
u I bur and 0 C may be~ ~at: temperature: {J : J 1.2 Lt:J- 3 K - 1
c~ : 0.34 kiJJ q:- l ~,;-J fmd :p ~ I590
I m ""J ~
1 '?.. A ubs.tanee mr wlrlcb is a comtmtllllllagoes ;m iwllBmal.. Jllif:!dmnically m~ihk

P11 from~ mll!t tP., Yl1) 10 ftld -.__, (~,. Va)... ~ 1' itmobr "lltume..
1
(o} bmiug Mth . . de6nition (){ ~t; .. sbow ibat 8: pdh of the pmce5lS o ~bed by:
V.;...:. AtT"'J e,x;p(-KPJ
(b) Detem1ine m Ul't ~ whic:b gr.teslbe ~work done on I mnl Of

thb ~nuu....- b$tanc:e.
3.& One IDOJ:e rof :m ideal ps with C:p :. (1'(2.}B and Ct. ;;; (S/ ZJ R e.~tpaods from Ps
a,bar r 1 ;;;;;; 600 K 10 P't, ~ l tw by each of lbc roOo~ paths:
(a) ~~ (b)Consnmt~ (,r) A~y.
~~~~~-.a~. cdcubtG W, Q,. 4lJ, and AH lor exh proees$.

~left exh [(lillb on a~ PV diagmm..
JJl AnickaJ~iqjtfaf)~ il.160lKand 'iObaf~nili;ur~~~icaU)! m\~bk

eyde in~ closed $em. In step ~l.. ~ ~ ~y to J tm: in ep
23, ~ ~ m ~ l'iitittDr co 2 bar~ in Mep 34. voh;ijn;c de~ ~
CQD._'QDDf ~ and in ~. 4 ~ " (be gas ld:W'IIS adiahatietLny tg its i.n.i.rud ~ 1'ae
Cp ~ (1{2~RdCv ~ (5/l) R.
(a) setdt lhe cyc;fe on o P JFd~

(b) .Delmniw ( here unknown) bod~ T and P for ~ J~ 1. 3. and 4.
<d {ldcllla:le Q, W. 411. ~ 61i fu.reacb 5tpoflbe q le.
1.10., An iideal gn. 'c,. c::: { 5/2)R' mt Cv = (3/2 R. ~ dt3ngtd from P ~ I 'bar and
v: : : :
12 1o A:= 11 bar aJJd, v~ ~ 1 m3 b)' tm ~ JIDft"'Jb:mlcnUly ~blc
~
(a) flOthamali eornpf i~

(b) Adi:abntic ~an ltlllowrd lJ:y ,cooJing w ~~Oft!.
(e) AdiabaDc mpms;si.oD folkN"ed b}1 ,eooJi:nJ at c:oostam vohlmie~
(d} Heating al cooscm TiVlwne ~ IJy .eoofmg at CQII5Itml ~

Jl3
(~} CooU.n8 ,at OUMWtt ~ fol.lm\"'41 b) llcminJ .al coosmm \-oJumc..
CD~ Q. W AlP, and 4 .H' rl;I

~(If dEse ~ ~d .$h.ldllb: pt~ of
Cl!ll processes 00 Q iingle p v ~
l.ll. ~ e:nvi~ ~ nik tlTt d:: chmtderiza am Loeallwiatioo ,of temjJCUIUR

m
'W'iib ~~ ~.'be em~~ ~ Annosphaie pm.me '\1lrie!. wilb em'i11km
ctc:cording to the by<~msimdc formul~t.
dP
h - -}Ap-g
~ ..\fl i mol~~ p molar cbsi:ty. Ad ~t.i5 IS kal ~oo of IGWi~J.

Asti.ume llhallbt adnuwpheR.l!. M 1deal gi6, ~itb T ml4red lD P bj - fiW~~ ror-
mlda. Eq,. (J..3k). De-.'eiop an ~expression fw the envirouromlallape rate inmtmon
to .J~., s. ll .. tad I.
3.12. An e\~lliUed tank is t\J1ed 'With gas from ii Jronslml(~ line. Develop Ml apms-
~~lb(:.~oftbc~iP~~tQ !fM~T' oftbpsm
the- tirDI:.. ~the psi! tdeal ";tb ~. hat cap:uritim. and ipc.R btw: ~
~ t:k ~~ 8Dd die Wlk.. '-ta m:ll ~ b.~ or p.R'Iiblem arc: rmd:d
m&.2J3.
l ..ll. Show how Eq-- (3.36) and (3~.31)

reduce m l.be ~ ~ (m l.be four
~- ~UQ or & ti51td rdtlcrwina [4. C3.37J.
114. A Wlk cfOJml \'ik~J\C ~ail 1ir 2!jBC 4Pd lOtlJ lh. ~ NDk i <;'O~td
to Cl C0mpl"e5led..mr riDe wbim supplies air at fbe aJD5Wil amcfilii:ms of s...c and
1,500 tpa_ A \'81\"e iA I~ 1~ i Ctac~ dttt air ~ s.l'owly bU:Olbt ~ant until
the~ equals lb:i ~ JBSWR If b ~ occurs sJow1y amup lbat d.e
"-u_..-...
it~n-
~"' . l"--
m m.
_ a. ~
_JJii! ,._l\..
!,nii . 8__ "~li""
-l .QJ L """" :ntn
'-r DOW' __ lzat 1'.~
. dJ -t u.UIY!
~ lh _e ~IA
,
lhooc... -~
air to be an idt;d p for wbicb C p ~ (7{2) R and Cu .~ (5/l)R .
l rL5., Ou 11 cooscmt T and P is ~I in a supply line conn:ectm thruufh a \"ahe tD a

dOiEd tank coatainiug the SaDK ps 11 a h:M-.:r ~- The vaiWJ ~ o.pcoed to allow
t10W' f)! pt'l imo me tllilkt -nd Uw:n is s'bot apirn.
me
(tz) .l'lc:vt.lop 8 gaJer&J equatioo rd.sli.Bg n v aod 11:',, moks r~nr IIJ!liSS.) . p in the
umt a. thi: beginning and end or me process. m propemcs u.md lll~ the
iotcmaJ ~nergy oi'" the p in du; bilk t lb: tqimri:ng aDd end of lhc. ~. and
fl ', the~ of the p mlie supply Ll:ne... and to Q1 ~ 1ea1 t~d to the
~ in lfle mot durlDs die pmeess.
(b) R.eduee tbe general equmon t!D iJs ~ farm for the speeml ct.iil: of an idea1
fSll$witbCOC~~ - -'
(r) ~ i!Cdu~ 'lbe eqtilllioll or (b) fbr me~ of,.. ~ 0~

(t/J P~~ dlo equation of (e) for eM~ in W!Lidl. in llddl~ Q = 0.

114
r(.er) 'J'b:nting qitqpn M i1Q idc:a1 gat for -' C;p = (7/2)R - awl) ~ ~
ecpultion U) me case in whicb ~ study mpply of ni1rogeD 2i c and 3 bar ~lows
mto an ~IIC\'Ittof ihWk of~ 4 ctk'ul* tbe JnOies of ru~o tNl
ft09I lntD the: tank to~ b ~ fOI' r" "o eases:
I AmnPe 1bat oo heal low ftom the
y 10 die taok OT ~Jb tho hiJlk wal!l&
2- 11m tank wci&bs 400 ~ h ptrictdy insulalat ~~~an mrlial ~ratul'e of
~bas a specitie heat oi 0.46 tJ tg-1 lK- 1 tam! is~~ tbc &a$ so
:tl~ to .. :Bil a. ~JC of tim p io ~lank.
J-16... De\'eltlp .eq,~ wbkb mq be iioh'ed m ~ me ft:nallrempetUIIlre u1 th~ gas .e-

nainq 1in tank aft" die 1m la!n bled fmm a:o i.uitiW IPR~ Pa tg a fiDW
~ ~, ~ ~ m m~ ~~wn; ~k \--ol~ be3l Qii~ty of
the gas~ totaJ beat Cllpi1dl.'y ,o f lhe oontaining lank. P1 and PJ,. .A.mune tile bilk w bt
always at dle Cemperatute of dH= ps Rmaining {n me~ and dlt' ru_k robe~~
imulated.
117.
_ A..:~~~~
"'-~ ~
. .g- tank. willh Ul \~of. 4 I'!PI~
...~ i ~~. diri~~'-
.....~ ~,...,., 'WO ~~IP
..... -181
hy a thin membrane. One side of the memJmme.. Jqllesenting 113 of tile.~ oonmin8i
~ Jl$ at 6 w
Qd ~w~ ~ lbe OiCixl $Ide, ~~ntlng 213 of the l*Dk, i's
evxwned. The IIH9Dbmne ~ i1Dd ~ ~ tiib me. W1k.
(a) What u * fi.fiaJ ran~ oUbc p? Huw lll.1:lrli 'UiWtk is done'? h tbc ~
~Je?
(b) ~a w.v:iibl~ ~ by ~illdl rtlm gas am be retumed to its initiall Slate.
lltiniil' m~ \\xmlr .is done
)1.'1& AD Hal ,gas. iaili.ally id J(fC =nd 100 kP".a.. n~ 1be foUoJAing c-)dJC prt'i(~
in .a.dO\Wd ~
(o) w~y ~blc~,d fi:tMcom~aa~ )to5l kP~
lb!m cooJed ~ a col'litmt pressure of. .500 klP:l1 to lO >c. and fionlly 9p3nde(l
~to its origioalstatc.
(b) ~ ~ rlntVe.rst$ ~,., tbe same thanps. 0f $18tC. bul edt ~ is rllCVeJ'5'ibl~
with m etficieocy of ~ compared ilb dte ~ tnecblmioilly re-
,ctSibJe p~ Nm.r. 1k bn'tiaJ mp mn no L01tpt be ad.iababc.
Caku1at.e Q.. Mt., AU. Wid AH for cacb 51ep of d. proceiiS and fCJI' me cyde. Take
rCp = Q(Z)Il and Cv = (5/l)R.
J..tt. 0.. eubk mdtJ' of an~ ut tiOO K tBnd JiCDl tfa ~ IJJ lb~ li:m.e:5 ~15 initial
~a$~lS:
(a} By DX.iwlieally ~ isothe_rm:d ~~~

(bJ fty ~y fO'>Wbk. adi.mtie process.

(d oy ap Mti~~twic., ~~Pille mwbicb ~ u apinM ~ ~
pressure of lOO iP.).
Fur each .caw; catculme me final temperumrc.. ~ wxllbe: ViCft dot~t: b~ die ,~
c, ; ; ; : 21 J mol -~ K ~.
,1.21. OUt: mo!e of air. ioilially at 1S(rlC arul 8 bat" g___~ die Ciliiowifii ~
re\wslble ~K. )[ re .lpmdi j.DJleiJD3Dy tOri ~fe sud~ Wt whei1 Jt ' 6-ooied
at ClW'Clnl \'Oltunc tO -SrC ~IJ final ~ ~ 3 bar. A~miq aiJ i5 an idcall p fm
whim Cp = f1fl.>R and Cv ~ (S/2)R. mlctliD.tc: W, Q, I.IU, :and AH.
3..11.. AD Ptm .[:IS ftOW5 1bro~ a .00~ '1:\lbo at iteady smm. No fle.at hi added and
oo sbali ""\lit ~~ The ctem-stdiottal arm of ~be cubt t~ with ~ad
l~ha atWiCS the ""Cwml)' lO dm~ Daaiw: tm QUiltioo rfdalin,g. tbe ~ tD the
Yelocil' of me p.. If~ m 150>c 110W$ put 011e ~of IJlttllbo nt a ~-doci'f
or l.S 1D - I .. 'ftiud is iU. tmtpGnture at ;motbu secUcm \VbeR. .iii vdoeity is 5) m ...) ?
let Cp == (7/ 'JtR-
~ One IIDOie Cl! an ide..1l ~ ioililalfrr at WC WKI J bar. i1. ohau,ged ro 130 C omd l&!bat
by thKe diifamt ~Y revmfb1e prt'IC'eSSe
The- firs:l he=nrd at oons.\l.n' vo1umc ~ its ~ is 1W"C; Olen it

is~ ~lly umi1 _its~ i LObaf.
- i- .!llliCI'I-
Tbe. tr.-:15 a-, ~~- ~...A . - h'iliWlf!tlionl lliif'lllio~...- .o!il .:-. t~nn""'"r.Jhll.._ J~. . "'~ :
I!P'YI~!i'!"'U r"_,.,....,..,..lQ},\g IW' .,.....::;::;;ill!iO.::nrH,.... I5 ~' ""'- !li.JIIi'll"
ris CMipessedl ~D:y ro 10 bar.

1"bc gr~ Hw fln.-t ~ ~~y tQ 1.0 txar; rbm it "'heate-d at co~
pieS.Sliiie to I 30- C.
CaJcul!ate Q.. tt. At l. ami A H irn eacb case. Tm Cp ,_ 0 /2)R :md c,., :;;;o (:5/l) R"'
Allemati"-dtr. ~ Cr = (SJ2,) R dd Cv ~ (3n)lt'..
121 Om! mota :an

ideal ,gas. initifilly m 3tf C ami I bar. ~ abe fcdlOwiD,J rtDedJan
it.illy ~~ ~ k is.mrnpmssr:d ~Jy JO ,&~point $liCb mat wiMo k is
hBated al eoD5Iam voh.lmr: tD IlOPC irs fiJ1:1:1l pn:s.sure is 1:! bar. Cakuial~ Q, ~ AU.
uoo A .H rm lbr ~~Take Cp {1{2)R m:xJ Cv ":"" (5/Z)R, =
334. ~~ ofitWO tep ( I)One mole ,o fmatT =lOOK aDd P bar is =we
cool'ed at co~ \rot-ume ro 1' !!!!!!! 310 K.. (l)1"Thl!: .U 1$ dJm hcakd mc:O()~ ~llfr
WJtil its temp!ra1UJ!e rcacle5 800 X. llf dlis t~ pwee:s:sc is mplaced by a sin!Je
1
~~on of i~Jc.:iitr ~ 800 K OJJd 4 bit tv Somt; 1imd prtssurc P, whM

die Wl!'tle of p that rnaka lbe ~-k of the two~ lhe. a.rt'ie? Assume~
t(MfSihility and~ mas .n ide~~~ wid~ Cr ~ (1/ 2)R and Cv ;; fS/Z)R.
~ A. sebemc 01 fimliltg ~ mterna1 volume v~ or a1P "' cylinder,~ otme foDDw"rftl

~- 1be cylindct fillpi with~ I*$ l(J a low ~ P1 m tmd (;(1Qr~JC1Cd ~ a
s:rnaU Line and! veilr"C to ao C\\'aeualal~e~ uDt of kllown vnlllme '1.be ,.'ldve Vl .
116
is opet1ftl. liOdl s~ flow~ lhroo,gb the ltine into Ole memnre tiint. After me i)!'Sicm
mtums to 0$ init"a1 m~ a scn.mh'r ~ 1nlruidiiCC'r ~a Juc lor
ox- prq..~ cf'tlnge .6 P i.n ~~~t cyllndn. Deretmint tfiC cylinder ~i,lme v~ fTOm lbl!
(Wlowing dala:
v~ e 25fi 001,~
J:.Pj P, r= -O.C6l9.
~ A~~~ oom.-'QOd~ eyliDda u-~ with nonoonducting. frieti01r

L~ flootin; pisrun w,bk-fl div~ the ~~ iBID Secliuml A and .B. lil'lie tvto bft':-
'lions ~ ~~1 ~ of air., inilKIDy ~ tfJc ~ conditions. Ta = m k a.od
~ = lt4nn). All ~{.';1) lbMting danmt :in SK-Jion A iJl. ~~ and rbe :rir tcm-
~~~ ~ TA iDSectioo .4 because.ofheatmmster.. ~ndl Ta in Scdion
B ~of~ ~~sitlfi lb~ ~ .. ow.tJy ~pi OD. 1'AC air~ an ida~
gr w"llb c P 111.,. and 1m nA be the .DIIIIftz ol odes or m iD ~on A. For me
!:;
p -~~onoo ~ mYing of'.qwmtiti

1fn) TA . Ts, and (1{111f,. if ll(fimd);; 1.2S(~IIJliJ
(," ) Ts~ QJJJA,. and Pl(k\Et if TA - 42,5 K..
(d T4. Q/RA md Pf~ if Ta ~ l25lt.
(d) TAt Tas rnd .P~fittaO, if ~Q /nA ~ l kJ mul-L.
1
121.. ODe mo1~ of ;m ic:leal &as~~~~~ W'KI~ocs- 411 3:rbiiara_r, ~

iQII)'~~- Show ~t:
II (-
A U = -. - ,A PV )
r - ~~
J.28. ~ 1D ~W fw (be YiOJk qf ~)w)ica__lly ~"e~ ~ ~CD

of m ad of a p from m iniliai ~ore P, La ,. frul ~rt ~ wbm tbr equation
,. tit~ I~ -.iria1 apamioo IF..q. (3. J ~l] 'tn!J'IcatW ~
2' e l - 8P
119.. A oet11d #fl.S :i ~bed b-y tho~ l'tf ~:
i' v .;;. Itt + (b - !!.._)

R-T
p
~ ,fJ. is a~~ a_od U , a ~1iou ofT ooly. F\'lJJ tbq,~determine ~icms

l\lfU'.Ie: i~ (.l~ilUy ~and (be lb:ln'ltd ~ ~lii.-i~nl (tJ'P/8TJr--
, ~pmsi_i s!wdd wmaiD oo1y r. P. e. d8 /dT. awJ ~

117
Cakulare the 'Aut of ID;ldlanieaii.Y ~ibl~ ~ ~ of I mol of

methyl~ dtlorid:e from J bm to ss
bar at -~~c.. Dase wc:ubliom Oil the foU.owing
rollD,S. gf the virial eqwtioo;
13L .t\Dy ~~~of state valid fot [5(-~ l'O rk Jtf0-pi'S511~ limit imp_lics a (uJISd of wfrial
ooeffiaem. SOOw a.at tbe ieeOOd .:md_ lhinl viriw ~ ilnpfied by the ~
cubic tqoltioo of o. f.q. (3.42). IJ'Z'.:
B ~ ,. _ a (T )
- v R'T
S~ize me m;~~ll for B to die RedlidlllKwr;mg ~ o 5lalC. ~ ~ iD ~
dnced fonn+ imd compare 11 ~ricidll)' wtut tbe ~ized ooaeJation iiY B rw-
~iu;qJlf; fluids. ~ (3.65). ~u:55 what JtJg fiud
J.D. rCalcolate Z amd V far dhylene at :ZSCC uml 121bar by the. following eqwl]OM:
r(BJ The tJlmCate.d,mal equarlon fEq. (3.40)) idJ ~be fot!bwml uJ!Qim_mt:IJ values
of ririal ~~Is:
6 = -140 em :i.'Dol-] C = 1 1200 cm.6 mo~-J
( b) 1ibe ~ vlrill eq!JiUttMI [F.q. (l .J8)), witb a \-aloe of B from the ;genaafized
lPi1uJ" OWKl~ [Eq. (3.63))-
(.t ) The ltedlk'biK\\1mg aJUn'lion.
,{J ) The Soin~lidtJiK,."Omg equation.
(d ~Peo~ ~.
3.31 Calcuh.te l and V far e(h:me a1. SO~ and l 5 bar by ft. folowing eqwniom:
(a ) The ~~ virial ~uarion [Eq. Cl~40)) owilh che f'elkrwin1 eJpm~ \'llloes
of virW eoetficiena:
(b) nt UU~ Wfial ~ P!q. (3.31}], widi a value of B lNiu me ttrErid~

Acze:r ~n [Eq. (3.63)).
(c) ~ B.cdliebiKwong oq,QILiiQn_
(d) ~ Soa:,dR;cdJidblltwon.g ~A
'(t ) 'lbe Peng/Robl equation.

ll
.
oons:
(b)lbe truncated viriru equatioo [Eq. (3..38)~. with u "Wllo of a fNm the poonalized
Piaer correlarioo {!Eq. 0 .63)1.
~c) The RedlicbiKweog ~OIL
(J) Tbe SoovdltdJiebfKWOD! equmoo.
E~) The ~;gllto~ equation"
For mlfur be.ufitmridt, Tc :: 18.7 K, Pi: = 7.6 bar.. \lie = 198 (:rn' mol- l .. and
w -0.216.
l.l$. De~ Z ~ v far~ at lS(PC and 1.800 k1 by the f~

a) The. uunc:m:ed \'irid ~qu:nion CEq. (J.40)) \\ritb 11~ folllbwing ~~ vaJtz
of 'll{i:ri;l l~c:ali:
<b) 1be tAloeaWI virial eqwa_tion (Eq. (3J&)~ with a value of lJ from the. genanli~
Pitzer COI'"Idmion (l?.q. (3.63) 1.
ed n.e 5learn ~hies (App. F>.
l-36!. With ~ to ttbc virial ~n~ Eqs_ (3. 1J ) ud i).l2). mow that.
. (az)
JJ =
aP
-I
T.I'"=O
B=(~)
. ap r .p::O
~pe: l / V.
U7.. ~ (3.12) when U\IIlea!ed to/uiUfCmlS ~J:el)" nzpmsoots (be VQ~da

for memaue ,gns, 01 ' c with~
(a) Use~ data ro prepare a plot of Z w. P fot oldlm;ne ar 1 9 C from 41) to 200 bar.
(b) To 1lilmt pJCSsures do lEqs,. .3.381 andl Cl.39J'Pf'O'Vide good qproiimations7
138.. Cakvlate lbe IDlliir \"'ktlDe of utunded li.quid .IU!d me IDOlar rol.wDe of ~d_ted
\;tpor by the Rcdlic:liiKIli0118 cqatdicm for' (JIIi.: of ~ rolkJwius and ~ ~ults
'Q.ith ,.,uua round by suimble generaJi1.ad anel.ati<mS..
(a} Pto;pane m40 C whew I'' a e 13.7l bar.

lt9
(b) Piupane at.Str-C where P ;;. J1.16 bat.

(t' Propane . we where p ==- 21.22 bar~
td) Propaoe a~ 7Cf\C where P s. .., 2S_9oi 1m.
f~) Buhllle al lOOOC 1bere P ~;;;; mS.U ~
(f) ~8QI.JDC at J 10 C wbcr~ P ~ W66 ~
(R) ~BDID.IIl'l at IVC where P ~ ..- 22.38 bar.
(h) ,..Bvmoe ~ 1301)C who:~ ,p ~ = 26.SQ b3J:
(0 ~~ nt 9Q>C v.11cfc P c: 16--.54 bar.
(0 lsobu~ at lWC wbac P === 20.03 bar.
d~} ~eat 1 ~~ v.~ P -;; 24.0~ bar.
({) f5obotanc- at t_ C ,,,.bere r :; lt..Sl ba
(rn) C.b.lorioe at 6Cf'C ,.,hcte P ~ .., Ul21 b:sr.
(n} Chlorin.~ 70'"C ~ P L = 22.49 fl..1&
(o) Clblorinea:~ l(fC ~ PJiat :27.43 bar.
c
{p) Ollori.ne.at 90 where p . ;;; 33.08. bar.
(q) SwfvrdioLkk m: C~ IQA -18..66~.
(r) Sulfur dla..tidr t 9i(pC where P -= l3 .3 ~ lm.
s) Solfurdimdeat ft(QilC'VbcTC p s>A ~28.74
C,r) Sblflll' diaxi*: .u IWC i~Ja'e P st~ 15.01 bm:.
3.!9. Use tbe SoowJR.edlid11K.wong equi.\tiorJr ttl mlatl:ate che moTar vatome:s of~
liquid and 5a~ma~al ..--.par rw UJt ml~i~ and~ li\~ IJ)t ...,_of~ pens or
Pb. 3.38 iiiM (.()ID~ resohs willl \rai:D.es fouod by mimble gent.ralb.ed ~
.:tAO.. Use tbe ~ .equa.don m ,C31_m~ 1he molar volnm.es ol:SaUJ.rata'lliquicl and
sa.tur.u~d vapor for the 5Ubs~ and rondilions ptn by G~W oi diG Pif1J. of Pb.. 33
and~ results wiJb wJmf!S found by Stiliah~ g;eae:mlfad correJmiom..
.14L Emmatt: ~bet Col.kl~

f d) The volume -e-up.ed b)' 18 1tg of etby1:ene at ss~c .met 351m.
(h} 1"bE ~ n e~~ contai:nrd iDa ~m3 cylfoder at SlrC arull15 barr.
lAL "lbr~pUC mt111f mlu:me (Jf a [pattirulu ~ndl ~ 23,000 em'mol...

atlOO K aPd 1 baf_ . oUber dam :tVe ~\-.t~ilabh. Withoot -- - Ji:ibiJ: ~p be ~ior.
de2.rmlne I~ ~E~ of rlbc roolar rol:D.JDe ot lbe ~apar i!llJW K md 5 bR
3Al. 1b a good approximatim. what is abe molar YOI.llfe of ethanol v,apor at 48:l'?C und
6.000 kPa? How~ this ~t ~~ witnlbeldW~ ~?
m
~ A o..3s-,m3 '~ i l1.'Rd m store~ propane;~ wpm pnmu~~e. Safely rt'(JMidu-
otlon ~ tbat _ a tcanp:raw~ at JlQ K ~liquid nnbi ~no~ lbim ~
of tiH: kiUIJ wh.u:oerof ltle vessel. ffJI ~ euodit~ ddmn.irJc ilhc of y,apor
and 'tiE lil'J:m or llUJiid iifi die \~l ~ m K -tile VdJ'Of ~of~ is 116.0
bar~

3..4:5. A JO..tfil :aank ronml:ni 14 m3 of liquid n>fil1qe In tqtri1Ibtium 'Witb iju ~at 2.'P C
P.Wmate the mas of~ vapor mebB. ' The "1lPW ptreSSUJ'e of n...IJI.Ilme 3l d:J.e
~~ ' .;t43~
(a) '11le .uf.e~Jr.meeoruaiiled iuaO.IS-m.J ~ Q;t ~Candl l4,.000kP'il.

(b~ 1'he tem;pennure at wbidl A10 kg of rdJnme itored iD & 0. 15-m~ '~ ~ a
)ilt:S$CQ~ 20.000 kPa
lAl . 'Th wt1a1 ~ does ooe JiU ,a O.Ls.ml ~ at 2C jn, ordu lD S:~ 40 kg of
cthy~Goe mil"l
3.4&.. !If 15 - afJilO bt a 0.4-m1 cootru:fief is beattd to .uxFC. l!kh$1 ~ , de~~?
149. ~ ~ holds ~:c ~~ lSrC and UOO tr.. If it . btated to 23r C.

whn pteHUR is ~~?
150.. What . tbc pm:rsure in a rOJ...ml ~ WRll l1 i5 ebupd with. 1'0 k, of cobcm d''tonde
iit.31PC'?
lSL A rigid ~ filkd to-~ m vo1n~ with liquid mti!Opo at its QOJ'ID.d MiliDI
point.~ adoaied torwmn lo 2.S~C. Wbn ~ ~ ~? Thl= mniDr vo'lulne of
lkptid 1nitqm at i1s n~ Idling point. ~ 34.1 em" moJ- l.
l~ 1'be ~ifie votmne of i8obulnD! liqW4 m: 3W K Wid 4 bar~ JL824 anl &-t _Ettitpb:
tM ~ftc Wlwnc 415 K and 1S tm-
JAl.. Tbe d!mity of Hqoidi n-peDtaoe i& 0.630 g cm-l at 18 and ~ bar. ES'timate it8 ~)
a.t ~4(FC and 120 bat.
l.S. l!stimate rthe volurJJE cblloge of vaporization for ammonia at2CJ C. At this b:mpemWre
die 'AQJOT~ of ammoaia is 8Si'1PL
3.!16. P VT data 1mJ be tOea h)' m~ fDIJCJ~Ni~ p~ Ama.\:!1. m ef a nbs.tnoce of

l:llOblr . /11 introduced into a tbnn~ ~II of koo-wn lOlBI lo'1;)]UJK IV~. 'Tbe
~ u ~"Cttw ~ 3Dd.lbe: ~ T mdl ~ p 11rt IliC'au.ttd..
(.a~ Aftmldma:tdy wlm paecnfate erroa,are aDownble mlibe. ~ variahk$1m,.

V', T and P ) uebe muimum.allowable mor in abe ~ ~com~bility
raaor z ls: J il:'1'
(b~ ~Y bat perce.ntage e.trer'S are allGVtable in me measured ~ 1
if
die maximum ~ Cll1:ll: iD calcolmed w:alnes of dlO seoond vidal ~IU
B !d ~ ? Asmme thrn Z ~ 0.9 an:d ~bat VIIDes of 8 iiJe calcuhtedl b)' Bq. (:1..19)_

121
3.51. f0fra;p$.~bt lhc R~dV'JtWQII~ r41~ IU1d fw 2 ~ ~~~

Tc1de-mop a:~ itnu for~ lWO li:rniitQJ sl~
um
~'"-o
(az)
aP .,.
lim
Ji-
~( ~)
aP r
JA U 140(H}l d g~ ~ "' ~ 60\ f) *-Pel L(atD) ~ atuh'dclll t(J l(lal) 'Of~ .~

foell ror an am~~ what u.."'OOd be rbe voJirme cf the ta:nt ~ to bold
~ .. l,DODipsil) and 60(- F) in .amount cqui\~. ~" l()(pl) ufpsollne?
Y9" ~a gpod estimate for l.bt: ~Dlty facu Z of lUI'IIHd fl)'dm,p ..,..
por at2S .K Qd 3.213 b3f_ f'w ~an~'~~ = O~nS7. z
Lim(~)
ap r
f.-o
.. o
(a) Stmw Um'l tbe ~ -wiD$11 ~ocm~ B b fft'O ~the Boyle~
(b) US~C lbe ~ oorrelation for B~ Eq. (3.6l ). 10. eslimne tbe tttditt:rtl Bo)'k
ttmp~nnu~ JVt sDupk tluids..
Ul~ N~ gas (~ pg~ ~) is dcti'fwed to a c.R) via pipdine It a voliW'Itltllic

rate,o f 150 million SL"U1datid cubic feet~ day. A~~ oondltfons ;are sorA
~-~). ~:
(a) ,.. \'Ul'llllldric ddivet} nne macrusl oubic fcei per day.
1
(b) 1ihe mobr cKm'aY rate in kmo1 per hour.

(c:) 1i1e ps velocity at delil'a) ewdilioos in 'm - m.
The piJ* k 2-4(1n) ~~ ltd ~ilh it$& di~ or n-~ m). s~

oondil~ are filf'F) wullfatm).
J.Q. Some ~ding--s:atcscomtaU'&D$ tl5C'ihc ~~ ~ilriUry bctoc X;: Pllbcf

Ibm die~ fookrtu, as a third~ The t'iJiQ ~of CD11'ela00n (age~
on ~.. Pc.. md Zeo-. tbB CltDer on fc,. Pc. aodl ~~} woold be eq:DNalent ,.~ t bme a Olli!-
to-o.ne ~_ndf~ bdwrrn~ ~ ond 414 n. dllta of App. B .allow a 1m o f l&h
~~- ~ a pl'Qt of Zc w. GJ to ~ bow ,..,"en Zc 001'11'Clltes -..rilh f.
~a Jlirtear~ (Z~ !!!!!!-a + btJJ) f rumpolar ~.
1.63~ Fagun: 33 wggesu ibm 1he ~ 'lJ.mbs af ccnsmm \o"Olome) am approidlm.rely

lrnight ~ ma PT d:iaJI'IUIL ~r ~ tbt: lollowiDi m.ocJ:el imp~y linear~
(a) Conmmt-P~ equation for liquids.. Cb) hlml-p ~ (t) v-nn l kr Wuh
equlltioo.

-
1..,..,.
3..61L Sbowo ~ is the Equanoo of SnJr<f lh!rtsion lM.r. for eadl item discuss the eaocfi-
oons approptime to i't8 Wiir.
(bj
(e) Cnbie ~of lill:e
(f) ~~~ eq~umUSJ~~ &~.. (3. 72)

L~.
~ An idea1p:s. initia.tJ).. tt !Sb:C and l bar.. ,~ lb otlowiog cyclic~ in a

~~ S)tSI!ml:
ta) lln mm:lm.nically l't'\'miible- pnx-C!!lSC-ii, it u linir ~ ~IH:Wiy to S bar;
tileD cool~ ill constnm ~ of 5 bM ro l5 C. ri1Jd Iindy expancled OOtbai
r~PUy k! itS originat pressure.
tb) "''he c~Jc: is ii:te\'miblc md cllcli !tcp bus an efflclmcy (}(~~with
the eo~fX!odinl ~.ba.Ricall!f ftNemble ~ Tbe cfdt: 5UI1 ccmim m an
adiabatic oo~oo !Kep~ WJ r~GilObg ~ Wldm ~~~ion..
Calcwate Q. w. All. md .AH ror e~ ~ of lhe ~ and for ~ ~11;. Tm

C P :: (1 /2) R :md Cs.. - (5/l.lII.
J,J66.. Shaw l&n rthr densily- erie$ ~ Mailc~tS an be deri\l:'d from ~1

\-otwoocric d:llai via l.he e~n:
B =- J)'-0
lim.( Z - l)fp
M7. U the eqwuion uf the )RUletling problem andl .dafar from table F.l. to olxam a \Woe
of B ror'W'Ulm" tDt cnc or th~ :ronowmg ~.a~:
(a ) lWC (il} lSl C (d 4GrC
0 bras p1 otegidas por direitos de auto

.168. ~the wlues of 'i t 'Ill.. ODd Z.r gi\>-en in 'fable J.l foc
{a} 11be Redlichlkwoog equalicn of smte.
~~b}' 1beSo~biKwoogcqumiuoof~
{c:)1 1bc
_
a-. r.JD..-,l..~Tio- N'Ui.W111r. lt"Fft.., -
!!! ~-L~ II'~- ,.,.,.._..OQ fJ .,.l.@&.e_
1 69. Suppose Z w. P, dar:t arr axililahfe m arnsmnt T1 Show tflm rhe ~ demmy-
series ~ rirW a:oefficient can be derived ffltiiD. ~dam via the~
Bm lim (Z ~ I )ZTr/P7
Pi~
3.7D~ H~ th: ~lilt of dx ~ing pttJbttm and d.alu {rum table E.l to tJbtiln a \ia1ur of
fix ~ ftmm a T,= 1. ~c~are the resub wilh 1lbe -n~ne implied. by Eq. (3..65)~
:111. 1be fOOolring cnnvrrsa.tian was ~rbeard in the oomdlu of.a targo eogioe-ma linn.
~- t~~gilleer. '"'HL boss. 'Wby dtt bis SI'IUleT
Old.limer: "1 1iM!l,y "WOD 111 w~ with Hany ~. from Resca:n:h. He bet me l1hal
I ooolda"l oome up wiD\ a ~t but ~ eslimaM fm llhc mobr \'cDme o1 u "'
80Jl.at ~c aud 300 bu. NotbinJ to it; I used llhc ideal..ps equation,. and got Bhout
83 cm1 :mol-1 Harry sh.ook bbl ~ but paid up_ Wbm do )'(ru tbiQk llhoul tbW:?"
Hn. ~~ C~oosnbi~g. hi dltnno ao; , think roo mus.t be li~ ri&ln....
Arpin 11 dle !italtd ~ is DOt :m idea1l p,_~i... ~ ~ric.dly wily b
oltki:mcr won his ~
3.'72. f"'rw mol of calcium earbide ~e eombioed witb H) mol roC water ma dOii'e'CL ri.Pl
hi,gta--~~ \'CSSC& q JiROO cm-1 :i-qtr_rnaJ ~mpcy YO!~ ~kfie p..4 " ~
bylk~
cac2(:r} + 2H!O(l) .....,. C2Hl(t} + Q(OUh(:r)
1btl: vessel contains packing with a ~1)' of 40Ill to pmreot explo!We ~

.'I'''IU
:. . ... (/1 r ~t.~H=
.. _ IKll
_~~. ~t:ne. WllJo I,<VI"""-!-IOTJS
. - _ ,_. _ ...:. an: as~c . _ t ...___
_ _ and ~Jil,l. lh.e
~'r ~- ..
~(JD
m
mmpld.jaq. "fbt ~~ is e!~ but owLng IU ht ~ 'l h find ....,im ......
DPCJ...,.
_ ......,
tu:n= is only 125 C. ~1M 1iDal ~ ln lb ~1!.

11
-'ot.r.; M l~C. lbe molar voJu:me of Otcoltb is 33..0 ~ ma1 ... 1 lpcn tbe effeeu
of any :1-~ (t~g~. air) inibally presmi ia lite ves..W..
(a} Store has. a gas ur IO':C :und I(Mml.

(b) Sore nas .1 :liqo:id in equi}ibrimn with a vapor at I~ and 6.294(atm). Far Ibis
rmode of l'liilf&~ ~of ~be WJk votlllfl!C b ~by liquitl.

1:24
Cumpu-e the: twu pwposal:s. ~ "lX6 wad com of eadl. Be~,. 'tll'hen=
~!ibk,
v
z = VQdal___p;~)
wht~ both WJ~ ~at Q)t ~ T $Ill P i ~all dltu M" iUaiJ gas b.=*~~~
5ma oomprbing panK:le51 .i.lb DD intamalec:ulM forws. Use tile. truui~ definition
d Z ro ~ 1bam:
(a) ~niliu mtracliom promote wl.ues of Z <. I .
tb) ~npv_l. ~ - m ptOI:i!~w.luesof Z > I.
(d .A balance af a~J~Ddinmand ~ im ilia tbal z - ~ A I ole m. an.i~ ps
it. !\~ I fmwltfth ~ QlCIJO ~tKl$OJ ~),
J_;rs.. wnre 1b; pmnl foml ~ut ao equation or .srutt ~:

Z- I + ZLtl'(p) - Z (T. p)
w~ z,.,(J)) Jt(Ot$J.ts ~from fql1ll ioos. ..m1 Z (T.. p) ~on;.
~ from iltll'aCti Wh:d are the repulsive Dl a~~ranift comn"'bmioos lo
lllt dn- . ~ vf~?
176.. ~ below are mar proposed ~ w the \i1WIJ der w.li equatioo ~f ~
Ate my or lfiOdiliclti____,i)lfi) IWI.~ Elplaio ~fuiJ)r; f\qtmJmts sucb ~~& ""'II
~~ adiJ.&:: in 'rofo:oJe.' do not cpalify.
3
RT a
(c1) p ;; " ~b - v
RT a
(b~ p = ( V -- b)! V'
RT II
c) p : l f (V .... b) - ~
11
{
IT a
(d) ~'=7 - i2
1'17... n..b J'dl!.,..nc~ ln lPb. .,_ 4 ] . ~ge; m to he ,zg) ideal~ ~ ~-:elop m I~

givin& '~be bi:AiseboTd air~ ~ ~ oi~
111. A pden I.KKw 1\'ith 1fie ' il'ata' \'~Lhe &'hut :.md die ocw.zle dosed in ate snn.- full of
liquid Y.,-atef. Initially., the~ B at ~(pC and t6 b M~ &i)fi'lit LUbe ~ lrmpmlturt
ol the watu rises to~ C. Owing n.lhe iD.aease iu tempea..twe. uad ~ aodlllhe.
rlastidty ofm ~ lhr intemal diatncrrr oftlhe bose~ hy 0..3'4! . ~
the final~ 0f tbe 'V.."'ta' mlbe bose..
Data: P, ow) ~ 250 X l r I(~ I ~ r(ave) ...- 45 X 1CJ6 ba:r~ 1

Chapter4
Heat Effects
r.be ~h~ iodostry, COD5ida;,

Heat U"'UD&fer is a c:emmon operaritm1i:Q ~le. the mr
mao~re t'l edlytez glyeoj (an a1uifreeze ~) by lbe oxidarion of eabylate Lo ethy~
Ut.hie. iiUIIJ
---AI __ ._ . h A.AI--.-: t t I "'fl.._ ----lih.. . ..it...!-- "' . .. ~ '
l:l$ ~~.q,~Sotq~ ~ YH!M(Jn "0 gl)\t'O ~ UIIH.~IJ~ OXlUllYIUU matiJoD itl lllOSt cuedlJ\"e
when cmied om m a.em~ oem 250~C The. l'ml.~ et.bylcfc ODd a:ir.. are thecd't~.re
beturd to this ~ bd'tn they cnaa- the~ 1'be pKbeaw design depe::nds em tbe
me of beat imlafec "JJM combustion ~Lions of edlylen-C! with ~y~ in1the ~ bed
~d to ~ lbr: ~. Hcwo,v, heal is. IUIIIJKJYed from the Maeror. and b re~
d.~ IK)( fise mucll tibo\rr 259':-c _ Higlmr ~ promote lbo production or c~ . :m
UD:~ produ(.'t. ~ip of the ~or requires lknm.vledge of the be:at~trll:M[er mte-. mid
~his depen& 00 lbe: beat ~ ~iatall witbl lite dJmDca.J mJCtiom.. lbc- ~:ylaJC' oxide
pmduet .is bydi:Dd to g]ycoJ by aMoqxioo ia ~ llm1 k -~"Uivcd M l only ~ ot t~Jc
~ dtllflge and d~ $OIUliOo ~ bgJ: ruso
~ Q{ dJe llydrn:tioa rcaaioo between tbe
disso1f'ed edlylene oxide and water. l?mny. the gly-eall& mcoiettd rto1n waau by dUtillatioo,
a~~ of~ aDd ~em. wbidJ re-sults in the ~p:ntltioo. 0f a solution iioto
itico~ts..
AJ] cf t1J,o importml he.al ~etreas are iDu.~ed by this relaiD:'dy simple cbemkalm:mu--
factwing ~- Io oonlrd$l m sm.sible heat ~ \Yhicb ll.J'e dl~ by lmnJ:tCiilltU~~e
dnmg:es. tk :hat etfects of chemical 1!eadioo. pba&e ~oo. aoo d'ie ~ and separm-
lien of salntitxts
. Drt_ ,.._............ _.. .L.r.-
~'""m~ ,,'l'iifl'rinu-nna~
~~~,....,.... QJ.,..... -
'""" ~.4!1 ~- .. -...~..- -
"" .o~AQg .............,........ ~
tiU ~.uno u;;;,rnper:l-
tme. In dais chapter we apply tbelJDOdyna.mi . m meet.~, of~~ or dle ~eft'~ lh1l1
~ pbysit4ll ruld clitmical opentio:DS. H<N~re& the bear eftea.s & f mU.ing ~
Whieb depend on the lbetmt1dlfuamc pmpe.rtics of~ ~ lft'~d in Olap. 12~
4.1 SENSIBLE HEAT EFFECTS

.tiel& ~ m o s~~ m..-.,hidl dine uc no ~ ttaJ:t~tium, no ,dlomicaJ ~Ueliem, and
oo th.aop in (Xl~tioo cames the t.empernture of me .system tu dmnF- Vk ~, ~
relalions 'bd\\rcen1the qurutlity of beat tt:n~J)sfczrcd and -.be~ tan~ dlaoge.
When the syst1m1 is a hom~eoet'IIIS MM~ -or ~~~ ~. tbe ~ rnlt!
india!IC8 dw fixing tbe wlaes of two immsive (l(tlpCJlic.~ cm'blish~ i 5Ute. The mom
or ~iic: intttna1 encJJ)' of a mbs.tancc may tlte:mme be ~ il!S a fttnrdon of two

orh~r .Jkde fi~J'Fibbln. Wlmllbese ~ mimmn1_ sek!cllld a1!l ilm'i~ and tltitl1m' or .speeitie
~~ U .. V(T, V) . Wbacc..
dU - (au)
ar v liT (au)
av T
1
dV
llU ~ CW' Ill' + (-au)

&V T
dV
The: final tmn may be set eqWL1 to lDO in two~
faraJI' oonstam...\'n1nJDe ~ret~ Qf ~
Wlx~JitWU lhf; mtaul ~ - ~ ofvolurm:. regardless of me~ This

is~._ ~far~ pse$ ami f~Je tltdd$ Qd ~.toly 1n10 fw 10911'~
press1lm pe&
dU -C,dT
(4. 1)
Far m.Edlallic.:dlt ~Jo co.~tanl--wltJ~ine pr~s... {2 = r.,.,u . ami q. 42. l9J amy be
wrimm tor a uW.t - a~ mcdc:
Similady, tbe.llllOiar or speciftc ~may be~ 111 fiiflt!.Iun of h!'m~

and~ Tben II = II(T. P). tmd
JH = (BH)
iiT p
ilT + (~)
aP T
JP
As~ ~t of BQ. ('2, 20) dU:$ ~~=
till~ c,.dT+ ( : ; ) / "

Apia. two drc~ dow me final~ m be sa tcr..al w Uf():
fot- aqy ooa~-prsS.orn ~.,.. ~Pldl~ ofrtbe ~
Wbcoere:r l.be: mdialp:y of "- sub$taDtCr H ~lil of ~1' reprdks of the

)'IIQIC'es&. '1bii is a:acdy mae for fde:d gnses. 1M appiDxim.mely tn.e fm low-~'l.tt't'

127
(4--l)
MOI'eO\~Ji'. Q ~ Jl.f:l ftw medJani~y Rlfttlle. ~~~ cto.H:plem ~

I[F.q. { 2.23)] Ml.d for die mam-1'~ ofht<M io $ttk.lldy- ftow C1Clbim8trS ~ 6E,. and /J;K are
~le and W1 - 0 [q. (2.Jl )).. In eitber case.
Q t.H = !. r,
1
; Cp tiT (4.3)
lbe COIDIOOil eJJ:gincerln.g a.pplkalion of Ibis equation is to steady..flow heat tJrallSfeL
Bw&tuatioo of tile i:mqJ31li:n JEq. (4.3) requiies tuowledge of the tempel'atiBe depeodlmce or
dw !baJt c;q):Jdty. 11Us is osl.lllly g.'iven b,y ao Dlpirieal equation~ tbe two 5impJest ~
af rpraclicat wtue ~
Cp ..,
- ;;a:+ f2T + y T-
R' P
wbele cr. IJ. 4Dd y w a 'll b~ and e rare eonsumts ~~ of abe panicubr mbstance. W"Jtb
me ~limJ .o f the fm ~. I~ qwdiDD."i am of* --
fonnt. We ~ C(JI}l\Jigc
diem to pn:widt: a single expremon:
~ ;;: .t + BT ~ CT1 + Dr- l (4 ..4)
wbeTC either C o:r D is zero. depending on lbe .iUbslani:e ca:Wdeml lleetmse the ratio Cp>/R
is dbncmicn___lcs$., tbelllllits of Cp arc p-emed by tbe c.b.oiee of R.
M mown in CIJaiL 16. for ~,rdir Uk41-l'tl hm.t ~- ru~lb:m lite acCWIJ llearm-
pxily ~ DAd mdle evaluaJion of mcb lhamodymnnic properties IS the cntlWp-y. 11Je :r eam
is that ~~Y t"'l"ahmtiou .i:s rmo11 o:m~niemdy aecompli~. in t\\."V ;ps;
lim-, caJeutruion of "n.tues :for o.llypotbetical h!Ml~~ Jf(Jl~ wllemiA idealr-gns heal ~tie!
BB ~ secoud. OIJI'RlCOOn of d)e ideaJ-~ VDlu to the real-gas w~ A Ral ps
t~ ~1 in~ ~ JimU ~ P ... 0; i.f it ~~ to m:n11in ideal when ~d to a GPite
prasur:e. il would cxisr ma bypolbeliall ideal-go ,~.. In i5UCb snncs psr.s ht~\'"Q propef'-
lies dmll .reflect lbeir molecular stl'Odlm.'! just as do reaJJ gases. Ideal~ beat ~
fdesignated by c; and c~') are tberefore different tor~ g~ atmougb fanctiom 0f
-- -;- - ~ ~nr
_.~~,:lfe~..-u1J -,
_ ~ -
lcleal-p betlnc=apama in~ smoolldy witb ~ WDpe_ralW'e rowmt an upper
limit. wflldiJ is. ~ached wtw!n au ~ ronniooal. and vi.braJiooal !'llOdes of ~war
mmioo m f11Uy c:.\clted Lst'C' Eq. (16.18)]. The-~ of ~Vft on c!'
tor~
ru~mgm. WUie.4 :uXI! .e~ dioxide ig illlnsll'illed in Flg. 4. 1. Tempetill~~te depemleDce u ex-
pressed aii8J;t1iadly by ~lions~ a$ J!q~ (4.4), htR. ~
ci'
_/!.. = A ' B1' -+ CT1 + DT- 2
R
128
v-~ of the.~ are ,gi.vea in Thble C. I of App. C

fM .a mtmbett of f!!llJ.1TJ.m_Oft ~
and iDJipnie pscs. M~ ~ bul tmm:c COIIIJJ]m ~.an found in the .litera1ure.l
11.,.re4J: ~btal
Q~ol~oi~
~ m4 OAtbon dioxide.
lu ilresWl oflq. (3.19~ l(be tWV> ~ beatJ capacitifi are related~
c~J c' .
___y_ - _L_I
R - R
Tbef~Qnpa~ &~~of C~1 IR follow5 fRm1 thC ~~~~~of C~1 1R-
The deem of (empaamre oo C ~~ ar C ~~ ae detennilled lby ell~ Q'k)SL aftea
f'Ivm ~ data and knowkdge o f molmllat t1Ufe lllrough ,takalafio blued oo
~ ~mcs. Where ~bl clru::a .ue .001 ~~ mt:thods of eafmariun ilJe
empluyaL ~ibed by lkid. PrausnitT.. and Poling}
Alfbougb i:dl:al-p bi:atmpaciti .are ~ly ~forn:al~ only 111 uro ~"
1be dqJartuK: of rea1 ~ &-om iidealily i5 5ddom iigniicant at~ below~~
;t
and Ml'eC md c~8 are wuaUJy rooa ~ to their tme be&t ~ties.
I Stt P~ A. AI:r and l. L .l.ft. tlriti4 P1itiD ~ \'OL 6. pp. 169-J'"J9. t l~ mil n bltdtapt;)by. M::O aho
T. E. Dn1i1mi R. P. Dmncr~ IL M. S ad C. C. . .~ ~ P~tn .of tw.
a~ tPi!fll ~. ~i(lf fr.vd~ 11n.t-. ,!JJS_
PA, es1if,ll
2J. Jr1 ~a E.~ mJ l f . O"CGffRdJ. 'IJI~ P~~ of~ tJ1Ifd Uquidxf Stfl ed... dgp.l. 11\k<JRw-
Hill ~ YlKi. u-
1~
Example4.1
The parameter"! listed in Table C..1 requiTe use o1 Kelvin l~f86 in &q. (4.4).
EqualloAS o1 lhe same form ~mat also lbe de'.telopedi 'far use wi1il tempeahlreS oc , m
(A). and (0 F). but the parameter vaJoos are dltfemnl Ther molar heat ~tty of
methane in tfie ~$ 81818:is g1wn as 8 functiOh rof ~emperatu:re in ketvifis by:
c('
; = 1.702 +9.0fU X lo-3'T -2.164 X lr'f 2
flheJe the parameter values are ffiOf'O Table C.1. Dewlop an eq,ualion 1\or ,c~aJR ~r
temperatures in cc~
SfJIIutlon 4.1
~oce. a fuootio:o af t .,
c~tl
; = t7a2...,.. 9.0SJ >< L0- 1 <r +Z7J.J!i>- 2..164 x zo- o +l 1J.lSl 2
Gas mix~ of coostam QOIDposition behave aactlly as do pure gases.. In ;m ideal...ps

~ dJt: 11:l01r:culrs ~ Jk) ip01,1Cm.~ em f)nc aQC4teri ~ r:.aCb ,gaS QL'St$ m~Rt (If
1
ttte others. The. id'eal-.p beat eapacny me

of Q mix.tnre is tlerefom mol~weigtned
wm of the bcal eapaci1ies ,of~ individual ~ Th.us for~ A . B. aDd C ~ molar lmu
capad1y Df a IDD.mte ift tbe ideal-g;.tbi stare ts;
(4.6)
C ~.
where 1 ?
C~~ ., aDd C are die mtllat beat C11~Jlie:s, of pure A . B. mid C ill the i.~p
sme .
. ~ ,... A. JB.
.....A, l 1 Mild_ Jc
-- am
__ mQI)_ e.....-li""
- ...1 liJill,.i
~os-
~ with~ die beat~ af al'tids and liqvids~R fuwJd by ~Ill. Pamxr

rw
e1iers 1be lemperanue deperulei'J:Ce of c,. as rei~ by Bq. (4.4) 3J!e ~veo [or a few mJids
ror
and lliqpid$ in Thtlks C.2 aocl C.l of App. C. Cond:Jtiom the bat capacities of tnm solids
and liqnids are gjven by Peny imd <item md by D:wbcrt et w.l
J R._ lt. ~llrY azd D. Ora!~ ~~ ~ ~ ~ 7th~ ~ :!. ~1fiLt N_ew Yed,
L997:. T. B. D-Jabm ct alt.. dJ.

130
EWflutftlon of lite Senslble-Hsst Integral

Bwlumion of tbr ~ f c, tlT is ~.o~ by s"bstilmion for C p as a fuoa:ioo ofT..
foDOW'fld by formru i1ll~oo. For" te~ limits oll'o and T ~he n;sult is oom~11y
'~~
D(r- J)
l r0
TCp
~dT =A Toft
R
.... l) + -B TrS(l'-
l
.,., C l
... ] I' + - T0 (f3 ....
3
~J +...... .............
To T
(4.7)
1
W~ TS -
To
Oh'al To .md T, die cai(:WaliVIl of Q ,or A II is ~f~ las diJrect is me eaJ.
colmi-
. - .. - OQ VJ - ,_u. h0 ,:and ~
' " T. 81 .(ri ot .0.11. Here an i.terra:l:ioo scbeo1e mav be useful. Facmm,.o
q, ~ '} .......
(T- 1,) from eadl tmn on the rlgbt--handl side oi:Eq. (4~1) ji'WS:
f'T c,dT [ . B ....2

};o R
,., CT.~" ~
= A1o +21c (r+~~,+l u'\ r- t + IJ + ..]
rTo
(t' - 0
T-~
T ..... I :c .....................
To
L T C 1.1
r11 R
- dT A+ -II To(r +I)+ C
c
[
2
. ? f) ]
..... Tflt - + r +I)+--:-:; (T - Ta)
3 tT0
We Klanif,)' rfte qumt~iry ip sqoue brae~ as {C p i.ol R. wkcf'l:: (C p }8 is ddi~ as a IDN1I
hml t:apadi.y:
D
r+l)+~ (4JI}
rT.'
0
Ect~ (4.2) may ~Ole be ~
AH D {Cp)"(T - To) (4.9 '
"'be:~~~ enclotdng Cp identif)! il, as a mean value; subscript ug dsnotes .a mean

vaJ~ :spedic to erdha1py cdculalions. and disdn~ this ll'i!t@D best dlpaclll)ll!tolo a $inlllar
.q~ introduced iD the~ chapret
Soiwoo of:Bq. (4~9) forT gi\;.~
ll.H
T;;;;;: (Cr)R +To (4. 10)
A tuting wluc feeT umd beooe for :r ;: TJTo) -.lltJW$ ~~tua~ Qf (Cr)H bJ &t- (4.8).
Sdhsbmil&Go of Ibis n.lue into Bq. (4.1 0) iJAJ"'ides a new ~ of T flum wb_icb to ~uatf:
{CP)u, kmti"n em~ eo~~ QQ .11 fiJJal vdue ~FT.

l3l
Examp1e4.2
catculate me heat required to raise 8-HJ temp8ratur8 of ~ rn.oS of me1ha:n:e from 260
to 6001)C In a S'lea.dy-ftow pr~ooess. a1 a pressure sufflCMtly hl11hat methane may be
~er:ed an idea! gas.
Solution4~
F.qwllion (4.3 ~ iln 1Combilwi0111 with Eq. (4.7) ~es lite ceqllired result. P.urdm-
t :t8 fot C ; 1 / R ccme fttom Tab~ C. l: tentpe~ .vt::
.8'13. ] s J 6 11
To:;:;;; 533.15 K T ;;;; 813.15 K ~ :11 J;
II 533.1$
USe of Defined Functions

1'bc imegrDJ fcc,. 1R) 4T !Clften appe~ i.n dlmDodynamic ~u~ As 111 ~tk7 of tonve-
~,. "'~ uu~refS rJefioe abe oJhl s;ide; off.q. (4.7) GS the fb:naion. ~CPH{JO.T~B,C,D},
and write a o.o~ RJI.Iiine far its C\1ttuation_ Bqpatioo (4.7) fbeo b'o~!
'f c, .
l
-~
~.dT
R
1'be funmum nrune is ICPHL and the- qmllldtic:; in p~~ ~ dJe "'Uiahles 7o and T.
foHowed b)1 piD"'.unetas A. B. C. ,and D. When~ ql'RUJtrues ue ~ nwnerical '*11lues,
tbe nomtion ~ a w.lue for rme integat lhils, f':mr tile ev-dluatioo of Q in. EL 4.~
a= s .3N x IOPHtsn1s~. a73. 15:1 .702.9Jl81 E-3...2. 1.ME~s.o.o>-=- ~9.~7s J

R.epresemlllive llXJIDptttef ~ fer C\1Hlurnion <lf the imeyal s;p; ~ in App. 1>.
IF'or added &.tJ"bility ~ prognms also ~val~ the dimensionless .qwtn1ity (C p )H1R as giYelll
by Eq. (4.8_t. The 118ht-bafid side' of~ ~ is ~Oiher fum;iion, ~H(TG,T:A.B~C,~D)~
Wdh tbis ddinitioo. Eq. {4.8) ~~
(~=)#! == MCPH(TO'.T;A,BC.D)

Exampla4.3
What mIM 1iMI temperaiW'e when heal in the arncAmt o1 o~.4 x to6(Btli~ ts added to
.2 5(b mol) ,of ammoofa irlttiafly a1500(~F) in a staady-tlafl process at 1(atm)?
Solution 4.3
~All is dk: nbJpy ~~c b l(lb moJJ1 Q ~ 111 !J.H,. md
Q GA x lo6
~B - ;;;;;; _ ~ l~OOO(Bw)(Ib muJ)- 1
n 25
~ lat~pac::iiy eq\lidioo ~tempera~ lD kelvins; mtltftlfe.. Cc()U\~H
-of ID .. to tile S1 S)'5tml is indkated. .Beawse 1 J mot~ is 1K[Llivalent w
o..4299(i9m)(lb DK.\1)~ 1 .. di~ dlr: ~108 rmrlt by M299:
.l!.R = 1~/0.4299 = 37.218 J 11D~I~L
_ 500 + 459~67 _ . _. .S K
With To= = s3011.. ~
~.8
l~mtkmbeswee.n Ibis equdoo and 13q. (4. lD) .llm1S \\ilb o "'"'W: T a: To. nD(l
I1XID~ 00 the final ~ue:
r- 1..2SOK

133
4..2 LATENT HEATS ,OF' PURE SUBSTANCES
\Vhm tJ ~ ~~ i!i liqudfcdlh>m the iOiid ~eor va~ frwin the~ lll.;om.tat
preDlll'e, DO dlaQge in lempb""rii:Ure OCC:.utS; bOW"eV~ me ~ ret[~ lbe trannet of a
finim 3llliOWL1 ~r ~ ~0 me tqtb~. T"bese be dlects 3l'e c aled b Wenl beat of fos.ion
aDd lbe JA~CDL heal of "iapoRDiioo.. SimihltJy. lbae are beats ef tnm&ti.tm ~mp;tn~ the
cb;m~ of a 5Ubmmoc &om ~on~ solid state to anolha; for ~ me beai ~ \\'ben
tbowh' ~lme .solfw ('mmge8 to r.ha JDOIIDCiintc Ullcrure _ 95ec BDd 1 bar is 360 J for
each ,-nmNJ.tom.
1'be cbarnefaistic f~ g.f aD ~ (Wocases u the coeU~ce of ~ro phases. Ac
e~ to 1he ~ rule. a twc"'PhMt- system c-~sring Qf a .smear~ ~ 1 wtivllriant. and
hs inlemi\re starte its ~ by me specifiemoo of jiN ooe inrensh-e. property. Thus me
I~ beat ~ompanying a pba:5e dw:lge 6 a f'UDCiio-n oft~ only. Wid ts Rl au::d to
b'
other s.ystm~ p~ n ex=t ~enoodynamk INJlWien:
I ~H=HV~ I (4.l n
.R rora pute ~at Ee~ f,

liN laJ:cut .beat!
&1"" = vWmne dJange ~~~Ole plwe dt3Dge
.tJ m ~ sanw~tiofJ ~
The derivatioo of thi5 ~Oll, bmwD as dJe Olapcynm C4U .00. is ,h'Cll m Chap. 6.
Wb:eo Eq. (4.11) ~ oppl1ied r:o lhe va;poriZ3Wm of a pure llquid, dP'd / dT is tbe dope of
dJ "rlij)Ot ~v~.,t~ mrve at fhe temperamre of~ A V is the difference
~..:en molar \VllltDCS t~f s:arurat4 \!'aPOf ;and! 5illtunl~ itiqui~ od H u the ktmt beat CJf
vaporizatiOIL T1als \'alues or AH ftlil)r be c:iilctdatm f.roln ~r~ Wid \"''IU~Die1ri.c dara.
u.tmt beats ltla~ al$o bt tneamf\tdl eal~tricalty. &pcriJ:DSDtal ,.'a]'uc.JW are availabls
nt s.elecUd empcm.wres fbi' 1D3AY ~. 4 CoQelati{t.OS for the l~ ~ ,of~ nm-
~ ~a, fuootion of ~em~ :m:: girm by O;mbed et at! Ne\.~ da.m are oot
a.lw.-a.Ji- a'W:ilmle all'be ~ of inlerest, and it;! ~ c~ dJc dant ~lll'y for ~P'
plitca.tion of Eq. (4.1 l} ar:G also DO( lmoWiD~ Jo 1bjg eveat appt~CMimate ~ ~R rused for
esaima~eS tJf me lteat effect ac~-mnpm~~ing u pb.ue ~~ BQ:ause beats of YB~n ~
by far lbc most iropoRa~U &om a [pDcQcal point of vi:ew. ~)' h!.iYG rccci~d most aiiCPtioo"'
Olle ~~ ~ use of a ~mnluoon ~ lmOWB as UNIVAP.6 Al:terrunhe meth-
ods~ one of two~
filedi-cti.on of dx:. ~ of ~z;atitm ilt dk- ~ lxiiliog poiuc.. i-,,, ~ ;.~ ~~ .m -; 'Of
~ ~ Ht~:~Jmpilere. lined as lOt .325 h
"'i. ~ acd V. $~ R.."it\(' a.emi~ lnQ 8cra No. n. ~~ O"dri l ; R.. H. Pmy aod
0 . GRm.. 10p. dl.. ~. ""
~- ll 'b~ tl :d.. trp. dL

ll-+
&imatioo ol1be IJireilt of ~ w any ~~ from lh knO\vn ntlw at a

single t=-,c:n~~
Rough~~ of brent ~h. ,o f wporimllon for pure liqoi& m dleir nor:mal boilin&
points are giMm ~ T'trJUIOf.t ~ rok;
~Hn - 10
RT,.
wbere T. u ~ absml~ lml~ of th~ ~ bo-il.iog poi.nl.. 'Tile units of AH~.., R.. :md T"
IIDlS[ be dx&m so dmll!..J4/ RT4 is dimemicmless. Dating fii'1Jfl\ 1884. ~flU, n.1ik ~1illJ [prtr\tidc$
a simplic chec1 oo w:Ktba values ~tJtawd by otha mtrbods ~ ~able:. ~t="Dtative

~val~ for tbtt ratio am Ar.. S.O: h~~ 8.7~ 01. 9.1~ HCJ. E0.4~ C~(i~ 10.5: M~~i.
~ 0;6\ and H20. 13. L
Of the' same .~. t.H am quite m simple. Is me eqwmon pmposed by Riedel:1
AHfJ 1.091HI'I! P4'" ~ ] Ol3)
- - ;;;::;; (4. tl)
R l'lf 0.930 - Tr.
wbem llr. i tbt:, tri~ ~ in hats and Tr.. i8 abe raiuced t~ure m T~. Equation
(4.12) is ~mpri~)' ~fur an e-mpiricull expression~ eno ~y exceed 5 ~IlL
Appli~ to water i1 gi\-es:
A II. IJ)92{l:n 2Z(t55 - LO 13J k ... q:_

~ c a m.J,,:,u
RT. 0.930 - 0.517
AN~ = (l3.S6)(8.3J4)(373.1.S) =42..065 J IDOJ-

"fbil ~ to12.334 J g- 1~ me steaiJ)..tJ.ble l"BBIu or U:S7 J g- 1 is lo\\1a- by 3.4 ~PL
slimali gf the )atml ~ of~~ of" pUn;: liquid at any lelnfXI.oil1Jre firotn me
known \'M\le' .at a stqte ~may be~ on a known ~til ~or on t1 value
~ ~ fq. (4~ 1'2}. ~ ~ PfOPQ~ JYr:. Wn~ ha.!t. found ~id'.c ~ept:mct::
All! == (I~ T,.,)G..J& (4. l3)

Ha ' - r~
Exam:ple 4.4
Given that llhe latent heat of 'VaPorization o1 water at 1,DCVC IS 2.257 J g- 1, estimate
the latent heat at ~C~

135
Solution 4.4
let AH1 ~ la.tcnt beul. u1 'IOO'jC ~ 2...251 J g- 1
A lil - late.ru lle&n m JOO"'C
T,_ = :)1'l~15/M1. l = 0..511
T~ ::;; S7J.I:51641.1 c V.a6
Then by f.q. t4.13).
All,.-
1-0886)
1(2..'2:51) ( -n~-n
1
0
'Ole 'Vllloe given iD (be stean1 tables is 1.406J @-.
4.3 STANDARD HEAT OF REAC110N
llear e~ disc~ so far lm\'e bem b physical ~- Cbe:mical J~~:aCOOIQ s,ls_o ~

accompanied either by lbe mmsfeJI' ,o f Ileal ot by rempe:mture chaoges during m.e COOi':Sle of
Lreaclion-in 50IDU Q'WS !Jy lbolb. 1besc ,eifects arc ~o5 of die mtfenmees rn nwlec-
lolar Slna(\llJ.1r"' and lber.efore ia energy, of a.fle ~ .and mtclnn~- f'llli ~Pk~ llbc resctnnts
in a eomtJusiHJo JeXtion ~~energy on .IKXOOIIl of rtbeir wucrure lhaD do the~
~, and~ CIJCEIY mU5it either be tlan5fmcd to the 5UH1JWldinp as but or produce [pnJducts
at an elevated temperam:re.
E.acb. of lbe vust I1UIIlbeJ of posstb!e cbemicaJ .fleaetiOOS may fbt" cmied OUI Ut many
di.OefeRI \W!)'&l dfid I~ R:".JCtiiJli CtJ..I'!ri< ouf m 3 putirular way is al:.compliD~ ~ ~ p:I!Jtku}w
beat dfect. iabu:latioo of .tttl possible bea.t effects for all powole reactioos Lis tmpo:.,~ib2e.. We
diete&JJ'C wlwtal~ die br-at r.~ for rcuctioos. ~ out in dh"tTS~: way~ lirom Illata for
reacii.oJJS Cill'lied our in a stMdmd \\-ay. 1lds reduces 'l hr .reqll:ircdl dma to ~ rniDUnUDL
The hal ~te.G wilb a spxijc chemitai reactiQO d~ on the l~ of
lbolh lile fC)CIDntS Stnd product&. A Qt'Htmt:eut (sla.ll<hu:d} basi~ for h:\!.alment of ~~ beat
etlecu remits \\-hen tbe prodl.l(;:ts o.f reaction md ilhe 111~t:mts Bl:t' an 111 the san~e relJI(itmiW~-
Coosider me Huw-c:aJo-rinlere.r tnetbod for llilCasl!lfiCmCIIt of ~rats of co:lllli;KmiDOI of :fud
gases. Th~ fuel mixed wilh air at ambient tcmpecamre and me mixtme SOW'S imo a t~m~
tioo cft1mber where ~on U(t11fl- 'rue: C\Jillbu5.1ion ~ clltcr ~ '11'~-jac~ section
in which 'tllley ~ cookd to d1e: Qllpc;md'UrC oflbe ~ BecaJJse oo sbafl 'Mlr ~ p.roduced
by the~. and the ealor~r i$ built 50 d:urt ~~es in ~:~t ru1d kJnmc ~Y mre
~JgJigi1>1e, the Gwcill c:oergy ba]an~ :&J. (2.J2) t reduces to
Q = ~H

136
for p~ of dati ~OD widJ respect to dJe rre.aaioo.
oA +bB ~ 1L+mld
the~ h~ of n;aclitm U ~4S 1be eolfpy'*"ang ~a ~(lies of A and b mol~
of B iD dim Sll!llldanl ~s m lc~rtlllmr T l'l:ad to form I' moles of L and m moles d" M in
tJeir lftlndmtl ~r Qt ~ UPfll" ~P~JP T.
A standard 11a1e is a particular atate of a apeciea at tamperablre T
and at pecllled eonclitJona of prnau-., composftiOf\ and physical
condiflon1e-. e.g.,,ps, u.,.ld~ or ecdkL
A mrJJ1JtJJTI-s~ pre.uUR df l !i'Umdard atmosphere {UU ,Jl:S h ) was mue for DWIJ'
~ :md ddrr ttat. Qlbolari<ms axe fm: this p~ 1ihc prrescnt sumdard b J lbar ( tfP P.ili)
hut ror p~ of 1hk ~me dilf~ isi of o~lisibJc ~~ WUb rapea. w
e~tiolll. ttb~ ~md:ud st.atrs ~ill dds c~ ~ ~ oflhe pun!~ For gases,
IDe physiad state is me ideaJ..p .stare and for liquids lad ~~ lbe real state a1 dte standard
state pi'CSWJ'e .and at the ~tern ~ lo 501Wf1afJ, rbe sta:rdardl ~ wed this m
c-hllpter are~
Gru;a. 1"be: pure mbS:Jaooe in the ideal-.-g u 5tate at l lm .
l.Jquids and wlids! 1'bQ ~ pw:e liql;fid or ~lid :11 ~ ~-
Pmpe;ty ~ in Ul~ ~ ~ :m; <krJgttd by (be ~ ~~- for Q~C..

c p is; me :!!trmdanlstale beitt eapa:city. Because the standard Q.ab: fm gases is tbe ideal-gas
-~ c ~ fur~ is Edenlical wilb c,;!,. und die dtu.i of "''atrre C.l app1y m 'lhe siMtdiml 8tabe
fur gases. AD eoo.dilion" for a sumdard ~e m: bed aa:pt tml~ wbich is alway5
~ 1e~P.1fe ortiE J.j'$JC;(J1. 81~~11: ~fties are ll'lemfare f~ of temperdmre
Ott! y. Th:e standrutl stille cb.osen fm gases li 11 bypiJibetical CillO. fur at l bar actud pses DR not
idoal.. ff)Vt~"i',u, IIley ~flolp ~i* iitniclJ from ideality, Bfilt mIDOI!.1 i~s ,enftWpies fOr
IDe mal,.s ~ at I bar and tbe ideal-gas state am Jiu:1e diffacnt.
W.lxm ~ bear Clf ~ .is gi~ .f or a prat1icu.lar reaction.D applies for the stoichiOIIlelrlc
ooeffiae1118 as wouen. If eacb stoiehiomebie coeffieam is doubled. the beat ,af tea.enon is
doob1ed. Pur ,e.itample, lhe ~ s~ Jleal:tEoo. ll'ti.Jl be wrtlten;
l~2 + iH:t -+ NH 4H:... :=;_ --.46.,1 10 J
- + 3H-2. ~ 2Nfu a HS = -92..220 1

The symbol! A~. indica~~ that lhc: ~ of ~OQ i.5 lbc $ttm.dard v.alo ((Jii r.t lt'mpct~
nf 29S- ~5 K (2SPC)l.
4..4 STANDARD HEAT OF FORMATION
Tihulalioo of data fJltSt tbe stttntlalrl beats of reactioo for a1l d the \'mt nWJ]J)er of posnftle
~ODS is impracl~al Partunlite.Ly, die u n.trm:t. lleal.of my rcadion em be mkn.lilled if

lJ.7
me SUindiJtd heats offontr~J'libn of [be> compounds traklu_,g, pun wlht ftaCtiou an toown. A
/onnt~Jfon reac1ion is. defined as a reaaioo whidl form-s~ a single romptKJrtd ftvm ita cmuti.tw!tll
t~.Fmram. Fnrexampb:, k ~em C ~~~ + 2lb ObOH is the formmoo ~on for
mdllaool 11:te reactioo H:a-0 -t S03 --7 Hl~ is ttor a fonmuloo re~c:m.. ~ it I~
$Uitmio ~ QOl fJoniiJ dlC' .clmJmts tNt from ocl:lcr ~. fwirmllioo reactioos .ue un-
derstood to produce t mo1 of~ me bem of I~ ics iberef(ll't based M J l1rD/ of the
fXIII~ fo'fflfb__-t
Heats ef ~lion ~ uny ~:tmperatwc CaD be ~~cutaxed from bc111~ity cilia if dJe
vltmoe for one t.etnpaarure Is kiirtowo~ lhe tabubli0n of dala cu 1tJeR'f(lr ~ m'JIJCI"d w the
Jmpillticm of S1111144111l h't't~U' fl/fofiJftflion ar a Jingle t~ftilllw~ The usual reltoice for
this ~~ iJ :l98, ~S K (If zsoc. Tb~ ~ bca.t of ~(JQ af a oompouod this
hmlpemnre ~ represenmd by 1Im &ytnbo1 il.Hj.,., . The ~ syrmbd ~ the ~tmdud
val~ ~pi I identities 01 hem of fonmaon. and lhe :298 i:s the ~ximme absolu-m
tent~ iftttel \fins. ntlJts, of~ vtl~ foreummoo~ !MY be found instandald
lmodboo~ but ~he lllOrSt eneasive t"'Dpil:aliODS no.rllB.hle ate mr~iml mf~tiCC wodcs.9
An altlridged tiM ,o f v.aTues i:S given in ThbJe C.4 of App. C.
Wbco clteinical cqaatioM are combined by addilion. the :Stal:ldaro beats of reaction may
also be added 'to gi\-e tfle standard beal of lbt: malring :I"CCiCtioo~ Tid$ is possilllc ~en
lhalpy l$ a 513te fl::ma~ .and it1; chan~ for giwn initial and 1inaJ states are r~ of
pd~ m~Lllar, formation t_Wlti(ms and~ be1n1 of r~ may~ be~
~ w prod]Jec any cksired eqwuioo (not ilse:1f a {ormation equaliml) and its ~ying
Slllfid3n!III:Jicat of~-
- OIQ """"~"" - "' iWri-.-
- .. G..-aJioo~ f-'- thioS.
'"'"'4'1UodJ. 1,11,11 -
~ -A
p.... . L .a- !-~! '~"i: tlo.. -
l-~ 11,.1!~ IDCUJ~ liD ~!OIY.Ciill! V1. """"'
pbysieid M* of each reacmm and pmdoct. i.e.. thl: ldler 1~ f, m 1 pJ~ kl ~
~ ~ d'.J.m:licaJ fotmu.la te show whelher il is a gas.. a tiquid, m a solid. 1lti.s mi@ibt ieeiD
UDrl~. ~a pore cbemic:al ~ lit a panicular ttm~~ a1Jd l hat CLIJ ~y
em CJofy in ol'lle pb)'1iea1 stat~. Uowem-, littnioo:s states an: oflen~ usurned for CO!Weftie:oce.
CoMickf the reactiOllll C~(g) + H1(g) --+ CO(,) + ltlO(r) m ~C. T.b.is wuter--ps..
llift reaction ~ ro.mmooly enooum~ hllhe cbemi.I!Jd indosll)'. thoogb it wms ptace oo]y Itt
lt~~ ~u above 2S&C. H~. me data used~ for l:Sq~ aDd lhe initial Slep in any.
caleulauoo ,o f held t-fl~ for this R'lH:tiDQ is .cva.Jualion lbt ~~of rcaetioo .at 25e.c.
The peninefl[ fonnation 1'e31:1ioo~ m1ld ~.heir hem off~~ &urn~~ C 4 ~;
c~~): C(J) + Ozf$~ ...... CO!(s) 6Hf:.. ~ --393..109 J1
fi2Cr:t Bccara.~ ~m an dc~nt 4Hia ~ 0

CO(g): C(1) .f. ~02f.g)-.. CO(g) bHf: == -110,525 J
H~): Rz(g}t + ~Oz(g) .-. th()fs) Hh. = -241~UI J

Ike~ Ebe ~ i adualb carried out QlliJe'l y in tbe gas phase at big)) temper1mll"e-, ron-
\~ diaal.'e!l lhw. tlbe smnd:mt &tateS of aU pliOdJlcu. and traJctaJIIS at "2S~ be talco as lht:
~For cumple, see UC ~ Tabl~ IIJd TIC ~- f'itbUp.-/l'(NP-

11~~ ~ 11'1~ of~ il'benDu;lJIIlllllfe~ ~ C'.cJC~ 1'tu5. A & M Ubiv. ~ ~P'
s.a. ~"'1"kNDS1!liblayte~~"*u.:,~;J.~-~~~~
"01. ll, ~~~pp. %.
8ft also. T. E. .D.mbcrl <tt aL. cp.. l"IL Whm d:"""a.ta m;
I ' ttiU"lJu~ bil5ed ant)' oa
~ wQiiitwe-m;ry be fvmld: b, 1M atelhods olL Con51l1lainoolllld L GmL F1J.titl ~ F.qt.il1Mm. \'OL Uil-.
~ lil ~ t9.i5..

i~ :ir.aie a ~ ~ even libougb ~camoot attmd])' ~ as 1 ps at ~ -=~
WriUDJ tlJt fonnlnij)O ~toos :so 1ballheir mm ~me dWredl ~on.~ lhii.l
lbe f()ll'tiatioo reaaJfJD for col! ~ wrinen li n re'!ieJ'Sej the hDal. of ~an is then of opposite
PAiJ.n to iu smndtud heat of f011D1llion;
'~(g) ~ C{r) f' 04(B) JlH~ e 393.SQ9 J
C{.t) + ~~Oz(g) ....,. CO(g) Alqg, ;;; - HO,jlS Jl

H':!(g) + ~ (h(g) 9 ' H20(g) all/~ - 24J t8l8 Ji
C{}z(g) -r fHl(g)...,... CO{g) ;- lizO(g) 4H~ =41.166 J

The meaning of this remit is tihal: tbe ~ of 1 mol nfCO plus 1 mol ofH10 is gremu llmlr
the mtbal---'PY ,00' ll'DOI t>fC02: pl~ l mol ofH:! ~ 4 .1 166.1 Wb.en eacb prodnct and n!.amm.is
~ IS t:be pure gas at 25'lC in its~ fllate at J. bar.
ln tbi:s eumpk the 5lmldald be rof.mm.atioa of rH,O is avai~AtJlt for j1$ h~tical
~ ~ ~ a12C OacnMigbt s~t me v-all& oflhe ~bent mlfo.rmm.ion of wa:tn
1 0 be IH&t.d b its aanaJ stale u a liquid at 1 bar and ~ As a ~r of fDa, ~oes for
lbodt are given m'lbbk C.4 ~ ~beN am :0011 fmpmtly UKfi"l'his i liW ror nmuy
compouods that oortttaDy di$h liquids lid. 2JC:C :and J bat. C..ses dn ame, howe!~.w. in which
I
a 'Yilb1e given oru1 for ~be &mDclard hUe as a lliqp:kl or u :m tdeal gas ~1leo wbat iB oeededl is
die odmr value:. s~ tms ~ tiJe caw for IDe~ CIC~T l!f'ilfl only me $1andard
kat of fo:rn:J;:W:on,of fiquld J.~O av-dilable... lle 'OOkl din. inelwte ,a ft equation for the pbysicaJ
dDm!J= lhat t:rruKfonm water from it& standard state as a liquid i!l'ltD its standmd Sl:ft as an
Jdea1 Them~~ for thi. physical~ is tk dl~noe between 'the lbm.ts of
fonnatiuu of-~ wits l\\10 #lindatd ~
-l4m.JJ8- (-285.830)- 44.0121
1bi.s iJ appi(J~}y llbe latml beat of vapOrlt.ati~ of ~at 25~C. 1ibe ~ence of~
. oo-w:
rOO~(g) ~ 1Q s) + 0%(1) 4 Hi9S = 393..500 J
C(.rJ + ~{}z(g} ._. ~) a~ - - tl0..52SJ
H2(g) + ~ Oi(g) _, tbO(I) AR 9 - :285't830 J
H!O(fJ ....... H20(s) AlfM :e: 44-.0ll J
Example4.5
Calculafe the.S1andatd heat at 259C fOr the follo'Wing reaction:
4HC1(#) +~(g) ..., 2H10(g) + 2C~(9}

RC(g); -92.-J0f7 J
4H0lr) -. 2H.1(g) + 2CJ;z~} h. H~ e (4)(92,307)

2H2{J) +~(g) - 2~0(g) ilH~ ;,;;; (2){-24118Ul)
4-HCI{R) + O~Jg), - :!H20(g) + 2Qb(g) 4H!9s = - ~ ~4,408 J
Tb.is. n;sul~ Is fQur ~~ lie $18~ ltc'-.1t or c;qmbgsuon o f 4HC1(g) sa below).
4.5 STANDARD,KEAT OF COMBUSTION
Onl}' a few fomWiDIJ readim)&, CIIII actual~)' be ~ed out at the cwditions of intcn:st~ :md
Lhae:f~ dma for these .reactions IDUSl Ui5iWJ.l'y be dele~ ~>'- One kind or~
Lhld rem:lilyleJids itself 10 ~mcnt is lhe C<J~Dbvsti,gn ~ and many slmldard beats of
formatioo come- from saarrdw beats of ~~em. meas_um;l calo~y. A 0mbu5.tioo
reactH.l i5 dlelined as a reaction between anelementoteompouru!WKlliux~.ge_~ ro funn~~
combttition ~ FoJ orpnk CA)~ ~~of~ hydrogen. iiDd ~ygm1 Olllly,
Clcle pJTOdQ iiU'e earboa diDxide and ~~~rati':J'.. but dB: SUite err file waa r:nuy be eitber vapor or
Hqoid.. D.ua Ut\ alway ~d 001 l mol ofiM' ~'flluul'llt'tt tmmi..':d.
A nr.ll:tion sncb ;b i1he. fotmarioo of n'-blJtil:Ot:
4C(s} T SH1fg) -to <4Hao(&)
1s ncn t'tasible in ~- Howerer. ttrls equation remits rrom C(!JIDb:inQtion ~ lbr, followintt
~"lion feaato~
4:C(.J~ + AO:J(s) ""'* ~fg) ~ 39J~SOO)
SH:lU) + 2~~(:1) ~ ~Dtl)

-
.dH; ;;; 4
AH;_ _.
I
~(5)(- 235,83{))
4COzeg) + 5~0(1}-+ CiH1M!l + 6~0z(g) .o.H;_ ~ 2~t71.396

4.6 TEMPERATURE DEPENDENCE OF AHa
hi the fmegoing sectioRs.. staDdan:l beats of moolion are discussed for a .referemce rem.:pemu.re
of 298.1S K. mtbi5 :sectioo Vi'C trdt rlhe Cl!l~latioo cr standard bem:s. ,of reaaiOCl a1 I~
~~ fmm koowlcdJe ,o f lllli: value m me .~ temper..tture_
'The pnend chemical reaction may be wriibm:
lfl.I'~ IAt + ll".!lAl + - I"JIA, + lv-41-4 +

where ltt1l is ~ stoidliometl'ie coeJ&ient and A ~ for a dlemical fmmub. "The spxi~ oo
tM.1sft .are mtetant5; ~on abe rijht. ~ 'l'hG ~ ~'tn:tion far }.II i U.i\ full~
positfl.-e ( + ) larp~ and .ooEBfive ( - ) far mac~
The ., with iheir ~ a~ ate c.allod stoichiometric mnnb.t-rs. fw exa.mple. heo
the mnmau.ia syn~ ft'at'!lion b. wrlneo:
rl bu
This 5igo OOJ\\~00 allows tbB deinition of a ~ beat of teactitalLO be ~prrss:r<J

~~by~ :sl~ equatloo:
Atr mE v,Hj- 0
(4.14)
j
where Hj is the enthalpy of:species i mill

SIBDdard !late and 1ih.e S:mrunation is over all products
auJI ~. The SWICianJ..staae cwh~y of a ~cail rompotmd i& equal to im bear of
fomtiltioo pru lbe smndard-scate emhalpies, of its conmt\l~t eretnen~.t. lf he surodnrd ~e
cntbalpms of all clanmiS .are ubitran1y set ~equd to .-o B5 th t.ls: of e-alculutiun. thD dlc-
!Wlfidanl...smre cnlhalpy o eadJ ~ is lis bear of fW'imlion. &i Ibis e\lenl. Hi !!!!!: A Hj
1
Md fq. (4.)4) ~file$:
AH0 '=- E IJf t..H~ (4.15)
i
\\ilue the suJJIImllioo is 01IY:I' an prorlucts and im~C(a._Ol'S. "Tlriis formdi.za the ~de
saibcd mtho~ ~ fot ~-'li!Qlioo or~ heal$ ol a~ rt.actiOlil$ froip $tim-
dud kms ef ffJJ'IIrul.1ion. Applied to lhe reactit"'ll.
HOl(g) + ~(g) ....,. 2HzO(g) + lCb(gl
Mf j = 2A/~ - 4 AIIfac
W'llh dlta from Table C'.4 fOI' 2'98.15 K, t!bis becorDeS:
ll.Hi9s ~ (2}(- 241..818) - rl4)(- 92,307) =- 1 ~ 4"'4 08 J

141
f01 ~~~and mi.cta~Its are aiW'iy$ at the .S~ubnf-.smte'p.I'C$$111t'Qf

~ bar. Smndard-stare em:halp~ He rrbeiefOfrt' ftmi6DS of~ Dilly. WKI h~ Eq. (l.2 l ).
dH? =C~.~ dT
where liUhs.eripe i ldei\tiJiti ii pattitlililar prncf11~1 CK 1~l Mult~plryillg b" U, frDd Silift~
0\'U ~ pwductB md imu:lMlU ~:
E ,. dHt ~ :E &.lC~ dT
r '
Oli d E ~II;' ~ E P~ C,;,. dT

f
1'be tam l:i ~ N," .i5 lbe~ beat of~on.. d:elirned by Eq. (4.14t asll.H 1be SW~da:rd
~~ty clum~ of gaeti)oo i fi~ ~mil~y;
dCP, = L Pi C~
I
14 .16)
~ d !!J.H ;;; ~ 6Cj, ,d T I (4.17)
This is lbe fuodmnenral ecproJiou .relruing beats cf reaaioo ro remper-awre..

Upon inqnuicn l!q. (4.l1.) beoome&:
r ~c -
611~ = t~.H0 + R
'" R
~dT
i
(4. 18J
~ 6H QP()I b.H~ .~~of ~ion at tempt:r.~IW'f: T and ul ~r~ tanpcmtUM Tij

0
respecti\;dy. It tbt ~ depe~ of lhe lheat c-apacity of~ produa aJlld ~

is gi11m by SQ. 4.4). lhen tbe ~ u gi.'--en by me analog &f Eq.. t4.7) t r T I Tu)~
wim analogvus-ddillitioos fOii 4 8 , AC~ and AD.

Ao alwmti~ f'OfD'Nlalicn JeSI1ltg whrJn a meatJJ be;J;1 ~t)l clmng.t! .of ~an is. ~
~in aoalo~ to Eq. (4.8)~
(AC~)H AB _ L\C .., , AlJ

ll = .O.A + --;- To(T" + Jl + - f 0 (f .. + T + Jj + :;:y
3
(4.10)
- r~
~n (4.11j lhco~:
!J.IIfl =A H0 + (AC,)H(T - To)

'The in~ of Eq_. (4. 1~) is or tbe ~ fonn . thai of Sq. (~-7). 2Wd in ~Oil$
fashion may ae set equal to a funecion:
. T . c-
aR I' dT ~ IOCPH(Til,T;M,DB,OO.OOJ
whm! "'tr' tknote5 ""ag . 1bc UM!ogy rtqui~ simi* mpla~:eman ofCP" by Ac; and of A .
ere_ b)' AA, et&. The same eontpurer [pi'Cgr.am sen"es f C\~uatioo of citber im~mt The only
dllfetW~ in abe funcnon mtme.
1\$ o!1!S Cunotitl(l MCPH :Is de:fifit'd to represent (C,.)y / R. so :fu:nclion .MDCPH IJy :mala
ogy is de:linedJ 10, tepresenli (AC ~), / R; dl~.
{a.C Q} .
:=~"- =~DCPH.(IiO.'T;OAJDBlOC~.OOl
I '
Example4.6
catculate the standard heat of the methanol~nesis r-eaction at aoo~c:
1
CO(g) + 21i:d'm -;. OH30HC9)

Solution 4!!6
A~y 4. (4.l.S) to lhi8 ~for refereo tempeRIUie To= 298JS K md
witb heaJ.of4ofmation dab from Table C.4:
l1J.IJ.8 :. AJr:m, = - 200.660 - (-110.525) = - 90.. 135 J
R't'"..dttafion rO{ ~ paratnetm. m&t (4.19) is !based 00 data 1nkm from Ta.bk- c_J ~
i ~ A I &J B ldt C Uj~ D
CH10R l 2..21 t J2.2l~ - 1.450 OJOJ
CO - l l.376 O.SS7 0.001 ~.OJ.l
'Hla - 2 ).249 0.422 O..(KK) 0.083
From its defiinitlon.

AA :c: {1J(22J l) + ~--){3.376) +(-2)(3.249) = ~7.66J,
Sintilarly~
l!B ~ to.si:S x 10-3 ~c = - 3-Aso x Jo-~ llD...;. -o.JlS x ~~

T1le -.~Jue of ~be iilteg.ml&f Eq. (4.1'9) for T -.; 1.-ot , L5 K .is ~~ by:
JDCPH(29B,.15.10~13. 15;~ 7.563~ 10.81SE.-3.S.450--6".0.135E+5) :;:::: = l~6l S.S K
Thin by E..q. (-1. '8'},
6.H 0 !:: - 90. ns .; s.J L4(- L.6t).5) _. - I OO~i6td

41~.7 HEAT EFFECTS OF INDUSTRIAL REACnONS
The preceding seaioM bMre dealt with ibe ~heal or ~QQ. ~ ~:ti~ aR:
JWCiy carried OUI Undec 5ta1Jdard~tlde eooditiions. fwlbamore.. m aetna~ reatdoos dte reK
tmn1 ~ QDl be presnt in stOidUo.mctric propoJ:ti-om;. cbs rAdion DJ3J not go' to completioJL
and; the final~ may differfmm tbe mill:aJ ~ M~, inell .spncies tnay
~ ~ imd ~ !Rdioos.may occur simullaaeousty. N~ caJculalions of tbe
br:Ad. died$ of OC1llat ~~~ ~ ~ oo a ~ already considlnd and are best
ll.lnitmted by exampk
Example,4.7
What Is 1he maldmwn tempemture d'taf can be :reached lby the combuStion o1 rne~Mne
witt\20% excess air? Both the methane arld1Ule air enter the b.Jmer at 25: c.
Solution 4.7
O.Hiw = -39.JS09 + (2.)(--241~l8) - (-74.520~ = - 8011625 J
B~UR: b. 11"12:rimum albioab'l.:e ~toR. (c.aUedl the lbWt-:lfctll ~ tmr.-

perallUe) i suu;:trt. assume tba~ the combustion rtactioo i~ to com,plelioo adi-
abiniaDy {Q ~ 0). If lhc kifielic- and po~Cotitd-4;UTjy dJRq~ ~ pr;~ligiblc: qcJ
if WJ - 0, die overuU eoe11Y balaDI:e for the procos :red~ lO A H 0. For
J!IU'PI)SC! of mlcuJMioo of the tioaJI~e~ aey cooveniml path between t1w
inilia.ltand finaJ Mates mar be used. The: pam ~ bwJl~ in me ~Vwlm-

When 00e mole ro f ~ buiJKd ls (be~ fur aJl tCaJCQlati~"i.. IDe (Q1Jow ..
mg ~ of ~gm and~~ supplied ll) tbt enktln.s air:
Moles t- reqWrod 1.0 =
~ CXL-es5 ~; (0.2)(2..0) _. 0..4
Moles 2 entering;; (2.4)(19120;; 9JD
The g;a.sa leaving the burna conlain I ll!lOI C02~ 2 moJihO(g). 0.4 mo[ O;t. WJd
~un~ JlK)J 2 . ~mr t.bccurhalp} ettmp DUI!it be i~ of pum.
AH~ + All;;::; Alf ~o ( )

"''btlrc tU a:rthalpir;s b'e em the ~basis of J I:'IWII ~ "burned The -eoftg.,, crumge
!C)( me pnxlocts as they are heaad from 298. ~ s k to r is:
f.)Hj, ~ (C;)s(T - l98JS)r (B)
~we die&ne (C f.)n ~ the mean heat capaci1)r{o: the mtal pl"('ldud stream ~
(Cp)R - En {C lt)R
I
...,__ ~~---A-- L . -
I gllj:: ~L~ r._. __ .,. . LII;01!11;<
~it
fill
cwn
10- .;, _. tbo
__ .-r;-ft ~'-cat~ -
1Jl_-w1 L ~. h., Pw'iiJatin.n.o- C......
. ,_~. ,.r -"1 - _ ...,...HI vm
the pmdncts. r:ooh llDlll:iplied by its appropri:u moie number. Because C !:31 0 far
eadt~d ps (Table CJ). Bg. (4.8) yields:
''C-.::)
r8 ~ R.t (C #.f'lf
;:;; ~ '-- ;;:;:;; R [~
L 11i A, ' + L.ni
-1 Bi T.
so( I' +. t ) .J-.. !:J n11Di
2 ]
~ tTo
D.ala from 'lbble C. I are combined B follows!
A;;;;; E ltf,4f ~ (J)(S.451J+{l)(J.410)+ {0.4)(3.~9)-(9.100){3.280) =43.411

E
Stm.lliHiy. B ~t:a ~ ttJ B j 9.500 )( lo- 31 and D - ~ n1Di ;;;;: ~0.64S l< to'.
Fort.:~~ {Cp)11 / R is merefoo: represented by:
MCPH(29& 1S,T;49.471 ~9-502E-3~r0 .0~~~-645E-+5),

EquiltiBBS ( A ) and ( 8 ) ~ (l{JJ]ibitmd IUJdi 50lwt.dl fm 7 ~
~ . . _ AH~91
T - 29 .l.S <C.P)n
~ We tfieiiD heru: ~ dqJmd OD, T .. lira evn.luare (Cf)ll for an as-

:swoed value of T > 298.15. ,l afl ~t/OOZ the le5Uit mthe ~~ QQUa.tion.
Thh )nidd.ll u 1CCW walue of T fat whim (C p)8 is Ee!W'..d.liared The pt'OC'ftlute
corWrn.Jes ro C0JM9'1,ence on lbe ftoaJ vafw.
or

&xample4.8
One method tor 1M m~ Of ~nJheSis gas. 1(a mixtUre Df CO and H:!) is lhe
catalytic reforming[of au
wlh steam ,at high tempem.tum and ab'nOSpheric iPfessur&:
Cll.(9) +H~O(Jl .....,. CO(I) +lh~(R}
The oo1y dJlet reaction to be considered is 1he Q\er-gas-Stlift reattion:
CO(Q) + H10(gJ ~ c:D.!{g) + K1(9}

th& ~s 818 suppled i.Q lhe ratio.. 2 md steam to 1 md CH.t~ and f meat is
llf
suppled to lhe reactor$& mar me pmducts nta:dl a tP'Ipctwabe rof 1.300 I(. ilaJ eM&
is tomplefett OOI'MJfled and the PJOdUct stream contains 17.4 rncl-% en Assuntlng
the treactant~ to be preheated to SOD 1<. ta~cu~ats -.e ftlW ~ tot the reattot.
Solution 4.8
The -~~of l'aldioo at t.S<>c for dle ~-o ~ ;ue ~ from
lhe data.of Table C ~..t~
CO(g) + HlO(g) 4 CO.! (I) +Jib (g) All.e s --41~ h16 J

These 1\la~ M'adion"' IDI). be .added to give a third~
}.~WI pair of abe tfuee

read:foos ~ iU11 in~ seL lb:e mild re:etion
I& not itldeptndent; ~ i obctiocd by l'UIIJbinaDw of die otla l\o. The reldiulu
mm1 CQII\utftll. to \Wd wi1b tJioi'e am lbe fin;t and mmt
rCII.J(g) +HzO(g).....,. 001&) +3Hl(g) tlum =205.SI3J fA)
at.f:l) + 2H20(a) C'Oz~) + 4Hl{8J AltfA = 1 ~64~647 1 (B)

Fif'5l ~mine 1M lmelian of Clla amwrml b)' ream of mese .fC'aCtioos. As 1
hu~ fOf ~~, tn l mol c.lt4 JU-.d 2 m.,. .skiiUD be fed to 1bc ractot. If
x met CRt~ by Eq,. (A).. men I - x moJ ~by Eq. (8)~ On l'hB busb lhl:
prod.DctS of me ~oo ~=
co:. ..
H1: 3.1 + 4( 1 - X) ;;;::;; 4 - .IT
Ci>.!: I ,.... x
H~~ 2- ,.~; -1(1 ~ ;r ~ - ...:
1\ltQJI: S mol prod.uJ.'o

'lbe mole fmtticn of 10 0 in 1lbe prodUd itJream is z/S ;;;;; 0. l 74: wbaJcc ~ :; 0.!10.
'llms. on. the bas6 ~~n. 0.8'70 mo1J QL,~by E4 (A) Wld 0.130 mal r:eaw
by .!4~ (B). FW'the'nnl'.ll"8.. me amoun:ts of tile species .mtbe produd ~~m~m ~
Mates ro = z ~o. a;;

Mokstb -4-~ !:!)J3
Mom C02 ~ t-x;:;O.l3
Moles ihaO =z ;- 0.87
We nowd~ 1 pail. fot pu~posti of ~CQIJtiM,. tm ~ fro~P ~ 11t

600 K to produiu ;~ttl.300 K. Bame data am awilable for die stmJdard beals of
reactiml. ~c. me rnmst ,tcm.Ve11i_em pdl D fb; IOIJ!e wbicb ~ tbc ~005
;l it ~.-c (298~15 . nn... is dlow.n ~ m1lbt ~onf'M)ring dingnlm.
'1bt cbs'hed ~ p~ me ac.mal path [or wbidl1the emhalpy ~ is, All.
~this f.iDibaipy ~is i~ of pail~,
......... . at1
and' I(
Cl.8JJ"MM(X)
3.,3mol Ht
13mol~
OB7~1J'l
For Ole ,eaJeufatio.n of AH ~~ (A) smd. {B)~ botb be IHm into

~DI. Bcm.iUise 0.81 mol Cll$ reacts by (A) and 0~ l1l mDl:reari:t& by (B)~
6-Hf. ~ (0Jf1)(105~R l ] ) + (0. ~])1( 164.,61) ltn4lJO J
Th_.e ~_]py dtan;e. of lbc ~ for ~oooling from 600 K.m 298. JS K is:
AH;, = ( ~ n,(qp11) (2911..15 - 600)
~lbe~of (C~)a/R Me!
CM..: MCPH(298, 15.600; 1 .702~9.081 E-3,.-2.1 64Ewa,fl.G) !::!! :5.32'12

RlO: MCPH(296.15~6t.3A~1.4&-3,.0.0,0.121 E+5} ~~riMS

141
The emhalpy change of lbe producH as mey me ~ fftiitl 291.1S to l.l(M) K u

cai~Lo:ttdl , mil~~:
Alip ., ( ~ tl ; (q lu) U.lOO - 2.98.1Sl
where (C~ >

el R '\1ulues,are!
CO: MCPH(298.1 ~1300;3.97~8,0.S57E~3,0.0,='ll.!031E+6) 3.8131
H~: MOPH{29fi 1 5 1300:3.249.0A22E-3,0.0.0.083E~ ;;; 3.60'16
C~ : IMCPH(298. 1S*'1300~5.JS.7. t .045-Et3.0.0.-1 ~ t57E+5) = 5.99~,
H20~ MOPH{29& 15.1300;3,47i0. t .450E3.0..0..0.121 E+5)1;;; 4J6599
Whtnc,
atr;, = (8.3~4}[(0.87)(3, .8131 + (l.l3ul.0016)

+ f0.13H.S.993S) + (0.81}(4.6>99)) X i([IJOO - 29BJ S)
;;; I 6t .940 l
The 1~ i.s on~ of~ ftow fur wbid1 w,. At~ 1lmd l:ui n. we~~
uegllgibl~ ~
Q == O:.H = 328.flOJ
Examp le ~4-.9
1
A boilei trs fired with a high1Jf8de fuel Oil (consi81ing 0111 ot h)ldrocarrbons) ~g a
stMdaRI lieat of oombtlstiorl of ~43.5115 J rr 1 at ~c with 00z(9) and ttl O(I) as
~ The te~ of fhe ~st and air entering the corri:IU&tlon dhamber Is,
2SC. The, air rts assumed! dry. The tlbe gases ~eaw at 300~c, ana their average
anslysis (o" a dry basis) ris 11.2% ~~ , 0.4% CO. 62.'% O-l . and 82.2% r4l. ca1cu1me
the fmotion oJ 'the heat ot oom:bustion o1 me Oill mat Is trar"~Silned a& heat to the boileT~

l48
Solution 4l'
Tab u alh 100 mo1 dry fl~~e pses. amisting of.
C(h Jl.!hnn1
co 0.4mo1
~ 6..2mo1
N2 s2.2mru
T~ IOO.OmaJ
1'bi ~on a dry b
does not tate iniD aa:ountlbe H:;O vap;rr present in
me b gases, The amoum oflhO fwmed by dx ~~on ~!!l f01md
from a OQ'~ ~ 'The' OJ; ~ in ~ .mtr repretents 2l mi.lJ..Sf.. of tbe.
air~ 1'be remaining~~ is~. whidl goes 'tfnrougb dle ~em~
~ 1iblls tbe82.2 mol N1 .ap~ in 100 fntlli dry flue ~ is supplied
wftb,~ . . ~ lbt: 01 ~~litis~~
Mob (}a emt:ring in mr ,_ (82.2)(2U79) 21.8$
Moles Ol in tlte my lie pses ;;;; ~ 1.1 + 0.412 + U ;;; 17.60

11m dlff~ ~ ~~ u dle moles ,c ( OJ tba1 ~ ~o rorm H10.
'l'bmfore .ao Ch~ bllsi ,o f 100 0101 dry Inc ~,
MolesH20f~(21.15- r1..60)ll) --150
M(JiW. H3, in Olie foel roolf:s of wm.er formed ;;;; .5()
The a.trlQJII1t of C in rdlc futl is giwn by a carboo ~
Moks C in Oue .~ :::J mula C io: Fuel - I W
:1. + 0.4 ll.fiO
1besc atPf)tDl or c and~ ~give~
~ or ram~ buned WI! {8.50)(2) + n 1.6){ 12) - IS6.2 g
rr this $110Utl1 .o f rue~ i~ bumed compm_ty to CO!(s) and H::z OOO at lS~C. me
bea1of~oo ~
6H;,. ~ (=-43,1.3){1$6.2) ~ - 6_;197.040 J

~~.the~ ~ally i'fJCC011in,gdoes DDt mpresebll ~te ~tion.
and the Ht0 is fmned as wpor Ritter tbam a~ liquid~ The 1562 g ofb t coo.~
inl c
of 11t6 mol gf and 8.5 mol of fb i is ~ by lhe e.mpirkal fmnla
'C1uJ1111- ()mil: rr:b~ 6.2 .mol (h. andln1 mo~ N:t wbkb ellb9' and 'leave rdJe reactor
~. rmd W1liiD tile ~oo:
Cn.~lf tT(l) + lS.6SOll ) ~ I LX02r( g) -F 0.4CO(g) + :S.:SK10fg)

11m ~llh iB obWued by addilkm of 1bc follo\llin,g rucriOAS. f caeh <tf wbi('h
Die sra~ hr4l ru- reamtlD ru: ~c rs :tnmin!

C~1.olf37(1) + 15~850:aJ:8) ....P Jl.~(l) + 8.5Hl O(i)
8-..SFb()(lJ ---#- S..S~O(g)

OA002(g) -+ 0.4CO(g) + ll20l(S')
1he ~ of~ ~EJS )Ulds the~~ md ~ 5WD of tbr L\U:
values gives me wmdwld b6ill of me reaction ()CiCUifing ~ lS~c:
ll H ::. = -(i797.G40+ (44.012)(8.5) + (282,.984)(0_4) c ~6.,309?7401
"The actual lfHCii!!O.U 1~g ~ m 2S~c to ~ at 300 C is

fmm
~ by dle d:Wled tine in ~be aompany~ dis~ FD pu_rpo5a of
cabbting .A H for tiM process. we may~ any amvenlent palh.. Th-e one d:mwn
wilD $01_id IJi-n.c$ is a lo~ 010e: A Hi!Je lb~ Wre._1dy !been ealeulatecl ,;md A H~ ts
ea&ily eval:lmal
The cnlhdp; change eau._d by beating die products of reaction &om 25 10

Jllre is::
AHr == ( f " (Cj\ )11) f.S73.1S- 29 .15)
w~ the <
C.Pi >111R vaha ~
COz: MOPH(ZStt15~573-'T5;5.457, 1-045E3.,0.0,-1.157E-t-5) :;:, :5-ll.~
CO: MCPH(29a1~573J 1S;3.376p..557E-3.0.0~-0~031 E+5) =l.60Ct5
f{zO! MCPH(298.1S~573. 1 5;3A70~1 .450E4~0.010~1211 E+5) ~tli'lS
02: MCPH(2!J8,_15)573.15:3.639,0.50f3E-3,0.0 -I.227E-t-5):; 3.1!61
7
~: MCPH(29a.15,573.1S~..2801(l.S93E~3.0.01 0J)40E+-5) ~ 3.5611

~"'DCe..
&Hj, = (8.li4){U 1.2)(5~2352) + (0.4)(3.6005) + (8~(-t.lTiS)

+ (6.2Hl-1261) + fJZ~)(3.56~8U.573.1 5- 29S.t5l
= 940,1660 jl

6H ~ &H~ + 4Rj.;::: =6-.309.7+ 940.660 ~ --5.l69~08Q J
Buame aha proceM is one msteady ft01 fur llihkh the slnd't vrod; and kiudic.
and potmtiaj~lJY w ms in ~ m<f ba1 [Eq. (2.32)) are zero or ~ligi
ble. 6 8 ~ Q. ~ ! ~ -SJ69.0S tl, ami..~ aD'lOtllBol heat ts ~ to
1
me boilrz for every 100 md dry flue pieS fonn:d. lbis rquesmts
5
~~080 ( 100) - 19.~
~7V1P40
of tbe tat o1 ~or me rDeL
In tbc ft~rti;OiDa ~~of ~ions 1bat m:eus at tJWD:tim.ttely 11 llnr, we~ ~tly
~ lbat the beat effeets of m3CMD are diet same ~ cases .are miHd or ~ an
aceeptab!D ~ for low ~ Ft.- mLCtium: a1 clewt"C:d ~ ~ may llot bl::
Ox ~ and ii ma}' be ~s:ary to ~Oil.l'd for lbe effects of~ and of ~8 on the
beat of N8dion. Howe\~ 1t1ese efJecb are lliDiiDy SOlllL
,. !I
~ ~
e_ _ +~ ~~L--. : ...
~.r uvw ~ B, L-- -r&.aoCN: 111!.lilppiWJ
~ _ ...UAU~~
~IDIIr.elv I!!Prnhi'~ - .-::r..
- - T -.!.~~-""'P--re. ~L-o. ;,... 'ibc
~ .. -
~ ~rttd!
o
Ce~~ ~... 1 SDol of~ u ~ rrom 200 ff.t ~ ~11J11(:?
(b) Wko ~ 2 mol of prup;tDC ~ f!rutn 25& to l ~C?
4..1 For ~y Do 1ltroo,glt a bear euhmpr a1 appmbmatel~~ ~c ~nret u -hat

. diO fi:na1 ~~
(a) When hem m me amowd of 800 tJ is added to LO moJ Q.f etby1et initinDy at
2000C?
(b) Whell heat in tbc amown of 2.S-M kJ is 31ddled to 15 mol! of ~-butene initiaDy at
26lr-C?
(e) When heat .in tbc ~ cf t<P(Bto) added ln -*lb mol) of~ initially
a~500FFJ?
U H lSO(ft~{s)- 1 of air m 122ffl and appnWmatdy a~c ~ ~ pm.aud

foi a oowbu.&tion p~ ro '9~("n whatme of ln:t tt"'lmfa ~. reqviJ41
4A How mud~ bea1 is required wileD J0,000 q of Caffi.J is healed ut mm~~ pres-.
Slll'e fmm SOilC to '8 8(r0

lSJ
4.5. II die beat ~l) or I substt_~ is~~~, rcpn;s~Jd b)!~~ of* form.
c, i;i A +JJT +CT2
show llb.al me etmr resulring u.'be.n (C p }H t8 assumed equal ro c p evaiua_red. :u iibe

arilllmdic me;m of die iniWd and 6nal tempetidllres is C(T! - T, )~/ 11.
4.6. U' th hat caparily of a~ iJ5. eOO""Cetly ~by an ~on of dl~ fom~.
Cp .... A+ BT + DT- z
8lmw that ~ mDii msui:dng ben (C p )11 is assumed otpW. to C., e\"!lfoaii!Q m a..
arithmetic mean of abe inilill and 6o:il tempaatURS ~
D (T: - T~ )
Tt12 T1+ Ti
1
4,;7.. Cakukte the be:n capgeity o f a p5 ~&om the foUowmJ informa1. n; Tbc ~e
pie ~ ro c:quilflviwn m a lbisk at U "C MKf 121.3 W".il.. A ~ k ~
briefly. aUowiog lhe ~to drop to 10!.J kh. With the stopcoct dosall'be flasi.
wanus, ~to~ md lh- ~ is mc:asumll as l04U0 kPa. 'Detetmine Cr
w Jl il:JiOJJ- 1 K - ~ ~ Ote .&tU to be idmll.ncf 1111c 19ptit!lian or i.be gas; rcmmt~ng
ml.be Bask to be ~b1e and MtilbaJ:ic..
4.& A )JI:'OQm ..trem:n is lheakd . a gas fiom125 to 250 C UJ coostant P. A quiet ~
r:nu~ of 1M enam ~nt , ~ ffOm &q,. ~43):. wim c,.. ~ . (1l!!P.$fJU111
o.nd equal to its vdue at 2:S C. b the ~ of a~ likely co be low cr bigh? Why?
4.9. (a) foT UD) of 11m. ~ liswd. in Table 8.2 uf App. B. e1.1u.atc Ilk blum beat
d ~ All0 ~ 1!4 (4.!2\. Huw ~\Ibis r:esnll ~ompare witb 1b Vil.lJx
listed in Tabte 82?
{b) HaDdboOk '\~ fo.r the lalalt bats ml~OD .ul 2SOC ,o f fOUl~
are &i'~ mme ~able. ~one d~ ~re ~ by Hq. (4. ll).. and compare
lhe result witll tbe. \"3Jae gh:en mnb1e B.l.
u.r... bctl5 of,~ it l5~c 1o J s-

~~~D:De J66.3 Betu:ene 4l:l.J
If~ 366~ I CytfoboQbc 39'2.5>
f..l4l 'Thble 9.1 l.i&B. the tbermody-uamic ~ of saturated H.qWd oml v,apar temdilJO...
~ Making use of dJe. \'IIU ptQSUres _ mnctioo of~ aod or-o.
5a~DF.dfld-Hqoid aiW!Il ~f'wpof \~~tare~ 111~ bltal of~
by Eq. (4. f ~)' a1 one of ~he foUOriri:Dg tempmnu.m: and ,mm_pare rtbe mmlt "Wilih ibe<
~ ~maltil f.J;oul 'tbc alpJ~u pveo in~ adllt.
fa) S 1). (b) lOrA. td SS( P), (d) ~F). {~) IOSf F).

IS2
4.1L li4Ddbook v.alims fot die 1atatt heab IJJI ~in J {C 1 att ~ 1in tbr table for
~ pt:tre liquids ar O"C.
1111 at<r'C
Oblomform l70J}
Methuo~ 1.189~
'11'ettadlfo~p; 211-8
for 4ft! of llbese mbso ~cak.ulale:
{a) l'1v; "moe of the JutcP1 bc!lt w T.w b}' if.q_ (4. 13), gnm ~ aiUe :n tQ;JC .
(b) The ~11J,ge or the latc'n~ belt a~ r. bJ Eq. (4+ ll).
By wfm pem::en'llf~XCS dO lk~ reml ~ differ frwn 11m wluc listed~ in T~le 8 .2 gf
A~fBll
4-U. T-nbfe B;t of ~dlJ D ~ide$ par-.ameten lft11 m~ equ4tti0t1 dw gi\ti pild fi$ o
fi of T Carr .a IIIIDib:r ef Jllll1' emnpaunds. lfQr one of~ detemtine the be:dJ
. I ~. at :..s ---r-_111 k.o.!iJ'
UJ ~011 -- M!! t.~u~<~Y ~PIG pmnt "'r _~-lOD
. fl..u .......H--f . ~
an "rl:j, .~ii 11~.1.. ..ua;
~..-.a
~lJ
elfWII'ilm. Evahw~ dP /tiT fr-om the Ji\\ea wpor-~ttre equui.OO;. and tL~ per..
aJiKd OOIJ'clati~ from Clmp. J t0 ~ L\ V. Compare lbc ~ \'Uble: with
Ibm: Yalu.e ol A 81. li$ttd ill 1bbk 8.2.. NOte Ibm no:nn'31 boifiOB point$~ list~ in ~
~ I aJtlUIIID of 'flbJe 8.2.
4Jl. !1\ mtthod b drt~l)~ f)( We~ vi:riw CIJdliticmt of & pun:~~ ~ on
the C:bpe)mu eql.tim .and measucell.lellls of lhe mtene beill ol \laporiz:diQO AH111 ,
0. molar ~IDOafWUI'tted liquid V 1~ and 1he "~ ptCSSPN: p ~- Dctmn- B ~QI
em' mu~-l for melbfl e1byJ ume 7.5~ fioollbt: fOUowing am,mthiist~:
llR111 ;:::o :n.600 J moJ- 1 v' ; : ;- ~49 em1 moJ '""~
Jn P Ji:lll{kPa ;; -li.lS7S4J - 5.622.1/T - .a.701 In T ('T = Kl
4..14. Ont hlmdtal tmol pa boar of ~ed tiqpid at ~ I( and J bar is ~d Ito
SOl K iD ~ steady-flow beat ~dunp. EsiliiDate '~be ~ clut.y fm kW) for one
of (be fdJow;ing:
(a) ~1. for wbi~ T ~ 36LO K 413 b:Jr.
(b) ~ for \\f~ T 0 == 3923 K: at J bar.
(c) Thluene,, fM which T ~ 426.9 Kar:J b2r.
4JS. Satnmed-Jiqobl beozeDe a1 ~-ure PtJ = 10 bar(~ ;;; 451.7 K) iil lhratBed m Iii
~ad,...Oow proa; so 11 p;~me PJ : l-2 bar (li - J:S .1 K}, <wr~ 11 i5 :JJ liq-
~ Dlixmf'e_ Estim3te 1:be moliU fiac,fion of lhe e:ili !ft'eam 1hat is \1lpol'- For
liquid~ c,.~ 162 J mor'
~o- f . lpoce Om <G'Il~ of~ 00 We mtbaJpy
ofliquid~.

4..16. ~ 6His. mruue of ~be follJvwing ~ a liquid at ~C.
ia) Aa:t)'ltue-.. (bJ JJ-B~ ~c) IEtlil)'lbc~n~ (dln-Hexane-.. (I!!') Sry--reD~:.
t.J7. A l:'e\"em~~ conq11~ or 1 tnt)] .Qf a:n ideal p in ~ pi!IOnicyliPdef devi aults in
a~ i~ from 1 bar to 1'2 and a temtpar~re inr~ &om 401 K m 950 K..
The tpMb (oUO'I.\ed by~ ,p during ~on is ,ghr~ b)'' PV l.J.1 ~ coo~L. mid the
mollar htat capaeiry of tile ;u iB -"en by: ,
Cp f lt- 3.85 + 0.51 x to- T 1[1 ;;:; KJ
~ lbe btatlnDSI'~ during the fJUCGSS .ad dJc firJal ~
4.JS. H)~ fwl~ can be procluced from~ by~~ the foll'tM,ing.

whim yid(ls 1-bw:tr:
6CHl0fi(BJ....., C6H12fs) + 6H~0tR)

~ ~ ~ lam of ~umbuitioo aa 2S'C of 6Cib.OHg) ~tb the stmdaJd
hCiD ,or "~ fil2SO'C orc~.l.&) r(l( ~~till ~~ co1(g) .!Wd ~0<8l-
.uJ.. ~ tiX!' r~ Bamt: ~~ ~ cdlylcnc at lSOC is bur'nrcd wllli~

ID) lh! tdJ.eurmQIJ iliJ.Uiml or .aif at z ~c.
t'b ) 25Cit ~ ilir Uil50C.
(c) :5(1% ~ w ~ 1S
~d) ~~ ~ .a1 ~~c.
(e) SO%- emess air pehear.ed to ~C.
4.2t.. What - the smodanl beat of rombuslion of n-pe1l1WlC ps w 2.5<-c if me c-om.tmsb.on

~ att U,OtO and CO-ltg)."!
4.,21. Deb:~ lbe (1~ heM of ~b of~ fvl~]q ~ Bt ~C;
fa) ~(g) + 3~ ) -.. 2H-:n,(g)

~~ii~ 4NII3cg) + S01(8) ,_,. + 6lb0f_g)
4NO(g)
(c) 3 01 (I~ + ~Otl) ~ lliNOJ (l) + O(g)
fd} Cae2(s) + UzOtO -. C2H1(8l + Cao(.f}
(e) 2f ib'J + lH10f ) ~ 2 ' aOH(s) + Hl(B)
V) ~(g~ + SNHl(B) ...... 7N!(g) + 1~0(s)
tg) C:!lb(g) + j0~(6) .__. ttOH~)'!)Q{gl
(h) C~~(g) + H20(B) -+ ((CH1h_)O(s)
(!) ~.lg) + lJbO(S) 4 ~fg) + 4Hzt ll
(JJ C~(g) + 3~(1) ~ CHJOH(g) + ll10(gl
<tJ ClhQH(gJ+ iO!{g) .,.... MCHO(I) + lftO(s ~
(f) 2H)i(g) + JO}.( ) _., 2Hf()(g) + 2S02(g)
fJJ) H~S (g) + lH-1-()fgJ -. 3Hlfg) + S.~:C'z,

(n) N1(gl + <n(g)- 2NO(g
(D) C4COjU) -+ CaO{.t) + ~(g l
fp) SO) {g)+ H20(f)- K~~ ll)
tq) Czf4(g) + HzOd) -+ C~H OHQl
Cr) ~CD (JJ + H~(S) -i> C_~OH(8Jr
+
4J) C, HsOH(h 0:t(gJ __. ObCOOH(I) H2-0(/)
( t) C2H~CJt01~(lJ)- Cl1.2:CHCK.-al1(g} + H2(g~
CN) C&H1o(IJ....,.. Oll O ICit012Cg) + 2K1(8l
(v.) C: H CH:CH~(gJ + ~Ol (g) ~ ClilafCH.<..~l(g) + H~O(R)
+
(1\1) -INHJt~' 6NO(g1 ...... 6HJQ( ) +S~(BJ
uJ - :! ) + C~fu(g) -r :!H .(g)
I~) CoHs.C1Ns (l) ...... Ct.Hs<OiCHl(' ) + Hz( -J
(~ C (.t) H 20 (h ....,.. H1fg} + GOtl)'
4..22.. IJdmnioe Ole 5ifmdard heal Ji lJ' one of lbe tcadiaw Df fb. 4.21: 1\ml (a) at 60(1 C.
Pur (bJ at C ~ 1/) : 6S C .P:m " ) 'II 7WC, P.m (11 at S90{-f). Pan({} ::.L
110(0f), Part (m ) at SSO IK. Part (n) at 1.300 L ~ o) at 800"'C Pm (r ) fll 4S{PC.
ftvt (II Ul (- F), Put fu) a1 1S0 K. J\u1 {v~ al i'tX) K. 11\vt r( w) ;n . C"' iP'au; (s ) Dl
115-"~C. Pan (~t) fit L,49i{aF).
4.23. De\~ a FQt!f.IJ.) Cqll:atioo 'fill' lbc stnndard beat of tc;fti(IO As a fw~tiO(I .of lOUipt11-
ntun: for ODC ef dle RUCtion lf\'ell mp:m fa). tb" (e). (j) . (g). (h I (J) . (t I ({).. (.m).
(n~ (o). t). ( t.),. tu). (~P , ( 1 }1 (.r , (.0-. tmd (::;) ofPb. 4..21.
4..24. . atJnl (~e [pl.m: illldh:lno) i deli~ lD a city \i ll pipcl.ioe 3l rtl \-olumet-
ric ro~ of lst roiiJiPn SUJDdnrdi cubi fe~ ~ day. If me sellioJ pri-" or t'- p is
SSJlO per OJ of IJilher be.a.U., value. ~hal ~ dx ~ted 1'\!'\!"CDUC in doDars pGr day/
~ g()Jtditjt)pS ..-e 60 F) .aad I (aim).
4..25. Nanm\1 are nn:ly pm: ~ bey usua1!Jy aim comain otbef li~ b)'drocar-
batd alfid nitmpn. Deraminc m ~ fur lhi: s.trwbnl bad: o f rombuslion as
nmdlon of compositiou for Q omblrd ps can~~.:ioin, ....~ -~ ~ aDd
n:i~ A~ licplld -w t as a~ of ~~ Wbirh of llr. following
oatumJ . lhe bi~ bciUl of ~oo?
(o) Yell~ = 0'. S~ Yc"!l b. ~ 0.02, Jc,J.l ;;;;; 0.02, YJi = O.rOti .
(f,) YC~ = 0.90. ycln. ~ O,.GS, rc,.t~ = o~03, YA"... = 0.02..
tc) ~14 ~ 0.81. JC:.Ii.t. ~ 0.01. :n;!f.h ~ 0.01.. '"1 e O.r0.5.
~ It lht bem of ~oo or nrea. {NH!J.aC()(.t}. u l:S""C ~s 631.660 J mo~-:m whtn abe
pmdcd:s arc C011g), B : O(f). aodr _ (e~ wtw is IJ.Hf34 foru.ra?
1
4..Z7. ~ /Ug-IU'r hemfng Wi/tJI! aDIV) of~ ru.eJ tl3 its I30dard bem vf rombusti-on w !5~ c
"ilh 1ticruid ~J ... a prodn~ lhe IIJ~'!1' hNllbtg mhl~ (LHV) is for waLer vapor m
product..

LS5
(c~)&plain lb= origins.eflhcse lalmr

(b) :Dctmnimli dJ: HH:\" ami the u.-v fur D3tllml ps~ ~led as pure-~
(c) Dctmnioc me H11V and dJe LHV for a ~bealing oiL modeled as pore liquid
n-da-'uflt Fw~ a~ Q..fr~;;: --249.700 J IDCill (.
4.2& A lilft~ fuel oiJ1 wi.lhwulverap ebmnicahX)mpmiti_onofCl~t h.~Jumed wil!IHJXYJm

in I botrlb coalllfiinlcter~ T.IJe lnt C\!Ohed b ~ as 43.960' J ~-l mr tbe ~em
at '!S;;C'. Cak"alal~ the ~"'l!tl ~l of (OJJ'Jliu$llon of che fUel d at 2S =--c -.vilh ~()(g)
and ~tf) pnxftlcm. -te maa me~ in lbctanb ~a.~~
~~ liqWd wata' 11 prodUQ. ;md goes to oupl:eQoo~
4.29. .tetlmne gas. is bumed ~rompktdy \\ridl 3t)CJ, eK'C!U air a ~ly aa~pheric
pte$SUXC. Bolb lbt 111tt1mrac and lb: ail eiiW' the funlare at lWrC ~ w"Jt.h wuu
v~ ,ilndl ~ tft.ue ~ ~\o-e dle f1,1:tiJ~~C: 41 I ,SOO'C.. 'J'1je Ode 1 tA . lkovtm
beal ~a:cb:mger fmm wbicb they emerge ~C. Pa- mole of mttbane, how mndJ
bl:iU is II)Sl fio~n the~ and bow IW!dJ bat i5l tmnSfarcd in the beat ~~~
4.JIL. Am.monill p eoten dJe ~UCtor of a :nitric acid plan~ miucl wkb ]Qt.~.; liiiOfre dey m
111m is ttqn:Ered for IQe compkte oonY'a:'Sio~ oflbe ammonia ro nimc otidc nod WQIR'
\lapel' If me f~ emer the ~&:tot M 15QC ( 1.61f fl]~ if~~ is 8~ if w side
.~jom; oo;ur7 and if lhc ezlm operai"CS adiabal.inllty. ~ ~ dte te:mpcnll~R t1f die
Pfd 1eaviJl8 dE rei)C(0(-'7 As$~ ideal ~~.
43L Etb)'leoe and sm:un ar 3lt'fC :md ~t: pressure are fed ma~ flllOte$$
m-w ~imo~M ~~. TOO PI~ pmdUO"J.s dhanQI by the~
Cllt,(g) + H_~) -... C2HsOH(I)

~ I.U:JIIid ~t:hanoJ en~ die:~ a~l!I,: C. \\"bat b ~~z beat tn~DSflU ~-.aed wdb
lhis o\\t.Tdl process per mole: of elbanol ~
,4..J2. A ~ m~ of lnft~ and ~ at aunosp~ ~~ a:nd 500 C is fed! 10 a

.~ ~ ltbe {oUOII\riq reactions. oca~t:
~ + Hfo~ 00 + 3ll! .and 00-r,.HzO...., ~ + H!
'1ibe pn.xitJCt ~~ ~ lli:Je; R~ at~ Jts c:QID)IIOiitiOO (mole fradiom) is:
}'CO:! = ID.oti5 )bJ = 0.1125 )"H.tO = 0.11ZS .)113 = ll6273
~ Cbc qnantily of hat~ tD ~~tot I* mole or pn'ldut ps.
t.Jl.. A f~J t(JQ.~islin.g of 7S mok~ DJe"tk__IIDO .aDd lS mol- etl:laue enten a furnace wilb
BC)Il. ~ air at JO"C. If s ~ 1o' t.r per :tg ~ o1 rue~ 8 ~ u lk:IH 10
~ ~, jfwbU~docsdmfiueps flnvetbe fUmz:e? wne~
~oo of die ftleL

JS6
4..34. "''bc p stRam from a Slfhfur ~ C(Qi$j of IS tlJl(aJ-~ SCh~ 20 mool-~ ~. ~

65 moJ..% . Th.:: ~ umm i l .anoosphetk ~ ~ ~C e:uns c:ata\ynic
~~ \hem ~86~ of h SOa ls funber oxidized SO.,. On me basis CJf J mol of
,g-.~~S ~erie ' how Ql~ PWSt bo ~ hm ~ tun~nu tim abe ~
Ji1Sft fea'\'e m .511FC?
4.35. H)l(lrogcn ht prodiK'ed by the ~tioflr. OO(s) H.20{8) ....,. C01(g) + ~ts~.
1be feed ~lie) lfie re;aC:tar . Wl equllnc1ar mi~ carbon !IDOOOX.ide and steam. or
~ it eQj~ tbt ~or m: ~2Sac ~md a~~ ~~ If~ of tibG H!O is
eon mcrl to l l1 and if~ prodiiCl.smmn lleave$ die re~ at4~ C., bow rnwdtheat
tnliW be lrnnsf:m"td fmm tiK" ~
~ A d[rectA.....AI .--~ - ~ ............_ 11 "-- ,..:I ~\r.;oJk ............. ' L-.....: . - ' ........ ... _ ,r 1' ~tu'Url\.. , _ ~
4. ~ . . n1~ 'I,IIJ}l- .,,a.n~ .. ' ""~ """' 'WI '!loll ~e:r 11~1Jg "ilii!JII; 01 ,.,VIAI\10 IIi~
[Prodeas of comhmlitm meCQ:(g) llfid H10(g).] tbe oou.tposmon @fitbe oil is 85;".\f,
c!llbolt W~ by~n. 21Jr mtrogen. and wwoiht. The Due~~~~~
l~ ~ b~r
rbr: dryer 1lf. F)i tmd ft panioJ analysis .show lh31 the) QOOtain 3 DIDI 00:z and
t 1.8 D:Jal~rq:, CO on n dr) 'Tin! fuel. air. a.nd ma.taial being dried enter die dryer
m 77CFJ. lft:h.c mmrins air tis arunt'ttd wi1h w - BJid if304oftbe neth~J:JS ~ Ius
df m: oill ~ alf(N'OO for lre--.il (mclutllng ~he ~ltle beat ~ our illl llw:
driGd product. bow DJUd) ~'Uta 11:\'ttpOOJted In ~ dr}w pee- Obm.t of oil bumecr'!
._,.,_ An equ.imollu mhrure e~r ni~ and ~ylcroe ~lnta'S -sa.e:a.ty-fiow ~ aJ: u~c
imdnbtlO~ p!c~. TheoolyJ~oo~l$: N2(g)+C1Hl-. 2HCN(g).
Tbe predud, ~~ tho reactor 6tlO""C md c u 24.2 mol~ HCN. M~' DlUClb
but $UJ'lp!iod to the ~pen- mole of~ ga,s1
4.3&. Chlorine is produced by me mdoo: -4HCitg) +Oltg. --+- ~0(8) + lClliJ.I:). The
rd stR-.:am to the ~ ~ of 60 mol- HCI, l6 mdlL-'ro 0:1.. and 4 mo1~1il 2,.
and.i1 enters lbe rtaetM at S C. lr the ~m~o of HCI is 1>~ .md if tlle JKt!1CeSS
i~ i~J.. bow ~ bc:a1 ~ be~ from tbt: ~f.Ot P" mo~ of'~
e:meriq
4..)9. A 8~ ronti~ C'Jiilly ()[CO .~ N2 is~ by puin:g!. .ndm ure Of Oue p and
mr
(hruagb a bed ,o.f lncandestent coke ( :sume pure carbon). TK two ~ that
(lr;(;Ur both g.() to tC:Qiinp4~n;
~+C-+1CO anti 2C+O.l~2CO
lbe) YR'kl Ui:_psqf~~ ~2.8~~ ~C01.3.7mot-%CO:!:.S mol~% OJ.

and 78.1 mol -~ __ The Oue ~ dim dx heats of the
min~
1('18" ~jQCj! ~~. :md ~be~~ Q( lJ'Be. .C'Qb: bed i5 lbtJd't0 ~ If tiUti.
rempenwlfC ~ 81 sJ'c..
if the ftlld :sue.am is preb=- to 8~5. and if the pnx-ess is c.
~ ,hat mlio of moles f fliue gu to ~I of air . mquiRJ. and wb:n is tbe
eoutpo$ition of du:: p p~~
4AO. A~~~ ~Nillg of 94 m~ . ~1kmc ~ 6 ~..~ ni~ i ~ wft_b lS .

~ air in a eontinOOI.I.S water ~- Bom roet and air ~emerd_,. ut 77 f). Waur

157
r
is bemed at a raae of 7Sflb )(sr 1 fmm 1-1 P:J to 2tt3 P'J. 1'be iiu. ~ ic;mrr l~
beaa all 4 l F). Of the anaing. ~ 10% burns mo cuban dioxide ;md lOfk
burns ro ~ mnoo1~ \\'hm ~~a~ ane or fuel gas :required if lbcft:
aN 00 hell ' w lhe ~gs.?
4.41. A pr"Q;S for the prOduc.aion of 1,3-butadi.eoc ~ fUMn ~ ('aljl]ytic- ddlycftogm~
tilm at at~ pre:,!l~tu:e of l .,b~ ~ lo ~reaction :
Ta ~ ~de: ~-~ tbe l -butt!pe !eod. ~ it diJnted widl ~ mdie mlla

of] 0 IIKIIr:s c{ ~ per I'Mie mJ-halene. 'The ~ is~ out ~Jl;r
a1 _s')_s~c. and ct1 this ~-em~ l3~ of the 1 -~ i5 OOII't'med to l.J...b.uad~.
How mud:~ lbcal i rr~retft'd rn lb: ~tor per mole of entering I~bmene?
~42. (a) An mcooledl coode.nser ~heat at rtbe rate of 12(\.Btu) tfg iiDlbtem .:air .at
70rf). If W: air tern~ is nllisltd l OCOFh what d ~ ~ vntnrnftri_c
Do.rate of lhe &ir'1
{b) RewOit Pad (a) for 8 beal-tra:ll&fer nte of 11 kJ s- 1, am1Jim1 m au 24~ c. aDd
ktt!pft~ me or 1 c.
4A,l. (a) J\n 8iJ"..:cm1clftioning unit e.ooi8 SO(ft)' ~~ Of Wr al 94(" F) t 0168('F). \\'hal B the
~~ ~~!tt nne in (Bru) - ?
{b) R~ut Pmt (a) ftrr .~ O.ownut of I.S ~ -t. ra lmt~ dmDF from :H to
2S -c. mxl units of kJ s-1
4-.+l A p~ YM~ bcatct dc&."CJ'S SC.1'Jl of the ~ beat of oombu.qio:n of t1r

pmpaAC [at 25r;;C wtlh CQ.z(g) tm.d ~0(8) a~ protfucts] to lbe water. If !he :pru:e or
prupme $2.20' pe-r ~ measiii"Cd at 25-C. wh:d i"l Ole ~~ cost in S per
m.Uiion (Bm)'J m per MJ?
4.45. ~ne lbc beat tr.m5fer rJl mol,) when ouco! the~ i~ below mheated
in~ ~rtiO" p~CtSS tta1n 35 m soo,c at ~~Um.~ ~~
{o) ~yhtilc'; (b) Ammom-. (~) ,.....Bubm\t (d) Carbon dim.ilk~

{e) c~ JIUJQO.U.~ c/) 8J)Ia; (8) H~n; (h) H~o ddt.2f'i&;
C') t.~Mbn~:; V> Niuie elide:II:) MlroFf~: (l) itrogen dloxidfo~
(m) Ni~ ~ (n) Oxygen; (o) ~~eire
4.46.. ~ dm 6:nal t~ far one of the gues of ~he: ~ problftn if lrm

in lbe41l1llWR of ]O.OOOJ rmo~ - iis ~ to the p . initially at 2.5' C. io Dl ste3dy-
1
flow pna::5 al atiDOSfherie p IUC..
4l.f7. Qoanl:iwn-e lhermal anal(, bas been wud .as a tectmique fo.r monlto:ri_n' the
~n eta bimir) ~ W!eruD. To :iillnswre (ille priDcl:ple.. do ooe. of dire follo'wing
problems.

IS8
(a) A~ gas miMure l8 ~ lft:om 2S to zsefC ~ 4ann) m ~y..

a ,1
Jlowt pro u = l SO) J mol- 2 ' ~is the com~ o!dle mixture1
(b) A ~cyeldhtx~ p s:nw~ i!i heated! from 100 m 400 C ot u~m) in n
strady ..Jlo process. If Q .. S4. (1)0 J uw~- 1 what is lite emnpositioo or tibe
mixlme.?
(c) A tobllme/~ gas mWI.II'C is llutld fiO:m 1.50 ~o 25~C a.~ J(ait~~t~) in a
~Cady-low ~- If Q = J7, 100 J iDDl- 1~ wt1at is the ~0!-n of tbe
mixture?
.t.AL SaW:raacd ~ at 1(31mJ mru~ mmimlolul)luxrc rs generntm

m.n liqma witer m.
l1(mnl and ~C by a-mal contld with bot 1 in 1 ct'1aDWftow be.d exdwl:~er.. 11be
X
m SK-adil), ut l (atm). ~values f(if m(~)ln(3ir) fot w.,, ~~

(d) enk9'S the acbanpr 11 ~ Jnl'C.
(b) enters the sc:banpr a1 SCIJ-C..
Forbolb C1S15. ~a mhrimwu ~ ~T fw bcol ocblmle or l1CJIC.
4.49. vtated wam"' "iiPPt Le-, $kfllll, is oommoot)' Med iih a heal soorte io bear-adliiiDgeT
~,pJiRtion~ Wliy mr.Jl1flled vapor? Why Sl:ll:lmed. Jtmeor vapor'? In a plmll r =lAY rw-
li(1J)J.'b}e w~ ~ '-l'ari.di of5ailll'atld SkUPMCt"Omi'D(lO)y nibble; fur ,~mpk,
~ted ae:am tu 4..5. 9. 17~ ~ l3 bat. Bm die hi.gb lbe pnlUure me JLYWer tbe use-
flrll ~ comem (wlly1)1 and tbe ~ 1be runil eo.u. Why tlwn i hi.gb~
i!&enmwed?
4.50. "''be OX1tb.Lfoo. of ,W~ ~ 11be pnntripa] soomc of ~~ fur animal eeUs.
n
AsmiDL'I die reaclilllD ate glucose (4!{~1lo,( md oxy~GD r~U') 11. The pmducts ~
~(g) tlOO fhO(lJ~
(a ) W....tt- tll s..-t---,_.

tul!iiol ~:. . . foc
t~'I;Q cqua-.;n .........,_,... .-:..~-:....... -d_ ~
__ ~~~!,LA., - _ the
.._etmin:t .. ~ ~t
of ~OQ at 298 IL
(6) Dtuitlg a day an m-e~ penan C005iUilXJ *ml JSO kJ o e.XI'I)' per kg of bWy
1\5~ d~ 1.hc $QI:e, ~ lltf~; C'JS~ l.he ~ ~) of
~ mqJJiJOO daily 1D ~a peiSOD ofS'J Q
(l') For a popuiiDaa ofllS miUion 1p crson5 W. tnmi of C~ ( ~ ps). i~
~daily hy u.re ~
JJiJm: Poe gt'IJQ)~ alii: = - n4.4tJ mo1-~- ~ 1t11r: ~at ~ftltperarwe
oo VI' br:at of~
451~ A oal\mll~ fuel cootaiti 8S lli!OI'i6 ~.. I0 IDDI- ~t.. and S mol~ nilro-
pn.
{a) Wbal is the 81.:at1danl hea.t of eombuslion (k.J mol- 1l of the fuc1 at 2S C with
Hz()( ) . 3 pwdnct?
(hJ 1bo lUd opplied b) c~ ~ ~i'IIli.SO'J ~ .:Ur, bodl e.nreill\g ill 25'"C~ 1be
prndwts ~-eat 60C.fC. llf eo~ i_s complete and if no d~ re~ weur,
~low mueb ~ 1fkf mot" of ftd)1is-~~~ in lhe fu.macc?

Chapter 5
The Second Law of

Thermodynamics
~is ama:med with ll'uDsfmmalioos of mern'.. mdi the 1lws ci thmncd~

ics deiaihc1M bou~Mb within whkb ~ tnnsf~ are ~"td to occut 1'bt 6t$l hnv
~ me u
obsuvali'On rdYd eucrgy is ooosenred, but im,peses oo' restriction oo lbe ~
direl:tion. Yet, ,dJ. experience tndicata tbe ~~of -such a R.Stridi~ llbe OOIJd.tie s~r:nenl
mwmdt~ tk: ~ln.
1ibe ttilfae-JK:eS bet\lt'tell me r.o mrms or ~..!b91 md ~ JXB't'ide SOllie imigld
into dm second law. ~n an GDC'.fiY b~ both WIJd: :litld beat are ~Juded as 5imp1G additive
~ impl~g lhar one w:rl1l of bal. a joole.. h equi\1llenl m me. SliDe unit~ wort.. All~b
dtis is uue wilb respect 10 an energy ~ expaieuce teaChes ibat them Is a ~ of
kilid bclw~n btae .Qid " 'oril 1lii ~~ b ~~by tbt follk,iwlina lias.
WoJk R!ldil'! ~ iDto ~forms of tnct',U~ for~ intO JP(IlmdJal ~
11 lly ~Je\-airon ol a weight into tin.ecic !el'laCY by aiX'denlkm or a ~ mm ~ca]
IIX'll)' by opuatioa of a pnmttol'. T'hese .PfOL'lCSia can be made to ~ a ~"'Cf5io:o
6t1iciepqr of 100'1 by dimimitioo of ~-Qoo. di~pi$-e p~ ttw ll'iiMfili'm& W\.Vt iDto
beat. Indeed. WOJt readily lr.mr~IIOI"l'Dedl oomple1ely iniD beat. as dcmomlnll:d by JouJe:'"
9~
On the otb-- M_nd, d ~ffnrb oo c.kviw a ~ fttt ~ ~ ~n of tr.a&
completely 1om wart or UrtD medkafikul ore~ ~ hiWe ftiikd. Reganlk~ of im-
P~ to die cmv~ ~d. com1:1'5ion dlicieocies do DOl u~ about 401;. EW-
dmtly, ~ ~ a fvnu or ~~y murm'icaDY ~ U$dUJ and ~a le$s ftlw.Mc than. an~
qwmtily ofv.wt .. medlmicd ~ ~
Dmw"ms fru.nher oo our~. we mov, 11m thr: Oo of heal. between l1"10 bodies 11-
ways tabs piaec from 'die broa- (0 the eoolcr body, andlue:ta iD 1hc K.va5e dim:tioa ~ 1.9t.
1bii ~ b of !!!Udl ~~ ~ iu ~t sa'\fft. as an acceptable ~on af lbe
SCQ)nd la'Ao",
~'~ Obras proteg1das por direitos de autc

160
5.11 s-TATEMENTS Of THE SECOND LAW
Sb.tmlent 1: o apparaw:s em opente in sud~ .a way trw iii. only dttct tin sy!.lem and
~p) b m omt\-rrt hem' ah~d by .a systrm cm11PI~tely imo wwt done by~
$)~
Wft~Mmt l : o ~ I)O$$ible ~ CQ.JQj51-~ ~ i:o dle U'all5fu of bw1 hm

ODe ~m levd ro a ~~<)De.
smtemtat 1 dOes nat d:w beat QIIDO& be. comremd into WOtt: only mm me pro-
ces5 ~ both dH: :&)i~ md ias ~ u:ncba11pi If an ideaL gas in a pis~
~ ~y ~~ rerm'SibJy and~)' In a low~~ Eq. (2..3' re-
quims (haf 61Jf ;;;; Q + U' .for ;m ~ _ps., llfJ' ;;; ~~ md ~ (J .... -W'. The beat
~ by g p fmm dir 8Ulim:Undinp il ~ tn tlhe . ort tliifisfmed to lhc &ra~lll'ld
lags by die m.'mible . M of the This might 4 CODb'DdictiOD of~ I.
~ m
lk Sttt'fOnodin 'I M ~tJ~ 11Mt ~omp1ett ~ of~MQJ iM"o wo:rk.. H~'a,
thi !itltemem .requ:ires iD oddi'tion no diange in d.e ~mA ii reLfui~t tbat i~ tux mt1 owl~
ro the~ in pressure.
p;oc.:m is tiPVtrd in.~ r..)
'~r;e thm: ~on~- utitJI:tattly ~
tb of 1~ ml'ftlll~ rutd api~A8ion ~ lbft'elo:re.. the ~tinl!l()U5 produruon of wod:.
from heal by llldhod ~ impossl"'bk. [[f die Oripul ~;ate of ~ ')~ i5 ~~ ~
to <mply ifb ~ R(JUi~ of ue~nt I, cnmgy ft'mn lhr ~ngs in tbe fcmn of
W'Oik ~ to enmprcss the .p& ba to it& anginal pressure-. At the jWDI} time ~y as
k...at Cmd 'tn 111m MJ~ 10 fm*i__mifi ~t ~- 'fbb re\~ pt1)(JdS
req:uires ;~~ me anto~m~ or v."Vlk piDed from the~ bmee none~ wom. Pfl'lduced.
E~ ~eli~ I may !be &\JII~ in. llD iifa:l~Giive 'IIQ)'" l!C:
~ lac [( Js knpussible b., a c)'clk ~ lO com-en t'M bein ilbsofbcd by a

em oom,p~'emly in10 wort &me by tbe S>~1em.
Tbe """Old cp;lic~ chat du~ Jli(cm l1C! ~ pGriodic;dJy to~ origiual ~- ln.
me ~ of a gas to a pktlmlql:irukr MS.eJnblyliJ m mhial apmion mny be. ro:nov.~ aJt b;y st .
rdllat l'eitore dae o~Uml ~ tlms IWQd.udog 1 complete cyclle. [f dx pr~-s i8 Jq1Cated.. it
bea~ a c.."}'dic. Pft!C ~ ~t'Sit,m cu .&tJ C)dit; ~~ to snr1~r ia amoltM!i to ~
~ limihllioo ,as, mat introdu.ced by 'file v;-OIR'.k ODIJ ejf.ea in~ I .
tbe. seamd.bw does not prdD.Oit b ~ of1lllt 6:om ~1- lQt it does pl~ a
1iiDit Oil h mucb o ftbt beat~ into a cydlc ~can be~ lnao wort oo~
lby abe ~ Wdh die cuept tOO of 1 and wiad, powa'. the patti&~ conversi~ of beat,
.: _....,. _.........J. . [L - . iL... -- -~-- "" ' 1 ~- -n::.'l .....-t-.-~...- - f ~r "'"L.- .1-.. . ~~ f~
.M!!,Y ~JA !l.L.III!;l llrVJI ~ 't !Yi1 ~~lal ftR!--~~~ 0 ,t"""'~ .... . J,m;i II,JI!n1L,.yll+t!...,.l 0
qu ti:mi'- ezpreaian b 'l he ~ of rhis OCJ'Weflion is lk ~ tep in i.be t~tta~mcnt oo

tlbe serond law.

161
5.2 HEAT ENGINES
Tbe classicall upp uach to the second Law is based 001.1. mMro:u:tlpiC ~ of pmpcnie$.
~ of y owkdp qf the struc1ure ,o f mil1ml' w beb:Mor of~ lit arose
&om ~ stUdy of ltwt efJgiM-J~ <kvicft ~ madli&la libal ~ wtai flam bea1 in1a ey~rie
An J----rr
m:mces;s..
li" lllli~Rmn'lc is a steam IVWW'Cf'
rr~ ~ in a.zA tbe_ '"""
nluilll
rVIii'D ~- a.-.w
'f t'IIIN!! !11<511 _ \Uil - ,.__..:__111
tU-O) )ll:lil.V\Pioil!Y_)f
liClWm to its origi:o;tl &tatt.. "11m eyole fin it ~farm) eocsist! of 1be. roBowin& Sie~
liquid 'WIB from a COIIdeB.su ~ ~ mm a boiler at. ~lN ~&-

Heat from .aNd.~ t4 oo~ of a. I~ fu~ o.r ~ fimJ a mx:~ ~Joo)
b ln05Ctmd mthe boik:r w the ~. aJnmtins it m higb-iemper:oure ~ at me
boilup~-
Energy i hJJSfw>ht . , ., WOik from tbc ~ tD the ~gi by Q device iliCh

a Oli'biJte. in v..hidl lbe ~tt-IDn cx}'11d.'t 1t:Q red~ ~ ~ ~pntur~
~ ~ fwm Ole tulbine is wodemed by ll'nMfer of b m to the. m~
prodttcing .Uqttid 9ti'Otef b ~dum 10 dJr, bolter,. 1hw ~ OK cycte..
&$tutJall'O all ht:at~na:L-ne c) _k:s are absorption of lal i:nto the 5)~ at a h~b km-
_peratllM. ~~ of !beat w me
smnnm~ Bl a ICMb' ~'81UR.. and ]'mldlltliuu of mk-
ln the~ ...,atmem oiheatengines, ~lbe twa~ le\'$ wbicb~~ lheil
o;pemlioo are maiotamed by heal ~uin. bodies hn:lgi:ned ~bJcs of absorbing or rejeeling
millmited: q~ o:f ~ Wilhoo.t IPD~ ~ge~. In~' l'bt ~ ftqid tOf
a had eogim= ah5101bs heat lON I &om a 1m1 reservoir. ~ o oct RIJ10UM' of WCIIt fWf,,
cfls.catdS lDw !Qc l to "' cotd ~. :md ~ 1o ills i.niiW stale. The finlllaw IIJmVo.re
redneesiCK
1(5.1)
The th1mtal ef/lc~ of ttl:e en:g~De is deiDl!d M: r; net worik ti~~trputlb~ ~ .ifb
Eq. (5,])dd5 bee~:
(5.2)
Absol~valuc sips o:~e used 10 IDiib: rhe equ-.dlion ind~r oll.be. sip Mn-wnrions
ror 'fl ~ w.
f., ro ~ mnty (101)1, lhamd ellieiency}. I ~Qci iDIISt be zero. No cngina ~~as
te \"ef becm built t1!iM ap;pr~hM l.biA amb: tmm is lliwat'"S ~ I() w WJ resttl'14oir. 11Ii5
obsen,W.oo rmm ~ri:nl ~ b 1 fl:w; basi for~ 1 and laol1tbe -.md ll'aw.
[f ;1. dJam;d elfidency or
1~ is mJt pos_sible for heal qi~ wl'l=n dim lktm:mfots
rM Uppet liRUt? Oftt wouJd ~ly Gqltd b tbmnal dfkicucy of beat engine lD depeDd
00 me m
degJee or ~ility -of ~ hldeed. a beat eng:Die ~ ,PJ oompletdy m
f"e\-crsible manJJer ils YVf spec:ial. and~ c.aUed 1 Clmm ms~n~. The .e~mtics of such m
kfe.al .e~ were first~ by N. L S- ~ mISlA. "l'be (Om~ 1t.1: ~ up 3
CIITIU1t r,'f'lf! ~ pedanm:d in lite foUawing onier.
t lbc ofat~ dlltl.:bix~.aftd~~~lr.. lllcdd~rrula:.
:: ~ LcmanJS&d)Cutm~ ( 11N6- t83.1l. 111 ~~

Stepl: A ~tam al m~inid:JJ ~amrei11 a onld~at Tc ~~a r~lYI'Siblt
adiabatic~ thai C1111Se8 its te~ to rise ~o tbat of~ bot resefi.W at TH.
SRp 2~ The )Wan mainaains ronwa. wiJ:h lbe hol.re~"'ir m T.n , and nndel:goes n
~re isolhen:n:d proees5 during Whieh beG ~ Q111is amoJbcd from the bot rcmvoil',
Stfpl Tbe S)'Stem ~{)CS a ~~ adiabatie )JI'OeeSS ill lbc opposi~ direeden of
~tep J thai brings its ~ back toihal of lin: cold ~'Oir a1 Tc.
:Step 4: The sysn;m maintains ~ ~ the ~~air .U Tl''" and u.ndcrg(le:S a ~

vmUrh ~ p~!i 1ft lbe OIJ.pc$te '~on ~ol srep 2 tbat ~ u ~BiB iDifia.lli
stMe ' bb rejl'.IC."tioo of beat Qcl to lbe eol.'d ~
nil Sl:l oL ~ can in pri:ngpJe be pafmmed ma wrry kimd of S)~~m, biin aoly ill rew. [Q
be. ~ later, me of p~ interest. ~ of the ~)'flem. the ~~ balance of
Eq. (5.1) ~dial IWI:;;;: I Qt~ l.<= lOci-
A Camot: eqins ~ bill'WI!C!U t'Q b~ ~~ in $.\Jell a "''&)' [bar llfl ~ @-
oriJed is Omid'rrm.i DJ the ~111 cempe_mture of the hat reservoir and llll beat rejec'ted i-s
rr~ 31 the~~ of the eold msel'\00. ~ m~1 ~~ apen.l
ing ~two beat~ ts a Csm.ot tngine,; a:n e:op ~ ou a d'.dl'trenl cycLe
JJi.U ~ly llJ7tUJ~fet ht4l ~ 6nittc lmlpetarure difrere.oces mid ~fore c-i.umot be
~le,
The proof :is ~ a lbe prwnise dmt an engine ~~!li witb a tbm:~Al cf.licl!CJM;)'
gr1lle dum mm of a OimtJt ,Mgine ~g becwen the same two bt2t reser'!t"'irs. Let me
Camnt engine abscJb ~ IQHl tWm die hot ~ir. ~ v,'eft 11ft. and dL~ heat
tQu 1- IWI to dJ~ coldl ~oir" E~ E ~ hmt I Q~ l fttm~lh~ hot resenm.. pcoduce8
& sam.: wml iWJ.. and disamls br:tt Cl11 1- IWI to me c:ald ~. If engine E hilS die
~~9
IW
->---
Uf l nnd
lf2'n l IQui
B~ a ~
m
m
is ~~~. il may bt: ~~ 1n fe\fene~ 'lhe Cm:ta1 cyel~
is lben tmvm:ed ~ ~ diR&IWn..a:nd i1 beeDDJeS a ~i'ble Hdrigvntion e}'\Ck ri()r
w
'\lt1rich the qwmrltier rQ HI. Qc I. and r 8Jie the ~arne: IS for the engine .cycle bol ~ .~"ef~
mdircctiGL IILct m~ driv-e me Cimot engine batkv.~ as. a CIUU~ remg.ermar,. us shown
~y irll Pig.. 5'. 1. For llbe eogble/refrigeraJ.or ammimltio~ lb~ net heat e.xtra~:ted from
lbc cold ~ir iB~
IQHI-Il[- On1- JW) c IOHI -- IQifl

Flp~ S.l ~ Ettp~ E ~:QJ a. Om:u:Jt
rcfiri~C.
ffN] - 111'11
The Del heal ddha:'ed tO th~ !hot ~'Oit' ]~ mso J Qu~ - lra'n l 1bus.. tbc sule ~t of
lbt: cQIDdrcfrigc~ comb:inaoon ~ the lniiSiiu of hm from tempen~~~re Tc w tfie ~gber
tmJpelialll.lm Ts. Beall.ISe 1.1\rl!S is in violation of ~m l of die Ra)Od law_ ~he od~
premise 'lbat ~ogme E has a g~ lbemul eflicimcy thaD tbe Camoc engine i'8 fake.. QDd
Cmioo~'
tkoRm is PfiDW.
In similat f.ushi~ OiiC G\0 prove Umi all Camot engipes ~ l:Jriv.,"'CCJ be4J ~
'\~am~ same IW(I t.empemt~ ha..-e the s:.une tbetmal efikie'ru:y. Thus aJ cor&Uary ro
C.tUJ~Ul~r Jbeol':r!M *t~
1be 1bennal etftclenq" ot camot engine depends only on the tem-

paraiiQ levefa and not upon111\e WCdlng tUbftanee of the engine.
5.3 THERMODYNAMIC TEMPERAliUR SCALES
lD lb: preatlin! ~Wit v.e ide:lliified tmrperanm~ ~ b) tbe Xehiln ~ad~ e!rob~
v,i tb ideaj.ps thmomdcy. nis ~ oot ;pm;lude tWng .~of the oppw1Wrlty PfO"'
\!lded: by lhe Cil.tnDl ~ne f.ll estatillsb a ~~~~'"11linii:c ~scale thai is truly i nM
~t of any m:m:rriillltp~. Let 6 ~t ~anpmltlBe Oft ~ elll,pirlad scale
that uru:quivomD~ idenlifies ~ ~ Ctmsidr:r two Ol:mol ~ o.ae OJ.Inting
~ ~ bOl ~vi_r :11 ~~811 aooa cold ~~1Ju at ~lk:. and '"seeond.
opera.tiag beR\'een tllte resen'Oit an 8c and a sriD oolder resen'Oi.f 3119,_ as~ in IFig. s~
The heal rejected by the fiB1 engine lOci is absorbed by ~be s:ecomt therefore tile two eng;ines,
"WOI'ki:mg ~ comt~ a third Cnot engi.ne- .~g he4t l Q H I from tilt resen'Olr at
1
IJn .IUld rejcctinJ heat I Qr 1m tbe eservoir wfJp. The ccrohlry 10 Camet's lheoRm ~
tiW the t~ e.flicitocy ()f tho first ;.qgi_ne is ill! fuacliou of 611 iliDd 9c:
- IQd
9 ;; 1 - H2,tl =,pee,. 8cl
)64
l!.pn U C.wilOI m~:5! ~ ilfilt 2 ~J: I
third -~
(5.3)
whee I is an Wlblcwn limotiou.

For~~ and third en~ ~ua.tiOl'ls of die~ f1U'Iaitmal form appl):
IQcl ........~ IQHI
lQr l =j((k. @p) ~ IQtl ~:: / r(IJtJ, IJF)
Di'Yhioo ,o flk ~of~~ b)! tt.: first g'n-es:
i!?nl !!!1 ..;;...;....;;..;......;..,;,..
-
f(9t~ . 6F)
IQcl /(9c. OF)
Com~ of thi5 oq~m With Bq. ('..3~ $hfiWS rrb3l me atbitm1J remperamre .o,. :DlUiJt caneeJ.
from ~fllle mdo 00 lbe rrigflt:
whele ~ ~ aootbe:c unkoo\\J"D fuDtllio~

" 'e from Eq. (.5.4) tbatl de w
e\~ at ND lhermodynamk lmJpe.ratm (6)
all! in the: ".iame mlio as me absolute ''llluc5 of beat a~ and heal ~$1 by a Canmt
t~~ ~ between mese WO ImDpemtwe ~~ quite inde-pemkm of tbc ~
~ ~~ b
of %ll1Y ~ Of ~1~ is rarbitnu'y. ;e: may Sd tJ etJu:d to lbc ~Vin
ldllpemn.tn: T: EQ- (5.4) Ibm hew
IQHI tfr(TH)
lQ d ~ 9{Tc)
Tb~ ~v~ lhc r~ v llb be~
Ideal Gas Temperature Scale; canrofs Equations
The C)-ell! uu..-~ b)l an ~ PI smriot; tile working fluid 41 a c...- ~ug;ine ~ ~
by a P'V di~m in Fig.. 5.3. It oollii~ of foar m:~ib/1 ~- c~in-J to Step$ 1
th:r<rugb 4 of me general Cwnot qreJe described mme preeedinf section.:

16c5
a ._.. b Ad.i.akttk mmprean un:tn 1tbe trmpetm~.IM rises from Tc ro TH ..

b - c bot.benaal e-lp&Mion Bl ~ poiJtt t' with~ ol 'heat IQTl l
e - t1 Adiabatic apansioo Wl1i1 lbe t.empaatme ~to Tc.
11 .... a ~~prr6Siourolheitrititll~With~tionorbalt iQ d-
~'\
,
' \
p
FipR 5.3: PV ~ ~ Ci~m
~ (01' m idt:1d ps.
If
Fm me isotbcf1113) ~, 11 ~ c and a ~ ,u . eq. ~ l ..'ZT) ,~ds:

- ~ ~
IQnl ::-: RTII 1u w- and IQ,cl ;;;; RTc ln .....-
~ ~
'Qu i Tr~ bt(V('j 11111

!Qcl - Tc ln(Vd! VG)
fotaB~ ~ Eqf. ().22) witb d~Q = 0 bcoomcs.
- CyR dTT tlV

~- ~-----..
V
For ~ep a ... b and c ,... 4 ~ i:ntegtalio:P giva:
t
v_. 1,"n --==fn- Va~
l Cv JT
it
-~
Tc R 1
=In -
V
amd
Tc
CvdT
R T V,.
Because the left sides of these lWO ~ons.ue lhe ~

166
Eqonoo (Sii) nuw ~
~ ofIJDs re~ Wilfrl Bq. (5.)) yiekk 1 me ~e~.-1 pos:slbl~ functioMII reJmion lor ,
n.tmdJ~ \f'(T) ~ T . We eom;]qde that die Kehin lellpnlnre ~ ~d (m, mhc propmics
of idGaJ g&.W5o,. :is iq fact I d:m\OcJy~ ~ ~ of~ ~ tO f any
~ s~~ Substi1UlioD of Sq. C:S~1) mtoEq. (1.2) ~
(5.8)
EquatitJm ~5_7) and (5..8) are known Ctmtm "B ~-tpllfliM&. In Sq. (S.7l the~
puWble. wine of 1Qcl o zei"C); Ubo eo~g v.alue of l'c i ,atrsotu~ m'tl w lite Kcl'rin
~ whiciu'JCOUSat -Z13-1:5,.C. &:itr~Ui<.lD (:SJO shows Ibm ~thama'l ei'lidmeyof a CMII'\(n
en~~ approach wmy oruy hen ru app-.wdles in:finit)~ or Tc appro~ ZWJ.. ~
condition exists on eardi~ ab t~ beat m~ ~ opentre wltb ~Ill efticlt-ncies.
1A's than llllity~ 1bc oold ~- available oo eMth are tltt Wl1!lfl~ 'll:d:es 4ltdl ~
4M me ~ I"OJ wbidl Tc ::::. 300 It 1iot ~~Din are objects such as. fumaoe.ilii "llere
the mmpermnre. ii rn.aintainedl by co~ioo of fossil fuels ;md 11uc~u :reac:l(d wbeR the
tnnpe:raturo is.~ by fission, of~~ FDr ~ T11 ~ 600 K. With
tbes.e vatucs. 'J ~ J - JGO/(j(J() ~ 1Q..)f an a.ppro:U1!'131e limit &I' llbe tbem:W efficieDCy of a
a.mot enJ,~ Adual h:at m,PllCS ate .ir:nwersible, md r, ~ly ~$ 03S.
Examp e5..1
A ~ceJBat power~ rmed aJ 8CKl.OOO kW. generaleS steam1at 585, K and ~discards
beat to a rlvef at 295 K If the thermal efficiency of me pilard iS 100/o oi 1he maximwn
possible vaJue, how muoh heat is <~sCalded to the IWer at rated power?
Solution 5.1
The mW1num ~e fhmmll ,efficiency i! gJ''eD by Eq. (S~). Wilh TH ~ the
~~nnd Tc m.dle ri\u~:
295
'him ~ I- ~ ~ OA9S7 and q -. (0.7)(0A951} .. (lJ470
where f1 i:s. tlle actml dtenml efficiency. Equatio (5. Jl and (S.Z) may be ~
1
biMd to e.lliminJib'!; IQ H I~ solutiuo (t'lt I Q,c I Ibcn ~=
IQd ~ ( ~ 'I) ;.~~ ) {1100,0001 = I ,505.)00 I<W

1 1 1
IV! "" (
'J'hU, beat rate of 1JOS.SOO kJ s- wnu1d GIU5C tt ~ ~of~ C ii.n

~~mw.

5.4. :Bn!mp> 16'1
5.4 ENTROPY
Equadoo-(5.1) for Eli CturtotCttgint may be wrlJuen;

IJ,Qs ~ IQcl
Tw ~ Tc
If cbe heal q~dE mer ~D me wa.ting ftuid oflbe eq;i:ne (mlher dum 10 the~ ~irs).
1be DtUDOrica1 ~ of Qn is ~ ami 11m of Qc is oegalh~ The equiYalenl equmion
WlriRen witlrout absolote-valoe sip d lha'efcre
QH
~
-ac
= ~
Tn 1c
or Qu + ~c - ~o (5.9)
TH Tc
~ for :a eompkte eyde of a Ca:root eqine., lb.e mwo 41~ Qf T w.x iaud with tbc ah-
ofdtc ,enginesum to zero. The W01timg tluid
sorplito~ ~ P;jti~~ 1(){ bet~ by dxo 'WOiting flaid 1
o[ a cydie eagine periodk;any remm& lO i1s bridal~ and iu. preperties,. c.g.r lrll:lpCf3llll'e.
pres~ and iutwmd coefiY~ mum to tleir initinl \'aJoa.. lndeecL a primary ~lc~ af i1
~is ll:tt ~sum of~~ 1& ktO for ally ~I:C; qdo. ~ rw
a Ou;uot (:)'de
Bq. (S.9J Rlgps~S the ~ of a~ wbose c.b:mgJ ~gi\'CD by1be quant:ities QlT ~
FlpDU:Aq~
f'IG'\Wbf!e cycJi~ ~ 4r~D
0: .. ,. \1 2 di2tpun.
Our purpose now is (D dKJw that 1?4 (:5.9) fM a m~ Camot C)'d ~

I:D ~r re\:-ersihie cy"les. The d<l$0d tur.'e an die P V~ diqmn of F~g. SA represenb u

I6S
W'biu'lty revenihle cycle tm\'mled by an. ad>i1mry ib:dd. Divide the eocloscd ~by Zl ~ CJf
tm'W'Siltk adlabatic ICUJ'\'Q; bet:nuse $u:cb. cune s caruloC ~ (Pb. S. J), they ma.y be dmwn
~!:) close bJ oo.e aoolbet. Se\uaJ mm eon are sl)owa on me fig~J.J"e as long 'hed
lints~ CmJ.DeC~ adjacenl adiabmic CUI'YeS by two mort rever.DJe isvlberms whim appliO:tima:te
lbe CiUfVe oftbc amitt.-y cyde as ~Y ~~e.. The~~ cleittly ijnpmves 11$
die lll([]a1Jra.tic ~.!!o ore more ~~ spaced. Wbm the se.p3l'atloo bet:o~ adrit.rariJy . _man.
Ole origiaa] cycle is faithfully r~ed. :.acb [pm ol adjaca)t adJabatic cun~ 9d ilhctr
iso!h:rn'wd ~ ~ ~ o Ca:rnot cydc for which Eq. (5.9) applies.
Eicb Camol cycle basH own pair ofisodlmns 1"H and Tc and associated ihe&t qtl8Jllit:ies
Cl11 and Qc. These are ~ted o o fig. S.4 fm arc~~ cydc. ~ the Bdiahatic
c:ufi"CS ate 10 dJOSdy ~ mat the ~ !iUpi are inli~ the heat qllWllities
~ dQ 11 mtd tlQc. ond F.q. l:i.9) for each Camot q--cl- is wrin~
tiQ.u + dflc ~
0
T, fc
liD lhk ~on Tu and Tc;. ahsolure remperntllR'S of lhe working ftuidJ of lhe. Crunot ~e:s.
am alSo lbe tmnpaliiUteS ~ t.y dlc wo~ JJuid of dtt' lrililfmy ~~ Swmrunion of
all! qumtiti~ d Q/ T fot l.llt Cat:lilOt dJgioes ~ 1.0 dJt' tnreg~Dl:
~ d~ Ill == I (~.'10)
\i!ilat: the~ in dlc: ~ sign ~es ~oo over me arbiDUry cycle.. and the sub
su.iipt ~ indicale:s dial abe cycle is '*"'CBible.
Th,os.die quamri~ d Qtn1T sum ro' :wo lfor me .arbilmry cycle. ~~ lbe c-bamc..
lefli:scil: of:a.propeny. We ~[(l(C wcr Ull:e ~of a p:mpmy w'~ difkrcmtiaD t-b~
fo.r die ~ cyeJe are gh~ by these quamdits. 11r ~ny is callrd B1rlmp.r (l'Ji tro-p ),
~fi~~afe!
(5-.H )
whaic: $r i the toaal (DUller than molar) enoopy of ~he' S)'SreUL Ah~y.
I I}QIC\~ =T dst] (5.U)
Pnifi' A JiDdJ B en me P 1 dil'llm of F.g. 5~ repr-esenl ~~ equilmnum lotates of a

partia.du :ftWcL and P* AC IJ and A DB mow
twu a:rbit.nu}r mrasible pnx~ f..'VtlliltctinJ
~ pOi:nts- lll1t'jgJation of Eq]_ (5. t I) fm eat-b (nth ~l\~
~sr -1 ACB
c~~a(el
T
and . s: = f
}-\08
4'!_~
T
mview cf fl.q. (5.1 0) me. two imegrm. must ~ ~l. We lha~f~ eopciQ& that tlS'
where
~ I()( pad} and u propcny ch~ ~by SIB .... srA.
"j;
If rbc fluid i:s. dl:anfed from slam A to :am IJ lby nn frm.-enlblt f:rooes.s... 1bi: entropy
c11~ l1IDSI mn be ~Jist = s~ - ~ . bQt experia~G~t ~ that l:bQ ~ is m>t gh~
!by f d QIT ev.tl:nnlat for 11x: irrei."'NSI"'Me pli'OOC'S'S itsdl became llh.~ .caJculation of e.nrropy
dmnp by dW in~gDl must m~neat be: aiong ~wble patm..

)69
~ .5.5: T"" Fe\~ patfis

joining equilibrium ~ alB.
The ernrqpy change of i:l hmJ R!Unwir, ib(lla"evef., i$ ~~ ~ by QIT~ w~ Q is

the quamdy of beat llmSfared to or from ~he rescn'Oif' d tempera1IJ:IIe T. Wi'betller ~ m:uW'cr
is f'C\1:1'SJ!1Jle ~"bk. 1be RaWn i!i that the effcet of btal ftmiSfr:.r on a be ~iris
me :Salllle l qi.b'dles!! of tbe l~pemute cf llte SI)U(lle or ink or ~he heaL
If a p:moess is re't~ "MIIIldfabarfe~ d ~ ~ ~ men by Eltt. (5.ll1), d~ ~ i l "l1::ns
llbe mtropy o f.a .systnlll u 00115~ dlll'ins a ~u adiabmic ~! and dE proce:ss is mid
robe i.smnvple.
'".Ibis di...~ on ,Df,~ can be SUilliDarized u tOollmw:
Einrn;,py cm.-es its exi'Sieoce ro lbe ~oond ilnw~ from w.bicll k ~ in l:fil:dJ lbe ~
'lq}' a inttmal ~ ~~ IJQm t.bc fiP1 law. Bqua.tion ( S .II) is 1be ultimate S01lliCe
of ,all ~_o:ttion:s ibm ~~me the cotliOpy to ~a5lllabk qiJalJiitin It does I'IOt. n:pi'C;5mt .a
ddinllicm or emro;py; mere is nooe io the. ~ of c~ l:bermodyoatnics. Wba1:
i~ [I)WVi~ iJ lbc IJICaD.'Ii fur cakWIIing drwJgeJ io lhis property. llB eMelltia1 mture u
~ b)' 11m ftdlG-..-ing Hiom::
'There exfats properly called enlropy SiF whllcb I .am !I ntrinsic

proptfty IJfa "~ ~ltr' ~ to'Ual measurablecoor-
diMIH whfcb ChlracteriD the spt8m. For a~ PN<a,
Chang In ttds piQpeiiJ are given by Eq.. ~111).
1'bc dmo;t W. ~nlropy of liiDY ~rS'Wm \II'ICkqoing 3 linite mw-r~ ~is:
6s' =I tl~~ (5.1J)
Wlltm a S)"Stmm undmgoes an U'm~~ pmc:ess between two equilib6llnl Slltes.,, tbt
muup)' dtaJJg: ,of ~ S)'$1em 4$1' b tv:duated by appkalion off:4. (S.ll) to an ad:!~
rmfill ~~ rm'1Bt'1ibl~ pJlJICnlhat ~the~ ~hxn-$-of ~ {15 ~ .~
jm)CC$S.. -~~ ii rws camed out fur me ~wble path. ~ e111mp1 is 31 state
funmomp ~w~ enuupy ~cbimp:s of~ im:t~ *fid mtrsib~~ me identical.
In 1tE spr<t-at ~ ot li rftdl~irolly ~mbk IP ~ (~ 2.8). die cobupy cban,p
of tm: ~ ~ ewn:dly evaluated from f dQ/T ~ to die aaual ~ even dlooJb

170
lbe ~alllftl.fiJfer bem-een S}'Stem and~ is me\mrible.. The fea.-~0 is bt it is

~as fim as die system ~ wlxtbcr die~ ~--c- C.ll5lng !the
lhRt ~ . aft'~ (maldpg the~~) (If fiaile. The e~W'upy t~ or a
~ .c amed by lhe tliliUfu ti/ herrl am aiHys ibo a1culal:ed b) f d OJ T , \l#"betber the Ilea
Minder iis ~ Iel'eJ'Jibly er ~.usib)y, H~W. wlml a~ is im~ on
aec~JWJt iltm ~ in Olbri driving r~ sm:b as pressure... me ert.1fOPY dump is
~ ~ " lely by tile bl:at ~~:aDSiit:r, aDd for iW cillculiWoo one rmm devise a mee'bani'CaUy
Je\,'"e~Sihle lllellm of aceomplishing abc s:mr dlang of state~
'ft.!- m--.J.... . ,.;..-, fh . fflilriW ..............,M.. il --- ......~.-- of beiif enoin:es is. dre clals"Sit:ill 9,p
--...
II~ ~~~~'!lUI . Y ~~Y.l":.f WUV'Ll~ _ COl)_ ~~Uilf .c;r-~
~ dose.ty fol!lowing lis actual~ develnpmrmt. A eomptemcntary .~b. based

on l1lOkaJlar ~pts and sat,tj~ mecb~. : , co~ bridly in Sec_ S.ll,
&.5 ENTROPY CHANGES OF AN IDEAL GAS
Fer one mole or a um1 mass of fluid t~ a me'Chanic:ally n.wctsibte ~ in a dcsed

~lim~ taw.. !q. (28}. ~
dU = dQr:eY: - P dV
Diffenm~Wion of lhe defining GqWIIioo for mdnilpy.. H = U + P V . ~Ids~
dH =-JU PdV + \'tiP
lEIrmmatmg
" ~ u-~u giWS: . d H = .d QII ft- I' dV + p d~" + v d p
dQ10 =till- VdP
f\or an ideal ,gas, J H ;;;: c;!dT ud 'V = B. rIp. With ~ su.baltmhOU$ and di\"i.~tt by T.
dQ.~n ~ Cf.'~ _ RdP
7' T p
A! a :rem~! of Eq. (S.ll ). dJis be~
"iil'il.wo S 1he mow mtropy Of 11ft ~] gas. lfl~tiOfi ffmlJ an Initial !tare m rofld:iti.ons To
md Pi) w a final !i1ale at condiriom T and P gives:
(5.14}
Allftgup Mrilred for JDCehanAlty ~ pr~ this equatiol1! rchl.~ propatics oruy.
~is~~ ~flhe ~s ea.mtng lhedlange of state.. b is tberd'011e a~ equanOD:
for me calculabon of CDIIOP)' ~of an idnl P'~

l?l
Example 5.2
For an ideal ga?S with coostant heat capaddes undergotng a rever&Jble adiabatic (and
lheretore isenlrcfJicl pfOC!eSS, Eq. (S.soo) can tJe 'Mit~en:
2 == (!!)'y-l)h
T1 Pt
Show that thiS same equation resUlts hom applation of Eq. (5.14J wi1h 4S = 0.
SoMfon 5.2
Because c ~s is ,cmt5tml4 Eq. (5.14, ~ be wrii.Iea.:
_ T2 R ,Pz
O:o:::ln- - - In -
TI C~~ Pw
Br Eq, B .l9) fur an ideal ~ withy~ c~ICt/:

R y -J
- - --
c;!- Y
Equation (4.4) for llbe remperature ~ of die mow- heal e~~p~cily c~ allows
mtqmion of :the tir5l tmn on the rigju of Eq. (5.14)_ "!be rewlt M ~om~Dtly ~st'd 4$
f Ct d: =AloH [ BTo+ ( CTJ + r~) (' ~ 1)] (r - I) (,.IS)
where f = T I f0- ~this ~ must ottcn be eval'u31ed. VJ include to App. D ~

sen.talivi: oompmer pmgrams for Us CVfilllil.tioiL lFot c~l ~ Jb;:J rip~ side of
1:4 (5.15). " dclioed .u lhe functi~ ltCPS(TO,T;A.B.~C. D)_ ~I!Wion, (5.1.5) mcu bet:~
r cj~ dT
/,To _RLT_ - ICPsrro.,TABfC~D}
1he compliter ~also cal~ a ftl.t4n hc8t capacity defined ~..~
t _ ffoc;fdT!T
{C .P )s ~ ln{ T/ To) (5.16)

Hoe.. lhe ~P ..s- ~ a ~ wJlte. $pcdft"C rro tRU'O(IY ~ DirlsioD of
Eq. {S.IS) IJy fD(TI To) or In -r tbel'dore )i~
(C~ Is "Q A+ [ ar. .j. ( crJ .v r~i) e; I)] Cmr') fW)
1'111: 1\&fn~afrhii;equatioo I ~ ~ftm~iiU~t MOPS(l'O,T;A,B,C~O~ Eq\~Wn

(S.11llhen ~
( c i~,
i $ == MCPS(TO.T;A.8iC1D)
Solnn,g fur the i~ mEq. (SJ(;) ~~
{ r c~~ d:T G: ~c~8> rn .!.

l ro T To
ndr EQ. (S. I4)~
Tbi~ (CPJ the cqu C)_JI ifbf ~- ~ of~ ibd _ ~ Ibis ~~ when ~m-e
~are~
Example5.3
Methane gas at 550 K and 5 bar undergoes a rENerSlble acBabalic expansion to 1 bar.
Assumiftg meD\ane to be an ideal gas m these CC!nldiliollsj fmd titS firulJ tempe~:&~Ure..
SOiuttoft &~3
F(lf ~ 4S ; 0. and Eq. (5. 11) becofii)C.~
(c;) m1~ ;;;; bJ P:! ;;;; 1n! ~ --t6CJ9..1,

R '11 ~" S
id}IOoq.~t:ml!i fromi~ C.J, '('C}f)5 /R is~ Rm1 by Sq.1.5.17) wrilkO m iu

functiamll fcrm:
(C~)s z= MCPS(SSO,li2.;1.,102Jt.Q81i~~ ..2.164&:..&tO'.O}

For an iDit:ittll '-aloe ofT! < !..~. oomp.tte a value or {C~ )slR tor s.ulmmn.ion
iD~ Ole~~~ fw T2, n. nc:w ~ue of 71 allow. ~of (C~ >siR..
1.rtd the~ OODiiDt~a. m L~f!~ oo o liDaJ "~orr~ ~ 411 .34 K-
51.8 MATHBtA11CAL STATEMENT OF THE SECOND LAW

~two heal l'eSlef\.-u~ 0ne at umtpec-arure TR Dnd a .W"J-,nd at'l hc l~ ~ Tc.
Let a qUUtity of bAt 1Qt ~ tmJsfaml &om ~ botter 1t0 lbe cooecla9Wir.. n.e e~~~ropY
c:bangt"S of lbe ~ i TB W1d. 41 T(.' (ll'e:
Asln e -I Qi
Tn
'lbese two mJropy ~me added m ~~
.0.~ = A.f.
B
.\~
c
= -ITJ!JQ~ + lru
T~
=IQI (TB_
- Tc )~
TyTc .
&a-. TH > Tl"t tbc tOial 1lll'O(lY ~hqe ~ a ~m of 1Im ~btc Pll\Xl!a . pusltiVL
AlSO. ~~ beoome.s ~llliillrer M Che dlfl'~-e TIJ - Tc &~ oWlet. Wben. TH ~ on)y
inliDitc:simaby ~~lxr dwJJ Tc.. the lb.cn ~ ~ l!a'em"ble. and~ appoacha ~
~ for d'le p~ of i~ible beat lniMfct. ASr.uw is ahva)'$ ~~ ~ng ~m
the~ beecmes J'e\cremhl~
8D
Co.Midn' DOW IDIrrre~ process in :II ekud 5j51m1. wheJ:cln ItO heat l!miSfeJr OCCUlS..
Such a pmce&S i ~ted an tbe I' V,~ diagJam af Fig~ !i..6. wb.jd) bows I'm ~~.

174
~Jdlatic expansion of 1 mut of ftuid fAMD an ini1ial eqc;ilihrium stan: at point A 10 .a in.aJ
equilibrium t~~eal po.im B. Now ~me hid ~ M inkiild ~b) a l'l!l~enibk
~ t~ 0( t'Wtt trp ~ ~ lht ~miMe-. adiabatic (aan1lttint-etttmp)l) comp;ressiM
ar me ll1liidJ mme iniWd pressu:rre.. and seooBL a ~itde. ~step th:d restores
me U.icial ''Otmne. ]f die mnw plfJCe$S ~ ill m entropy change of tho fiuid. ~n dae
must~ bcattnmsfer d'uliinglbc revasib~ to- tam+P Ste.OBdi q> sud~ lbaa:
A ~~ = ~ "" -= ('A ,cJ Qn.w

~" ..... "'"" - "'B ..... JIJ T
1'be original Jmwem"'ble pll'QC and 1he mcui~ nsrom1iwl ~ ~titJUte a cycle rw
w&Wb AU -;;;:; 0 and fur whidlJ tbt \\'tXk is tbcrd"~=
-IV~ Q,.. "'LA JQ,..

u_
.nuWe\-". __s:_ ILo BWemtll
ao:::ll.IIU!D~ il. 1.t a
_ 0.f lthe -~~ --
_ .. ~~1111!! ~ ll
~w. ~l'l:'\' ~ ......,.
~ ..:..... ...ted
y .,.
U-Jl..l~. 1........
__ 11'd6 1,11!1;;:
1r.m,. for ~ cyd~ would ahen. be a proce$& fOt fie oompk':te com-ersioo inm cwart of lhe beat
m~ l:llm.. f aCl~ is neptive, udl it ro~ t1m1 ~. - s~ is also ,oegam~ w.beN:e.
S'#j > ~- &cause oriiBmJ ~"We~~ adimtic (AS~ -= O),lbe ~ mtrOpy
~of me syStem mu1 surnmndiap. 8 a.~h mr lbe ~ ~ a~ ~ - ~ > o.
In l.lm'iviDg ~ tbJ.s ~ull, 001 ~ is tbd dte oripnaJ ilrra'Cini.ible process :rcso.l.m
in 1.11 emmpy dJange .o f l.be 1fluid. If tbe original pme.eu is in rae.:~e. lhen lbe system
GlB bli-. HStUJtd lO i inkr..d Wt by simple ~]C acf.iab.aijc ~ This ~"etc t$ ~
~JICd wllb 110 heM ll'iiM.fer and.lhuefore witb 110 net om. Thus me ysrem is restored
witbout lavi:q D)" cbaoge elsevrbere.. md lhis implies that. die original process ilt nJ'>~II!!
Rlb:r Df~-
Thm ~.tie s:a.me mmlt ls fou-nd for amabati processes a:s for <~ired bea~ ~rnnsf,w. .6.~ is
~ pOSitiw; ~bing l'aO a limit t~ lbe ~ ~ ~~e- 11tis ~
mndmroo t'iDl be .Mmorm:ni.ted Jot my prc;ag wb3teeL L~ ro. lbe geDmll eq110.oon:
(S.l9)
This ~......_,.of MtCOIId 1ar1 dln'n$ dud ev"Y

proceu proceed ln1audt a dlf8dlon ifhat the IDW en1ropf change
IIIIOClated lidtft H II. positive~ tilt limiltQg val'illli Of atO Deing &ttainMI
onl; by ~ pt'OC88._ No proceu Ia pouible tor which 1M
't otal anti'DP decreesn..
We ntt.um IIDft to C)-die beal. ~ ltmJJ tabs in be3t lQf1 ~ fmm a lbc!at m~_r nt
Tn~ and~ heat IQcl to an:odler heiD resen"Oir at Tc , Because me engine operates jn
eydes. it undqt~ei oo net changes iD its~ The total entropy dlanp ofrtbe proeess ~
rtberefliiiC lbe mm. of he r:ntropy dm:np of tJ:te. ~~cat reseHoin:

l75
The work pmduted by th~ e~M as ghcm by .Eq. (5. 1) irs IWI !!!!!! IQHI- IQcl. Blimimition of
IQc I between 1bese ~~ equaliom. bfld solnlion for I1 I gi'ti :
~l\rl - -Tc t.SrA + IQH I (~ - ::)

This b dJe ~ ~'I.Wion fot wonc
of~ lltcat t!liJ8itiC f' tc:i'119mUu.tt: le\-rk Tc amiTy .. Th.e
minimnm -,._'Ofk outpm m~ rest!hill!g ""birn the ~ is. mmplete.ly inefficient ruxl me
IJI'1lCeSS degooeJDtes i.uw~e me\oers.ibJe beat t:ri:mrSfer ben\'eeD the 1%-o beur rese:rvoirs. (n
lhh ~ $0huion fOii 6S,. yii!dd~ 1hc t'l"larion ~~rntd 11t ibc ~ning of llhi ~ion. "fh~
~om work fi olml.ioed .hen tb~ eogin..: ls reversible.. In wl'Lich 4.:nst A~ = 0 . .aod Ole
equ~~ ~ to the~ kml on 1M rilbt the w{,.'l[k of a Cmoot mgin.
Example 5.4
A 4~ steel casting {Cp ..: 0.5 lkJ kg- r K- 1) at a telllpetaiUre of 450"'0 is qurmdled
in 150 ~g of oil (C,:: 2?5 kJ ~sr 1 K- 1) at 25"C. tf there are 110 heat losses, whal is
the Change in emropy o1 (s) t.e easting, (tJ) the o~~ and {c) bou. eonstdered togetler?
SoluUon 6..4
The firutl mtnper~ I of ilie ohl ~ dJe trd Cll$dog is fouud by M ~y
balance. Because lbe ~in~ otEbe oil im!l ~reel k:i~ mnst be~
(40)(~1. 5)(1 =- 450) -T- USff2...SHr = ~> = 0
(P) Olm~ in l1tropy of the oil:
AS~:;;;;;: (ISO (2S. ln lll. tS + 4fi..S~ 2613kJ K- 1

) 213. t5 + 2S
c.r) Total ~mropy ~hange;~
6~:;: -16.33 + 16. L3 = 9,80 kJ K - '
bas~
.
N.ore lhm ab:~..a.. -~ ~.
~ abc ~-..- . .-P ~ - -
..,..,..,na.,. as" posttn~. y~- eot~Qpy
. <~"';Irk..
u~~r ~-uns


17()
L7 eNTROPY BM.ANCE FOR OPEN SYSTEMS
Just ~ ~r b:llaDce ~~:an be

wriltcn for processes in urbidl ftuid ~ nits. t'll 8mvs
rhi1lll&b a rootml ,,-'01~ {S<:t-.. 2..12), so rot G cn.tropy 'hab.nce be VrTitllm- 1'belw: ~
hoarever~ Unpomun diffmmoe.: EfuropJt is nut ~nw! 1'be. ~ htW~oj states 1Lha1 dlC
tuial ~ ~ ia!Cd wilb any pi(USS am1 be -~ ""1dJ a limiting '\~De of
zero for a reversible IJl'OCb~ 1'ttis requbement is rabm :Uno aoooonJJ by Vt1riting t he mtrop)!
~ b: both die ~ and i1J siiiNUDdin~ ~ ~. and b:!( incJuding an
t:nllOPJ--g..,mdon term to lllXOOlJI f the il:m"'tml!tilid~ of the pr.t'lL>eS This bum is me wm
al dime obe:n: one for l!be dttrerence in etlbopy bel, 'eetl an and enlriltiOe .Mremn$.., Qiiie f
mr.opy danp within ta. aJDtrol volume. am1 mm 1m mtrop)' c1w1.ge mlhe ~ u
lb pKL~ i ~'!tile. those t11:rec ~.U~D.s m_jJI to mo.. making A~.;q1 - 0. l'l lbe. process is
&mteu'ibl~ lbe:y sum to o po!iitive ~y.. lhc emmpy-gtDC!f*tioo irm..
the stliJBlllent of balanoe.. expressed 85 rates.. is &:berefore~
Nt(rateoi
Tt:IS taft uf
change o:f
chmlge in
I ~.ror
+ eui_ll'Opy
i~ Cl,DIIfiJl
Oowing sll"eams
""d:IIIDe
Tbe equi~ ~imt ofenJm.M .l xJIJitu is.
6( Stift.r + d(m~~ + d~ ;;;;; S6 > 0

.J'f5 d't dr -
wbefeSa ~-rated'~~ ~r.Jtion- lb. ~ooi:sfbc&t0t'111J~ fwmofthe cntl'q1y

I ~q:~pJkmle at my instanL Eacb (enD a~DJ lW'f with lime. The mst tenn is simp]) ~
~- -
~-~VI -" -~~m
=m: .,pfifi"'"'tW e ~n
..,..._ ...r.r VI4 --'
A QJ. ~ i ~.~ rtb~
DUWLg-~ -~ .~.~ ~~'Ill.~ lh
YJJI I!;~~~~ tne ..~ , ..
v~m.al f'r,nftv
-,.,.Jt'J
k'mipW'led om by exit Rrea~Ds aod the toml emrop,y D'DmipORedl ~n by emmoce ~ The
~ ~ ~ tbe lime tate. of chm,p:. of the tntal ~trOpy m f.ht fluid ~ \\i.lhin die
c:ootioJ wlwoc.. The Wn1 term is the ~ rre o( ch:mge of du= et:dmp)' of ~die slllTOilod~
~ldtin#fNm~~~~gdj~
~
l.el ra:lm of heat II.J'"anSifcr
with r (l.} \\'here
a -~tt ro a puWu}.ar
i whb
delliJ!e~
mbscripl " J a
pmt or lbt conttol wrlate be
[allpeml~De in the. SUDOdndinp. 1'be
mte. of emmp)' dla.nge mtm: :smnmn~gs as a result of this rmmfer lis; [ben - OJ/Ttt.l " The
minDs ifll eonvertJ O J. detioed '5\'iib leSJ'Cd to tbe sy~~ to a hal rate w:U!h respet1 tc. the
~ttp. Tilt' dWd rr.rm in Bq. (S..20) i lllerdom iDe sum of all such quwni tics:
dstWJf =-- .... E~

dt J Toe.}
(5..21)

1?7
'The JimJ:I tmn.. represemmg lhe rat(' pj ~tmpy ~ SGt refteas lht ~law
requiniD.teol ttw it be. positi\e fot me~em"ble ~e&. 1lrere &U'e llwO ~ of ifrevmtibiJ.-
i~~ (a) those wi/hiJr lhG- cootml. ~-o!ume. i.e.. ilriUildl. ~~'w:rsibilities, and lb} ~~hose resulting
from hem ~fer~ fi:nj~ remperM11R diHt'tellRS between system aod SIJlTOOtldi~ li.e~
aumaJ thermal ~ies. In the bm:!tin<g ~ where Sc = ~ Die ~ mu be
c-ompie~dy n!I"USibte, implying;
The proe~ is inlemaiiJ m-em'ble "'ithin l!be~ontro] valu:r:ne.

Heat transfer between ~ control l'Otuute and us surrovodirtgs is re"VeDJMe.
The ~ itan ~~ c:ithr;r tklt hcllt raeJVOirs ~ iooluded iD ~~ RJ.m.nm~ wUb. tmr
psatures equal to those of me control &UJ'fitf.'e or l.bal Camot e:ngin~ :lfe ioreJ"p~CAd ~n me
~ bctw"n Ow controJ....s~ temptlilblrOS .and~ tOO llcm;...~p,-oir t~t~
For a s:t.ead:rsuuc ftowrhe mass mid mcropy O'f me nu:id in ~ rootml \olnrne
~
~ ~t. tmd d(,..S)t;'{'/dt zero. Equation(S.ll) thm beaMnes:
H' maddition lhe11e is but 1J1I1e eotr.mce and one e.gt., with mlhe. same for both SIRams.. dividing
dltoot;b by m~lih:
(5.23)1
Ekampres.s
In a steady-state ftow process. 1 moJ s-~ or air 1600 K and 1 attn is continDously
~ with 21'tl01 s- oC air .81450 K and 1 atm. The product stream is at 400 K andl
1 arm. A schematic tepliMerrtation ,of 1he process iS shown in Fig~ s.7. Oetetmine~
1M rate ot heal transfer and tile rate ot entropy generation fo.r the ~. Assume~
thai air 16 an ideal gas wifh Cp. ;;; (1/ 2) B. 1ha11he surroundings are al300 K, ~and 1ha1
kine.1K:e and poterrtial-enlitJg Ch.Mg&S are negligible~
SOlution 5~5
.By Eq. {234)). ~itb J~ rep!~ t.y n.
Q ;c nH - n11 HA - ii 8Hlf c,l 14 (H - H~tJ+ iis(H -- H 8 )
= n.,..,Cp(T - T.d + liJ!'lCp(T- Ts) ;;;;; C~ {liA CT- TA)+llB(T- r_._)J)

= (7/ 2) 8.J14l [0)(400 - 600} + {2)(400 ...... 450}] = ._g;n11.7 1 s-1
S~Li- 1
0
.,.. ~
JL__
11&Ufe5.7:
P., tX;1I(.31
described
ex_ :S...S.
I
I
I
{l
ExampleS.&
An [nvantor claims to nave devised a process 'wt'lidil takes. In cnly SB.UJrfafed steam ar
1 oo~c and which b; a comptiauad set'in of ~ rnekl1t heat C(lfttfnuoustry ava_llable
at a ~ ltM!I of 200PC,. where ~000 kJ of enetgy as heat is ibemted 1or
every kilogram jof steam ta1mn ili1tO me proeesa Stw:Jw WhetleJr or not ~is ~ess rs
~ To give 1his pcocess the most favorable oonditibns. .assume cooling WBIM
ava~ in unlirnfted qLJanfity .a t a ~re of 01t(:.
SoJullon 5.8
Pot .my ~ss to 1~ ~~ lheorctic:aBy po 'bl~ it mus:t 11DGCt the requirao&mts of
tb8 fu5t and seoood laws ofthennody!Wlties. The detailed~ nd ~m be
known to drt~ whdla drls :is the caR~ only ~ overaJ1 resnlt .is reqmmt. If
the maims of 1dte m\~nwr ~ ar !DWS o1 Uamod~.. I'PCaD5 ror- lieldil'Jng
lbc d aims am~ pomble. The detennimm<m cf a~ i llbenJ a.

179
I , .. - LODDIJ
Flgu:re~
-- -
fll - a._o
-
ProetiS
ll11 - U1U t:J -'II
8:, 1.!JS~Sc tJ _ ..1 171 SJU ~~in
Bx_ ,.6.
l(l,
~~
T.v 1!!11 D"C
~--)
matW of inp.nl!rity. Ohervt~ lbe p.roce!IS u bnpasm""ble" :ntd no nwd1__auWn ror

canyms it out can be de\ised.
In dJe ~~ iosti.Ilee.. a cxmtinu_ovs proeess laW in Aturmd ~and bem
is made continuoo$ty a~ at it 1~ Jt,\~ T' - 11WC. 9~ ~1-
in,g W3ier is availahle at 1'~ ~ 00~ maximum me- a madr of the smam If k leav~
the pR'USS at liDs kmpcr.atuJre. 1\uUJDe tbetefore that d1e steam is coodense:d.
Me)~ and did!Ulf'd rrom 1h~ prt~C"CS$ :al w-e and .aJ ~pkric ~- '"411
the: hem liber.Ued io Ibis operation cannot be made available =at mmperature level
1 1 ;;; JOOOC, ~Dse this wooki l1oiale s~t 2 of the scoood b.w. \\k IIIU5t
su~ lh~ so:me Ileal Q 41 d.lmllSfetred 10 d1.e cooling wnte'fi . Ta ::!!t OOC.. ftlore-
over~ the ~ 11m..~ satisfy the ~l taw= dim! b)l F.q. '(l.:U >~
where 411 is the enthalpy dlam,ge of tbe stea.Jn as it lftotwi tbrongh the ~"
rus $nd Q is lhe tfflal hteat 1111Dd'er ~ dta a:ppuattli ud & ~_nd~
Becali.lse no shaft l\'ll1:11. ooemnpmies me process,. W ::::r 0\. 1be m:mmn~ tfiD..
sis~ {1( C'OC1Ii:q
'1.\---ater. w.bicb. acts as 11 heat ~rvoir at ~he ~ lelllfJS"Jtllre
of 1'11 ,_ CFC. and a bem .~ at T ' - 2lll C to ~ b=aL in lbe amoum.
or
of 2.000 kJ is ~"for each tilopam deam euleli:ns dle app;IJ&ti!JS. The
diagram of fig. 5.3 .indlc:lte$ me 0\\tfi~U resdt of m~ .~.
Tile values of H and s for saturated steam at uxrc and for liquidl \\'ate~ m
~c arc ~a~n tromlhe 5ttam rabl (App. f). 1ibc total but tnmsfer ~
Q = Q' + Q g = - 2-Jm Qc,
6H - ().o - l.676io =- -2JXJO ~ a~ Q.,. - -676.0 kJ

180
'\VeD(IW r~UQ$~ nttt MiiJfnoffk ~]3W(OdQ~W~

os... is ;greamr th:m or 1t.1:ss than Rrn for the proo.eu. For I kg of sceam...
AS - O.ODOOt- 7.3554 -'7.31-54tJ K-'
2.000 _,
ll. = 200+2.73.15 = l!tttmlltJ K
FQI the amu .-e.~ PRWid ~~ .m coWing Vli'als at o&
c.
tJ = 616.0 =2..41481rJ ,K- 1
0 + 273.W5 -
1lms. A~;;;; ~ 1.3554 +4.12-10+ 2..4748 .. -O.r6S36 t.f K.- 8
1'bis ~ub means that die proa"~U as described is i:m,po55ib1e. be'ause Eq_ {5.19)
requim 0.~ 2: o.
'Jbi$ dos g('Jt IDC'U W3l dJ. p_~ rO{ mb. genmd oature elm lm(J!OS.Si'le.
bul cmty dw.r illE m~ 1lMl e-1~ roo lllll.1dL Indeed, hilt ma:rimmn 81ll01111t of
hat which caD be b"anSfcmal m tbe beat ~w at 2001" c is readily calruJMed..
1'ht blel(O' !babnt--e is:
Q'+O.q = AH (A )
Si.mihdy~ (be eld:l'oJIY babl:~e ofEq. f5.lJ) :is
-'S .....
y
.fr Cla
ra . 5 G
.d..
..... TJ.
4
lb(!t malimtnn be4lt tejut'ioo1t.0 1he bot ~ir occm,wbm the ('rOCCSS is c~
pletdy ~e. h:a which case Sc; .. ~ md
g:.Lfk~ as (B )
T' T T.o
ComblDttioo of~ (t4) and ( 8 )1and solution f Q' yields:
r
ft = T ; ~ Tfl ( AH - T. AS)
Wilb T6 - 273.15 K and T' - 473J5 .~ tbis becomes:

, __ 413JS ., . . . -1
Q ;: (---.676.0 +m .ts x 7.3554)- - t ,s11.1 u kg
200
1bis 'Wluc of a' d mralls- in magnitude lf:wfi die -'1,000 -~ kG-~ claitnM. o~
al5o no&e.i!i; that d:te invmtef, dai:m i:mpies a n:eptive nn of enti'Op)' ge-oerarlon.

5.8. Calculation of Idea l Work 18 1
5.8 CALCULATION OF IDEAL WORK
In any steady-state flow process requ iring work, there is an absolu te minimum amount which
must be expended to accomplish the desired change of state of the fluid flowing through the
control volume. In a process producing work, there is an absolute maximum amount wh ich
may be accomplished as the res ul t of a given change of state of the ftuid flowing through the
control volume. In either case, the limiting value obtaj ns when the change of state associated
\:vith the process is accomplished completely reversibly. For such a process, the entropy gener-
ation is zero. and Eq. (5.22), written for the uniform surround ings temperature T(l , becomes:
b.(Siil )Cs- .Q_ = 0 or Q = T0 b.(Sni) rs

Tu
Substitute this ex pression for Qin the energy balance, Eq. (2.30):
b. [ ( H + 1u2 + zg) m]rs = Tu b.(Siiz)rs + W.,.(rev)
The sh aft work, W~Crev), is ~ere the work of a completely reversible process. If Ws (rev) is
given the name ideal work, Widcat, the precedjng equation may be rewritten:
Wideal =b.[ ( H + ~u 2 + zg Jni ]rs - Tu b.(Sn1)f (5.24)
In most applications to chemical processes, the kinetic- and potential-energy terms are negli-
gible compared with the others; in this event Eq. (5.24) reduces to:
(5 .25)
For the special case of a single stream fl owing through the control volume, the terms o f
Eq. (5.25) may be expressed as rates or upon division by ni on the basis of a uni t amount
of fluid flowing through the control volume. Thus,
Widcal = 1iz(b. H - T(l b.S) (5.26) Widcal = b. H - Tu b.S (5.27)
A completely reversible process is hypothetical, dev ised sole ly for determination of the
ideal work associated wi th a given change of state.
The only connection between the hypothetical reversible process and

the actual process is that both are associated with t~e same change
of state . "
Our objecti ve is to compare the actual work of a process with the work of the hypothetical
reversible process. No desc ription is ever required of hypothetical processes devised for the
calculation of ideal work. One need only realize that such processes may a lways be imagined.
Nevertheless, an ill ustration of a hypothetical reversible process is given in Ex. 5.7.
Eq uations (5.24) through (5.27) g ive the work of a complete ly reversible process asso-
ciated with given property c hanges in the flowin g streams. When the same property cha nges
lU
Ol'EOf in an actual~ tht: Bi.'!Wal wtxk ~- . .P~'al by an CDOXY balance. can

(<JI" W.,)
be campG:I!ell v;Hb die ideal work. When m (or .is posifive, it is ~be ntinimrun M-'Vrk
ret[IliJWl to bring .abolll a. gil'en dmnge in lbe ~ of die flOwiDIJ m:e.am~ and is smaller
or
ltJep1i(~. fD lhiJ ~ I tbtJllltld)'DIIDic ~r '11 i Gc1iDcdJ a5 tDe ftllio dJe ideal wort lO
l.be acraall "~
{5.28)
Wbe~ ft.~ (or WhSt:d.) is negaJi've,. I W~I Ii$ dJe ~imum ~wut obfginaW'e fuJm a~
given dlan~:c iD 1he pmpe~ tJf 1M ftn~g S1KDIS, and Wp1 lhan 1 w,1- In litis ~!be
~~ efficknf), it defiacd ats t'bEt ratio of die-~ wt~~k to the idrzal wor
(S.29)
Exam,ple 5.7
What is the rt"UDinlhln wcrk thal can be OOtamed m8 :Steady-stale llow process from
1 moJ of nitrogen (assumed an U1eal gas) m 800 K and 50 bar? Tate lhe(emp&rature
and pressure rA the surrouftdings as 3oo k and 1 ~0139 llt.
Solufian 5.7
1"JE muimum :possibl'e woa is obtliDed from atll) l completely 1\e\'enihle ~
~~ ~a. \JJ tbt t~~ and pmsun vf ~ s.urrmmdiog;s, i.e~
co lGO K .and 1.0133 bar. (~gain in wark. 1dooe by~ nitr~ i:Jear~ISe of a fimd
tc~ ar ~below that of1he sunouod___iJJP wouJd be at lean eqoa1ed
by 11 k 'Ark ~~~ tD [pi'Odoce the final coodilion.) Wbru is required ~ ~ the
~ d w,~ by Eq. (5.21)a in whidlllS and 4H are the molar emropy
:md mtb:dpy dmnges or lbe lllitroge.n as its :stm dt:mp !rom 800 K and iO bar w
300 K fiOd l.01l31bar. P-or u idt&ll ps, mtbal.py - indGpeodEOI of~ and
in dJim!e is gh."eD b~
AH = ( Tt. c~ dT
J,..
The \~lw: of this integtal u ftnmd trro:m Sq. (4.n, at.~d is~ b)~
&3~4 X lOPH(SCQ~3..280,0.593E"31ao1~0.040e+5}t;;;: - fS~l160 J mol- 1
The parameters mlbe. be:at~"'il} equation f01 nitru,gm ~ from Table C. [.

Simnuty.. the entropy obaage is found from Eq. ~S.I4)~ here written:
:r, ,6 dT . ~
IJ.S._ Cp ......... -- Rlln -
/.r, T P1

'The ''ntue of the Uneg:ra.L found tfoom Eq. {5. ~ 5)~ Is rqn'esentedlby:
8.3~ 4 X ICPS(800,~00,0.693E-3~0~0~0.040E;-S)
~ -2~..373 J mol-l K ... ~
~- tiS== -29.37l - ..314ln IJ~~JJ = l.04ZJ mol-~ tt-
ith llbe$c ~~ <lf Ali .:md .aS, lEq. (S-27) becf1Il1la:

wiiltitl ~ -15,060- t300)<J..~2 1 = -t.S,973 J ma!- 1
The signi~ ,of thi! sitnple calculation bco1Qii'::.s evide!U from :oamin:Won
of tbc *ps ,u f specific i\:'\~Je pr:oow c:bigmd to bfiJl,g ab(Mu the tci'*'en
cbange of stne-. Suppose me oi~Jrogeo js coofumO\ISly mangoo toils. finill state m
1.0133 bar und T! = T01 = 300 K by tbc lolh>"'in~ lM~Sil:fl ~~:
"'tep 1: ~~o. 'c ~ion {m. i_n a mrbinc} fiorD initi:W S&te
P1~ 1i . 111 to J.fliJJ bar. Let T' dmom the di&clla..rgr; tt:tliJXtmu~.
srq,~ CootEng (ocberui~. if T' e.1~ l1:mii T2.J w me tirnd tC'ItlpZJl!tQ:fc Jl
at a~ ~"llre ~r I ~OJ 33 hilL
Por step ~ , a ~ead] -slmr Oow pmrcess.. dllJ: cnergy ~lance ~ Q + K'.r = .Q H.
Bcelll.lb"'e We J,iliOCeSS i Miiabuic. 1IUs redllces t~
Ythcic H, ~ lfle. critk\lpy .:u th~ ~ i:' Qf T' and ~ .0133 bill.
If mmmum WiH'k pmttm:K'tiuo.. $tCJ) l musa aliso be R:'.!Cr$ibfe. ";th ht-allratJ:i;...
(en:ed ~lJI'i m ~ swmuodints nl T4r. ~ ~enu iW rmil:( !b~ ~eat
~ eq@ht~ "'-mott re'Q,.;vc ~l firJm the megcu.. produce: ~VIIi li-~~ md
rejea li~r rotbl: UffOW'Idifigs a1 T"'. Because me f~m of [be lleM ~
~ nitJ'Qpn. deeR~ frum f'' tv 12. Bq, {S..8) fOJ lbe work oi a Camat engine~ js
Wtli!tal in diffctenft:a.'l fonn:
dW~ = (1. - T.)

j 1Q
Here d(J tef'ers to lbe nJ!ro~. wfDch ~ lakC'!. M n1.e r.ystem. illltegnltiOO }idd-
l"bi: firs~ lam M1 tbr: right is me heal tQMfft'm.l widit I'QJ)CJCl I() lhe n~
gh1:o by Q - 1/2 - Hr. tbe integral ~ lhe cha~ in entrop)l o( lbe nii'f'OFD a.
ir i COl>~ by l1tc C:atnct eng(~. Brx:a~ ~t1' I oa:urs at co~ entropy.. ~
iutegnd also repleSmts AS 'Mr both teps. Hence..
Climol ~ ( H~ - ll'l - T,. b.S

134
The sum of w$ aDd w~ gi'WCS 1M ideal wmd:: thus,
~- <H~ - H.>+ (IJ:- H J'- r~ li.S ... <lh - .II,> ~ T" fl.s
1
OT
wbidl tbe ~ ~ Eq. (5.27.11~

1iibis derivation mabs clar the diffmeru::e between ,Y,. 1d:te ideal (revenibie
tdla~J btftl\-otl. of 1M ~ amllll ~. The ideal "''l.llik includes l!lot only
me~ daaft ~bin~ aU .~~Ie by 11\e c~.tton of be$~
fw 1be revembk ~r of heat lo die smro~ at ~ .
~xampe5.8
Rework Ex. 5.8~ making use om tne equation for ktleaJ wol~
1'bo ~ ht:tre- o Gdculate tile: 1DIIXimum po;siible wort w~ wbidl eoao

be obtained from 1 kg oC &team in a ftuw pmce as it~ a. chmlge msu~
fl:om satunted Slam ~ 1CKf'C Jiqwd water aa: ~o-- aw tbe problem reduces
to the ~ of wtw.her ~ liii'IKJbDt of wmt. is ~tdfidcfil! lo op;w i1tt:" a c..n.ot
ldlipl111ur ~~ ~000 kJ as lint ~ 2aW'C and lakiDg b!:a1 from the unlimiml
wppJiy d ~g water Ql 0~
Fe~ me steam.
4.H = 0 - 267'-0 = - U76.0 AS = 0-1.3554= -7.3554

1
Wub negliWbk tinetie- and poten_tial-erler.gy tenns.. Eq.. (5.211~ yields:
Wide!~~;; b.H- Ta JlS =-2,6'16.0 - (273dS)(- 1..3SS4) - - 666.9kJ q .... a 1
If 1his amoUDt of work. ntlliH!'Jicai)y 1b: maximuJD ol:mdnable from the .sleam. is
ll$ed lo drive me Cuool re&Jge:rutoc opcmt~ng bl;n\~ tb~ tePI~ or o:~ c
.aod 20011C, the ~ mjeaed is "fwml from Bq. (5.8)~ solved for IQl:
JQI :::l IWI T ::::l (666.9) 1(200' + :rt.t~S) .::=! JS17.7 kJ

T., - T 200 - 0
This i$ the JDRlnmm possible 'hem ~~ at 201rCi il . leS$ than me cfaim.!d
,..alae' of :2..000 kJ. As in lh. 5.~ \1t'e oondude that dll:e ~ c&es.en"'bed is 1101
~ib:~

.5.9. L Wort J,85
5.9 LOST WORK
'Mlrt tbm . -:remit 0f URl-ersibili (n I process dDed lost hm'ol. l' - and
\\"al_stcd 1
i ~ .s th diD'~~ the Eldll~ \\:ott (d' :a p~ and ~:be td~ ~1)rl fur abe
poees . Titus b) delinilion.
W e W.r - \
In~of~ 'W~= \1"1 - W~
1k ~G! 'W ~If' comes fro f"4, (2.3'0)~ Wid ~ ide:a.J w nm: gi'-.m by Eq. (5.:14):
IV_, - A [ (1:1 + ~u 2 + ::g) n:]I'J - Q

K'iJ&sll ;;; .1[(H + 1~2 ...- :g) m]ir. - T(i a <SIU )&
Substirud!Dg these ell:p~ons tcr ~v, and ~ in Eq. ~S.l 'l )'icl~
I~ = TcY .1(Sm)rs - Q ~
fm lbe case of <Ill Jingle ummnd"m,SJ ~ T.,. Eq. tS.-!2) ~
. ll?
Sa ;;: 4,(Siizha- T; tS }
TeSt; ;;F TQ' A(SJfl }.r.s - Q
1be right sides of tb~ ~ri llDd Eq. fS.Jl} am~; therefore..
I l}r. - Ttf~ I
Ax a~~~ d)~)~ tmv., Sc ~ &. u ftj}b\~ th:tt U' > 0. Wlicn ~
fs txn~ reversible. tbt ~by bolils, and \i'it61 = 0, ftlr ~~ k ~ tbe
~Wlli ty lrol'd.~ and \~. i.e: lh: 'etiCJWY 11w becomes unrn.~ r..... ~ort. u ~1).
Tbe engineering slgnlficanc:e of lhl ruu1t I clear: The ...... the

lnt!V&rSibtmy of a ~me greelef the rate 01 entl'OJ)y prOductiOn
and the greater 1M amoum of ~energ--y tbat beCOmU Uft8\Wilable for
.ortt. Tllaa .-ry lrnwetaiDllily ~cattltt w1th ft a price.
for Ul pmew case of ~ magic stream ftuwm,g llhrou,gb the COIIIIO~ \~ ni fm:tors. am1J
~ a IIIJ.1lttptia of abc ~tropy ~in 6q rS.Jl) ond (~.33 lbc~ diviii(Q) by l"~
~.all tetlllS to tile b .. of a unit amount ,o f ftmd &wing dlmo~ the mmmi \~ume,.
nus.
'W~::: mTa as - Q t5.3.SJ lVlnil ~ Ta 4l S - Q ~S.)6)
~ . s
k~1't6 - --
Q -.s.m SG -=4S--
a (S.llfl
Tu T., . -.

J86
(5..39)
Example5.9
The two~ baslic lypes of steady-now heat adlargef are characterim bV ltl:eir now
patl&ms~ OOCJJmml and ooun~Bmur~ent The two types are, indioaled in Fig. 5.9. In
cocurrem now, heat Is vansfened from a lhot stream, ftoMn:g from !left to 11{tit, 10 a
cOld sham lowing in the .same ,direcUon, as indicated by arrows. ln cotmterctJJYem
tlovrj the cold mream, again flowing fwrn left to ~. receives heat nom Ole l'llot stream
flowing in the,opposlte direction~
The lines relate theterqaeratwes of U1e hot and cold stream&. T, and Tc respec-
~to Qc, the~ rs1&of heat atklitioo to the cold stream as aprogt8SS88
1htough lhe ex_chan9el' from the !left end 10 em arbiJrary dOWRStream location. Coos.ider
the tw ASe&; b eaon of which the fo11oY.ing ~1ons apply;
T111 ;;;;- 400 K 1'Nz = 3SO K Tc, = lOOK n11 = I mol s-
lhe minimum tempemture diffe-rence between the rlowing: s1mams is 10 IK. Assume
=
that bctb mea-ms am [deal gases wHh CP (I/1J R. Find the losl wort for boUl cases.
Take T., ;;;;; 300 It

5.9. ~.os~ wo.rk 187'
Solution 5.9
The followmg ~oo.& apply ro both cases. As~ ocgligiblc lrinetic~ and
=
poieniW-eoergy crumgcs. Abo ~~ 0, and ~flm by Eq. (2.30):
iiH{6H)H .- nc(6 ll tc = OJ
or in \rlcw of Eq, (3:28).
,lHCpf l'H.! - TH1) ncC/I'(Tc1 - 7C"m) :::: 0 (A)
'l'be oW. .-.ne. of,e~uropy than,e Cor d~ ft;rwm8 stllQIIBS i:s:

A(Sii)fl =-ti!Jlt.S)H +Jic(4S)c
B) f4. (5.14), with the uswnplion GJr negligJ"ble ~ daange in tbe fiowio:g
:IL"treams.,.lftis ~.
~
1~{$l!)h
.
= ''HCP ( In ,..
Tn."' + -.. 1c~ )
lie ~ ~ (8 )
rll. fill ~c.
Fm3lly,. lby Eq. (5.32)~ wilb negligible~~ ~to lhe $mt0l;l:fir.lin~
,.V~o~~ ~ Tts A (S1l )& (C)
Case t Oxurrent trow. By Eqs. (AJ<. (JJ). 41'1d {C);

lie 400 - 3~
~ e ~ l.25
nn 340 -. 3CJ)
6 (Srilfi == (n(1f2)(8.3L4) (In=+ t2Sio : ) ;;; 0.667 J K -l s- 1
w~ == (3(Xl){0.M7) ; 2fX). J 1s- I
Case ~ ~~ ftow. By Eq,s.. (A}~ (BJ, dDd (C):
~ = 400 .... 3,0 = 0.5556

ny 39()- )00
ll {Sri>tt ~ UH7/2)(&.314) (In: ,.. O.SS561n !:) ::::2 0.356,1 K -t s-l
1VrM = (.3Gf~)(OJ56) = Ul6.1 J ~- t

AUhough lhe tootl mre of .hem u~mster i~ the s:ame for ~ exdaaJJ~. tJe
lem~ r\i5e the cold 'StJ1eam in C0U:If~ 6ow is OlOJie dlil.D IWiee dlm:
fur oocu:rn!fil Dow~ On me Olhet band, tbc Pow :tnJt of ~ ~fed &lP jn ~ ~}TJtla
is less tbao lllill' dmt of the Ja.tre.c fMm tm lhermollynam.ie J10,iru of view. llhe
~case is mudl li'ltKe,dfrcknt.. 9:,rg_~ 4 (Sh )& = $(; .. bcJib the rt1Jle
of otron ~oaauoo and tbe ilosJ ~tk for me. coeorrent ~~'e are Deady twice the
"'lllnt':.S f~ dte oou:ntcrourmll ~cafie.

118
5.1'0 THE THIAD LAW OF THERMODDfAMICS
Measlll'ellleDI& ofbe.a1 ~ a1 very low temper.t~.UteS pro~ dam ror lhe. caECU:Wion 11vm
!'4 (5~ iJ) of cmropy dlanps. dawn to 0 L Whim ~ calwLalions arc nmde for di.fferent
e:eyualliM fo:rmg o.f l1le :same ~bemical ~l_lleC~ ate etltlMPJ at 0 K ~ t o be l)lc s;une
for an funDs. wen lhe fmm is ~ e.~~ or~~ cakulmiom shoYi
tlit1 t1tc anton of tbe ~ rudom fonn b. ~ llbm thai t~f lhc crystalline form. Sueb
akolaciarrs. whlcb ate' so.:rnmariz.cdcl51m.\\1Jerc.1 ldd todle po_smb.te that me ~oillle. mtropy
is um for ali PM/~ ~IIlw .rubstam::u ate~ ~m tempi!T~Jttm~ Wlli:il~ me essrntis.]
~ wcm adVBDCed by ems~ and 'PlaoCk at dJC beginning o1f 1he twentieth eeDllD'y, more
~t 5todQ ..._ ai roJHFV ......... ~--- ba\"e :..........____...a ,- nii:....L.- - i .L ~- --~- ...... w'"'=-L
A"''-'~~ - ~ . """"'.1 ' NW' -.......--- ...- - ~ IIJibl~ C'QJ..!H~ ffi ~ pt\I:M~C:. WIPU I:S
NJW aecepted 0! the rhird Law.
If the enlnJily ~ ZmJ If T ~o L dtcn .Eq. (5.13} lends im=llro lhe cldculaticm of~
bite ~ Witb T .c. 0 ~ rlhe lower linUt m ififit;r&ti<m. lbc= ~bsolme mttopy of a gas at
~ T ~an calorimdrie data i~
S= (rt (Cr)s d1. + A!!f + ('~' (Cp)~df+ ~Hp + fr <Cr )' dT (SAO)
fo T Tt Jr1 T T" Jr. T
'Ibi-s equanOii" is h~ ao the:: ~lit.m tbaa ao did-state~ take place and lbli.S no
heal! of trnMifinn need appear~ The only c.OftSlmlt..lempetamtre beiU efiew ate 1J}lto.i of ft.t.~(on
.. '7'
a1; ., 1 BJl..l'
__ \,ll ~rgo
. " " at .J: ~.t- \\IL-
... "'r _ ' IJI;UI a_ so""" ~ ...._._1nmSI.tton
l:.l_...a,ocn " OCCW'5'.. a. tam
-. it. U f T.
y.u, _, "
l1i -..U l-..1
~LIII:ll!d.
l.11 ENTROPY FROM THE MICROSCOPIC VIEWPOINT
~the llDDieeule-.s rgf an ideal g)lS 001Dol imemct. its mlemal ~.nt:rgy resides wilh indJviill.m]
r.oo~~ '1bis is not ~ o( rb! ~ldmpy. 1"lK; microscopi.: ~talioo of mttopy is based
oa m enli.n:IY diflmD coocqx. as ~ggested by the follOwing exampfe.
~ aft iJmlkted ~cr. ~ into two equal vollllneS. coota.ins A~s
narmba N A of ldcal-,ga.~ m~ in ~ &:don and 100 i110lcml~ in the oth:. Wbm lht!i
partition is w:itbd.mwn. the .molecules quickly disttibnle themselves unifonnly 'throUgboot tbe
total \!Obulle. The ~ is an .adiaba1ic e..-q~amion dlal~.JCc:olDJ')liibes oo work. Thiftfore.
4.V = Cv dT = &
and idle t.tmpe.Atllrt: ~ QtJt tha..nge, HO'\\~, the pressure o f UJe MilS dcaea5e:S by balf, and
1heentrop;y chan~ as gi\'WI by &J. (;S. l4) is:
as~ - .R 1n ~ ... R'm 2
4
~ .C.rf~ ~ IZQilJon ~ rrfsb1 u tJQ!l a p:Jdi~ M ~~am~ ~Je ~cr / 1' ~s. ~
as:f-40.

Bccau. this~ tk tvbll wtropy dwl~ lhc ~ iB dArly ~ib:l~
At me .imwu wbeu the pllfllititJ is ~ (be 000~ OCL'Upy {mb' bair dJt. ~
waibbte to liben.L In Ibis momentary imtiaJ stan! tbe moleeules an: not randomly distributed
mrer ~ tnUd 'd~ w whick fhey havt: aa;es !but PR ~"dod into j ~ b!tl lbo ~otd "-;ulume.
In this sr-nse the) are O'Kllrt- ord~d tbam they are m ~~ fiul Mate of uniform disuib.ttion
t!Jfoogbcvt: the entire wlume-. Thus. die 6na1 set~e can be reprded as a. nwre Tatl:dom.. or
~ di~ state dwl the iuirud srate. GmernJiziJng from this cumpl.~ one: is led to Ole
OOilion thai in~ disorder tot~~ sti'tJC[um) CD the ~ulat level coaesponds [(I
inacasffi~ CDtm.P:)O:.
Th~ file}Oms 'for~~ dist'IRkT in a quantitntive ~lJI)' wac ~doped by L &ltnmam~
md J. \V. Gibbs tbrougb o ~Di.it)' D . defined w. me mun~r ofdiffitt.nl wap dllit :micros~c
panicles can be dismoored aroong 111e ~~.., nca:siible to dlem It is W"-'CD by tile general!
f~
(S-41)
w.'heK N is tbe total number of panicl~ and N[. N2~ Nl-. ~... repeseru the~ of
~~in ...s~~,. 1. 2,. 3.. de. 1'be torm ~st.Jte'" notes the ooodition of the mi~mscopic
partieles.. im.d mhe qllOtalioo ~ disting.uish this ttlea or s:t:s:te fmm, t~ uwaj tht"fiJJJIdyomllc
me.uHo.g as appljed 'IO a macroscopic S'}lstem.
Wilft m;pect ro av-r example t:betc are but t'WO ~sm~- ~ti.ng l~on mooe: lbaif
or the Oiher of me tl:30fiUlir:Jer.. 1'be touil D~ 1
0r ~ is NA moltcub. aDd imtially ~hey
a:re all in a single "'state."' Th~&&
D1 = N~t ! =a
(N11 !}{01)
ibis fe$U)t c-on tirm mar initially lhc molecules can be dist_ributed betW'eto., lbe ~"0 access1b!e
'*states?!' in just me way. They ore all in a ~n ~sm~e,F" aD in just one half tJf the C'Ofi.Ui~r- fot
&D asSlliiled f'imtiJ CCJDdition of wllrorm diSblLbulimt of the moleeula between be two lhal ves of
lhe oonl@ifier~ " :: fl2 = NA /2.. ud
N..t !
O;t ::l [(N,J211i'
This ~oo gi\re a \"ef:Y large number ror flz. lrufi~ lhat th moiecul.m. can be ,c&..
U'itruted wrlfctmty betw~t!ll b: t\\'0 ...sames"' in many di:lfe.rent w,llY!J. ~tmy other -.'!lll of OJ
ate po$$fbte. each o.oe of which i3 ,~ v.ilh Ell partjcul.ar l.wnuniform di~tio.n of the
moJecules between me 0\1\) bah~ of lbe oonliiiner. l1x milo of a patt.iculm' n1 to l fle Aim of
aJJ ~e ~ues is the proltabiliry of1flat particotiU' db,Lr!bo:don.
The mnoedion estab~Ubedl by !Doltt.mWIIl ha"Weeo en~n:~py S aod Q is gj\.-e>fi by dle
~oo:
g,
s-. - s1 .:.....tm ~
... QJ

190
..._it.ttti
Su~ ..... 5. , ........ g..,
~. . ..._ .&.!.
~
_ _ ng Tta.\~ :~:OJ 0-1 liUU _ _ uuru our CXJIIDP'"' into UIJ;l) GPfOSSIOO gw:es:
S2 ~ S't;;;: .In NA !
l(N~/2):!]1 ;; k(bl N.t!- Zln(NA/2)! )1
IBccausc N.1\ is wry la~e.. we tab adivmmp of Slimng'"s I~ for the [oprilbms.of f~lD
rials of large numbers:
In X ~ c XInX - X
Sl - $, =.1: [ NA lp NA - NA - 2 (~A In~~ - N:)]

;;;; tNA ln N.A -.iN~ lnl ~ R ln2
'" N_,.jl Ill
'Ibis wb iw me ~y dange ol the cxpmsion process ts ~he arne .as mat given by
F.4 (S.. I4.), lltc d~~ llimnudynaudc fonDllhi fer ideal p.scs.
fqlaliom {5.41l) aDd .5.42) are: die ~ for reTal:bl; l:bamadyntlnllic pJ"Opati~ tu slatiJ.-
beaJ nJtcl1aliics (Stt. ~6.4~
PROBLeMS
&1. A,Camot engine reeei'WeS 2Stl kJ s- 1 of beat from a beu-sooree reset'VCir m 52:5~ am
~~ hbl 00 a bcat...'!l;nk ~ nt ~c. \\flm .2I,IC tho ~1i dev.eloped and the
beat ~ejected'?
U The following bcu engines prmtucc po"'o\"ef of '93.000 kW. Delefmilte m each ease
b mes m wbicb heal is ~ from ttx ho1 re!iet\'oit a:tJd discarded w the cold
1a) A tC'.a.mot engine operates between heat re:setVOits at 150 K .tmd 300 K.
(b) A pmcti.cal S8J,i:ue ~ between the same heat reservoirs btn widJ a. llbetmiJil
~'I~O ..l:S.
SA.. A panirobr power pJ.am. ~~ \\itfJ a ~-$1.ll.Jn."e l!e~"'ir at 35<1C and a he~e
Y:ot ce5efYOir at 3(Yi1C. lt bas a themlal elfieiency equal to 55CJi of 1be Camot-e18ine
lhet:rnaJ relm:icney for dle ~e te~n~
{a) ~\fhat is the dtmnal efticiency of1he ,tant~J"
(b) To ~bat temperalllle must me heru.-soum: rescrvohi be IBist:d to ~s dte ther-
mal dlicimcy of lbe: pbmt ro 3S'$? J\p[n ~ is 5:.t of the Camot-engine value.

191
5.5. Aa eb'Si i.nilWJy 4\ rest. i! ~ 01110 B ~ W'f-oc:e; tt breaks. PI'Ol''e ilial. n~~e
~ i:& lrre\rallibk. In~ mfs p_l1lrL-eH ~~tie epas 0.: system. and~
the ~JC of 5Uil6ricuttimc fur the egg lO ~ to it5 initAt ~-
!.6. Which is me IDOfe eJiedive way to .inuetae me d!!emla} ,efficiency of a Camot engine:
to mere~ T, whb Tc QODSt:m1, OJ to~ Tc whb T, COlJSla_[Jt? For a~
en~. which W'W)d. bt thE: m(J{t practil;aJ JNa.y?
5.7. Large quantitia of liquefied ~~atural gas (LNG) are .shipped lby oce-an l:mlka. M the
~~ pw1 pnrrision i. made f01r ~.atiw of tbc LNG 50 tba11 it may be ddJv-
e.tedlUJ p~ M P- 1'be LNG t1iDw:s in lhe t~ at~~ tiDd
1J 3.7 K. 3Dd n:~ a possible ball sink ror
use as he roW re.ser,ro.ir of a h=t:
~nsme. For unkledi.ng of L- G as .a vapor at (be me of 9!100 m3 1~ as me:a:5GI~ m.
_ Ctm.d l.Oll3 'b u, !mdamtllrinBsh~ .a~ahiity o/~~a.tehatsomt:eal Jl()DC,
'Vrhal :b me IDIAimJllll pobSible poq d olnaioaif)le aDd 'what ti lbe rate uf bmJ: b'Wl!lfe:r
from 6Je heat souroe'l' ~ tt.t LNG at ~C and I .0133 is an ~ gas with
tht molar l'1ll:t$S of 17. Also 3SsUillle lhllt me LNG "\1tporbe$ onlly~ ah$otbing omJy its
fateut bea.HJf S12. kJ kl- 1 at UJ.7 k.
J...t. With~ ao 1 kg ~or liquid w-ater.

(a) toitWiy a1 10PC. it i5: ~ I'Q 1000C by ooumct wtdl a ~ mmtoir a~ JOO!!C.
Wlm1 is ~ ~ ~hu.n,ge of the water? Of dlt bent rfSeiNOir--? What i~ l.S1. t?
(b) lnitiall)' a.t O"C. it. is irs~ bl:~d lo 5()QC by oontad 'Widl o beat rtSeJ\'Oir at ~C
and thm to ~t::MY'C by ~contact with ~ J'eSG'VOir at ~(){PC: What is 4~ ?
(c) Bxplm bow tbt W'ltu migjb1 ~ :bRta~ &om OiiC to lOCfC 50 d1ac A5t(Jtal -;;;; 0.
!.9~ A riglid '~sel of0.06 m3 ~:wne-conWo8 :m ideal~ Cv ~ (S{ l)R. ~n.SOO IK &Del
1 bar.
(a) If beat mthe: nmtJUnt of tS,r( D) J is ll'ilmfmed rto lhe gas.. delamiiJne ils emropy
~
( b) If t..__
~ ~~ ......1 1;;5 -~ with
fitt-.4 _ ,..,
a .,h.,.._.
P_!!I""J. tbal
_ 15 ., __ _ b-
....,._tid ) a- h
'__aft
_ .,...,. o~t..- WUI
o;n. ~.~<@. ,... [fl die
.-..A- _
amount of 1.5.000 J is- done on trhe ~ what is the entropy ehmge. ,o f the gu it
me~ is adiabalk? 'What u, 4~? \Yiml . die fncy;eniblc lmure of 'the
~?
3.l0.. An id~ gas. Cp (1/2) R. Its heated iDa steady tlo beat exchanger fr.om '7l:fC RJ
1~C by EIDiltber 5tJreaJil of the 5oQRC .at ps whidl art.cJ'$ at 3_ C. The ftCIJW mU:s
of me cwo ~ ure tbe $~iDe. arut bt:a.t hmes from me ~.r~ negligjhle~
(o) CWeulale the nwlw m tropy diM~ of~ ~~~ gas ~ f ~ ~Je1 and
c~tmll How In rbe~a:nger.
Cb) Wblll ts. AS~ madl case?
(c) Rq!~At pii1S (o ) and fb) fuJi' wu~~WWU"em ftov.r if Ill: latmg $IIRm ~
J(M)~C

192
5..11. Fer ~D idetd gii'! with rot\'Dani beat. et~p:aciti~ mow llttr~
(ll) For a ~IIIIJCfi\~ cb:m~ from T1 tQ Ta. /J S of llw p:s . ~ \\b~n lfle chango
oer-JltS a:t roM1run p~ ~ban when i't ~at ~t ~~r'OI~.
(b) F ill pre.!iSillte cbmge &om P11 m ~ 7 lbe sip of AS far an ~ ~ is
Jl'{XJSll~ tlw f-w: a ctmtmJt~wJume .dt:m.ge.
s.n. For an ida] g prove d:Uit
~s =:;; { " cl ~ +In_

.R J10 R T Vt~
5~13. A eamot mgioe ~ bel,.,'ftll twu}init#' bed ~ ~of tutW heal eapad:my ctH
wul ~-
(Q) ~dopan~ioo~gTc to Tn ~my tim~.

(b~ ~e an~ for dle fi."'r obW:ned as a fmtetioft of C},. Ct. TR. ru~d.
111e i.Ditial ~~ 18., ~ rec.
(c) Wibt is tlae rrw:;d11gqq ~'lll"k obtn___in:nltl-, This ~nds ,t o infinifl! lime., wtLeu
the ~'OlliS an:ai.n me ~ lempeJ"alil.ft..
lrt capproaching this problem. Ill~ lbe diff'cmltial C't.ltrn of 'Camoi , equation.
JQff Tn
~c~~
dQ.c Tc
.and a cfdierenual energy batlmc:e for the en~
tiW - drQc - dQ11 = 0
J-..14. A Camot ~gjJM operates belween an infinite bot reservoir a.nd a fotl~ cold reservoir
or tc.JtaJ beat eapacily ct..
(4) ~ ;m e.xpres.._~ for me wort obai:oed as a f:UEtioll of Q;.. Tn t_- oort~
luO. Tc .a;od 1he iWlW C{l]d..~'Oir ~~UR Tcg .
{b) Wh_at is the m.tmwr~ ~omt ~hie? Tb:b ~d"' In infinite tin:t. when
Tc ~s equ.alto 1Jl.
"nn.e il~ 10 dri5 prOblem jg th..e ~ a5 fur Pb. S. 13.
5.15. A bctu. ~e ~ io Oll:lef ~ im}' be~ r:quivaltJJt roa Cuo eng~
opeeling bet...w:een. ~vin at lmnpera1lWe;S Tn and Tc. The only way beat c:m be
dt~ from die e~ it 'tJy~ tb~ .-- ofw~jdJ is gh-en (~wximatoJy)
by.
IQc~ = kA~
wbete k is a ~ aDd A i& the area of the radiator. Prove rur
fb.ed power
output IWI3Dd for tued tcm.pm,ture T11 .. abe: .radi-mr ma A 6 a nrl-nimum when dlo
1e-U)pt'l afutt rnmo Tc:lTn is 0.75.
19l
5.16. b-ugine that a t~tanu~ffh.rid in $teady- ~How SCT"{:S ::s beats~ for an infinite
set 4lf Carnot engioe:s. mc1t of whkb absotbs a ,dl fferenlli1tl mttotmt of h81 fiom tbc
~ CBIL_m.g i llm:lp.'nltUre to ~c~eatase by .m. dllfeR.o tial amooot. and each of which
rej~ a. dlffe.c~tnial iiiDilWLt or
~t to a~ ~'Oil~ t~~JJJre To . A a ~l
or
of d:te opel1tiOD t!be Cutnot &ettgine&. abe tem,perdlllre uf dre ltuid deli~ fimn Tt
to T2. Equation (S.8) ,appli~ here in diJJcmntial f'mlll. \l'~ J7 is. deiined as:
qadW/diJ
vrbeT~(1 is bcaJ tnmsfer itb respect to tbe 001\--ing ftuid.. Show dut me t"Olal work of
me Carnot e:q:irlle$ i$ p-m by:
where AS andi Q bolh refer 10 the Hul:cl ]n a p.uliUlat ~ die ftuJd i.s ~ ideal ~
Cp;;; (1{2)R. forwtJich 1it :c: 600 K Wild T1 ~ 400 K. lfT~ == JOO K; whld ~the
value of lf in J mol- 1" How mm:ll beat is diBc.mled to tbe: 1\e:at resen-otr at T~"' \Vhat
is the enttop.. .cbaop of the: hal r=n-oitJ' WbaJJ is ~~-~
.5.11.. A Camot engine opemte:s between tempernture levels o f 600 K and 300 K. II drives
o Cmlot :rc.friJlll'Pf._ wbidh prmitfe:5. cooling at 250 K attd dist:.ards beat 300 K.
Determine a.rn1:met:iea.l \"aalle forme rario ofbein ,~dftcd by the reCti&~(~~
kllllf1 l(J tbc beat fkli:vcn:d to the r;mgine r~g load'}.
~lL An ideal gas wah eonstm1 beat capacities u~ a change (If ~tate fmm cooditlons
T1 1'1 tocondltlonsT2 P:_. Dctetminc~ll (JIIlltJI- 1)and4S{Jmol .... L K- 1)!wone
of the :CoUwU.,g cases.
(a) =
Ta 300 K. Pa ;; l.2 bar, 1'2 ;;;; 4SO K. /!!;;;;; 6 bar, Cpj ll--. ~7:/2.
(b) T1 -. ~ L PI ::::l 1.2 bar,. T1 c 500 K.. Jll=r 6 lm'. Cr/11 == 1/''l.
(c) Ta == 4SO K. P1 ~ I0 lb:u. T'l ;;;; 300~ K. ~ ;;;; 2 bar. C p/ R ;; '5(L
fn 1i ~ 400 K. P = 6 ~mr, r~ = JOO :rc., ~ = 1..2 bar,. c p 1R = 9/2-
le> Ta ~ 500 K. PJ ;;; 6 1bar. 1"1 ... 300 K. P! - 1.2 bar. C p J11 = 4.
5..19. An ideol ga5, Cf =(7J:2) k and Cv == {$/ 2) /f., UD~oe5 ~ C)'C'Jr C'(IIURQg ~ tlhe
following mecbanicalJty ~ersible ~~
An o.diabalic eom~i0p fwm P1" \11,. Ta to ~. V!. T2.

An isobaric expansioorfrom ~ .. Vl~ T2 ro P3 - Pz, ~rl~ 13.
An fldiabstic eql:msim from PJ., VlJ . 'fj to P!f~ V.:t-. T"'
A CtlfiStaru:valltllte pr-~ frOiD. I'.;~~_ V,.. T.; lO Ph l't = V4, '{].
Skteh this cycle ooa Pll di~ nml determ:ilte its~ efficiency .if7i = DFC.
r1 c 1.m,.,c. wu~ Tl ~ m .,.7oo~c.
Obras protegidas par dtreitos de autc

5.20'. The infinite~ ~iris tm ab~o. o&u BJJ~ in e.o~g appli-
oalfuns lby hrge bodies (if rut or Wi!lel". ApPly 1lbe clo~- ~ (Qil'Dl Qf 1t)Jc ~
'b;danoe lf4 (1.3)] to sudl a resen'Oir, ue:.uing it as aronstant\'Olwne S)'mm.. How is
it lbat ~ no..~~ to 'or (rQJJl ~ ~ ti.".1D be ~ ~t the temperaWR o'f die
reset'\;c,tiF ~ oonstsnt?
~1~ '0oe mole of q ~ ID C P = (1(2)11 ami 'C v =

(Sfl) R~ . ccm~ adiabal
icaly in 3 plsrool~~ dr:\':ice flotn 2 bar and 2SOC to 1 ~ The ~ is im-
vemole aod r-equiJes 3S'Xl more work thaD a ~bte, arliabalic rompressioD from
me $lifi1C im~ ~II)~~ .w.me tini1 ~T WMt the c:olmpy cbnge of tbc gasr
5.2.2. A m~~S8 nr of liquid WiliQ at ro~ptmatl..JJ'C T1 is Q'Ux't"d ~a~iedly and isobari~y
wilh an equal IJJaSS oi tiquid water at ta:npermu:re TJ. A.ssu:tnm-g cOMtifilt C p, moo1
Jl.~"" ;;;;; .6 e . ..., ~~ ;;; 2m C P fn (TI + T,J/2

~ ~ - (T~Ti)m fl
illl.d prove dud lhb i:$ ~t~" Wbt\1 M-ould k dJ li'!SWt if fie ID.IIS..~ o f lhil water
weft 4ilfe.n mJ, say, m 1 and m2?
5.23. Re-versible adiabatic [pJIOCe~ ore UOirmpk. Are ~~ ~~~ ~~y
revi!I!Sibb and .adiabatic"]' If so. exp.lain wby: if not give rui ii.Iusttmil'~ ~
5.24. Prc.ve thai me mean bear. capacities {C p) R and (C;p )s me ~y pasmtre.. ~'hdbrf
T > To m T < To- E'lplam uby dJqr m;e "~ ddiocd for T = To.
5-lS. A ~"ttstl>le cycle ~~d b) 1 101cl of DJJ ideal ps for wflicb Cp = (5{2)R and
Cv = (J{2)R OOD.Sists of the foir&wi.ug~
S1attiua at Tt = 100 K and PJ. = J .s &ar. the Ja$ is CIOOled at comumt pre8SUft.
ro Tz a:: Jji() K.
Fwm 3SO K and 1.5 bar. the pg is com~~ isolhenwilly to~ PJ..
The .~ t'et.tl:r1lS to ib initial 5tak: QD.I
01 p;ltlJ uc Wb.i PT = wo.stant,
WMt is llbc tlfm:mll ~ oftbe cycle?
5..16. Om Ulok nf DD ideal Pli is comprr.~ isodlcnmdly but iJ rtllier.sibly at 'I ftom we
l l b31' to 6,5 bar in il pistoolqt~ evire. The work~ is J&it, ~ tbatt
llle. ~"'Jd of ~m'bl~ iwd511lli11 w~ The he tramfeJTed from lhe gas
during romprr :!iion .~ tO a heat ~noir at 2S ""C- Calcuf.am lthe entropy chmlges
of the gas. the heal reservoir. and A.Stocat.
5.27. ror a steady-,ftow process. al ~mlliiDII'ely ~erie p~ure, what i dW! entropy
cMfige of abe ps:
(.a) Wbtm 10 mel of S01 is heated! from 200m I, JWC?
(b) When 12. mol of propane is heated from 250 1 0 l~C'?

Probkms
5.__2&, Wh:n i 1be entropy change of IDe gaa. beated .in a ste-OOy.i) piDI..~ nt ;apprrndmiltely
a~~
(a )When 800 kJ i.s ttddtd to l 0 mcJI of elhykne inrlial1y a1l 20C1C"?
(b) Wftc<n 2..500 lJ added 1hJ JS mol of (..botene initially at 260 C7
(c) When lotl'(Btu} is ~d tOJ 40(Jb mol) ofei:bylew: inillially at 5(J()r(9F)7
L29'. A dsvk.e: with mo !m(!rv:iftg pilrtS pro~ides a 8!teild)' ~am of drilled a1r fil - 25.:-c 4fid
J btt Tbf: ro:d LO lhe ~~ is ~ ai1 Hl2SDC and :5 bu. (n addition dJiC
s~~eam of ,cbilled m"(1j fiet'OOd s~retUD of ann air ~nows from me ~ce m1s~c ,ru:xt
'tl
l bat. Assumin_:g d~b;Jtic opeq60~ what is libe ratio of chilled air 'CD warm air thai
tbe de\"ice prodn~"! ~ duu air is an ideal gas for whidJI C P' :;::: (7 /2~ R.
AJQ~ All m~ntur has dcvililed a comphie.atcd IMHiflow pmees~ in wb:ieb 1 mot of a1r ii$ (tiJe
\\'(If~ R~;~rid, The ~Jet dr~-ts or dla ~I are cbimed 10 be:
A dmlge in stare of 1 me airfmm' 25WC and J ltat r<> SOOC and I bar.
1"bc produt.::Wio of I.SOO J or \III'Oft.
1be ~ or a:nlilldisd~ amt:)IIIJt gf han IQ a beatr~ ~ 30'C.
~ne wbdT.her dJe claimed pelformanee of the ~ if.. oomisrent wlrih me sec~
ood law. ~dmlai:F i$ art~l;~fQfwhicb Cp =f1J2)1i.
UL C'onsitb- the lr,atin~ of a house by ~ furT181%, w.bkb ~ as a heat~ r;zseJVoir

Cll: a hgb remper~~~.t~re TJ: _ lite ttousc acts as a hrBt-sirik ~'"Oir at tcmnperatu.rc T,
and heat I(ll must be added to dx lhonse during a pa:rtic:lldar lime imerval w 'm ainltliD
Ibis te~. !Heat I~Q 1 ew1 of ~()I.O'Se tr ~ d"mxdy iirom the furnat to
me home..~ is~ Lbwal pr-acfice. Howe'\"e.t'" u lhW bt;atiC'Scnulr i,. ~~~y ,a;..aiiAbfe,
11'3J11rl}1. the ~inp il t:empeooure T(l'. wtridi e'UJ ~ as~ l1eia ~.
dill'S,reduring m_e runonru. ,n f beat rtquited from thr. fb:rnncc.. Givm lbut TF = 8 Jll K.
7 = 295 K. T.q =
26S K., and 1Q1 = l.OOO ld. ~ddennuu~ the ml ilimum amount of
hr.at IQ F l wihich must be ~ f'mm lhe b~l...scu_n:o raen-oir (t'Umace) ~ r,. .
No
olh.er SJOIII'Ce'S of~ art iftl.ID.IW:IJe-~
5..Jl. ~eoosi*t lhr fiir ~uniog or a ho~ tbroqg.h ~ .rR solar ~ At a parti:cuw
localioo experiment bas s.fiDWin tl"ilu solar rnd1arloo dllcJWS a lln:ge cm'k of pteSSllrttedl
water 10 be maintained at l 7j"JC. ~:>wing ;pa.rtlculm time im.en~ beal ifi me wnoum
of ~ ,300 kJ must be~ from dle bouse~ mainmin [IS tem_pamnre m24-Q-C when
tlx: ~ tempe.ralll:IC is 33~. T:matlifl8 flbQ' ~nk,. vf Wi!l:QJ", lhe ~. !,!IId t!bc
SUil"'UUldiDgs as ~ resen,.Dils.. determine tbe minimum amoUDr of beat rbas M'llm lbe
extrdcled from ~ lmlk of wllter b)c m} dnnr built to accompl~b the- Kqmml ~-og
of lbe lwu:e.. No' other~ ofeDeQW ar.e ~
,5~ A rdrige:nltootsystem coo-1~ a blloe rrom .,. e 10 - ~cat lhe. rn.t.e 20 kg - . Hem i
discarded f{) t:be aJmCtqphd'e Bl a ~'tllre of J05.C. Wa.t i:s cbc power ~f'm~WII
if the lbenoodyoamic efficieDC}' of me
sy-.stem ~ 0...'''11 Tbe. ~ ~l a.f dlt' bi1roe
1
is l.l tJ \iC ~ ~~c-

5..M. An electric rno~r uillder~y bid draw~ 9.l ~~at 11 o vvlt&~ ~l delivcl'l l.l5{b-p)
of medtmteal te nagy. The tem;~emture of tM ~ is 300 K.. Wbai is the rol:ll
1
rats of entropy ~ in W K... 1?
~ A lS.ohm rl!:Sistor at ste:xi:y state drawi a a1mmt of II- ampes. 1~. te~ is
l J.O K; the rempcwu.re iJJ tbe $Uff(iUQdings k 300 K. What ii We ;OtaJ ~ uf mtrop)~
gm:miao Sa? Wlbat i5 inl or~'?
5.36.. Shaw ho\\llle: geoeml rate fonn of the entropy ba~Dce. Eq. (5.21 )~ redooes ~o Bq. (5. l9')
for dte ~of closed ~'JSt~
5.37.. A li~ of common mit operations foUOWtors:

() 5~~pi~ beat exdlanger. tb) Doohle.-plpe bem exchan~ (c) P\mrp(
(d) Gas oompmsor. (~)Gas~ (ex~) ; (/) 1'lt.totl1e \"ftl\<e: (g) ~e.
~~I ~ ~ rmm of Ute ~mtl ~teady~ entrop) b;;ilaoce appJU()riille to

eacb opercmon_ S-m.te attefnlly and juslify, any as5ompdoru. you mJlb_
5.3L Ten bwl per bow' of ai.f is throttled th:m1 opmeam ooodibC~B& af u;c iUJd 10, bar- to a
downstream pressure of 1.2 Ibn Amllne air ~o be an ideat p with Cp = {7/2} R_
n.
(.a) Wbal the ~ t:e:IIJpCI"Btlll'e?
(b) What is die entmpycbange of l.be air in !I moi-J K- 1?
{c) WIW is the me or enll'-Qpy .generru:ion iio \\' K- '?
(d) If abe: swmundin,g.:s ate atlWC. whal 1s the lost wart?
5~ A :Sbady-&7w adiabG.ti~ IIIJ'bine (expander) ~s gas at amd.iliom 1',. P 1.. .md .dJs-
dlar:p:s alll c-oadiliom Tzi P1,. A~,g idea] ~ dcn:nuinc (F omle of gas) W.
Wkal~ ~. wul SG for one of the followi~ cas.es, Take T17 = 300 K.
=
(u) Tr = 500 K,. P'r ~ 6 bt1r1 T2 = .311 K_ fJj_, = J..1 lin, Cp / R 7fl.
(b) l'r = 4SO K, P1 = 5 bat, T2 = 316 K.. P1 = 2: bat. C,./R = 4.
(c-)T1 ~52..1 L PI~ WObv. T~ ~ 458 .K. 1'?, = 3bar, CpJR ~ 11{2.
(d) T1 = 47.5,K-. Pt ;;; J bar. Tz .-3-n K.. Pl .. l.S bat. C~jR ~ 9/ 2.
(") 1J = :550 K~ P'1 = 4 hv. T2 = 403 K.. Ill, = J.l ba~. C p / R ~ Sfl.
SA Consider b: direet beat ttansfer from a beat resen"'ir ru Tt r& aoodt~ beall.fbeii'Volt
at rtnnpc~:arure Tz. w~ 7't > T:z > Ta . [L is: not obvi~ wby 1he lnst t1Qfk CJf
dJis ptc:Ja:SS should depend CMI) ft<r dJe temperntme of the smro~ beeaDSe [be
m~g.5 a:re li-"'1 ilwol-ml Jn1abe adlttal bear:-~~ ThllUugb ~
use or the C.amot-eogine foanul-a, sJww for tile lr.1.llifa uf an iliboU.Dt of~ eqwd fO
~ QI tlnlt

5.41.. Au KaJ ps at ~ kP'a V; lhrottJed adiabatic:m1y to 1SO kPa at the me of 20 mol s- 1
Pet~ S.; ,lniJ 'W~mt if Ta = 300 L
SA~ AD ~toll' claims, 10 bav.o ~ a cyetie engine -hicb e1dtanges hem will'~ ~
~rs 3.1 ZSOC aad 1SQPC. 1lld whidl produces 0.4S U of \\'ork for eaeb kJ of kat
ex~racmd from the 001 JeSen.-oil. b; me clain beliwbic?
5.43. Hear in abe amount of 150 kJ ts ffill\Sfetred ~y flvm ~ llot ~ il! 1'He 550 K
=
to two IXIOlt:r ~oili5 ~ Ta ; 3SO Kand T1 Z.SOK. tbe ~ tmnpemrue
- TiiJ~ 300 L lftlbe beD trdll!tfdred m tne ~Lit Ta 1$ balf '~ ~~d to the
~at T~,. calculate:
(a) The entropy generation in U K- 1

(b) The lo&t work.
.5.4t A nuda~~ plmt geoel1ltes 150 !r-1\l; &be maa tell~ is 3 l s~c md .3! n'Wr
with wao:r ~ of:2(f'C ~ H~~.bk-
(a) What is the mnimum ~~hl~ thermal efficiCOCJ of me pbm. aru1 wba1 is me
ill'iinimwn rate nt. which &Ql ~ be dlsea_rdullO lhc river?
(h) If lhe. acma11 lherma)l efDcieney a1 me p1a:m i 00% ~of tilt: mtr:dmt~m; :Ill what 1'\8
IJ1lUSt beat be~ to the riYer. and what :is lhe temper.IIIII'e rise of the. ri'k>el' if
iirbasa~of16S~ s- 1?
SAS. A ~ Ja! ~ ~e~ a ~liS ~ condiiliom T1. P1,. and le;r,u at Pfl ure ~ .
the p~QteSS. is i.UILabatic:. Prove mat dte owlet I.Cmperonl~ T2 for lbi: :lCtWll (irre-
"'iC'mbk) ad!ie:\Wk process is gmna- dmn thai for a mYnible a.dmbmic p~oeess..
umc llhe gas ls ideiil wilh ctlmtiifii beaJ .caplicltim..
5.AG. A Hi.lJidl 'Wlll mhe 6peJ'3Il:S 'with no mo-\iog meduurleal piU'II. and splits o .gas~
into,two w~: one wanDU"and the: other cooie:rtban II e~~.tcrtog ~. ~.tum
hlhe is I'CpOIUd 1:0 Ofen\t1': wdh air Clll:cring al 5 bar rmd 20, C. a..od sir $11 tBUI$ ~
at lrC md -22C. both ,zl.t I (atm). Tbc JII3S8 D'owrate of w;um air lei1vill8 is 6 1imes
11m cf me ~ air. AJre ~ resu~ p;!$$ible? Atwame alT to be nn iaf - ar libe
ewmli-om given.
'5..1/. (Q) Air ;!.1 18(6F) a_Dd l(a.cm~ u cooled at tbe nne d I'OOJ)OO(fiY(hr}- 1 m 20( A by
refirigermioo. For ,a :mrmtm:dinp r.t:mpetari.U'e of 1i F). what ' the minimum
~ tect~m(hp)~
JJXJO ~ hi- ~ to - C b1 ~...
(h)' Air ill 2j9C and 1(mm) r~ cooltd ar l.be me of
fripratian. fo:r a 5UIIUtiDdings ~of 2.S~c. wba1 is the minimum power
requitemenl in 'tWWJ

5.4& A 8dt p_.l} i.s CODIM. fmm 2.,000 r. JOOrF)~ ~ m~ beat is ~ m g~ ~
5~.eam at 212 .F ) in a boiler. "''be line pbs a tleat capacity gP.e n !by~
c; =;;: l.ea + O.G00306 TJ(RJ
W.ater em.e.rs me boiler m :n2("F). and 1& v~d mnm tempe.rn~JtJre: its went beat
of ~mmw is 97Q.3(Biu)(t~-J. -
(o) WidJ rd"etelle ItO a swsoundings ~re of 1()f'f'J, what ts lbc lost work of
~ ptm:ess ira (Bm)(lb moie)~ 1 er Hae p1
(b) "'Aidl Ieierenee. ttl ~ smmundings te:mperamre ~or 1(1(0 F). ibal is me 1Miimmn
wvtt in (Bau)(lb mole)- 1 gf 0 ps dDt ~ ~, accomplishEd by !the ~~
Steam m21'l~P) if it ,~s only. und does llOt subcuoli?
(') Mow does the answer to Pan (b) compare l\-ilh the maximum wort lbeorai.caDy
obea~ from the ftue p itself u it is oookd fmm .tOCJO to l(J(}(-'FJ?
JAJ. A Due ~ .is cooled from ~ .UXl to I S6(')C.. and the beat is UKd to ge~ ~twatJ
steam at 1WC in a boiler.. ~ flue p .bas a hmr caparity given by;
!._ = 3.&.1 + 0.10551 1'/K

R'
w.r entsJslhe ~at IWC. and is~~ 1hiswmpcmllun~; i15 llllmt he:at of
vaporizariao $ 2.)56.9 tJ kg~ 1
~a) WUb Ief-cteDu to a AifiDUilllitlgs lfm~ of 15~~ Whar is llic lo~ ~ of
this pux:ess in kl morl of Jlue ps?
(b) sib rd~ 10 ~ S\llTC:JUndi:fig ~tme of ~c,...,.hat is the rnti,Wnum ~'(Ilk
io .kJ DIDI- ~ of ftue ~ tbeu can be a&XOmplisbed by tbe sah.llufed Siteam at UXPC
it it c.orvk-mes. t:m1y_ and does not suboooi'?
(~) Bow does lbe mswef (G Pan (b) ~ wttb 1be ll'IOXinmm work theomically
olnai____nabk Uoin tbc flue gas ilsdf M i1 b cookd from l,100 w lS<rC?
~ E-t:lryhme vapor :is cookd at1 atmospbr:.ric ~ nom 830 w J~ 'by direct heal
1tWJ$Fet lO ttre Strfl"'undinp at .a m~ of l!PC. Wilb respeol lO Ibis sunuund-
1
inp ~ wat ~ me kxst -..'Ode of the. PJOOe8S in tJ moi- 1 "'! Show t1w the
SIDJlC. msDlt .i5 obtal_ned as ttbe IDJd. whidl CjO b; deri'-ed from ~bk heat en~
opecuing wbb &:he emylene vapor as beat so:uree and 1be smooudtings M; sink. The,
b~ capacity of <Ctbyle-ne is gi\o"CD in labk C. J of App~. C.

Chapter 6
Thermodynamic Properties
~of Fluids
~phase rule (~. ~7) tell$, us.tb spccl~ ,o f Q ccrtlin ownllcr of iiJ.t:c:nsiw 111 O(_Jetlbes,
of a ~-rem also ~be$ o.e. \~ oJ all otiJer ~~ ~ Ho~d'~ &be ~ rule
providEs no infmmiltioo abom ~ '~~ for dle:se olhu properties may be ObtaiDed.
wnerical vaJu~ for 1hermocJynamic ~ ~ ~ o the cakulacion of beat
...~
..-~ rwurk {j-~
"1.~~ f~ .,. j...vi-..A-..;.-.1
.J..II,,~~n~ r.,..,~~ ..........h~.o. -. """-
....,.._,.._ r......,.Qi.n~r .i Hftn(t.., be
n,.. --u~ ~- _ WF
\AI!!. ~ - _~ "f
- - inti ... ~
a stacty..51JLte eompresscr designed to operate rulia'b aliailly and lD nme. the ~ of a .gas.
from PJ 1 0 liz. '1his WfJit its given by EQ~ (2..33). ~ tbc 5mi.H lrl:nmo. and po~antW
energy dian~ of rtbe gas are oegl!eaOO:
"""' ....... .,1...-.i't ... --a..

u~~ Lilli' -M~.B IIY'II,III~ ~ iP~:mtnJ
:"t! .~......h. d_ nU ., ...Y~t!
L M~ :B
uu..tt-I<=OCWt L.-t . . . . ..;,-II - -..:1 ~---t -th-l
~~ ~~ I IDwm .miM l!Lqjl """"'- upy 'hu'Ua 0
- I f
me .gas_
Out itlitial pwpose iD dDs d:lllplcr is to de!Velop &wn th= fmt and~ laws die. fund.:l-
~ p1qx:J1y ~ebttioos wtDebunda& the~ s.b'Udllfe of dis~ From1
~ \W ~ ~ llt'bidldow ealwlatioo of~ IDd mi!OpJ - lfom PVT
mdl Ileal-capacity d:lta. 'Vre tben dliiaiH the dl~ and tab1es by wlticll p ~ ~
are pret5t.ntal ibr ~oouvtoian U..5e. F'mdy. we ciGvelop pneraliad .~ which~
,e sfbnIWJl of ~y mua in 1he absence of OOIQPW cx-pntmenlaJ bd'orm:ali.crn.
6.1 PROPERTY AB ATIONS FOR.HOMOGENEOUS PHASES
Eq'U~ali-on i{2J6). tlie IJni.c law for a clOS< systm of 11 mol~ may be written for lk special e~5e
of lie\.~ proc~:
d (n:U ) ~ dQ ~ + d'Wft:t
~ <(1.2 ami ~(5. 11) as applied .ro dris proc:ess are:
d(l~ ~ Td(nS)
199 Obras proteg1das por direitos de autc

200
T()Jdbu ~ th_r~ ~arm g~~;
Id(t~U) ~ T ci(IISl - p tlf11?} I

'lifwbete U~,
S. aod\l ~ molarli t&UlS of the tin1enaa1 au:qy. eolmpf, and 'OIWEJ.e.
This equalion.. E:Ombining. th~ tim .iJDd setood Illw .d ui\vd for the ~ ~ nf ~
revll~ P~- Hnw~~ it amtatns anlf p:lf.lfJenin of me sysrr.o1.. ~es depend 0'111
$We alone;. .m d DOt en b tiod of process lba. leads tolhe same. There.fum. Eq. '(6.1 is 001.
~tcdl in ;;rppli'CJt11i01l to reva5Wle ~ Howe-.~ 1be ~t'lim~ pi~ on lht nature
ofrite ~11 ~ be Tda:mt Th.us Sq.. (6~ ~luppl:k$.1.0 dJI1 ~in a sp1em af t?OnSJD111
~ tbat res~ in a diff.eRidial dta.Dp limm one equilibl'frlM SCil. ro motkr. 1lle S)'54em
may eonsm or a 5io,gle phase (a ~i*mS -iSlCm). (Jf it Ili!aY be made up() sn'"tmip'ba!ieS
(a~~ .. mn)~ Jit may be:chemit'ally men, or k may under&a ~~ reaa.ion.
Ttie onlf NqUIJWI'Iaftla ue 1hat 1t1a aptam1be Cloaad end that the
dlanp occur betwaen equllHxtum atatea.
All of abe prlltJluj1 llhermodylmnic peopmti P,. V, T! U.. and S- ;m: inc ~Deled in
Eq. (6.1). dditiouall lhamad}-namie p~ aiE onb by dditJitivn, in ~ to dt
primary pro]K!fti~ T1k ~tpy, ddiPetJ Ill Cbap. 2.., a ntUM of ~r:n~, Vi~
IH u + PV I (l. U ~
Two addidorud pmpenies. also ddiDed ror com-eoieJK~~ .:ve the llahulwl~ rn,..,-gy :md me
Gibbs energy:
[A= u - TS I
l0 H - TS I c~Ll)
Eadl of dt defined p:rupatics leads cllitaltb to m eqiJII.tiou like 1:4 (6_.1). Upc:m mul-
~ n Eq.
I a.
f I J may be diJfw:k'I!tiatQ111) ~
dfnR) c d(n:fJ)-+ P d(tJ'V) + (nV)d~J
Wbal dtnU) is mplaced b-y Eq. (6.1 )_, diis ~tO:
f?(uH) - T d(~t~"l + Cn V)d P ]
l a\nA) :. - P d(n lf) - (nS)dT I

In amlogws bion. ~ {6.3) .tmd (1i..4) cambioo ~o yield:
. dtnGl c:::: (nV}tl P -. (n~l' I (6.6)
Eqwltions (6.4) llrmugb ( 6.6) ~ subjecllo the same restr.if:Ciom. as Eq. C6. !)~ AU are ~~nen
{(If tbe e~ massw any~. ~
Our .imJnedinte ~cation o-1 ~ ~ms is to one mol~ (or ro a tmi:J mas'S) or n
~ flui:d of OOilitmll mmposinon.. For tmcase.. they :simplify ro:

201
dU = TdS ._ l'tlV (6~1) dH~TtiS + VdP (6.11)
tJA. c - PdV - SdT (~.9) dG = VdP' - SdT (6.10)
These~~ tetMJoneare general ..,at1ons ifot a

homogeneous 11ukl of constant composition.
A~ $d -of 1;1!1\Hitions foUOVP1i from [qi. (~7) dlrougb (6.10) by app:1icalion of lbe
criterion of emctn~ for a ~ e.tpre:ssi.Qa If F == 1'(~, 1)~ lhcn die total di__ffaentia1
of F is (!fined as:
q
..~,. -tix .)' d;f,- + (a)
=(aF) -.ay .~ J )'
dF:; .~ d.t + N d) (6.1 l)
1be order of ditierentiatioo In ~ se.md deril1dh"CS is immate'lial. and Uw5e equations

comb'me togive:
(!!!)
a, . = (!!!.)1
a.x 1
{6.12)
When F is a fun___,CI;[oo of x and y. the rigJn side of Bq. {6.ll) is an ,~, di/J:umtilll ~.dmr;
beca:use E4 (6. t 2) mast tbQQ bo. .satidiJ, it ~ ;as abe mteriw of euctoess.
The t.bennodymmrle properties U, H . A, and G are bwwJJ ~ be ~ons or abc \'gj.
able$ on the riJlt,t sides of Bqs. (6.1} tbroo,gh ('6 . I 0): we may therefore Wl'ire the relldiomhip
ap.re-Ued by IEq. 1f6. 12) fm each of lbrsc cquldi~JtP. "'lxy ,an= knovm ~ Af~dr~ erpilllions~ 1
(ar) (ap)
av s-- - , as .,
1 (6.Bl (sr)
iP Cv)
rs r
5 :::J:
(6.14)
C,.)
;rr v =(~)
av .,
1 (6-IS)
(Wt = - (~t (6.16)
EqWI.tioJIS (fi.Jl through (6.10) are tibe basi! fiDt only fm dlrivarioo oflttluv.'dl"s equa.
liens bdi naSI) Qf a far~ mnnoo of ollwr ~uations reMin,g thSIIIOdymunic properties. We
oo-dop here only 4 f~r ~ U!Sefid fOt evaluation of tbennodynamic prupt'JtU:CS fmm
ex~tld d.atL 11:tlrir de;__rfmioo requires appfiCitNn ~or Eqs.. (6.1)- {6.1). (6.15)~ .md (6.16).

102
1he lOOit llite!ful propeny ~ions f ~ enthalpy and entropy of~ bo.mogeneoui pb&ose cr:esnli
when thSe p~ lU'C ~ressa.t as functium of T end P. W'bttl M!. oat~ to know is hew
H ID:1d S vary wim rem~ aad 1~ 'Ibis ~D is contained iD die~nti\J"e$
(aHJatTltt. (6SJDT]p. (IJH!fJf'lr~ .a_nd HlS/DP'Jr..
~i7 tan1 f:bc ~ ~ tiqnat~(m P.,1Q) (fer~ ~~~ ~ily .311
conslnDt pteS'SDR::
( :~)., =Cp (2.20J
A!nolher up~~ for lhis quantity ~ oblained b)' dWisioo of Eq. (6.ilt by dT ~od re.mi.ctioo
ofti:Jc Jiem.llt to ~r 'P.:
(:;t .. r(ift
Combilt~QJJ ofmis ~ widJEQ. (2..20) ~;
(::), .. ~ (6.[ 7)
The ~ dc:lfiwtive of the CDttOFJ RSUI.ts d:iroetly &om Eq. (6. I 6)~
(_iP&s)
~
T
('n")
z=..._. l ~
iJT p
The ~nding dcnwdve for abe mllmlpy is foood by division of Eq. (6..8) by dP and
:restrict~co tfO tons1anf T:
(-au}
tll'' T
~T (as)
-
. 3P T
+V
As a res-llh of f.it.. (6. 1S) II$ ~es~
(6.~9)
tll'cl = (IJii)
-
ar P
dT .._ (811)
-
aP r d. I> dS = (Dar
- S)
1
I
P
tiT (3S)
- , dP
&P r
The JPiBOal ~~~by Eq-~ (2.20) and.{6.17J through (6.19);
dH;;; c,.JT + [v- r (av)

ar ,.
JtiP 1
{6.20)
f _ tiT
dS=Cp T - _ iT
(av) p ~P' I
f ~(i.21)
These are genaul equ;dioos ~ tbe ~ mJd elliiOpy of ho.mogeoooas fluids of con-
staue composition 1o tempemlUR and prwure..

200
lntemsl E,.,y a s Function ,o f P

l111ttnd coc~ $ S)~m by Sq. (2.11) as V ; H - PV. DiJfe~ yidd5:
a~ v) . . . (!!!__) _, (av) _v
( aP , aP , aP ,
(av)
8
-
P T
= - T I-(av)
3T ,_
- P (av)
-
p,
{;1 T
(67'!)
wbcJe ~ '1g:~ ~ 4UJ ideal-gas Yallue:. These are merely Jet~tat~Deats of equmions
fOlf fib~~ ~l}t;d in~ 3.3 !md s...s.
AltemBIIW! FDITI'IS tor Uqulds
AltmiBtiie fomns of!Eq.s,. (6.18) and (6. ~9J result wben (o vf iJT)p ii replaced by fJ v (E:q. U.2)J:
~(ar
~) r ;;;; - IJ v (6.25) ((J<ll)
I -
:BP T
- (I~ JJTtV (6..26
An alltemali\-e fQJ'Ill of Eq. (6.22.) ~Is if, in oddldon. (oV /a P)r is roplacod by ~K V
tp.q. (3.3)]:
iJU)
( il'P
- =:1 (~P- IJT)V (6.27)
T
These equ:nion5. ~g fJ aDfl I(, lltbotlgb gt.flmd. me~~ applkd ool)' to 6qui4...
However. for liquids DOl11elf d:le ailiea.11point. me \roltmle itself i 'SIIIaJL ~ il'M {J am E . 1bm
ru DIMt Jnditioll~ ~ bns littkl e!ffeer on d'Je ~ of liquids. The .im;pnrnm1 ;&pecial
t:&W of an t~ret;mp~fb;iJ {Sec. J .l )1~ ooresi*MI IHx... 6.2. m
R.qJbcmg (tJv flll), in Eq.. (6.20) and (6.21) bJ ~v [see Eq. (3.2)1 yields:
dH,;;; C,-dT + ll - fji)V dP (6.29}
Beew:ue 1J mxl l ' .are weak fundiom .o f ~re ror liquids. dJty are uslilaH)l umcd aJDStant
;t ,aJl~HqlUiate ~niP ~"'lves tor mt.epruion <O f me tina] tmns of Eq&. (6.2-8. mu1 (6..29).

Example 6.1
Determine tbe enth~ anti entropy manges of liquid water lor a cha_nge ,of state from
1 bar end ~0 to 1,000 tt s and WC. Data for water are ~ in 018 fOllowing 1abls.
1fb'C Pibar c,IJ 1molr1 K- v/cnt1 mar-l ptK-1
251 11 75.305 18J071 256 X U)-6

25, 1 ~,000 ....... 18.012 l66 )( lo-'
501 11 15.314 18..234 4S8 )( 10-6
50 1.000 6o . . . . .
t8.,114 S68 x to-6
Solutton &.1
.applicatiool to me dtanp of Wile ~ Eqs. (.S.28) LlDd ( 6.19) require
Fa~'
~- ~lp)' ,aDd mtropy ~ ~~ fu:octions, and the pGtb or iotegmtioo
ls arbitmry: 1be path IDDSl mited to the giYeo. dam i! shown in Ag.. 6. 1. Becw:w:
the da!a :indicate m. C, is a wm fum:lion ofT mdi dial both V and fJ. are went
fin~ti\W or p 1 UJ~Q!l wid~. auilbJnttic means b salid'ac10ry. The i~
fonm of~ (6.28) ud (6.29) l1ml :resufi are~
llH :;;; (Cp)t(T! -1H + U - (.8) f~ )( V)(J>:- 1-a>
AS e:: {Cr ) bJ ~ - {.8)(V)Il~- Pt)
T1
forP .. Sbu.,
(Cp) ~ 75..305; JS.l'4 - 7S.JLO I ruo~- K-~
and fur f ~ SlP~
(\f) ; l .234; '8-174 = lS.204 ~ 1001 _~
<tn _. 458.+.,. :S68 X 10-6 ~ 513 X 10.. .,.6 K- 1

-
G) 81 lftd B, et llia~ ~
I
lF1p.re r6 J ~
Cal.cublim:W path rm
6.t.. 6.,],,

~1Vtioo of~ m~ \-al:ues into rl.lte equmoa f IJ. H 8i\.-~
6/1 ;:;; 75..3110CJ1J. tS - 298~ lSl
[I ~ (513 x I0-6)(3l3.1S)I(l8.204)(1 .000- I)

+ Lo~bail' r 1
;:;; J,HSl + 1.511 ;;;;;; 3..400 J 1001- l

Similarly f~ AS,
4S = 15 310 lP 323.15 - t5p X I0- 6 )08.104)1 ~.000- J)

, m .1s 10 ~ &ar s-
~ 6~.06 - 0.93 ~ '5. tJ J mo:r- m K-
Nole lbilt die dfea of~ ptessure change of aTmau 1.000 bar 00 tit~= cnmaJpy Qnd
~cmtropy of liqu.1 wat:u is Jess th.'m.lhat of at1tmpemwre change of only 2Soac..
Internal Energy and l!ntmpy as Functions ofT and V

TeuJptmt\1{(: IUid "WUWC: o'.ttco ~ z ~ com:.-enieJB independent vuiables dla do temF-
aiJII:'e and --""'!i-ure.
..,..__.. ~ lllO!i1 mtfu'l rni\ni'tiii'lffif
-r- ,; ~..d .....: ... - -lben
~~ - v __ _ .: - -J.Q'!,g
I 'IX' - -- L~ Ctla'g)'
- __ - - !inll')'.
and-"~
.R.equmd bae am tim deriv:oives (fJUj aT) v ~ (iJU/ iJ V) r ~ (t(ISI an 11, and (a$/ 8' V ) T. The 'firm
l'NO of lhcse fo(lcw ~1 fro.lii fq, (6,.1);.
( a~3vr } t' -- r("s}

aT ~
{~) r=T(~)
oV r aV r
1
- P
Cotlthtniltg ~ firu of~ wilb &]. (1.16} md lbG ~rood l'>illb Eq. (6.15). \R pt
(6,30) (au)
-
av r
_(a1p)
aT v
;:;; 1' - - p (6.3B
Tbecbosen rl'mldr6tla1 relw.iom! b:ere..u e U ~ U(TT II) und S ~ S(T. Vt Wbeoc_~
dU = au) ,.,df + (a'WfJ}

(iT T dV
(as)
riS ;;;;:; aT . \' dT + (as)
IiV
1
dV
The pattiaJ daivatiws ~~iva by f.q& {2 I 61 (6.3 I J~ (6.Jo). :and (6. ~ S"t
dU ~ Cv dT + [ T ( iJ.
aT'P )' ., = P'] .4V
r( 6.JJ)

'Tbe:se are ~ eqnatiomJ relating tbe inrernal eneqy and ~enttopy of h~ fluids of
constmt cmnpos;itioo to tco:tpeNturc and \'OIU_m.e.
Equatioo (3.4} ~lied. tO a~ flf mt~e: 31 (t.l~tlmt "'lwne ~:
(6.J..I)
(6.35) tiS-. Cv JT + IJ ciV (6.36)

r llr
Examp e6~2
1
Develqp the prqperty relations appropnate to h I'I'KlDmf'ressble liuid, a mod!Jt flUid

for which both fJ and fir an1 ~em 1(Sec_ .3. t )- This is an ld&aliza.tion often employed ii-n
ftuid mechanics..
SOlution 6.2
Bquotions (6.28) and (6.19) written 'for an ~c 6uid become:
JJH =c,JT VdP (A ~
dT
dS = Cp -
T
Tbemlbalfy o fan ~"ble ft\lid is r.berefore fll~~telitm of hub remperomre
and~ whereas the. enttopy a function of~ ooJy. indc~t
=
of P. ith fl ,;;;:. JJ 0. Eq, ~627) ~~ lhai dre inmFruill mergy i~ .USO a flme-
uon of mnpernmre only .and i'S dlaeforo give:~~ by the equlliOJ1. dU = C J.T.
Equation (6.12), the mtaion of GJCtu , qpplied lO Eq. (AAyields:
ac,) (ev)
(ap -r;;:; iJ T p
H~r. the ddinitioo of IJ. gh~n by Eq.. (3..2). shows lhat.lbe dtrivathre un (be
right eqWLLs fJ V. Vf lricll is :mro fo:r an iJJconlpressl:ble fluid"' Thi means that C~ is.
a function of te~.re onf)\ mdept:udcnt of p .
The tdation of C p to Cv f an i.orompressi'bte rtuid is of ~t. for a gi\'en
dlange of mw; ~ (6.29) and (6.36) ll1USt give the- same ,ru~u~ for JS~ dry ~
~n: c!I{Wif~ ne 1rC$ul.tifig ei.pm&on. ~ ~nem.. iis:
(Cp - C, )dT = IJTV dP -r IT J V

I(

Cp - Cv = flTV ~(~)
ar .,
El:imimilion of lite deriv:tti~ b)r Eq. (6.J.l} yield.!! ~
Cp - C\~ - ~TV(~) {:8)
Becml5e IJ c 0. the rigbl side of d:rl equillimn is tell~ pruvidtd dw ~ ~

:mi!nate nttio ,.Itt is finite. 1bls ratio is indeed :futile for rea~ fluids. and a contrary
JliESlUilpiou for 1he m1d fJuid wwld be irr.rti:ooal Thus lhc ddinilion of tho
ioeomp~ib1e 6uid1 ~mar dUs R.UQt is ~, and 'We (:onclnde rar $ll(:b {\
.ftuld lbat lbe heat aapacllle$ at C011$~il::.Qt V and m ~ P are icbttical:
77Je Gibbs Enwgy as a GeiHII1lflng Function

The fundamental prJty relations for bmnogeooo:u fJm& of const:un oo~on gjven. by
E.q.4i. ( 6.7) thrf.Jup (6.10~ $how ~ each ol ~- ~__jUJ)iC (li1JPCI1j I) H ~ A and a is
I I
fnnc.iiftBIB'y relumd.to a~ pair af' nrlables. In~.
dG ,_ 11 iJP - SdT
the funaiomhl relation G = G(P T). ThliiS dlr. &paciBi f a conanicol~~ ~bb
el()E"eSSf:S
fur Clle Gibbs enagy are te~re and ~ Bemuse lhese vnriables an be direc1ly
measured md cxmli'OHed. the Gibbs eaern i.s.a property of ,g11ea1 potenmi utility.
AD ,aftcmalive fcnn of Eq. (6..10)~ a ftmdamenlal propaty relation. ~oi!CJWS ffrom tbe
~cal Id-entity.
.I G
dG - - dT
RT BTl
d ( G) = l'
RT
H
I(Tdf - RT2-df (6-.31)
'fhc lldvantq-e of 1h~ equation iiB that all tenm are dimension.1ess: moreover.. in oon1ra&t to
Eq. (6. HJ)r lhc mthalpy raaber tluw the eo_~~ on rdm rigbt~.
&tomons sud~ as Bqs. (6..10) and (637) .re t(I(IJ geQI:Ql fur dirccl p-tit:al ~:l.icati.OQ..
but ttbey are- tadiJy nppiied in ratricted foJm. Thus. from F.q. (6 .31}.
Obras pro egidas por drrer os de auto

_!_ = [S<G/RTt]
BT aP r
Wbm G/ Ill' I know11 .as a functi<m o.f T and fl. Y I R r and HI RT follow by simple differ
cn1laiion.. The remaining ~ mr- gi\'-m by ~fulJng equ:~tions. ln panicular.
S H G U H PV
- .!:::~--- ~ tliiiiRiiiiiiii~~ ....... ~
R RT Rl' RT Rf RT
1bus~ when we know iho'w fi.f RT ( G ) is rehlted tD 1m canonrical 'Wri:lbf~ i and P. Le.,
wbeu wa are &h-1m U'/ RT .;;;;; g(T. P). we ca eval:uate aJI odilu tbermodlyna;mic pmpenles by
d_m~ ~lical~
1be GJbbs en~~~gy wtMm gwen as, 1 tunc:lton1of T

1111d P serves ,as
~ /undiJIJ' for lie OIMf tha-rmodyruunk ~11~ ,a nd
lmpllcl:tJy , . .. . . . completiJ ~ ,Info~
Eq, (6..10) k:ads to ~~ns fm all the~ prope-lti~. so Eq. {6.9)
Just 1
IC$kbl the~ L"tll'lnming ~Yll=-mk PJiOJidtics to~ ~;;uuc~ (~. ltt1-...a)~
6,2 RESIDUAL PROPefmlES

Unfmtuoat:ely, oo ~erltal metihod for abe ~L of numerial v.rdu~ of G m
G{ BT is toowo.. and ~be ~!qua~ wbkb fdau: otbtt ~ts toth~ Gibb& t nagy are of Ht-
111= dired jp radial use. Howe\~ me coru:epl of d:te: rn'bbs ~~y ~ a geoer.tlin8 funcl!ioo fWi
other~ propedies ca:m~ ~rto .a clady R.la.ted property {@I' whicb numeriad
VJtlues t readily re>b.tai:rlal. Thn&. by ddDitloll lfle n!!5i.rha:l <iibbs mc:igy is: GB = G .... G'',.
where G and G'' me the ad:Wil and the iidea.l-gas values o the Gibbs ~ at 1 nbe wne kiiP
pcratU_re ud ~11IV- Oihu rcsidllld tpmpcrti,es a:r~ defined in an analogous way. The raidwl1
1{of~ b~ is.;
v 11 =v- V''. = y. . . R:T

p
~ V - Z RT 1P. lle residual \'Ol'wne and the compressibility factor are :re1aled:
yl ~ BT (Z -I) (6.40)
p
1lle ,fd:initian fw too ~c ~~ ptop;ttty i~~.:
[ M, Ei &I ~ M'' I (6.41)

209
This;~Ml miclutJlpro~WfiJ' ~/mien .L1ppties to ftuids of oons

~'ti'Wti!d forms~
<6 A 3 > H~~. -= _T[a(G"JRT>] f6LUl

R'l' &T p
'The residual Oiblu ~ .. a. generming fuuabm for lh~ C.u~r ~iJil _ p~ has
dim:t link with e.~ect. It - pmvided b)f IEQ. I6..&3).. wrhtm:
oR) ,
(RT RT
t1 -
. c=~dP
.~
teollSt n
lot~on hm zero. ~ w ubi1rm)t ~ fl yjdds:
IG "= J
-
RT
+ 1"o (Z- L)dP
-
P
(rons1 Tt
n
___,~- T
RT
1' (az)
o
-
. aT 11
-dP
P <w:vnst n {6..46 1
The defiomg ~tiQ'D lfw k (hD\Js mmgy,. () - Ji - f S.. Dli!ly be wrJtm:l for the
~~~of~ idetlil ~. fis = H's - r sf ; 1Jr diffV~Cnce. a' H" - r sR. m =
sfl 8 s 6 11
R:;;; kT- RT (6.47)
Combiniq this equ:LtioR wilb Eqs. (~6.45) and (6.46) p .
~
R
-.-r1P (~z)
~ oT p
~
P
~J -1-
~
P<z -- l)~P
Ob as protegidas por dir eitos de auto
ln applicatioo lhe need is always for entropy rlijffi'ml:;u. Eq. (6..41), ",.;ri;rt~:n fW' llh
tnttopy and reatmnFd as S ~ S;' 1- S" .. .1Jl3)f be WI'ii:mm for two different ssnte~ 8y di:ffCe_rmce;
AS s S! - S~ ; <si' - 5i ) + (S: - sr)

Beeaose J b a oonsran~ it cancels om of me residnal~y diffetet~Ce 1in dfi.t;. elp.l~.
liCJ:JCe i . value is of 1\U ~~ and I may be amitnrily sa e qnailo :Rl'O, nae \\'Orting
~tilion fUr s is then v.'tium:
sR= - T
-
R
_lP (az)-
()T ,.
dP-
-
P
1"o . tiP
( Z - 1)-
P
- foonit T} (6.48)
G~
-
RT
e:
11
(Z - 1 ~~
dP
P
(6.49)
1llc ~"bility C.ctnt i$ dtfiocd ~ Z ::;: P V! RT; '~ of Z and of (CJZ/ fJT);p
m:ry be ~ from aper:imentaf P VT daln... with dtt two' mlt!.gJab in Bg1L (tt..lil6), (6~~ ),
d (6-49') ~11b~-e<t by own!Uieal or gntphicaJ mttbods. Aitem:rtH~IY~ lbL'l rwo ~ nuy
bc-~1~ 8;11_3lyliailly ~beD Z js ~sed a l\n'lelio.n ofT :rod J! b.!i '"G~!a~t
tqllMiwt of m.te. This ~ OOOntlCI:ioo. 'll<ilb ap:rimeot llb-s evaluation uof ~ residual
properties il H and s~. which are ~~ ta lbe pmclicaJ appli.c;a.ticm of~y.mn~
RB/dfiBI Props.rtlu ln the ~Presure Limit

'1'he (lOOSfllni I, omittm from Hqs. (a46},. t6.48), Wid (6.49), i,s tbc vulue of 0 8 / RT 1n ICbe
.limB as p ~ 0. Us origim becomes clear from a geoerol ~~ or ~'id\llll p~ in
this linriL Because a 1P5 ~ tde!d as :P --+ 0 (m .~ sense that Z ~ 1l. line mi@ht
suppo.se lba.t in mi.~. limi1 an retidna1 properties are U;fO. 11tis is not it'lgt~Ktal ~. as ~ tasily
demo :toted tbroulb eomi.dcnnion o b ~ual vtJbmle.
Wlill.cn fo:r vii .in lht limit of .um puts'SWC Eq. ~6.41) ~-
6:m v = lim v- lim v-Jt

P-o " o P o
8oth lmm on. ~ riJ}b1 we infmi~ -nd tbe[Tdiff~ is indctcmdnlite. E-xperimental insight
Is pmv:ided by Eq. (6.40)!
tim
P u
Y~;;;:; llT Jim (.Z P-I);;:;; RT tim(~)
P--f'J ' oP

P---0 T
Thus V ll j R. T mthe ltindt u P .--,. 0 at a gnooeo i ~uals the~ of 1ibe z . P isodletm at

P' = 0. Figure j ,g shows clearly dmt lbese ~ are finite. and oo& in @cuenll zero~.
Forlbe irntaut energy, u s fJ - l) il. Beamse .u Jt is o.t fllllieOOB ofT Ofi'ly. a plot
Df ur~ v P l6t a given T b. ii ~~ time ~-8 b) P =
0. FOT a ~ ps with

211
finite iote:nnoleadm forees, an lsodlermal exprumoo to p _. 0 resnl~ in an IDcreasg m,u y
beamse. the moleeule8 move a;part a,gaiml die Come! of mtmnolemlar 30Tt~ecioo. ~OD
to P = 0 (V =: QQ) ~cs; ~ fOfC~ ~C)' mv. aactiy .in an idea! ~ and ti:ladO~ at al]
ttempennures.
llim U ~Vii lim U 'R ::r 0
P ..-:1) ,....-.()
From the de6nilioo of enthalpy..
Lim H11 .- lim lJ1l + ltlm ( PV 1 )
P40 P~ ~~o
For rbe Gibbs~, by if.q. (6.37):
tG) = -RT
( RT
il l - v JP
--
(C6DQ1)
G J8
RT
~ ('GRTl8) PJIIII)
-+ (P !!_ =
}0 P
l((?g)
R.T PeO
+ lin P + oo (ooMt T }
For finite Vctlue8- of (;i'l f ;RT ,at P > 0. \\e lil'l:m lla\t lim (G'' I Il'T) ~ - oo. ~ tftis is
. ~~o
m.te for G .as well,. \\if: oonctllde !~that
GR G G ft
11m ..,.........,.. c lim ~- lim~ c 00~00
P-O RT P~ RT P-.0 RT
Thus GRI RT ($Pdl Qf (l(Jurte GR) is. :likt: vR. ind~n!P in ~ limit u p ~ 0. [o
case ~f no~ means aim fur finding 1i:be limiting wltre. ~ "~ halt
oo ~ rn pmwne i1 ~ and lbe.Rfore regard i11ike fim~...-..o Y k .as finite.. .t~Dd 111ot in
~ncnd 11'0.
F..qua.llmt (fi44) ~1des iUi OjlfJ(Jttunily for~~ ~ym_ We write it tior lbo ~
case of P 0:
As already muv.m. H R ( P ~ O) ~ o_ and llx-Idmc 1f'le (X~t demaiJ\IC i5 mu_.M a tesnk,
(z;:)F=O ;J
where J i11 eoostaat. ~ent ofT.

212
Enthalpy and Entropy trDm Reskllllll PtopertiBs

Apptkd to~ emhalp}l and entmpy~ :&J~ (6.4m)ts written:
Thus, H nnd S follow from idtaJ..p and residual propeni b}r mnple adillthm. ~ml
~s for H l and s4t nre found by i~ of lip~ (6.2.1) ~ (fJ.24) from an ldell1
ps ilale refcre:rJCe cooditiom 7(J and 1\ to rdJc ida_~ -.();:1 Dl T und f ~
1Pa = ifil + J: c;t dT

Slib&tilutim miD the preceding requafioos give-s~
H= IT c~ JT + "g
H~~ + {6.50>
Ira
s = ~ J.'~'
71)
c~'!!.
T
- R In !.. s8
Po
(6-5 1)
RaU (~ 4. Jl uod 5_5) lhm fur ~ uf ~-oOlJ!I01illion lbe i~ i_n ~ r(6_50) t!Ddl
(651) am ~ted by:
lr. elf
r dT = 11 x IOPf..I(TO~T;A.B,C~D>
r ~,. dr . -.
~~ioM
lc
~
p -
7
- Rx
~45.SOJ 4nd: (6.5 ~ t have :iltemarivt
lOPS(TO,T,~B.C.D)
fOJttl$ 'i.'b~ ~~ n~~ ~ ~-pt~

6e by
eqniwJeo enns 1bat mchlde the me;m lhRt capacitie:s .incrodu.eed in Sees. 4.1 WK1 5.5~
H == ~~ + (C~1 }11 (T - Tol + HR. (6..52)
S=~~ + {C'~ }s lq !_-

..ro~ lb + SR
To R ln !_
1 (fi.5J)
lo Eq ~ (6.50) through (6.53), 11 8 ;md SR are gjvcu by Eqs. (6.46) and (~48). Again. :fw
o~~ 11~ me IIDCim br:ul cupactlits are ~wll by:
( ~~)~~~ = R X MCPH(TO.T;A.,B,C.D)
{C;~)s ;c R x MCPS(TO,T~A,B,C~O)
Appljcatims of tbmDodymmlk requin: o:ni(Y dilf~~ iD r.otbalpy and ~nhVpy. The
tefcrt~r ~~icms To atld I\) are ~.ore ~d lot. t<lm~tctto.e,. and vallit'!; atC
~ to ~ cwd 1.,
1 arbftnuily. The onJr data DCded for appiiemoo of &p. fi6.S2) and
(aSl) are idcal-ps beat mplkiti~ and PVT data. Once V, H, and S arc known M ~.a
oollll'.titiom ofT and P. the other rtb~ propenies. foi.W from deB~ equations.
31'hmnodjllli1Dlc ~ fiX~~ ill~~ mite ~ ~ bf M.. Fmitd. G. I. ~

K. tt Mmh. Ci. K. Ito
d)
or.-
CmU~r.T~A&MU. ~~
c
R. 'Wilboit ~~ 11/~t c~ :II ~Om Slate. tbun
c .. T~l~.

213
~ual ~~ ~ validit for 'both Wld tiquid..~ Howe'"~I. ~lid~ of

Gqs. (6.50) and (6.5 I) in appl1Cllion tD pse:s is ~hat HA lifid Slf the terms wb4iJ 001Wiin aU
i
11 compW; calculatiom.. a~e ~IJ 11m .are 'DSuaJ~y small The}1ad a.s ~ lo 1M
tr4jor ~ IIi.~ ;mdJ S'J. For liquids, this .advantage is largdy lost, beeaDse H ll and SR mRS~,
includt: the . . enthalpy IPldl e~ c.;baP~ ef ~WI. ~ dl~ tlf liquids
*R uswilly ca1e:uhled by ~~ fonm -of~- (6..21) and (6.29)~ as iDastr.ated. irn EL '' - L
Example&.3
~caJeuJate tile enthalpy ,and emrop, ~elf Ga1urated isobtdane WfJQf at .360 K ftonl lM
foll'~g information:
1. Table 6.1 gives ~compressibllily;;faefor data (values of Z} for isobutMa vapor.

2. The 'IIPOflp resnJe of i~ at 360 K ~ 15A1 bar.
3.. SetH~~; 18.11 5.0 J mo~- 1 ,and 1o'
=- 295.976 J roo~- K- 1 for lhe ~-gas
Nf~ state ~at 300J K ,l fld 1 bar. [tl1ese vakles are In acco"-' wtrh the bales
adOpted by A. D. Goodvtll and W. M. Haynes Nat Bur. Stand. ~U~S-)~ Teeh. tto1e'
1051, 1982.]
4. The ideai1)1S heat capadty ollsobJ.laJl8rvapor at tempemturu eJ interest [s:
C'/JR:;;;; 1.1765 + 33.037 x ~o-J r CT/ K}
1Dble 6-.J t Compi"!:SSSbllhy Jladon Z llr tsomdane
p~ 3401{ 3SOK 3}1X 370 K 380K

0. 10 0.9!1700 0.99119 0 .99737 0..99751 0.'99767
o.so 0.9874S 0.98830 0..98)7 o.9S9n 0.'99040
2 0.9:589.5 0.916206 0.964$3 0..96730 0J909:53
4 0.92422 0.93069 o.936l' 0.941l2 OM:574
6 0~88741 0.89816 0.90134 0~91529' 0.9ml
8 0..84575 0.8621:8 Cl.B7:586 (}.88743 0.1!1743
ro 0.79659 O.ltlll? 0.84trt1 lt85695 0..8:-706[
t,2 .. ... 0 - ~
o.mro 0.80103 O.WIS 0.84134
14
tS.4l ' .- ... -
0.1~)06
0.7~121
(17,8531 OJUl9'lJ

Solution 6.3
CD!rnl~on of H f< aoo :sJl ~tl60 K and ~S.-4 1 bat b; i!pplicatiM of EqL (6.46)
and ~(6...18 req~ e\~l'Witim qf two ictegnl
P dP
f. (Z-U-
f'
GllQihidmregrarioo te~l'implelcts of (aZf rJTlt / P and (.Z - I){P l P .

Vahles f ( Z ,.... E)/Pare found frmm the compressibilil}la.dor dm at 360 K.. 'Tbe
q;utmtit)1, azt&T)r / 1:' m}Qirfi f:\~Jon or the pam~ ~\'It azJ&Th~
@J\"en by Ole slope of 3 plot0r Z \'f.S. T m ron~rw pri5Sllre, For Ibis Plll'pl'l!~ s.ep
mate plots liR n.mde of Z ~" T fur eiJdl ~ ;s~ v,..iddJ oom~Jily-fActor
dlatu m ~~ and a dupe i ~ned .at.3(i0 lt 1for ~~ t:ur\'.e (for example, by
coosaruakm of 1bmgtmt line ,u~ .360 K). Ibm for die req\1iRd plats ate shown m
Th.ble 6.2.
Table U; Values of tbe lntq"'aAd:s ~ 1n E-16.3

Y..liltres m~Jheses ate by extr.t.polmon.
0 (1 .180)
0.1(} 1.700
o.so I.St4
-4
"1 l.M
1.290
6 1.195
1360 L352
10 1.m 1.592
J'2 LOll L658
14 2.432' 1.750
I '"'I (27.llJ) {1.835)
NR
- = -(J60)(26,.J,7 x L ~ ~ - Ct9493
B.T
s
1l = --t-~93 - (- 0-2596> - - 0.6.&97

21S
Fer R; &.ll4 J mot- K- l,

8 11 = (-0.949J)(~J14){Jfi0) ..:::l ..... J..84~.3 J mol-1
Sll ~ (-0.6891)(8,314) == --.5.134 J moJ- 1 K-1

Valt:!e$ ollbe inlCglals iD Eqs. (6..50) iUld ~6.51 )131'e!
s.Jl4 x ~CPH(30'J~3S0; 1 .nss.33.037E-3,o.o.o.o) = 6.324.8 J JOOt-
8.31t4 x ICPS{300.360;1 .17'65,33.037E4~0.0~0.0)-=- 19_114 J mal- 1 K-]
Subslimlion uf ~.all \11)ue& itU.Q Eqs. (6,510) m:ld (6.51) yields:
H ... lS.E l!LO + 6-..324~8 ... 2.Mt.3- 211~9&$ J DHil-2
S c 2%.976 + 19. 174 - 8.JJ4ln lSA I ..... 5_iJ4 ~ 286.616 I mot .... 1 K- 11
AJ:tbou,h caleulations ;are beN carried ow 1ior jus1! one sta~ en~ and
---r- _
.~tn~ Cfdil L..o. __ f,-
~ CYfilWitm_.,. ).lllf ' Dlml- b .,_f -
__ ... --.. . -
gn~n ,-....c.-...... .--
.1--.
~-.- UAUL .a.A-
.tu.u;:J
having compJeted a set of cakulmiens. one is ooc fne.\~)' mmmilkd to tbe

pmiliailitr \:alue$ ~f H~1 ~ tor
illit.mll!i L~~Kd 'l1Je ~e of v. ues. !either ror
lbc aJllb;dpy or the eJ'IImpY can be sMfied by addttion of a. C!ort:!SCifif ro all val~
En tid!; "'ll)' (Inc~ giw arb~ ~tv H BUd S for 50r11e puticub state so
as m moe~ seale8 ~t for one purpme or another.
The catcula.tiun of~~ prq]JCrdes is .au QJICti__j!g UISk, seldom :reqWed of

an engineG. Ho\\:ever.! engineers do ~Date pma(a) me of~ ~- ;and an
~g of~wlationaJ llldhod.'s bould SUJP5t tbal ~ tmeertainty ~ ~ wifh
e!r"eJY pmpm.)' value. tna.::curacy derives pari.l)l from ex~fal ~ d:a~ ~ ;110mme
abo~tly meoorpl~ and DtUSt be e1.ended by inter"pOWion and a.uupolm.OD. M~
e1en with ~ P ~'T d~ a 1m!& of accurncy- ~in the di ftCdtiatim 1~ req;abm
tn the calcWal:ioo of~ ~ Thus da~a of a h:ilb Ofida-,or ~ ~ ~J'bl fO
pl)ducie ~alpy mid mtro,py \~toes !i'Uitable foJ cngineemg calcuJatiOI'IS..
63 RESIDUAL PROPERTIS BY EQUAn ONS. OF STATE
An ~-e altemaU't'e ~o, me IIJ1D:riaiJ ev-.lluation or intestab m~ (6.46) atld (6.48) is

dJciJ" anal}'lial twalaatioo by equaOOm of ate,. thi& teqllirM an ~h ~ ~ tie ,eft.
rrcdy 501\'td for Z (O V) as a fn:octicu of P 111 ~ T. Such m cquamoo of~ b said to
be 'WJlumw! a:plidt~ m.1 o.e ool!y exumple~ iu ~3M tbo irid ~in P'. T.ltrJ
ot:br eqamtions oF~ m-e prunur explicit; i.e.c. rdwy can be solved for Z (m P ) as tlllldions
of V at comum .T . ~ are not suitable tfor ~. ~with &J'5- (6.46) and r(6A181~ Tbe ~
~sioo in V and aH cubic equations of ate are ~ splicit." md dlar ose fror ,~ua
OOIJ ef residllill pmpettiM requims ~ re!Gnmdntiao of!Eqs_ (6.46)~ (6JlJJ., zmd (6.49J. fa what

216
.f taldUIII ~ lmm fhe VIdal Equallon-S of Sftlle

Equation (3 -I}. the t~ virw, cqua_li~ give5 Z - J ~: BP1RT. Subs1iwtioo in
Eq. (6.49) ~it toe
OR BP
- = -
ll.T RT
~.: -=T[(J1(G-' /In]

llT aT :P ~
~: ~T (!) (~!!
R T dT
_!!.)
Tl
or HR.
RT
~ !..
R
(!! - ~)
T JT
(6.:$5)
Substitution of Eqs. (6.54) and ('-SS) uno Eq, (6.41) ,tields:

s1: P dB
7i' = -idr
E\--aluation of miiduw au:ltatpies and midu.ai .enttopies ~ Bq. (6.55) and {656~ i& strdigbt-
fmward. fQr giYm Vfilw:s ofT, P , awJ composmQD, provided QJK: hn tilllllicimt data to ~1lluate
B 'IDd dllf dT. Tbe ~of awlk:rbilit:y of lbese equruion is me same tl5 For 'Eq~ f ;l.]8J. as
d:isalsscd in See. 3.4J
Spiiuloo (6-46}- t_6..41)., arul (6.49') me i:ocompaliblo: w~. ~~~e-~plicit FXJUil.tioDs of
~ Wld t be uamfoonedl to llll!ake t' (mr molar dimsity p) b variable of irnLep'3fion. Jn
~ p t a more ~:~ot nri bk lh:ul. l!, andllbe equari~ PV ~ ZIIT. i written
In the ~'e- fOI'Illll.
P = ZpR.T (6.51)
dP o RT(Z tip p .d ZJ (m.U T)
lin ~'binal.ion wiJh tiq. (6..57). thi$ ~lion is~
dP ilp dZ
-p_
- - -p + -z raxmn
Upon subsDlutloo fot d P 1'P .. Eq. (6..49) ~
GR
-
RT
=
leo ( Z..,. 1)-
d,p
p
* Z""" l -dnZ
wtere the! bl~r.al i8. e\'illwlted at romiDW T. Nett: abc Um-m p .,. 0 >Yt'hn P ""* 0.
Solving Eq. (6.42) fer i15 final tenn and wbstitming for v 1 b} Eq. (6.40) }fieldS;
lJ'-'
~ d'l'= nz~n~~~
.dP (()B)
~ I
RT~ P RT
Obras pro egidas par d1reitos de autc
217
Di'YnioD b)t d f aDd rcsbittioo to~ p gi\~
f!_, = Z ~ 1 (_!_) _[acG:RaTIBT )]

RT.. P ~T #' 11
Dift"acfltistion of E.q. f(i,..51) pmvtde.,r;;. the fim derh"81ive oo the rigbL aDd diiJe.mrn:intioo of
Eq. (6..51) ~ d.Je socoOO. Substitutio11 leads to:
-
11
11= - T _1/J ("z) ~ tip Z ~
~+ I
BT .o aT P p
s = lo Z - T
........
R
1"o (aar.z) , ........{} ---1p
~
dp
o
.,. dp
(Z: .-.. u~
P
Z - ] ;:::;; Bp + Cp1 {3.40)

Subslinnioo into ~ (6.51) lh_fUlllh t6.fil1) lads to~
G1 3 -
RT = _s, ~ 2c,1 -mz (6.61)
-s~ == ~h z ~ T I - [(B + ;da)

. .: :_ p + -t(c
- + ,-rJc) -]- /}'1. (6.6l)
R . 1 dT l r 4T
Appfiauioo. of'tbcse cquliliunsr ~ b' ~ up te ~c ~ :nequirt$ dam

for both thrt ~and tbild iri:al ~coefticlents.
RfJslduaJ P~ by CUbic EqUdotN ol StaM

Results. Gf 50ille gcnendit) follow from appJication of tbe g.enenc cubic eqltlh~ ,fM' ~
p = RT _ a(T) n 4 :2.~
V- b (V' - ~.b){V + vb) ' "'
1
Deri~ with 1hJs ~.U.UQIJ are mudJ IDOrc ~ when il is ~ te yield Z with
dmii1y pas me in~t ~~ W thewef~ div&h: Eq. {l-42) tkroagb by O''RT and
wbstimre v = l,/,p. 'Willb q ~'CD by Eq. (3.51 ), die result afru sume.alegbmic ~om ilc
z l pb
a J - pb- q (I + ~pb}(l +trpb)

Tlk l~-o q~til ~ ~fOr' e,,aJU!OI!R>tJ of rtbe integtQll\ fn F..q&. t6..5S>tll.rokgb (6.60l. Z - l
~nd ~c 2 /aT)~- are R"adily folmd from 1lhiB equafion:
z .... ~ ~ pb .... q ~--p--"-~- 6.6-*)

1 - pb " I+ Epb)(l .J.. upbl
1
rtJ (dz)" dp dq l,.) __d_(p_b>_ _

Jo :JT p P =- JT .'o tI <tpiJ)
1'bese two cqua.ti005 ~lify oo:
,. dp .
l ( Z - J) - c: .... lnll - pb) - q I
f..t
Case It l .- ~ t=
u -
~
~
lo (
1
+upb)
( . ~ph
(6.65a
Apt;lknti0111 o! Ill is ond \lJ.bseqUcnl ttp.Jltili~ i& simpler v.~ p is elirii..illlamd 1o fAror of Z. 8}
E4 (3-SOJ a.D()I the ~filliliun of Z:
li-P' p fJ pb
fJ -RT
- z -p RT -;;;
z
l {0.65b)
/;; pb - fj
I + pb l + ~IJ
Tnr: v~m der \\~ I!Qllilrloo the ooly ooe WIUlicbcd here to \\. bicb C.asc rJ a.ppl~, u:rkl lbis
equation abc:n minces to I ~ ~1 Z .
'With e1't11amioo of the ~ Eqs, l16 ,Si) through ~6,60} reduce to:
Gil
....!_ = Z- I - In( I - pb}Z - q .l
RT

2;t9
GR
---- ~ Z - t ..... ln(Z ..... ~} - q I
RT
(6.61)
sR
- c:= ln(Z - IJ) +
dma(J: '
.r ql (6..68)
R Jla'l;.
Pr-limfuary to apptic3boo Q( ~ ~~ one must find Z by solw.ioo of Eq. (3.52) for a
np.v pb~ o_r Eq. (3.56) for a Uquid phase.
!Example &.4
Find vakrU for me residual eJdhalpy H' and lhe residual entropy ~ for n-bul8ne 1gas
at 500 Kand SO bat u given lby the AealtdVI<YJnQ ~
Solution 6.4
Far ttw giwn mditiQnlt.;
.5~
T, = 4E} ~ 1.116
- - so
P.,;.;;, l1.9fi = 1.3 17
By F.q. (3.5.1). with n far ~ RcdlidUK'\VOP_g ~ rn:un Table: J. J.. .,. 9S,
A= .... Pr: = (0.08664HLJI1) _ . ll"'l'r7.r..,..
"' q Tr ~ .176 ,. . .,. 0"" 'v~
With values far and a~ ~with me e:tpmsion cr(~) ~ T,..... Ifl &mb T"~ 3. l .
Bq. (3.54) yi~:
""crfl;.) 0..4:!748 11M
q ~ a-r, - <(0.08664)( 1. ~ 76) r: - 3., 9

Subg]'rufiun cnf fJ. q., ~ ~ 0. owl o ~ 1 buo Eq. (3...S2) rtdutU ilw:
<3.86tl9)(0~D9700) z~z~ ~~~)

0
z ;::J J + 10.0000 -
Soludoo Qf rbis. cqwtion >ield$ z == ~0-61.:'50, Thm;

Z +Jl
I ~ In z :r 0.13247
\VIib llur(T,) ~ - }hiT,. d l:rurtT,.)/ J tot;. = ~~. ~ lqs. (6~1) :tllld (6.6lJ
becoole:
IJR
RT c 0.6850 - I + t-O..S - l )(3.8lJ89 (D.l3247) = - I .. 38
sR
R ~ ln(Cl6850 - 0.09703) ~ (0j){3.1689l{O.lJ2-47) ~ ~0.78735
Hx = (8 .lJ4)(.i00)(- l .OKJfU c -4.505 J .mo1-1

sR ;;; ~8.314)~-0.78715) ;; -6.546 J mm- 1 K- t
These ~are co~ with those of other cakulnlions in 'tilble 6.3.
'idW Eq;n. 0.6608 - 3JY37 ~5.424

&X !q!l. 0.6850 -4..SOS ~6~
SRK .Bqn. 0.1222 -4..&"24 -7.~13
PR Sqn.
~t
I 0.6901
0.6988
-4..988
--4,.966
-7.426
-7.632
H~ 0.1Cl60
t ~-!L-.1 t ' - ~
~~~m~!"f "
1
; ~ dcm''od from nv~ mTabl~ 2--l.W, p. ~-2-13,
Chcmlctd E;uuu:~n Hattdb:ool. ltb ed., Don rOreen {edJ.
M~w..[J{'\11. New '{.prl,. ~997.
6A TWO-PHASE SYSTEMS
illte coo; ~n 0111 tJw tT ctmgmm of~ 3.1 ~phAse. bound!ari~ roT a pure ubo
:s~ A p!lasc U'illi!iiioo M oonslilm IL~ and~ O."Ut& rv.1l~ ooe- of these

221
CIII'VeS is~ md as a te:mb lbe I:D01ar or specific 'Wilue.s of the ~-e tbeooody.namic
propel!titi~~ abmpUJ. 1lnm the molm or~ l'Dlmrte of Ill satvnlledliquidl " 'Vf difw
rentn from ihe molar or spceci_oo
\'VIUillC or
Aturat:cd wpor :n me
same T and P. This ~ uue
as well fm- iman.al ~. ,mib3Jpy, ..md Mlf09Y 111. ~~I& mDlti.r ot ~ Gt1Wts
~. wbicll for a flW'C s~ ~ not dt~ ~~ 111 pt:mse tra.nsilwn }ttch mdling,
va:pgriz:1.tion~ OJ' ~o~n. Comider a ])11m liquid m
eqnihDri:u:m witb iw ..,~ in a pi.s-
tunlcyli.ndrr ~l at ~Wit: T and lbc co~]Jmldin~ vapor~ P .,._ Wbm
a diff~ ~of liqUid i$ ~ l'O e\~ t.t ~bull T ~ P ,!Eq_, (6,'6 ) ~lied b)
me ~ reduces to 4 (nG"J~ ~ '0. 'Beeawie tbe number of n10Jes n is coostant. ,c/G = 0~ and
lhi ~ lhe molar (or Specific} ~Gibbs c::ue-- of di vapor to be i~ widl that of the
liquYL More genendty,. for two phase~ a and jJ ttl a pure Apecie$ ~ at equilibrium,.
(6.69J
w~ Gtz smd c;/J ~the mol~J Ol $prx-ifi(: 1Gfbb-s ~~ ofw~ iJKtivid~ pb~
1he Clapeyrvn equmoo. first lnlrod!.lOed in See. ~ follows &om tim equality .If lbe
tonpeiBtm:: of a: t\l~ sySIIml changed. 1dlen tbe p~ must also cb~ in aeaJid
\ritb Ule rd~ ~ '~ ~ a_fid tqn~ ifll~ pb~ CotUinm: f:o C(Jaj1!
mequilibrium. Bet.-au1e Eq. t{(t.69'Jtapplies lh:iroojbout d:W. llhanF.,
dfr' :;;:; d fill
Submtuting ~~ions. for tlf? Will,dGtJ as gi~ by Eq.. (6_ JOt yields~
rycr .rJ P a~ - .SU dT := y l d P ~ ~ S~ J T
wbicb upon re.ammge.rnem ~=
dPm
~~ --
S~ -s- -~~
A~
dT - \~If- vcr - dVatf
The enrropy obang'e Asafl aDdl Ole \~b:me ~e 6 vofJ ure ehm,Jd ~hldh QOctrt h=n
..t unit
UDOUDt of a rpure cbemiml spme.~ is DUilSfened from phase a ro pbase fj a1 die. eqWIBwiwn T
md P. kit~ f .!q. (6.,8) for thli ,~ yidds dE latent llat of pba5e bll.milim~:
{6.70)
'n1u&. 4~ =t.H~11. mid substihltioo in ~be preceding~ gnu:

dp jfJJ tl. F[UfJ
(6.71)
tiT c: TAV<iJ
\\1rich is the Clapeynm eqwtlcm.

For~ ~laiJ)' ~ etl#ofpllam ~(;jtion fr~~ID lii)Qid ,l to~ tJ~ Eq. (6.71 J
is writtro:
dP ,ngie
(6.12)
dT = T6\f1'"
Bm .6-Vr~ !!: ;!. 111!,;
wbt::m IJ3Jr ~, !the compressibifity..faclm cban~ of ~pmizafton. CombUmttion of the bst two
~gr.~ an ~getrJen~::
dlnP
(6-7))
dT
E.q~tkms (6.7l) lhrou,g.h (6.74) are 't(Jtlivalent, ~~ tV.nns of be Cb.pe)1'Vnl equatic:m .ror
p:lllel-specias "1lpO.rimlioD.
Solution 8.5
1k ~ rmM:tons
1
az -
D. Hit; = - R cJ In p :Gil
d(I / T)
this appnuJ.mate eqoaOOn. tnov;10. lhe Cb!.usimfC~ equatioo~ ~es

lbe latem .t.at of ~ diRedy to the "11(1Qf..pressme CL1f\l!.. Speei6ctily.
it~~ 6Ht.r is~ b) lbe Jlope of 3J !Plot uf I~ P ,~s.. l j T .
.5Dcb pl~ of D~ data prod\Jce Jines fo.r many .substa.ooes m~ .:rre n_early
maipt.. According o the ~:peyroo Gq'UWion, tbi imp!m lhal AH1ll ~
almost (."'m'mrmll. \itlmally indepeDd.mt of T . 'Ibis is 001 ~~ /J. nt decre~
moootoni~ witb rinceasing te~ from ihe rriple poin~ to ifbe criDCid
pcim.. ~re ir beromes mm. ~ assu~ em which dm Oausi~npe)TM
~on are based ba\'e approxmntle '~icy cllly a~ low :pre~

Tems-tature DaptlntltHtce of lhs Vapor Pressure Df Uqultls
The CiapeyroQ ~uatioo i$ ao cucc lhermodyns;mic rolatinn. pnridina a \inlil ~~on be-
l\\-em me ~ of diff.eJent ~- Wilen appllrd ro r1r ~on of J.at:em bmls of
v~tion. its use ~poses lmowJed~ of the vapor JK~ure...vs,...n:mpc~ ~
B~-uR tbPtniod}'tlUli im~ oo mo&d of mataial bcbvior~ either iA gmmS or fpar-
o~ ~~ sud!: ~ ~ empirical As [ffi(ed iu Ex. 6..5. u plot uf ln. P i2l l/ T
g,~eru~Jy yidm a li:ll&' that is ntarl:y ~Right!
mp1:Jitl ~ A. ..... -B (6."B)

T
where. A and B are con&Wm for a gi\1etli ~~ l"11Eis equation gives o. ~gh appmximation of
tbe vapor-:~ relation tor 1be emire tempermnre mnge from the triple pcin1 ro lhe criticaJJ
paint. "'f~, it (lfovidcs an ex-oullent basis fur r.ntmpolaliuo betwcm tasooablly s:paa!d
-valtJes of T ..
The An1oine equuioo. whklh is more sansfaetoey for~ n....~ 1m die lome
lt
In P ;; A- (6.76)
T+C
A princi]i)a[ 3dvanta~ of~ eq(Qlfja,n is lhat 11-al~ of tJic. oo ts: A~ B,. .and C arc ~y
available Cot 111 lllfi.'C nulldft of ~-.5 Eac.h ~~ af .conSi:lllt$ wlid far a ~ftl m~
mre ~ and should- be used mw:h omtde of llbal Glllp. V:il1es. of ADioine COilSiaiiB r(JI
sekded iobSllai"Q!S are ~o in Table B.2 of App. B.
~ Beco:ra.te' ~hftiao of wpor-pr.~T: ~ ~I I ride ~ n ga.p ~
qui~ an. trqu:ation llf gmta romplexity. '1'he ~~:is rODe M. ~ beQ: awila'bJe: if
~.resse.s the reduced '\rapor ~o:re as a functioo of !reduced lempmlture:
. N~t
lo pr ~ .........
A1r ____ + Bt 1..s-.........,cr
_3 _ _ 6
+ DT.
(6.11)
l - t'
r=I-T,
.and -~ B. C. and D Ott oombmls. Values of the conwum eithu fm lbi& cqu1:1:1hm or for
Bq. (6..76.) me givetl by Reid. ~nz. ,and Poling& C.ur many species.
Cotraspondlng-Sisllls Conallltlons for vapor Press.UI8

A numl!ielr of ~ndi:q - eorreliuions an: a,~.le far rfhe v .tpOr ~ of oa-
potar_ nn~ming liquid'.s One of me simpbt. is lbat of Lee and K.esltL1 It i3, a Pi~Rr-~
corre~ ot lbe form:
~S.. '~ ~ Aidel ilJasa B(l(.li: n/ ~ Pi'Z!mUr., tam BOO!k P\lti&llli:nli (D..'lb\)'0. ~ 91f( 'f_ fla;;YJ't.
v. ~.ru~ a Hata.. n~ \Slpor ~oJ~s~. ~h..,.~-~*-
6R:..c. ~I. M. ~iD.. iiDdtB. lE- ~ 1lN ~.sqJGrJsu6114,~, 4!h cd... 1\JJP~ JokC~HiO,
19Bi-
1~ ll.ce ~1t'I..G.lKc5kr.MC1JJ.. ,o;g~, ! tl , w.'lo--su. 1'91:;.

16.09648 . .
ID Pf<Tr ) = .5~927'1 4 - T,
- 1.28161 [o 7,. + 0. l 69l47Tr' (6..79)
J tS.611S ..
lD Pt {Tr) : l ~ ,_2511 - T,. - I3.4nJ bJ Tr + 0.4JS77Tr6. (6.80)
Lee and ~ rcrom.meOOJ that the VfLiue of Cd used whb Eq. (6.'78) be fowul from me tYJrrt,IJJ.
lltm bJ requiring dW i1 repl'Odw:e iibe C!ID.li1:a! bQiling point. In~~ , w {Of$. p.W.:ial! la:
~[s. ~from:
(6.81)
Example&~&
Detetmine the vapor 1Pt81SI!Jte (m kPa) fot liqukt n-htWlne at 0, 30~ 60. and 90 c:
(a) Wlfh 0Qf1Sfards from App. 82. (b) From the LeeiKesler ooJJelation for Pl~.
Solution 6.8
{a) Widl ~from A'pp. B.l.. lht Antoineequation for n-ba.ant is:
mP fkPa ... J3.8]1)J ~

l
rc1696.04
+224.317
Sttbstiwtinn oftempeiatJne$ ~ lhevalucs of P under the~ --Anroine""
in me UJ.Ne below.. Wet&~~ be eqth~l 1tb Jood ~til \1\loes.
h ~ im'il ~nnine {tJ flrom abo ~lcr oomlmoo. At the oo.l'l'OOl boiling
pci:nt of r:-ht.J.ane tTablr B. 0.
T.. = 341.9' ; 0-.61.) 6, n.

= I.Ol31S .n n'i
30.25 = 'V.UJJSO
1
~- S01.6 ,.-~
ApplkMion of lEq. (UJ ) .-o ,i)"eS ~ value of~ fur U5e wi1h &be ~
~ m t= 0:198. \Vtlhdli:s "tafuc~ ~~foop~ the put "'tlt~
~in the~ 1k Paape dim:raa from the Antoine w.ltJeS is about 1..5%.
rrc p lkh I' ltPa rr c p );0/kP-..1 :P ~iik.Pa

(A_n~) ~a) (Antoioe) (Lee!Kes'ler)
0 6JOS2 S.B35 JO 24.98 24.49

fiO 76..46 76.12 90 189_0 l90..0

JWo.:Phase UqultlfV4pOT Systems
WibeD 3 syslr-m c:onsists of ~tMJ-Iiquid and 5atm-a~qpo~ pha:scs ~oexisdng in cqu:llib-
riwn. me eotal value of my ~~'-e propetty of 1he 1wo-pbase- ~:Uem it the sum of :We roroJ
pro;pcrties ot~ 1M phases. "\Vrilttn for the ~"'itU-ne. dlis rerlatioo is:
whtre V il 'tile rmmlur wiiiiDC far a S}r~em oonlaining a tond ollllbTCJ(WQ!a n ~,, + n !.t.
Di\isiGD 'by ft gi\-es:
v = .ll!1v' +xvr
-wiJWJ ~ and x rspr~~rrt the mass tiruaio.ns of ibe tolnl S}'"item dmt .are liqwd and "~~':lPO! With
x' = ] - .r".
V ~ ( l - .x ~ )V 1 + .x V 11
iJn Ibis equation tlte p-ope~ ll V 1 npd V EF may be cilher IJ'IIOlar 01: u.o]:r-ma ''111~. The
masJ or 1oo1llr ftaclion of the s)lSU:m art is \1lpoE .Yv lis rnUat lhe qllllli1)1. Anilo!IJJWS equ-.ill.fQo$
can he ~ for me od:tft' elltensive lbetmOOynamic properties.. AI Eof 1irese rel:ri.ions ttre
.v~rotedl by die gcn~c cqwtionr;
(6.K2a)
~htre M ~ts l 1 .. ll~ H .. S, &. An al,ttnla6;.-e foon~!KDIII:;~ ll!idul:
M =M1 + .r'!! A.Miv
6.5 TH'ERMOIWNAMIC DIAGRAMS
A 1betiDOdyFllltD.lic df.a.gta.lb ro& a .gmpb shov..mg 1ot a parbwlar $ubstmK;C a lid of prapcrti.Qi,
1
e.g... t , P. \'~ H . aod S. The most oommon. tf~ are: TS, PH' (rusuaiJy mP vs. H )~
~ liS (c.all~d ;1 /tlo!IU'r di~). TOO desi~ ~tw co tbv "~llhlcs chosen fur the
~ Olherdiagmms are pO&Sib!~ bw are sdd()ro ~
:Figures 6.2 lhmugh 6.4 s.bow lbe general reat~~ or 11bese dlugtfim~t.. ~gb ~
on data f(ll" water, tbrir gWCJal di_ar.~cmr- similar COT all s~ The lwg,p:basc sta_t5.
r~ed by tines; <:110 tl he P1' dhlgrnm of Fi~ J. I . llle t:rmr ~~.rur in tbtK diugrum$.. and
me triple point or Fig. 3.1 ~ a ~- UPc& ~f ~bUll qamlity ~o a ~d!V"l!PO.- ~
pro\ide diredl.y twO~ property yaJues. 1"be a:ilkul pohn is irlftti:fied by ~ r~ and c.
tbl; said w~-.:: pas...~ lhrwgb il~CJJ~esellts std~ o f smuratedl ljquid (lo the leA of C1 and of
~ \'aPOf (w t.br right of C). 1be Mo1&t diogmn t(fig._ 6~4) ~ nol t11$1Ul0 indudc
'VOlume dam.. In dJe vapor or p regioo_ lines for ctlrl8tmt te-~ a.od etlll9tmlJ'HI).-m
a.ppem. Supctbcai .is a rcrm donating the difiQmte br:fi\.--cen ~ ~tCt~Ial t~Piurt :::md lhl!!
sal.'W'alioo t~mpe1i'31Ure at lbe ume ptessll:l'ie. Thenntld)~ LEu~ ffi.clnded in lt.iis book
ate me pH diq;rums for ~lhane Wld tdfa.fh.JOfOCtbane in App. Gmand the - ornadiagram
for ~eam on me i.Midc o f &be baclt rmwr.
lhtbs 1Jf ~ 11'0 amJy need 'Olll. a lb;rmodynamic diagram. FOli example,. tbe
boiler of a srewn [flltN'er plwtt lms llqarid \Wret ~ fe~ nt.u rte~re ~low its boiling petinl.

226
:F ipft 6.3: T S d~
am! ~ted ~eam :l!i prvdueL Th~ water is beated 3l ronstanl P ro itB sut.utmion remper-
a1Um(li:ne E- 2 in Fi,p. 6.2 and 6.l)~ vaporized 111 ~ T mtd P 0Utc 2-3~ wul mpabcnrrd
at~ P (line 34)~ On a PJJ diaaram (Flg. 6:.1) lhe wh process is. rep~med by
a bodmntnl ~ ~ m 1be bcller ~~ The~~ i sh-own on 11m TS
diapam of P"1g. 6.3. The COIIIpiessibility of a lliquid is mWI for tg~ f!f,--el) bdtiw Tc
1M liquid-pi]~ ~ c~ ...~. sft1w1J wJdl ~ The constant-P tines on driB
diqmm mr b liquid region 1betefore lie 'Yeey' Close m~. and Jl.oe. ~-2 lll:llfl)" O(liilcidrs
;, lhc !i:Bl~uid eun-v. The istntropi(: pat1J uf the fluid in a m-eruble: adiabatic lUfb]ne
orcomp r ~ o both ti'ic T s rand HS (M_ulllct) di~ ~a~ 1.enc liom
die iniuat tD the fumJ )JfeSSUfe..
6.6 TABLES OF THERMODYNAMIC PROPER11ES
IP ~ dlortmXIynamic p(Op;ltie!\ ue ~ This has ~ a~Ytmtige lixlt dlatl

ean be presented more precisel'y man in ~ 11m me ncct~ ftx m~mion is ~ntrod'uctt'l
~c table:s fw sallmlled Re:oun fmm ils nmmal :lireezins pm.Dl to the critka1
po1m and fw supefheated smam ~ a S11hstamial ~ ~ in bOib S1 and mEngttsb
unils. appear in Aipp. F. values are given il.'t intervals cl~ ~gh lha:t li:!mr mwpoladon i~
~.1 'lhe first tabk for ceaeb sy.stem of unit5 5ibows ~be equilibrium propaties of 5atua
r:ned Uquid and wuraredl vapor at~ ~ cf tern~ 1'br mthal~ andJ oittropy
'"Slibitw.uiJy ~~ "VldllOS of~ for ilbe I&Umltcd~Jiqu.id 5tab: gj r.be lripie poinl. 'The S~
cmdl tai!Ne i8 for the gas region., a:nd ~ pttJpertits of !ill~ sremn ut rttmpe~ high

dwJ tbe satvmlion tcmpaaturc b a xiv\m ~ \ blurne ( 111 iJ1~ encqy (U). eutbal!py
(H). and eurmpy {S) are aabalatod as fundions ~of prc$$UtC .at various.~ 1be steam
lnbles iD"e the tDOst ~~ oowpilaJion of~ for my single lllo1lelia1. H:owever.. tabl~
are aV3.1lable for u number of oCher substa.nea:.4
l!xample 6~7
Supefhptad steam ori{lirlally ar 1'1 and T1 upands through a no-zzle to an EtX.hamd
pressure P'l. Assuming Ute process 1:s reversille and adiabatic, determine the dow~
stream state of lh8 steam and A R fnr Ole fOllOwing condttioos::
(a) 1\ = '1,000 kPa, 11 ::: 250PC, andl P2 - 200 ~
(b) " = 150(psiia)~ 11 : 500(~., and .~ =- 50(psia).
9
~ rar m:mr ~i.MIIII ~am ,st\m hy fL H..~ and D. ~ ~"J ~ &s'JJJIMfS' 1/NJ-
IitJt. l~ ~ ~ 4 M~ -04: 1996.. ~abc IN. B. "-fllfdk. ~I:/~~ tl{
~ Gr~re.t. ZdC!l. Hmi..c;pbc:re - Qup ~ OC. 197S. DR~ focrefri ~- eM
ASt~.Etf~ ~~-~. ~ SQQ.ety of~~~-~~~~
~~ l 99:.l

Solution L7
~ 2!W4 ~ ~
5
Becmllie the proeess l1olh is, no clmHge in the

~ ollhe $ft"JiDJ,
(a) For llhe initmJ temperat:urc of 2SWC aJ. 1JlOO ~ 110 ,m trie appar !II 1hc Sl
tlblt5 fD~: ~ strJJm. mtupolarion fbetweeo Yn!l\leS fOf 2~c am 260~c
~at tOOO kP3J:
H .. ~94:1.9 tJ q -1
Fcc the firnt11 teat 200 ~
S':z ~ $~ = 6~9:?...51 kJ kg- I K - 1
Beemse the~ -of satmued Ya1X11 ~ 200 kAI . 1

~3ttt tfu.n S2:. tho state
is iJ:i th.e t~ liquidl\ilPQf ~ Th\B 12 b ~ satnraltDC te~dlllfe M
200 tPa. Jl'-'Clll in dlr Sl superheat tables as t2 ~ t20.:23~C. Equaboo (6.82a)
applied lD dte elltfOJJY bect~~DCS:
Sl::::: (1- .qt~ +x!S!
~the \'DIDD 1.530~ ud 7.1268 ue entropi crsatJimlbW liquid and :JtUDilcd

wpor at '200 i.P;a. Sotring.
.t.1 := 0.964C
On a mass basi$. the m~tuR i '96.~ ~oxpor Md 3J~ liquid IB entUipy is
obiQtned by furdle_r applicaUon of Eq. ~~823):
H~- {0.0360)(5Dt1) + (0.%40lt2.700..3) !: 2~621.0 kJ kc-w

F'o~II)t"' !J.H- Hl - H 1 = l.!!J27J0 -- 1..9-12~ .- -Jl:S.9 kJ tg~l
{b) For the i:niti.l 5la'IC .~ ~~}1 md 5(1)f'F) data from Tlib1C" FA fDf' opel
&zrfd ~ mBt~gli.m uniu. pmvm~
In me ruw .swe m. 50(j)$ia.l.
S1: ~ S.1 = t~66(l!(Bru)(~- 1 (RJ- 1
~rim~ of1B.blc F~4 &hoQ.!& lhar St is ltere gre4ler dum 1be emmpy ol satliJ:Jatal
\"nJlOI' at SO(psia}. Hence tbD final itate i.s in lhe ~region. mfapoliUWn QtJ
mrqiy at ~O(p~) Jkki$:

For a oozzl~ l!lDder me stated aswm_ pmoos the &teady..ftow ~nczgy bala:rtoe.
Eq. (1.~2a). beoomes~
l ,
aH - Au.. ~ o
2
1lms the decrease iD enthdpy :foond :for pw1s (a) and (b) is iWict1:y ~~
by an~ in kiooic ~ of tbs tluid. ID otbt;- WOrds.,~ mle(:ily of a ftttid
inCTeii$C$ ~it tlb'W$ through a !lHlZ%1e, w.~h B lts ~~'mal~ Nozzles :tre
treated in some detail in Sec. 1.1.
Example 6.8
A 1_5.....-nJ tank OOOfaifis 500 kg m liqUid water tin equillbtiumr Wi1h JlUr& water wporF
wn~h fills lhe remainder ot the tank, The tempemture Md pressure are HX C and
1rG1r.33 kPa. From a walef Une at a constant temperature of 70'= C aOO a COflStafi1
pr8SSUta somewhal: aboYe 101 .33 kPa, 750 kg of liquid is. bled Into lhe tankA If the
lempefa~We and pressure ltle tank are not to change as a. result of the process;
how much ene~DY as heat must be kansfe:ued 1o the 1arlk?
Solution &.8
Oboose: tb!; tanl a.~ the control ~"OIUf'D~- r~ b 00 wort. and lantdc- uml ptemial-
encrgy ch:m;ges D.te .a$Sbmt:d oe.glilible_ F.q;aalion (2.29) lherefc:R is written:
d(mO Jtta1 _ H' ril ~ Q

dt
w'--
,,,.;_ne' ru~e
.L._ pnme
' . .J_,.._
l,lll;IJ.,.._ the-.. - .;,f
. .,...._, ru~ Inlet
""' ..Jl......, . oSb'e!m.. ~ m&$S tr'.tl.:l:ace.. nl !::
dm.-jtlt. may be rombined 'fllr~itb tbe .energy OOiaooe reo yield:

dlm f1 )IJiDlc _ H' dm ..
--r::::~ Q
dt tlr
fum ..,- . - - :~;,.
~ ~ ""-t'l~OO u)t aI t an dm .
_ 11'! "~00 _ ~tmte
0\' -- ..... H
( W'fm~ 1
_ ~ t'~~
-
1
Q .. L\(mU JtWt- H Amr:m
1'be dctmmon ofendWpy may be applied ~&me enilre eomtmu at lbe nmt. to~
il(m.U ,- ;;;;: 4 (mH) - A ( PniV)I2nl:
~e Wlalltimk -.rotume m
V and P ,are oonstaru, A ( Pm V) 0~ ~ witb
4(mH):: (mlH~)tJd:- fm 1HJ}antc,. dJe twQ ~eqtllations ct~~R~bililC to
)"ie'Jd=
(Al

bei:c 6.rnlirN1."' lhe 150 tg of 'W1Ile:r bled into the lank! and ~bsaifl!l!! I IIDIJ 2 refer
m condilkm mdle Wlk at de beginnin,g and eQd of the PI'~ At tile w d 10C the
~ the tank still mmins M~UtDted liquid ~ ~~ '~in ~Qili'\Irim:n
at UXf''Caod JtUL331Pa. ~ ~1H1 and 111JJ:I2 eadl ooasisfl of two n:nm. one.
ror r~ llitrltid ~ (!.D(J one for lbt ~ ~
The lnliiJel"ka1 &OluUon ~ use or me follkJ:wing, cnlhalpies ~ from the
~e.ammbl~;
H1 = 293.0trq- ;~1iquidat70~
1
11/.. - 419.. 1 tJq- ;~ liquidai.IOW'C

1
I~- 2,616.0tJtg- J; ~'~at IOWC
The wftDDe of w.,por in the tank ~nirially is ! ..5 ml mh11ls tbc mlu:me O"U,picd by
IDe 500 q of liquid w te& 1'llus.
_,. J.3 .... ( :wl)(OJOOI044) ~ liTt. m ..
m I <:s: l.fi13 v. C
wb=re Ul01044 8Di1 1.673 m3 ;q;- m.:: rhc spociific \'tllumt$ of :nurattd liqu:i:d
8Dd saJiLJ:mted vapor ac nlO,.C fmm the steam1mbtes. Thtm,
<m1 Ha) ~ m~ nf + mrNf = 500(419.1 I +0.172(2,li"79.0);;;; 21 1 ~616 tJ
At tire eodl.of ~hi} ,~1 the. mas:ses of liquid arid vapor art dbermintd by a ~m~.,_~
~ ;md by ,fhe tact thai die ~ Y01lll'&1e ts still 1..5 m1 :
11l2 = soo + o.m + 150 = mf + m~

l.S- ].67~ +0.00Ul44m~
~ e Ll50.65 k8 and m; = Q U6 kg
~. wi:tb1 Hl ~ /If and.Hi - H~ ,
(m1H2)1 .- (1..250.~65)(419. 1 ) + CO.J 16)~ 2.676.0) ~ 5Z4~45SkJ

SuMtilutino of uppnl-priatt: \~:UCS illto Eq. t Al gi\"eS:
Q - 524.4:58 ..... 21] ~616 ..... (750)(%93.0) ~ 93~002 kJ
6..7 GENERAJJZED PROPERTY CORAELAnONS FOR GASES
Of 1be lVV k:mdli of dam occded fw evatuatiOB or tbmnod~ pJ'OJ)el'ti~ beat ~.u:U'n:s
aruJ P V T da~ the lattetr are most eq~y otissing,. lfottuoawy. lhe ,e:ne1111imd mnethock
developad in See. 3~6 ror dJe ~sibih)y faetor are also :8pplk'ab~ w l\e8idual p~tlie$-

231
P = P'f' P, r= ~. r,.
iJP-== Pc dl', dT~ Tt d.T,
(6.8])1
The tmm oo the right sides of th...'Se equatkm depel!ld only em the up,pcr limit P~ oftbe
m1:egrab and 011 the reduced !~pC:rDtu.le at which they pre ~11lmrto:L nrus. value
of H I RTc
aod skf R may be determined tJOCe and fbi' aU m .any reduced tempemmre and ~Lilte. from1
1
g~. eom~billity-faa.or dam.

11Je ~oo fm Z is ~ on EtJ- ll-57):
z =::~ Z0 +wZ 1
Differentiatim yields: az) (azo

(CJT,.
-
oTr
)
Pr
c: -
1",
(azt)
+ w [ -
iJJ;. ~
ZU'
"'be liBt integral oo lhe ril1lt sides of ~ rwo equatioos rrta)' be e\-altuucd wmerically or
gmpbicaDy loli wri-oos vruues of T, and P,. hoo1 the data tor Xi' given io Tables E. I imd R.l't
a_od tJx: imeg_ruls wbidl follOW' <U in eec:b ~u;atiOP may be muihtt}y ~vab;d from the data fur
Z 1 gtve.n im1hbil~ E.2 MWI R4~ ;\l~rh'ely, meir ewlnrnioo may be ~d oo an equatlmu!ff
&ta~ { h ~}~ 1.ee ;md ~r used a ~~d bm uf lhe BeuediiCt!WcblYbbi:n eq;wllioo o f
&Ute (0 ~{efld tbelf ~mfdrd (~treJatiOOI H), ~dm(l ~~
If lhc fin.t terms on dte right sides of tbe ~g equations (including ate minus signs)
are~ by (H 14 )0fR 7;. ill:illl 1(S)0/ R BOd if~~s wtdtb follmv(l;).. tQgdbn' witb
the JJRQg m:im..l5 signs. :e repwsented by (H 1 ) 1I RT~ Mid (SN} 1/ R .lheo:
(H Rj O' (HIR ) I
(6.85) {6.86)
RT.r =- RT. +ro RJt
Obras proteg1das por aireitos de autc

%12
~d va1urs of ihequanlffics (11M)0 / RTn (IIR.) 1/ R.Tc . . (SS)O/ 1. and ( SR) I / R as.
fietgrnMnedl by Lee mdl ~are given as U11C1ions oCT,. and P#' in Thbles liS ~ IE.l2.
11Jese values_. IDplftet with F.qs. (6.15) and (6.86). allc;JW ~tiou. o: ~ldUJJll eulhalpies and
~ oo die: ~ of the dlree-parameter auresponding-61ae& ptinclple as ~optd b)
L.e:e H1d Krs'fcr l~. 3.6)_ Cdcubted wlilrs of Z. H~~' .. ~ sR fur n..buta;ne at 500 K and
SO lim based oo lbe ~ oomla1ions am inclwled_ i:mi l"'dble (i.l.
Thbles. E.S and B.6 fm (Nft )Ci/ RT. and Tables E.9 and E.lO for (S11 ) 0/R~ used al011e,
prcwidc rwo-~cr ~diP_,g-Sltlte5 cortdatiom that quiCkly yield come estimates of
me l'P.\idJJaJ ~peniet. The il3Dll'e Df lhese Mtr"elfifi{)D$ i$ iQdicptd 'by ng. 6..~. . which 5ho~
a ~Jiot of (H"P )0 I RT~ vs. P,. f m jgJibm:ns..
witb tbt. ~ ~lll;llR bility-.(J~.CU:~r ~n. the tCOmplai'Y of lk (mlC
'tions cnRtJI RTc, (1fR) 1 / RTl' .. (S 8 }0/ R . Wid (SR) 1/ R p~ lheir ~I ~~
'by simpk ~qualiom.. Rowe~~~ die ~oerat~ seoom:J..,riJi:d..eodJci~t conebltioo rcxms (De
~ ror analylit:ali eQfitelndOO$ (If lbe re&itual ~ m low ~ lUcaU Eqs. (3., 2)
m:l i(3.6J):
j c BPc ~ Bo wB'
RT~
Qwmtirieg A. sO., and B ~ are fmtcti~ of r,. onl). Hence,

._ T~
dB =~ + m!!.
tiT,. dJ;. d.fr
233
(6.$7)
1
SR
- - ~-Pf'l -+~
( .dl11 JB )
(6~)
ll. JT, dTt
The depen~ of B 0 and B 1 on~ te<mpcral~J:re is eJ"Ym11y Bqg. 43.6S).m d (1.66).

~~ ~f these equations provides cxp;es8ioo:s for J:BJ/ tiT, and! J B /dT, . ~ lbe
cquarif!IOS roquiRd ferapplicuioo of~. (6.&7) :md (6.8&} are:
0
rfJ == o.oSJ - ~7 ~oJ' B' == o. 139 - u:,.,~"';
r r
~~-----------------+------------------~
JlfJ 0r615
1
JT,- T,M
Agure 3. ~4~ 4.1rm\~ speciJica1ly for tbe oompRUihilltyfad ~"OTWtmon. 1:s also WL"d,
- ~ guJdo to the rew.bility or d!te eorretauoas of residuld propcnies 'b:L~ OJ1l ~
~ Ylri:MrneJiicienu;. HQWr'Vcl; all ~~rtyc:uud3ti<n~ ~ Je!j$ ~ th@ ibe
~llil)'-faaer correla~ 00 mdl lhey are fbl~Si}d mtd ~ o{ cowrse. least reliable
for ~Y polar and a.~ialiog mokades..
Tbe gen_er.ltized ~ns for yR and. s1i,. tog,etber Wrth ideal..gas be31 ~
a!lllov.' allculaaitm of ellthalpy and Gntwpy values of 1 a1 any leiiiJ't:~ and ~ by
l!.qs... (6~) ~ {6..5 1). RJr t1 4;~ rm.m siM:c ~ w stAit 2, writ &J- (6..50) for lbotb r~e$;
The nthdlpy ~ for the ptoce&S., A.N = lf1 - ~~~ ~ B. ~ ~ ~ ~ tWO

eq,uali~
Similuty.. by Eq. ~6~ 1-..
AS~
l 1'1
T1 i dT .
C/ -- - .Jlln -+~ft-
T
Pf
P1
sr,
Written in ~ee furm. these ~equarloo' become:
li.H;;;; (C~'tt_,(T~ - T~) + Hf - R{~ (6.93)

I&
~s == ~cr ).s In
T~
t - R lo p;~ + ~1 .... S1
1t.
(6~94)
Just as web\~ gjvm u IIH'8 to functim oSftl in ~'31n:Won ofthe i~ in F.q,s. ~&9 J)
mxl ~6.92) m:~d the mean heat ~ in Ecp.. C6.93} and (6.'94)1. so~ do we name fimc.
mom ~ f~r tv:~hKtlion of 11 and stt. ~ (6.i7), (3.65t (6.:89'), (3.66). and (6~.90)
rogdhef pttWfde a funcUOJ) for lbc it\'4.liL1tion of Hill RT~. na:mcd HRS(TA,PR~OMEGA}:
:~ "" HRB(TA,PR.OMEGA)
A~ "i41111I~ ul II Ris dJere'foR; ~by:
R T~ X HAB(JR,PA.OMEGA)
Simi:TMly. Eq~ {6.83) ~ltb (fiiO) ptav.l4e a runatan for lhe ~~ or 5 111R~ n~-ed
SR8(TR,.PE\OMEGA)~
s,B - - -
If ~ SRB(TR.PR,OMEGAl
A llU1IIeria1 "Y'illllle of SR . (bmeoo ~ lby.
ll )( ~PA.OMEGA)
Compu.trt I}JOgf'alllS fWe'iQtmti:lls dtese f'uac:d.ons ~ l(veQ in App. D.
'li'JIIR' "-'= 'ro.l 01131 ~Ib Cor ~crty

~ etHwJilS.
'lk~oolbengbl~ol~ (6.9~ ) tmougl) (6.94} ~mtdii)T ~~-.

ma t r:klllatlonal tJ(Jih leading_~ an ini1tlll m ~final - of a~- 'llluu. in A&~ 6.-6~ a
ocJunl paJb from stile J to stare 2 (dashed Une) is replaced by a tbree-sLep calc::ubliooal ~

235
St2p l ...... 1; r: A hypoth.!tical ~ chat tnm5forms o lit3l ~_s into W1 ideal gns 111 Tr
and P' Tit~ dtlhfilpy and tn1.1t1py dldfi.gd rm- lhti p~ ant:
St.~ I 1' _. i '~ Clmm.~ r tr idellJL&a"' mt~ from (T1, P1) to (Tz, ~ ).
Ln 1 For lhi
F~'S..
(6.95)
(6.96)
~ ~g -.. l: Another hypolbdleal process that ~l"'!m lbe: ideal gas bxk into a
leW p LU T1 and Pl- H~
~ (6.91 i11Dd (6.'92) rllesuJ[ from addition of me ~py ~ eowopy c~ r(lf tile
dlree !ilepJ..
Exa1mple 6.9
1
Esdrnate v. u. s
H. and tor 1-butene vapor at 200'"'C and ~ bar if 11 and s are se1
eQua~ tQ ~l'iQ ror satura1ed rnqu1d at o~c_ Assume that 1he ordy data aWilable are:
Tc : 420.0 ~ Pc = 40.43 bar

:r. =266.9 K (oormaJ boiDng point)
C~' t.R- 1.967 + 31.6:>0 x ao-lr - 9.837 x 1o-C'rl (TIK)
Solution 6~9
The olume f 1 butene \'afJOI ar 2BrC .mdl10 O:u- is ~ ~Y from tbc:
requa'lion ' ' ~ Z RT I P~ v.me l i.s gj~eo uf Eq. (3.51} wrlb
v--.d.oes oi z0 md z 1
intetpalared in T~ E..J ru.d .E-4. 1Rx rtbc ~ ~
i!il 200+213.15
.. ,.. ;;;;; 4'20.0 := 1. 127
the compregs1bilily (aaor and mow \ 'O.[U'IDJ! ano:

z zO + w2 1 = 0.4&3 "'l"' (CJ.'I9J )(0.142~, ~ O-S m~
\l c ZRT e: (0_512) 83d 4)(413.~S) == ?0'7 : ' - '3 __ , - m

p 70 ..;...o s,
1
.,..'" 11-.N
Obras protegidas por d1reitos de auto

.For H and S, IUs.e !11 ad~o11al p~b b"tc r:ba~ nf Fit+ 6-" kmfio;g &om an
dillla1l ~are of ~d liquid 1..bu:rene at {PC. Wilen! H and $ :R zeroi to me
finiil smle o interest lo diS case. an initial vaporizl.tioo 5tep is Nqaired. t.eadi:Qg
to lbc four.. cp piltb ShuWllliby fis. 6-7, ,._ ~kp5 .; n:
(a) ;porizalion at. ~ rmd P 1 = P w.
(b) Thulsitim to ~ idealtgas wne at ( f ! . Pt ).
tel Cllange to ( Tz. Pl.t mabe ideal~ slate...
(d) Tli1ii'ISl1)on to iLbe actual fuW stale al (1'1! ~}.
Sl-tp (): ~Q'Q. of~ Jli4ltid l..turette m ~C. The vapor pres
sure IDllSI. fbi: ~ a5 i1 oot gh-eo. Oae method is based o.o tho cqua-
tit!IP:
ln.P (6.15)
The '~-fJr"e"8$1,11'i! ~ mJli.iliJrL!i lbolh me normal boi..lins point for wbicb

=
PQI I.Ol33 bara.t266.9 K. a.nd tbcleri.OOdpo.j11 twwbicb p =40..43 bft.T
a1420.0 K'"' 'For"rtbese: tw<J pgirns.
8
bJ40A3 =A - 420.0
Obras protegiaas por direi os de aut
137
w~.
Rlr ()9C (21.1.15 K). P w ;;; 1..2711 tw. a result use,d in steps {b) r.md 4C,J~ 1
Here.. lbe latm1 hem of~~ i:s mqoired. Equation t4.1l) provides ;m
=
es~ ~ ~be nonnal boiling point.. wllm! t . 266.9/420;@== 0.636:
tlll!r: = 1.092(b1P" - J.OlJ) = l ~C)I)?..(1la4tt43 - 1.013) = 9.9"79

Rt, 10.930 - r,. 0.930 - o.636
\V~ A, H~ - (9.979)(8.Jl4Hl66~9)-= 22.~37 J moJ- 1
n~ latent bmt 01 27J_I5 K. ur 1f c :27l. l5!-420.0 ~ 0.65:a is gn-m by
~- (4.13):
6 yt~ :::: ~( I
- f.. )iUS
~~~~~ 1- r,..
at A H' ;;;: (12.. ll1l(0..3S0/0.3~)OL33 = 21 )llfl J Jl!QI- J
By&J- (6.70~
o,~'-~ = ~H 1 "1 T = 21 ~810/~73.1.5 = 79.841 mor 1

K- 1
S.ltp (b): Transfonnaaioo of Wumted 'r11p01 1-buteoe into am ideal g~ at

dtt bdlinl eo:oditiens ('Ji. P1 ~- B~ ~ iPJeSSute is n::lari\-dy l(IIW. dJe
tfilua 1of Hr and Sf are~ lby Bqs. (ii.2t1) and ei.SS) for the red.,-..ed
cood1tiolls. Tr = 0.~10 and P,;; l.lnt/40.43:;:;ft03[6, 11le eompntatimal
"'~ r~mro m.~
HRB(0.6S0~0.03116,0. 191) ~ -O.OCJS5
SRB{0.650.0J0316~0- 191 ) ~ ......0.1063
w~. Hf ~ (-o.09RSO.tl1J)(42ttOJ '= -344 J mo!
Sf~ (-0.U)6.l)(8.)14) ~ -0-.88 J mol-1 K- 1
As Utdieatad in ra,. 6.7, tbe pmpe11Y clJanges for this :Slep aN -Hf and
- sir ' becaU:5e ~chan~ i~ from the reid (0 tib.e ~..ps.stile.
Step Cc); Cbang.es u. the ~~-gp ~ m.- r2'1l.l:5 Kr 1.2111 t.J m
{473JS K, 10 bu). H~ AHJ'..' and a.b""~' me pm by Jjq;s. (6~9:5} and
(6,96.), f whlch (5~ 4, I ~ S.St.
s.J E4 x acPH(213.. 1SA73.15;i1.987,a 1.6.100...3,,.f).837E~.o.ol
e 20J64 J m;o~- l
8.314 x ICPS(273.1'Sr.47a15~1 s91fl~1.630~~~~-6.0.0)
~ 5,_474 J mol-1 K- 1
1lms. Eqs. {6 .95) and (6 .9 6) ~kl:

1
l!H18 = 20.564 J uH)) -l

2:38
asJ& 5S.414 r1L3l41n I

10
~ l2:.13J moJ- 1 K- 1
-277J
Slep ((l)~ l'ransf{~~onof l~ef~llbcilk~.,l38~ rod:J:~..g-ot~S
e Tl and A.,. Tbe 6lml redueed aJOditiom are:
T,. = 1.1l7
At tlr higlrr ~of this stql, ~ and if ~ found by~~ (6.85) and
(6.86). ,. . witb tbe ~ eorrelatioo. Wllh iruerpobtcd \llii!K'$
from Tabla E.1.. E.a~. .1 ~ ,. md B.J!l, lhese ~quatiDm @i.ve~
n,N
it~ - 2.294 + (0.l9U(-().713) =- 2.'k10
s:
R ~ -1.566+ (0~ ~9lJ (-Q, 26) ~ - L105
Wbenee. Hf = C-l.430)llt314){420.0) = - S.48S J tl'tiO!"'"
Sf ;;;: t- t.7QS)(S.J.J4) = - t4.J8J moJ... J K- a

1be sums of tbe emltalpy and emropy dmnges fC!f' lbe foor step! p the ro1al
dmtps for 1be pnx:ess leading fmm me initia1 ~nee suate (w1Jtfe H .and S
an; Kl ~uti m zuo) toUJC fimd Qtr.
H AH- 21.,a1o ~ (-:344) + 10564 ~ 8.4SS =.JI.W J tnOI-~
s = 1.\S = ?9.84-- c-0.:88) + .22.18 - 14.18;;;: 88.?2 J mol- 1 x.- 1

'ilbe. mremat ~ k ;
u = }I - p 'l l ;;;; 34~3 - (10)'

187
.S} -- Jl..ll8 J mol- 1
LO a:nl bar J-1
~~are in far hdret ~mmt Mlh ~lal wlue:s than would bave
been tbe case bOO we iiS~.o:al J-bu.Ume wpoc an ideal ,~

The values ~ rOOIDinl!d ale the. mb.tm:e w DIJd p:seud'oaiticaJ fetDpt1'intUfe ood' presmn:~
Trc ~ Pp.-. whidl TqJkice Tr ID]dJ P; CPr~ PT~tu/.o~d ~Ur.r.
1' p
Trr - -
1p.r
(6. 100) r l pc
(tiiOI)
~ repl~ T, nod l'r or reading entrJesfmm tht: lah'~ App.. ~ :md ~ m \-:d~
or z by E.J~ o 57~t J~ll/RT. ~ Eq. 6~ - ilHd s~ fll by fA1 ,6.86,.
Example 6.10
Estimate ,,. ~ HR. and s tor an equfmolar mixtu'iiD of ea.rboJ1 dicudde{1) amfl prgpane{.2)
at450 K and 140 bar by 1M l.ee/KesJer conetatinns..
Solution e.11D'
The ~caJ ~ nm found by Eql). (6.'17) lftrougb t6..99) wil.bailk:Jl
~Vn:~il rmm Thbl~ B. I or pp. B:
GrJ _l'tc:ut .'-':Itll t0~'10.22-l~ (0.3H~tr51)- 0. ~88
T. ::::: .Hl:t -y~T. _ :!:; t0.S)t30-1.21+ rt l. t 69. ) -=331'.0 K
140
p -:;; - - 2..41
~s
By Eq. ( .57*. Z= Z0 -r- toZ 1 -;;;:- U.691 + (0.1 0..!051 = 0 .1
1~ ~!!!!. ~ ~0.136U83-~ .I r{4SO) ~ l96.l rn:~~ mnl-1

f lJO
Hfl ) I
( RTlfi" = --0.169
Hll
RTIX = -1.7.10+ tO.I U-OJfit.)) =-1 .762
Ob as p1 o egtdas por d1re1tos de auto

H~ == (8.3 14)(33'7.0)(~ 1.762);;;;: ---4-"7 J mo~- 1
F-.I'QID ThbJes R I J .and 1!.12 lind !Wbstinni.aD inm Eq. 6.86).
sR -
R;:;; ~0.967 + (0.188)(...0,.310} =~ I .WJ
S11 = (S3 14)(-t ~029) == -8.S6J mol- ) K- 1
PROBLEMS
6.1.. StartUt, wilb Eq:. (6.8~ ihowd-=n ~an~. in tbewpor ~ion ofmMollier (H Sl &pm
DJU$t blavr: po,;iti'lie s!o.PO IJ1d positi'I!V euo'Sblre.
6.2., (a) Making use .of me fiicL t1w Sq. (6.20> is. no 4Uet tlifr~ ~;oo., ~
that
(IJC,/S P)T =- T(aii.v /i11.)r
Wlm ~ 1lbe resuh ol appHmooo of Ibis ctpll!llion ll;) ~ ideal ps?
(b) HRt capacitiM Cr 3nd c, ~~~e ddined as mnpera~me dem~ respecci\ely of
U md ll . Because rhe:se ~ Me rela.ted, on~: .a pccs lbc ~ ~,acitiQ
a1 ro be l't'latat Show mot me poen~ e;:qJression ~'"tlng c ,- to c v is~
6-3., lfV ~~a fundion ofT and c,.

/J .. die ''aatun.J"' keat eapac:ity is nei(ber Mr
Cp , but m.tla me. de.rft-alihre (Sf! /DT),. .. Dr\'dop dlt foDoll'"ing coiJIJC'IClions be~""'Gal
{flfi/~ n:P. c,.. and Cwr:
(au)
ar ,
- a
(av)
ar , -= c, . . .
C1 ~ ' ~ IJP'V
-ell'+ (r (~P) - 11] (~) ~ cv + k~UJT - ~P) v

aT v aT P
ib wJW db mesc ~~(or an. filS? ~:at inco~iblc liquid1
~ ~ p v r bemwior of 1L certain p5 is scribed by the eqt~ation of stale:

PO' -b) = RT

14-1
(o) u is a funotion of r only.

(b) y :;:;; wo.st..
(~J For ill ~banieallly ~ible ]JJ!OO:SS. P( V - b)Y = COOSit..
6,5,. _ A ftuid is desaibcd by tbe canonic41 tJlW.ltwn ofsttite. G = r(T) + R1' rn P ,

I_JW'e
w-heie r (T) is. a ~uhsluncc-spceifk. functjon ofte.IUpelatllR. ~ennine For $1Ch a fluid
a~ for Y, S, H. lJ, C I'' ruJd C v. 'I'ht::se :fhiiiH are ~tent witb ~for
an impo:nan1 model of gas-phase behavior. What is me model'l
6.6. A pe:re ftuid. dleQ..'Yihed b)' the (;(Jjt(jttJtal tqt~atWir D[state: (; F( T) + K P . where
F(T) i$ a ~.specific funeboD (If tanperatum aDd K ~ subs~ance-~lk
,CfiMtant. Derermi:mef~&tldi a tlllirl e~Oil!l fl)f \' ~ S. H. ,u,. c,, and Cv 1~
n=suJis me eonsistenl with those for an impommt model or liquid-ph~ bebaYicx \Vinal
i lbcmodofl
m
&..7.. Esti~rt tk cbnlge tnbJpy a11;d ~nlropy ~ liquid amlbOni~ ett 270 K is ~m
pre&Ud from d:s. sallL1mlloo fP R:miR of 38 I kfa 10 :1~ kPa.. For ~ liqoid
~8 at 270 K. v ; l..SSl )( lo- 3 m~ kg- t . and~; 2,()95 X .o- K- 1
U.. U(}Ldd i$tlbutunc - tbttled lltJv.-gb a va:J\-e fl'>(JQl ~ i.tJJ:1iat state of360 K a.Dd 4,o:wl kPa
to a find ~ of 2JI)O kP'a. .Esr:lmate tM rempmrure dwng-e and llhe entropy
cbimge ofdie! oobuUme. The specific beat ,o f liquid_ iwbu'~ at 360 K ' 2.18 J .g- 1 Clc- 1
&ti~ or V and p mu.y be fnund fi'OflllEq. (3. l 2).
6.9. One- kilogrwn of water '(\"1 ~ Ul03 an3 q- 1) ma ~cylinder device m ZSOC
and ~ bar ,ig ~ in a mechani.callly revemibie, i&odta:mal pmeess 10 I r;SOO bar.
Dctcnnine 0'. w.
AU. 6H. ,a gd AS gjveo thai~ ;; 2SO X J() K- 1 and J( ;;;;
45 'X lo-t' lhar- . A. ~DCWJ)' o..~ptioa i 1M~ V is tl~IU ~ its ~tnOtic
1
li\ren.ge w1~K.
6~(),, nr ~ c and 1 bar liDs a ri@id v~t U" bem Is added m me ta unUll
Uquidl \\'ater
i ~~ ~es SOPC. wbal ~ dcr.:eltoped? The ~~ ~ue of fj
o-
bc~m 2S ami, ~o= C is 36.2 x I 5 x:- 1. The wine of r ar J hilt wtd SQ;t C i!t
4.42 ){ Ut"5 bar"""I, and may be ~d iodepeodent 0f P. 11Je spec.i:JK wlume of
liqni6 W"'uter .$1 25~ is: 1.0030 t'mJ ~~I _
6.11.. ~M' a.prtuioos for G ~. H R, and st tmp&d by the l.luee~ ,;ri. tqmstioo I
iD wl~ Ell- f~..W).
6..11. ~~~~for GR ~ n, and sJr Implied by dlit \'all der W~~ab eqiDl(ion of
~~Eq. (3,AJ ).
6-IJ. Determine~ for G 11 .. Hll. mJd s implied by lbt Dktenci ~~llatJorc

BT o
P- V - IJ exp(-v.;u)
~ panuneten;. a aJJd b ~ function5 of ~tioo aW)'.

~14.. caJcoJate: Z ~ HR. a.Dd sP. by tile RedlidiiKwoog equation for one of lhe fo/Uowin~
and~ mu.bs wi1b values fn1lnd f'rool suiiablc genc:ralizrd oornlutiDIJ3:
(a) A~Lene at 300 K llnd! 40 1m~
(b) AfgoD ill ~75 K aod 75 bar.
(c) ~at 515 K rmd lO tJw-_
(d) Blmmo at500 K aDd SO biT.
(r) Cdloo dioxid.e ,aJ 325 K. and rOO bar:.
(f) eubon ~ at ~ 1S K ~~md 60 bar.
(g) CatOoo ~t;lltlcllJQfil.le mS15 K imd 35 bar.
(h) C)"CJobaalie at 'so so
K ,aJJd bar.
0) Etb~lme at 300 K ~and 351m'.
(j) Hydro~ snlfide at 400 K Wid 7& Udl:
tl) Nitrogm vlSO K aud SO bu.
fl) lt-Oclane M 571 K and I 5 b.'R
(m)~ nt l'JS K and 25 bar.
(n) PKlpylau: at 415 K aDd 75 ~~
"'l~ ~~ z. H11.. und sR by the Soa,~e(l~.cbfKWGGg ~00 for dlte substmce m1d
rondhtiom given b)' Olk' of ilhe pam of Ph. 6.14, and a:rtnp:tre ~l!lllS wbh values mund
from suitable ge:ooralized QOIIeJWoos..
6..1~ caJ:f;U:k\tz. HR., and sR by die PmJ{Robinson equation !or~ ~aooe and C01l..
ditlons gt"ven. by one of the pans ef fib, ti 14., and oo_mp;:ue res-nl18 with \-alucs fGtmd
from suittble ~ corrdwom.
6.17,. "fistimate tbe entrop)' c~Jaqe of w~oo ,o f benzene m ~C. The ~r preh1.d"e
of bemr.ene is givtm by rthc cquatieo:
In p lilA /lPa = U.BSS8 _ 1,788-.'1 1
' FC + 21{1.79
{a) u~ Bq. (6.72) v.-ilh an~ mluc of~ v 1~-
{b) 1J tbe ClausilJS!Oapepon cqumioo a:f & . 6.5_
6..1& lbt pLw and P,sa be V'ld~ Qf~ saluraliWI ~~~of a )JUfelliQuid al absolme
tanpemmre:s Twaoo T1. lmtify lhe following ~rpolatiml fotmJ.lllD1 for estimation cr
1be \"1tlpi[W p.~ ,P a1 imamediate ~mre T:
~ .. P J:ilJ = .... ., lim r1~ r ~ r. > _~

ILH "'"'' f""] + T(J2 - lH 1Jt P,Dt.
6.ft. Aisu.ming tbe validity of Sq. (6. 7S'J. derive EJml...I(Ur~s formJdo for e&.-lim~nion of Ute
~cfai.~
3 ( _..............
w .... 9 ) logP~ ..... I
7 [- 0

t6dG.. Very (JUliC liquid Ql:cf 'am be sebcooled at atiiKb--pbaic ~;,qure 10 cempcrat~~m~ wr:ill!
belcnv OOC. ~ t.:Eud 1 q ba been ,cvdkd as a liquid t ll -6~c. A 51Dall ~ cry-.1
(of ~ m:b8) Ji ~ 10 "seed" me l!illbc:ooled l.iqoid. U dk: 5Ubs~eitt change
occurs adi:aixttica11) at .aliilOOpberi.c ~ what fractioa of llhe )"b~ freezes md
"'bitt is the final tc:mpr-t~? \Vl!mt ~ ~Su.r:.J b lbe ~, ~pd WJl'!al j r~ ~
"~le feallille1 1'he hu.ent heal of fwioo of w~.tlT ru O""C is 333.4 J g- 1.. ami the
specific hc:at of ~~lro lifp.id. \l,'BfCT is 4.226 J a- l I
6.2!. A ~ SY$LCDIJ of liquid WU~er ~ ~ vapor wequilibrilRfi ~ .S~OOJ kPa coo-

- ~ of equal '\"'I~ of ll.iquid and V"u;put. If die mL1l "'101~~~DC l'J : 0.15 ml YA~at is
lhe n:Ka~ entlharpy H' and 'li\<bai i tlbe toUd emropy srl
6.11. A vessdl cootaini ]l$ ,ofH~fi ]iquid and "ttpor in equilliHiwD at~~ kPa. U~
\1t{)Ot occ~pi~ 1M; .ultoo ~lume of the ves:._~L ~ II and S for de I kg of
H10 .
t6 .M. A~ "~I~ Jliquid.watua.od ~vapor in-equih'Drillllllat l!ill(Of). 1be

tocill m:rss. ilf liquid and \~is 3(1bmJ). lf ~ \"'lume of'~ t~ SO ti~ 'tile \"Olu:tne
of liquid. what iB the tom~ ~py of lbe contents u f the vesel7
6..25. \Vel slftlm ll[ lJ(F c bas it density er 0.015 ,g em-J. Dftmnine X~ If. m~d s.
1
'-2:6.. A vessel of 0.(5....m 1 wlume conmbllll8 Sllmmred-\'iipOt team m ISO::C ~ cnoll!d to

JOGC. JD.:'tmnioo lhe dnt\J "-otmne and ma."i ofUquitl W31"er in 1h~ vessel.
,6.21,. \\'e.1 stam al 1.100 lkP8 expands 3J ooostnru eodmlpy (as in a llbrotidiog ~) to
lO~JJ ~~ WIJ~ itll. ~it~ IO:S~~<C Whm.is lbo qu~ 11fthe steam roJl:i.
initial $Wle7
6.2& Stemn at 2,100 'kli'a and 1Mcc upands at coost.ant enlhalpy Cas ma tllrottling poeess)'
1
1to 125 tPa What is, the u._~ of the !Steam iP 1 6uul sta~ ~ wh:lt is Q mtropy
1
chan~? \\'bat TMJUid be the fimd tw1pe1 utrn; o!ll1d entropy ~ for :m l~ 1
~. s~ m 300(psiaJ :md SOJ( F)~ a~ COMimlteo.lbalpy ( ma thmtttmg ~>

ro 20(psltt). Whar h lhc. ~.empernue oflhe ~m in iu finultl'llt~ 4Pd what i$ its; cntmpy
dllmge"! Woot WDUid be the tlioaJ tem,pe:l'tl.1ure md mh'Op) dt:.m~ t'or em ida1J p 7
6.JO~ ~ kmn at SOO ~and lC)(fC ~~can, to SO tPa. '\ \lktt u ~ts.
Jiftal enthalp)~
tli.ll. Wbat ~ tile! IJ'Iole ~of~~ "~rin air that i ~with "alm' at lS-C and
101.33 k.Pa? .AJ 50"'C and JOL33 kPa?

6.32.. A rigid vessel COI'llftins 0.0 l4 1nl of saturated-vapor SleaDl in equilibrium Vtith CUJl t ml
of saturated, fiqaid water at 1100~ Hut is. tnmferred to the \'USSel unlil ,oae phase just
~ aid~ sin!tle ~ ~. Wbi~;b ~ (liq~ or vtqJ{If.) ~maill5. attd
whai .are im tempemtllre and premue? How J~~Ueh beat is rmmsferred in tbe process'?
'33.. A vessel clll2S-mt capacity filled. with tm:ated st!am at 1.500 kPa lf de vessel
if C\'lO.bl umW 25 petceQt of Ute~ rna:s ~ ~ muc:b bell! k ~
a11d! wtw. ~ tbr: :lliml ~?
' .31. A \'CSSel of 2ml ~~ contains 0.02 ml of liquid watu and 1.98 ml of water \~d.por
at 10~-13 kPo. llow lll1X"h lbea1 nmst be adtlcd lO the oon~me~ of'th \~-se1 so thllt the
]iquid warer is jlW. e~mu:d?
61l&. A rigid ~1 of 0.4~ ~vJ~ b filled with ~!DiD mSOO kh and 3Scrc. How mu.cb
~ fJlWSI be tmlil5frtif'M [A,KU 1b.e ~to ~ iL~ lQ;nftf~ 1D 'lO{FC?
~ One kilogram of steam is couWned m a pisitooleylmda de:vWe at 800 k.Pa and :zoo~ c .
{a) If a Ullile~ o. med.'!anlc.:a1ily rew~JS~""ble, i~ ap:tnsion tiD [50 ltPa.. l:ltJW
much heal cioeb i1: ~rb?
{b) 1r it uruikrgoes a rrevenibte. adiabatic u.pansioo to ISO kP'a. what i:s its fi.nnl !lem-
~tmr and bow mucl:JJ wntk is dane'?
U'7. ~ at tOOO ~ cootaining 64 rnoilihlro i hced ut <:Ott'JtBot prcsswe to ns~c.

~ wudl boat l!i n:qu:ircd ptr kilogmm~
~ Swam at 2.100 kPa and WJ"tb a quality of 0.90 Ullde.IWJ'CS a ~1;rsilifc~ adilbattc ~illl"'
aon LP a tmon8(1W ~ to 400 kPa_ h 3;s ~ hratrd ill1 a.IDSUmL "tOh1m~ tmtiJ tt is
~ vapor. Determine Q and It' for 1 ilie process.
~. fouJ: .kil~ of Sle'am i:o a pbtomlcylirukr dc\1H:~ 400 kPa and 115-:.c u~iJieS a
I
m~y n:\t~Sible. i udlennid oompressloo rom fiaal ~ mcb thm die :Uc-.am
a
is just satur:ned. DetenniDe and tv for lhe process.
6..4& S~tn u~ adJaq~ &om ao mitim sl3t~ <~f 4S<fC and 3.000 kh 10 a fma.l ~
of lqot';JC and,235 t& Detennine A H and AS:
(a) From srea:m tabie data.

(b) By ~om fw an ideaJ P..'
tc) sy .appropriate pnaaliud Ct!lll'datioos..
6A1.. A pittBnfeyl;ipdcj devioe opetatlfi8 iH a cycle with itt:illi1 as 1ht wutti.ng UurEd ~res
the following ~tep.s>
Steam ai))O kPa and 20(FC is lbeated at c:onstmt vo!nme ma prressure of 800 k:P&
Jl1bcP ~~ reversibly tmd a:diiibatic_.ally, to tt.e mi~ru ~bite Gf aoo-cc.

24S
.. .FinaJJ;y. me steam is ~pres~ in a tne.clmnka.Uy reversible. is01ben;na1 process

to b initial pMSER: of SSO kPa.
What ~ tOe lhermill dficiency o.f me C}'Clte.?
6Al. " pisetJll/cyUrnJer &vice f)P'iating in a ~eycl~ "ilh 5team ~ llhr wrkLng ftufd ~
'me rotLov.in~ ~:
ream at JOO(pshi) i& brrubd at C005tilru preuute ro CJOOCO F)_
SMui"-Mdl-~upor
[t tbeo ~ m~nibJ)' and adiabaticall). to ilie initial iltmlpuatme of41 1.35\ :F).
FLDIIIIy.. l&e~ is, ~ in a~ l'I'ICC~.f re\~ ismbeftl:'t31 ~
te> tlhe inibal ~
6.43. S~MRJt'.ntain; ~ l\lrlrine ;n~tOOJ tPa aod 4WC expands ~tbl)f and ldiabmicallly.
(a) For wbu ~~pressure is lbe exil stream a saluratcd vapor?
(bJ For wbat discharge~ 1 lbc ait saseam c& ftt \!8p()r 'with qua_lity of 0:95?
~6.44.. A &team turbine. operatln8 re\-eBibly il:Dd ruf.iab3tiailly~ ~ m sopefbealed bmam am

Z.OOO kh and disdaaJps. al SO kPa._
1(cdWbat i:s Lhc mioim\!m ~tnqviml so d:ud tbc u~ con~aim 1110~?
(b) \Vba:t is lhe power ootpu:t of lb.e turbine. if it~ ull!dell' tlhese condi1ioos and
1hc tQID~ is S kgs- 1?
6..45. An ~B ~est of IIi Hl$11 ru.tbifie ptoduc);:S die f~I1Wiu~ ~u.!h~ Wi1h st~ ~p
plied ro the turbine aJJ [ .JSO k.Pd and '31:39-C-. the exbimst from 1he WJ!bin.e ar 10 kP.I
hmmUng aditlbatic openltion and negligible e~ mkioelic
i.5o a.tw'a.tatJ \"appO'.
~nd ~nl ~~ de~ dJC turlline ~fficimcy~ ~ dJ flltirJ,uf ildUal ,,.--gJt
or 1he wrbi:ne to tbe wort :M a turbine opcrat.ifig ~iclilly fiiotu the a.me initial
oorulitions to dle sa.1'Jl1te ~ pressure.
6.46. ;~ 5~ tuJhme Open~U:Sl ~iabatica)]y ~~ a ~~llDJ imle W2S ,kg s- l, ~ team is

1
uwJim a.1 1..300 kPil and -4DO"'C mw:l ~ ru: 40 kP';. and lOO~C- Oelm'ltint tbe
power outp~JJJ of th& IID'biD mid. the efficieDC.y nf itR o~ in ~ wilh a
twbioo tbal operates m'f.o.usibly and ~adiabal:it:alty f:lom the same .initiai conditions to
the~ final prcssum.
6~7. from ~table da_~ eMhnaie '\-aloe_s [or lhc "R':!dduaJ ~e& J' R, lJ R., and Sll for
.steam at ~C and 1.600 tPa. md compare with ,.."afu~ fouodl by a mimble pnern1-
uACI~mioa
6A& From dam in tbe steam tables:

(a) f>etenmne wlues for at 300 (iP f01 satumJ:ed liquid and vapor M 1.000 kPa.
Should~ be ~!be~?

246
(b) Dml:mi:rm vDhles far IJ.IJt IT and AJlr at LOOO k_Pa.. SJ~ould these be the same1
(c) f'i.lld ttalne::s for V JE., N 1 , und S1 for saauated \'aJIOf at I ;00) tPa.
(d) Estimate a. v-dlne iot d p- / dT at ~tm t_Pa ~ appJy tb~ Clapeyrofl ~00 lO
evaluate As'.,. a1 1.000 kPa. Does ~his resol1tagxee with me :steam-ubfe \'l\lue"?
Apply approprintc ~zed~~ far cva!UIIion pf VW, HR. and sR for stu~
lB'a%ed vapor at l ..lXXI kP~ Do these~~ wilh ~'~found ~n (cj?
6A9. f1rom dam in the team tables:

(iJ) ~ wlues. for G' Met G" for . amruted liquid and ~al JSO(pria,J~ Sbculd
these ~ the same'?
(b) Dt:femdoe values,lfor a H 1 1r and AN' en ~ Sfi(pgmJ- Sboold 'these be mr ~?
(c-) Fmd ~ ftl' v~t. HR .. ;md sJ fee satumted w3por at 110(psia).
(d) Siima1e a ~"aiue fer d P / dT at ISO(psia) and appt lbe cmpeyroo eql.wi(irlllf."l
,evaJume Asr m ISO(psia). Dora this result agree ""'"ir.h lhe steam-table vaJue?
Ap~y appropriate geraaJ..i.zed eone:laOODs, for e\o'JhWfOD Of yR. HR ; and $R: for $Sl-
tJP.ttd vapor a 1SOfp~i.a'). Do l.h~ RSUks ~ with the \~Ues found in (c)'?'
6.50. ~pane gus ll1 ~ lbarand 3:SCC b emnprt~ 't o a final stateofi3S bar ad 195 C. Es.-
cimate d:te ID01ar voJwne of me pmpane .in rthe fi!W s.tllle and the enthalpy nlld e:rttrtopy
changes fm lhe proeess. In m initiaJ gta-re,.pro:~ may be ~d aJ) i~ Pl
651~ kopaneat 10'"C and 101.33 kJP;~ is~ ~Y mi,)OO !kPn. &ti-m~
AR ~ llS for the prooess by sui~e ~ COJJkniom.
6.51 A ~ of pn:J~ gas is p3rtially liqUGfied ftJy tbrotlling irom 200 bat and 3'10 K
to ] bar. What fmaioo of me gu i~ llq11teJJrd in lhts ~7 ~ "~ ~~
of ~apge i:5 Jif.OU by Sq. (6.71J with~: A ~::: -6~.722l~. 8 :n 1.33136.,
C ~ - 2.l3S68. D ~: - L3S5Sl .
653. &lilmtte tbc molar ,..'Oiume.. enthalp-y. awl emmpy ror 13-1~11adime as a sittlimtcd
vapor and a sa~ liquid at 380 K. --fbe~py and entropy are se~ eqool to zero
fer dte i:deaJ-gas mre .31 1o1.33 kPii ailld uc. The \'a(Mlf" ~ of 1..3-bl.l.ladime at
380 K is l,9l9.4 kPa.
&.5:5.. 11m fbllllste'"..un demandrof a. platrl ovn the: period of an holiT is 6.000 k~ but lnstan.
~ de.m!md ~tes from 4 .:( ))0 to 14l(O) kg lbr-1 Steady boiler Oped'allou at
6.000 kg hr-1.i ! ~by hJcliiS'if.m of an~ aecrm:rulutQr~ ~ 11 tank CO'IP
mining mosdy sa.tnmted l'.iquid waiet" Chat ''Hom on the ~me- between Um boiler and

dle plant- fbe boiler produces satumted steam m 1.000 kPa.. .and die plant ~
with Slum at 700 lPL A c:ontrol 'llll\-e regulates lbe steam pres_quoe upslream Cmm
lbe ~ dd .-. ~ otmtrol -w.~ ~ k ~ d.ow1151RWD from
lhe aecnmu,Ja[-() WheD iilea!D demand is than boiler output; Sfram flows mb) (ll'ld
is ~Jy ~ by 6quid RSi~ io dJe aiXUI!Dolat. in the ~ iDt."re~
ibc pteSSDii'e liD 'Waf~ ptslef" dJan 700 !kPa. \\~_g tilelm ckmJillld i ~ tf bm IJvilcr
(.IIQtput.. ~-ater ii.o dle OOL-umtdm:or ~ and srea:rn ~~lows out. dJus ~ lie
~ lo values JCSSo dian ~~000 kPiL 'Mw acewnu~a.~or wllf.lllle ~ ~ for lhi!
~ee if ~o ~ tbal95~ of its volume sbcWd be occupied by liq.uid?
6.56.. Pro~ ps Dl I 279 C iit:!d 38 bar i$ lhrottbJ ill .a _cady~ Oow 1~ h;J I bar~
wbele it nmy be assumed to be an ideal g2S~ Bt]m.;He ~be linn~ l~utt or the
pfOpylenc and its eau q~y elwJF~
'-57. Propane gas m 2l bar and 423 K is throo.kd in - ~y-w.k flow ~ r:o 1 bur,
~timate the eldroJf1Y dmnge of the propane c:aused b} this ~ In in lfinm ~
~may be~ rti be m ideal ps.
6.SIL Propane ~ al too.a c is compressed isofbeJ"'I];i)J]y from an initial ~~ of l bar to ill

final presmre of 10 bit ~ :\H l.md 4S.
U 9. Hydrogen 8Ullide p I! "~~ from an initml ~ d 400 K arut S to a ~ina~

Slate of600 Kand 25 bar. lktimate AH ~ I).S.
6AQ. ~~o d.ioil{id- e...:~d.li: :;d ~t ell'tlmlpy (as in a tbrottli.og process) from I JjOO kPa
;mdl4l' C t9 IOJ ..33 kPil. &Limllre AS f0r IlK ~
6..61. A~ of elh)'koe gas at 2SO~c and j,..goo. tPa expands isentrtrpienlly in a. wmine
m l JO t.Pa r:terermiije the~ uflbt ~pa1Jdd 82t' and lb wnrk ~ if
abe ~of edi)'Jme are C'ak:ulamd by:
(a) Bquuio:ns f an ideal p; (h) Appropriate gm_erallnd. ~
6.61. A sa:rea.m or ethane gas at 22IJOC lUJd 3D bm- e-xpands lsmnropic-,~~Uy m A tmbi:oc ID
2.6 bat_ ~n.e abe ~pe1tilUJe of abe~ gu and the work produoed if the
prnpenics or-em:me are catcubted by:
(a) Eqtwiomfor an idea] gas,~ (b) AppKJ!pfiutcg~t.ed.~
6.6J. &timare lhe final tcan.per.n~ nnd tbc WOlk ~ whm l mo1 of lmfall(l is C ODF
pressed ~yin a -teady-lkrw lfli'OOCSS from l b.llr 4llJd SCfC '0 1.8 bar,.
6.-K ~the ~iinwb ~(If wwt ebiainable ma Jl\Jw ~ rrnm_ I q of

Kemt\ aa 3JIJOI kPll and 450"'C for~ Cli1Qdi1tllil$ or 30) K Qd ~ 01..33 kPa

&65., 1..iqWd ~t:a at J2S K and 000 tPu ~into a boiler~ the ram: of ](J kg - Land ~
YrU,JIO~~ prodooint; rormd \'DpOf" t 8,000 kf:l. What i.oe; tile 01anmum fbcrioo of
tiD= h=at added 10 abe wou:1 in me bo11a lbal an be c~-rted imo woct in o J;lfOl~
w~ product ~ wa~ Zit ioitbd Q'il-uditions.. if Too = 300 K"r W!hat haplJCil:s to the 11
ro
of tM. heat1 'W.bt b ~ rote of ~iiOPf ~ge the ~fmlll:lldings .as a .resuh of U~
worl-prod.DciDg pmr;ess? In 1be syilmn? Total?
6..(6.. S~ llfle ~rulted w die Water in me Milu lo 'the rpmc~~ problem OOJOOj ffo.ID
~ ~ 01 a~ of~ C._ What is lhe 1ctnl mte of entropy genemri.ou as.

ft'lsult of the beating ~'7 w~ is 1~ t1
6.f/1. n icc plant prod~ Q5 k:g -J at Dll.te ice at ~C from "'ater ar 2CY'C CT" ) in a
oontinuoos !Procc&. It lk hnmt beat Q( fmioo of watu 333,~ kJ lk;g- 1 and if die
tttCf1110d}.1WIIic dlicimq of tM ~ ~~ wb:lt ~ b 1J0Wf (E(Jllimnnl of die
plant?
6M!L An ifi\rentoc bas developed a 7inpli~ated ~ far ~Dilkmg hem cootifiuuLWy m.'UiJ ..
able at UD ~ ted lmlpCrntw:'e. s~numled titeam. IOI'FC islbe only ~mr_ree of~
,Assuming dml there is pleotjt ef eooU:oa w.:un o\iailahle Bl ore~ WMI L ~ mn.'dmnm
~~~R' ~'d m whlch in1lbe omotml of 1000 kJ am M made avilililble for
eaf:h,kilo~ or rem~ nowm, tfuoQgh de~ 1
6.8~ Twn bai~" both opt"mting M 21X)(p_'i'ia). d~ ~unl a.mnunt5 of sr~ into the
~ steam main.. Steam fJtOm the lira boill:t- ' supa1Dcm.ed m 420COF) ilDtl sk'.am
fmm the second is !g,~ with a q;ootity of 96~. ~ adinMtic mmng and negli.
~ole ~ mpJteDUd and tinic ~fes. WblU ~S che equilibriUIU (X')mditi(lll n~
m~1ng md wbat il'l Sc me~~ (lb ) of ~,p liteaof7
6,14l A ri.gkU:rtdt of 80(rtl" ~~ e,untai:nt. 4. UW(J.b , of:1W_lllffitcd liquid ~~ret at4l0 " .
This amoon1 ofliqllid almos1 mmpldely fill& the ' idm smab Jmlaining. \'ol\uru! tJe...
m1 ~by ~vapo sta~m. &a.~ 3 bitlllOflC ..'"DiJOT :5p3ce u. abe ll:ui1t rs.
v..~ a '~"'-= :nib hip of die t$lik is~. ami ~nrmcd-~ stea:m is vented
to the a1mosphere untiJ cbe tem~ i:n tbe rant Mls to 4201 f) . Assuming no lh.~
~r rc to lite conlal15 of' lhe lWlk.. dt(mioe lbB mus of tcun \-ented.
6.11. A laDk of Sfl.~ cap~ty ~~ tam at:4.50Q kPa ~dl400PC. Sttam is~~
fnxn the tank dmrug_b il Mi.er vah-e 10 me ~-pbere nn.til me pre.wue in lhe Lank
fnlls to 3.500 t:Pa.. lf the vmtiq p1i0ees.ii is' adiabatiey atim__ate die- fiooJ lempeia!Ute. of
me t~m~~md 'tbe 1~ or~v~
~12. .1.\ Emit vf .&.m3 ~~lY ctorttmiU IJ00 kg of fut.nid ~- 25~C in cequifibriwn
1
~ilh its \-npcl'. whkh fi.Us me :res~ or1be lank. quantity of '1.000,kg of Wa1et' ~ 5 C
js pumped imu the lank. How mmch heal 01118t ~ .~ dming this process if tJx
~re io die tank is not 10 change?

6.71 Liqwd ni~m b $10~ in o.s-:m3 ~ tlmkJ dial~ ~&biY im1,iktJ. Clnmc.lcr
tbe pmt.dS 1fif fillin: an C"v-4~ t$.nk, ini~Oy a1 295 K.. It is a~JU~Cbed to a line
conJaining tiqWd ni.lrogeu at ib. oonna1 boiliQ: point of 77.3 K and at a JR sun: of
5t'vcr.dl~ At :drls amdition. ~ts enthalpy is - 120.8 tJ -q- 1. Wihcn a vah~ in lbe
lltiJle lis opened. lbt! nitrogen flowing info ~be ~m~t 81 tint ~~ in UJC! ~
of ~ me mnk. lf dte tatrt has a ma&i of 30 kg and me meml bas. a specific
heal capaci-ly of 0.43 tJ 'k.g"" 1 K'"" 1~ whal ~ of ~ JmJSt :Do-w inbJ &he hmk
j-w-1 lo toot it ~o a ~lUre such that liquid' oitro.wm lqim lo ~ in 'lbe
tank? Ass~ Gr.at ~ nitrogen wu.l dte mnk are alway!. mdn: SIIDIIe rempem.ru:n;_ "'be
propmies of saturated tnitrog'en vapor at several ~are ,givea as follows:
TIK Plb~ vl'Jml q HiflllJ ~8 -11

80 1.396 O.rl1640 7lt'9
85 1287 O.UU1 12_3
90 JJ,t}) 0-06628 85JO
95 Sr398 Or.~ 86.8
100 ;_n s 0Jl3l26 S1J'
105 10-83 0.0212.,1 87.4
110 14.67 0.(U598 8S.6
6.74.. A ~mntotso.mlvolumeinitiallyconra..I.M 16JDlkgofwata'~buted.

~ liquid and Y;lJ)Of pbase,s at 25~c. Saturated iteam a1 I..SOO 1Pa is admiued to
llhe lank until lhe prtASlire lCi!Cbts 800 kPa Wibu lila! of~ i& addc<n
6.76. A 2-ro-l tank i.nirullly oontaim a m..ixrure r& f utomre-cj..vapor steam nnd saturatMIiq11id
W"Bter at 3,000 th. Of die t.otal. mass. L~ ~ vapor. Sat~D"3Ced--tiquid 1\~tcr ~ bJGd
fmm the tnfit chtoo.p .. val\-e until dtc lvtailll m We tank ,~ ~ of tbt: iniliallOtal
~ IfdWiing tbe ~ lhe ~mpennure ofl be cooi~m~sof 1M unk.is kept~
he\' mttdh bcot .E tmnsfcmtrl?
6.'71. A stream of~ m ~C flOwing at the rme re f .5 q s- 1 is formed by mai.:Dg wat~

at 24~c widJ 5atlmikd steam at 400 kPa. AsSlDDing ardiahatic opcrmon. at what ra10S
are tbr ~m ~d v.'B'tet fed ro ltlc QJi~
6.18. In, a de&uper~~ liquid \liat~ at 3~UD kPa alld .Strc l$ ~ lnro a~~ of
~ steam at l~OOO kPa and :t7sec in an amo110~ wdJ. dmt a single strtam
of !itl~"\'Bpit st'atn 2.900 k~ .flow5 inJp the ~ ~ ~ ~ ()(
15 tg s-' . A8smning adialwic opermion. wtm i! lhe IJl35'!; lflowmm at t:he. water?
What rs $c for lhc ~? What is lb!. iJreveniblc: feature of the pJQC.'C!SS?

250
6.79. SUpelheared ~ ar 700 kh and 280 C Oowin~ at the: rute of :50 kg s- 1 is mixed
wi1h Liquid Willet at 409C to produce steam at 700 lk.P-a a:od 2(l(JDC_ Asmntina (Jd~nlic
OperU1(0Jl. a-t wbM ~ i:s ~ ~u.,w&dl to uhe nMer What ~ Sa for me~?
Wha1 B the trre\~ fe-ature: of rhe pnr('SS?
6JIO. A 8liiemll of air at 12 b.u arid 90D K is mil.cd with 41nndtrr ~m of WI 01 2 bill and
400 K witb 2..5 lime5 die JDaSS tkJwm H' lbis proo~ Wft!e attOHtplis-bed mrt:rsibly
1
O!Dd. adiahatical.Dy. w!lat would be dis 14mtpcqiW'e and~ of lbe ~'Ulli:og air
sbeU11 Assume air t<J be m ideal gas tot \\bid! c,. = 0 / 2)R_
6.81 . Hot nitmgm gas i1t 150 F'}1and mmospberic pressure flows i~o a w-illi;~,-.hc:-41! bQ-IIer
m rbe fide of 4f(lbuL(&)- 1 iU!.tf 111ln$f~ besllO watu boiling al l ratm). 1'1le Watel'
I
feed to tile boiler is mturu.Ied liquid at ](atm), nrul it ~c:s lhe boi~r as ~u~md
1StCam ~ U;~~~) mid .300(~P). II~ !ll_'hrogu ~cooled ~o 325f; F) and if bea1 b lo~
to 1be ~ 211 o rate of (JO(Bm) fur cadi (lbaJ (}f sttnm gtmerated1 v--mt is lbe.
9.vam~tion nue? If die SUIJ'OOJiding:s are m 7~. what i2i Sc ru:r 1he ~1
A$9Jne 11itr0~d fD,be u ideal ~ fur which Cr = 0 /2) R.
6..1!.. Hut ~ren !M at 4{lPtC .!Uld !llDtospbtric Jf"~ 80W1' into a wutc-b:w OOilu :t'
the: rnte of 2U kg s- . and lmnsfers be3i to a.ter boiling at 101.31 kPa. Tbt: Wlillrr fc:~d
to lhe boiler i utmared liquid at ~OJ.J.:J k:PL ami t lea~ the booer a:s su~
steam al lOJ.J'J lkPa alld l5oPC. If me nitMp i~ Jakd tcJ 17Cf"'C aJJd if heat is lo~
to ltbe ~ngs. 4l u ta.te of 80 kJ fOI' euh kilOgnlm of Sfea.m ge.nera:led. w.bat is ~
steall]}sgener.dicm rate? If tbe mnmdlngs ~ ~~ 2-S"C. ~b-] is Sr; for tlr proccs.~?'
Assume nitrogen to be an ideal gas fur ""'ilicb C, = (1(J.) R.
liJI3. Show tlmt Bi~ m1d i$~ J;w:\."'m po:siti'\,' slope$ in the ~plulse regions of a
T S diagram. Suppose that Cp ::::z .:a bT _where a and b arc ~tive c,:-u~m~~ ftgw
that dJe eu.natu.re of u ilobar is aL'iO posithte. For ~ilred T ami S .. wbidl is ~
an isobar or an~? Why? Nom lhlil Cr > Cv-
(aH)
I
I
as , = 1-<JJT - II
-
He. fJ is voh:m.le e'.lp3DSivily. Jf die v-apor is ~n'beQ by dre ~t:enn 'liriirl eqwrticm
iQ P; Bq. t(l.381 what ~11 be ;said a1wut ~sigN of these dcri:\'3-tives? .Assu:m~ tbat
for oonnal tt:mpe'mtu:l'eS. B is ~e Mid tl B ftlY' is ~v.c..
~~~ The tempe twe ,c~epenc~ence of tbe second.virtti eoefflcienl 8 is mown for ni~ on
Jig,. 3JO. ~jtDiiYtfy.lbe ~of 8(T) lhe- MUJ~e for all gases; qtWJtitatindy, the
:~tor wln1:h B o 0 oorre.sponds m a l'fttucrfil ~~dll!il'e of abot.u T,. =2. 7
for m~:my ~ u~ tb~ Qb,.~ to slro-w by~ {6.$4) througb (6.5(0 tba.t d1e
tesidn:311 ~ieg ,G R, IJR ~ qfi(L 31l ntt ~~~ f(lf OlGSI .~~~;S at ~l p~
aae lfiJOI'mll tanpentt~. W'b.;d can you 5011 about lhe igns af v and C$?
251
~ An GQUiJroofar mtwe of methane and ~ is disc:Jw:ged fmm a ~ at

s..soo~ :amt 'to=-c ar ~he Atlr or 1.4 kl - ~ If rbe ~ity mthe dischatle ~me. is not
to ~'rcdl30 m -. wh1 is me mininnnn ~of die disdJqc: tmc?
~.17. ~e 1'2 11, aQd .S11 fQr '0 IJt of abc followiog by ~N)Jrig.. pna'31~ ~~
Lalliom:
(a) f,.J..Buradieoe M SOO K a.nd 20 bar.

(.b} Carbon diox.i:de 31 400 K aod :!00 bar.
(t-J Carbon dEsolJiide ru 450 K and 00 bar.
(d) ""Dceme at 600 K and lO bill.
(~) Elby~ne Ul t620 K mtd 20 bar-
if) Methane 250 K nnd 90 bar.
(g) O~ypn atl.SO K wad 20 bar.
(lr) .:Pentane 3I 500 K aml lO bar.
f,i ) Sulfltr' dim.ide lll4SO K :mel 3S bar.
{j} ~;n400Kmd l5 ba1'.
6.11& Estimate z. n R~ and s~ fer one ofthe tollowln;g nz,tlitttofm ~by die ~1
co~
(<ii)BenzeoeJcyclobeune. at 6-50 K and 60 bar..

(b) Catbon ~~ ~:fide a1 300 K and 100 bar.
(e) Carbon diolideln-ocume 111. 600 K and ~00 bar.
(d) Btbn~bjtJent at 350 K and 75 bar.
(e) Hydrogen mbidelmetblme at 400 K and l so bar.
a
{f) ~~llilto8dl 200 K aJid 1S bu.
(g} Mctbaneln-~ at 450 K and :8() bar.
(6) Ni~os~p at 250 K and 100,bar.
6..89.. 'F or ~ Mwrsiblf- i~lll compression of a liquid fnr wbicb. jJ IJld fl ma.y be- ~
mmed i~ndertt of pressure.. dlow mat
- v.,- y l
(a) lV - Pa Va - ~ Vz -- -"'"""""""'""""
fC
(b) 6S ;;;; ~(lit

K -
- v,)
(e) 4H = 1 - jJT f V! --- V1 )

f(
Do not Mmme lhat V ', ~t at u a"~ge \.-alrJe, but use &f. (3.5) for its f
depc.odence (""ith Y2 replaced lby V). Apply these equatio11s to tbe condJtfl:m smted
in Pb.. 6.?. Wbat do tfte. result$ ~ Witb ~to ~:~SC or 1111 ~"~~ ni ~or V?

630"' Ia ~ fOI :m :atQmuy dlamod)"IIIIllk-JlfOilGllyola pwe ~ M = Jf(T. P ,~
\\1~
63L The ~lpy (If a pUJt: i~l 38$ depelllds on ~ only. Hence. H 1 is often
said to be 4ndependeot of ~'" md one wri~ (aH '"' ta P )r - o. Detenni:ne
a~om. for lll HI.J J& Ph~ .and (li H1ta P)s. Why a& ~bese qua:nlilies lKX znc?
dS;;; C_v
T
(aaPT) -r
1
d
p +
Cp
T
(~) dV
a~" p
~~ 1be da:Watihe (C)L/ !8 V)r b: ~ cal!Jed ~he ~mttl prt~. at'ld the product
T (9Pj fJ1' )v? dJt:, dle:mwl.p~. Pind eqoatiODS fur tbcir e"afgglian Cor.
(a} AD idea] gas; tb ) A van der Waals Huitft; (c) A RedlkhiKwoog. Ouid.
6S4.. (o) A pure ~e :m desaibed b)' an ~on for G (T. P ). Sbow bow tO dt-
ltlim:i:fit: Z. I). 4Dd Cv . in rrla~Km to G. T, arnd f ~ lkri~"' of G wHh
respect roT and f .
(b) A pm:e ubmmce ; , dc:saibed by an aprcssioo (or A (T. V). Show bow 10 deter~
~~line 2 . R , ami C~' i o relation to A. T ~ and V andillf deri\>atives of A \\-;th re~
toTaodV .
'-95. U~ s:teaiD tables tO ~ 8: or..'llhJe of lbe tcen~Jie faotor w f.or WaiH. Compar-e dte
resull ~l]]h lht ~given mTable B.L
6.96,. The critical~ tfot &eltaft~e (~t HfC.. 134a)are J(Yen in Table
B. l~ and Table 9. ] (p. l 19' llmw ~tm ~for die Mile ~nt. Fmm
tbcsc daa. *~ the .aeentrie f.v:o tu for HfC.. ] J4a. and co~ it 'ifrilb the val:ue
given in "'1\tJit- B.1.
6.97. A$ ru!ll'ed in IEl. 6S, Al/ 1" is om i~nl ofT; iD faa, it beeomcs ~ro al Ute
Cllilica] [pOint~ 0:1:' may S1l.tl1I'3Ied vapors ml'.twml be ~erecl id~ ~ \\!'by ~
ir then dW Eq. (6.. 75) fPI1CWides a rtaSonablc app:nndm_:ttioo oo \'BpOT~pNSSUN beba\-lor
~ ltbe eotirt liqllifl ~1
6.98.. Rationalize the follmvlng nppro.WW.te eJ:Jlfe&~ou for solidiUquid sartmltion pres.-
&'Url':lS:
(a) P;/ ~A BT: (b) :P1fl =A ' Bin T

153
6..99. As ~~ 'hy F'JJ,g.. :ll. die slope of the subJimatioo cu:rve at die mp1e paint is gen..
emlly greatu Ibm that ~ lbc "Y8p(lri1Akoo C\ll'\t in 1dJ,: ~_fl!Je m.te. lbniona'liz~ tb.is
~on. Note dial triple-point pres.smes .ve lbllidl)' Jew.~ h:ru.:e ~ foe lhis
exercise lhat AZ11 ~ AZ~lt ~ 1.
6.100.. SlwJI.\ ma1 tbe Clapeyron equation for liquidlr.oa:par tJguillbrium lflWJl be ~"ria.en in lbe
mJQCXdfwm;
where
6.101.. U~ b RSult of the preceding problem to estimate the heat of ~iiOIII ~ ~

~tmal bmlmg pai-m far one of 1lbe Sl.lbi~ lisn!d bel'ow"~ Compare die resu1a ith
the \"aaoe given in Tab~ B.l of App. B.
~ciOimll Rile.: ~ P, sat \lith Eq$. (6.78}, (6.79j1 and (6.80),. with co given b,
Eq. 1(6.SD. Use &p. {].61)~ {1.62)~ (J,_6J), (3J65lt aoo (3,.66) f(lr r. 4fitt &J- 0~13)
for 2 1. Crilical properties aDIJ aDd ooJJD1d boilillg poin&s ue gjwo in Table B.~ .
(a) ~e:. C:b) is.n-BU~Me; (c) Catbon ~ride::. (d)1C)'Ctohaane:;,
(r) n&Deaule~ (/ln~~e; (&) 11-0ctmr:: (h) To!umo: (11 o-X)~C
6.l02. R.itdcl ~ :tdiird ~~-sooc.s p:nmetera:lr- trelared to Clbevapor~ore

curve by:
m simple Huilbi. ~ent shows tm.t at ~ 5.8; ft:lf m;)tt- ' 41ple IIllich, ac inefea___IjJ;5
,...i;tb .incleas.ing molecular complexizy. HOw- weD ~ tiE Le~r ooadutklo fur
P,fi2l~~~?
6.103, coo.rdinates fur ~carbcm dioxide are T, c lW6..55 K and P, = !1. J70 lbat.
Tripi~point
~~t; CO:! ~ oo nomta1l boill:Dg point. (Why?) Nevertheless. one am define a
hypotMlkm DOl'IIW lboilling poinr by emapolatioa of dx: wplt~ mlve~
(a) Use the ~ier OOII'ellalioo1For Prw in con.f.tmclioo ~db lbe uip!e-,1Jl0im itiiP
dbmte! to estitate (U fl;l( CO~- OJ~ it with the value mTable B.l
(b) u~ die ~Ia CAlt'l'clldioo to estimate 1he ~ lltli'D1a1 bcilins point
fut co2. Con'l~Di:M oo me Ulkdy ~~or thi:i rc.~tt..

Chapter7
Applications of
Thermodynamics to Flow
Processes
1'be diGimoo)!IWllies of ftow is !based oo mm:s. 91a8Y ood entropy balam-es. \lihkb 114n-e
~ ~'~doped i:~~ ~ 2 od S. h applicalioll o._these WtQil~ to specifie ~ is
C'JODildeftd in lhis d!apt. The ~pnne. lmdet~yq lhc ~y of tlow u fl:~d ~_ni~ m
wtddl ec~ llot Gilly t:bc bda~ m tbenPod}'mlmics bi.JI alfiQ lbe finc;B"-tn~J~mentum
principle r( Newtm g seooodi law~ This om]{es :Hur-d JIJfldlanies i1l brooder ~:d nf (Uti~ - The dis-
~doo ~- thmJJCNiylu.ulliuproiJI.ems ~Jbti~ct problmu ~d- oo whelber
lb.B principle is R.Yfllitet.l for solmioa. 1'buse pm'bldl!li wti.o:se sduiioo.t, ~ ool~ on ~
~ aDd ou the IDI\W of tbemloclynmnia :11\'l commonly set apan from ~he mJdy ef
vhl ~ ~ QJe ~ co~ o ~o4yuamic.s:. fluid rnechwJ:ics au.~ deals
witb the broad spearum of pmblems wl*b .~~ applicatloo. of ~he motJFUifi printilplt:.
1bis ehisiou is Dbitrnry.lml ii is mufitional aod ooavenienL
Coosidet fiw example the low of gaslhlvogb a pipdinc. If 01~ a1U andllhmnod)'Damic
pupe:mes of dle ,as ent~ and lea\~@ the :plpelfne: are. .trio m.. 1tben upplictrtioo or me tl:rst
lllw ~btishe5 1bc mapitoott of the ~ ~ .il!JI the w;.nvuntfi:np of me pipeline.
The nletbanimt o:f the ~ the tail .6{ now_ llt1d lbe srot.e path attn::tlly f~llm.ved by ~
ftu.id bc.t~ cQ,I:RinCe aad r[ 3j( me not ~nt ~0 1h~ a.kultllion. On d~ obr b;md. it
ooe.lb1b. oolJ Hlb"'tlmplere tauw~e of me inititd at fmal ~ or ~rn.e gas. thrm ~ dchli~.cd
i:nformaliDD about die ~ is needed buf~ any calcWatiom me ma_dle.. Par exampf.e. lhe
exU ~ of me gas .may ~ be speeiktd. IIi dlis ~- tJnt; mu.~ ctpply the moJnC'ntmn
priocipt of fluid l:l'ledmUcs. and 11m reqlJ:iJes :m an.pirical or dreoretieal expressioo for llbe-
~ . at diG: pipe ~-
lNQcl ik~F'lmd ,/(PI'~~ ~~-lrdcd., ~~Hill Nftt ..~~ ~- ~hj ~-

j~ ~~ ~ 1!1 ~Gl pK1 ~~ lty R. B. ~ W.
Of e.
SLC'Qt. and! B. N . ~pcfotlt mTIMQ.llt:lf"i
~ ~ ~JobQ ~ . ~ Y~ 2001; by C. O.lknlidl ~liE- Mycn m H~ II~ .vJ Mw
T~.. 2Bd ~ ~~~ 11., ~ Vc m ~ tryJ. L lfl'tl~ m limu~r:l ~~ F~t i!U4rb. ~
~ ~ Ymt.. 20JJ. tJr D. P. ~l".kr a l l A.. r~ . JI~ ~ attJ ~ 'f'rt~~.rij'u ~ -
-~Jmd Dd.Jrcr, Y ti~ mliby D. B. m ~-, hfMr, PI~ S'yJli
~~I , ~IDOVSR..~ New l\ldi. ZfQl.

tlow
~ inevitably ~ll from~ g~ wilhln the fluid. ~~~~
~ yeJQI;ity. aDd ~~ ~tratiOll ~;raditnts ro~ exitt Vlithin tbe ~g ftw.d.
Tills rOO~ wiib Jtbe uniform roDdiliom 1hm Jftvail Dl equilibrium in dosed 8)' rem& 1br
distribution of conditions mdow systems .requires l.ba.t properies be dribul,e d m point lllAb~
of ftuid. Thus we assume thal iotcm~ I H'opeJties, sudJ as demity. spocifie ~. . specik
l:ifll':IOj)}\ ctk_, w u pmm ~ ~ :saJcl)1 by tli.e tempcq:ifi1.1Ct ~.. and romposi cinn ~
1he ,point.. uninfhleoeed by gradients aba1 may aJt.st :11. lbe point MomJ\~r. '\lie asmme. ibm dJe
Buid e~~thibiu dJg ~Kit ~f,inw.nl'ii~ ~iia. at abc point as tbougb.im ~ atoqvilibrium
dl Lbe santa tcm~ p_ressmt.. md C()ID.pM'il:iOD. 1'ht Pt.p1iilalkHl d rhM m1 equm~ (If . .It
appliC$: lGCaiJI.y and instantlnCOD&ly at any point m a flaidl ~tem. :.md that one may invoke a
~ept af IOCGI s.tatlt,. iodqJeodml of dJtC ~ of afuitibrium.. E.~ show tbal d:ris
leads for ptactica1 purposes (0 ~rs it\~ wilb obsetvarioc..
The eqoatio:m. of balimce far open sys.tems from Chaps. 2 ami S are :&1.UiliDal'iled be.re iD
TabJc 7.1 Cor rza.~ rt~!Xl. Included aJG Eqs. (1.1) and t,7.2), W&trictcd forms of lb J'llB.SS
l ........ - ~
......
~~~ ~ ~"'~
pft '.- tU:m
...,tw;_ we
__ _ dle. ba.Hi; f('r tt"- d................l . ......,ic an.ihih"'
~ _v-r .,t~ LJI!I;'IIIII!IIJq.yo-i!,J_
.f iD .t..: and
f@H!Uij' '.. ._ 0 pll~ClJ.JJU __
\,!l!l __
the~ lWO ehapre-A.. w~ ro~ witb lhennud)mntrC P~lfJ ~~ISr .lbey Bilow
eakulalion of proc:es 1r.ates m:td s~ states.
7.1 DUCT FLO\V OF OOMPAESSFBLE FLUIDS
Such p'dbklm as the miug ,o f pipas and the shapi.JJB of IJ.Q'Lif~ ~~ application of me
~ p~le af ltrid ~i~ 1 and rbe.refore do oot He within 1he pnn~oftber
modynamics. However. mDIIOdynamics. does provide equations tlm.1 inteJ:reJme me cban;ges
O!.~ng in pressme. velocity. tro ..-secticmaJ ~ emhalpy, mtropy.. and ~ \'Oiume of
B1 a-.. ..!D g ~
.LWWI . Vt'- .. 1 - hcrre
~('(10$'(~4: _ .L-. SdJababc
1!11111; _ __ ;
.--.1
OL~j'-Qatl:. . ..g_.__.. ..--I .a
DPe"'U!JJI11:1J5JWIAII. IIICJIW 01..t' aOQm-
pres!i_ble Huid in lhe absence of shaft wolk and of dJanges w porent.lall ene_rgy~ The pe.ninem
~namic tUatiQm, a.Je fi:r5t .,,~ ~ .u e 1001 applied to flow in pipes and no~.
Tbe approp iMe eoagy ~a.Trulre is ElJ- (2-32j. Wllb Q~ ~ IUlld A:. a.ll ~t eqnal m nm.
AuJ
AH --~ 0
2
dH = - udu (13)
1lw: a:1fltipu:' ty ~~eivll. leq. (2.27). i5 .also appieable- lkcau5eni is wns~m~~ n difkT~
enlilll form i..~
d (aAJ V) =0
{1.4)
Zsce W. L MtCabc:. l C.. Smith. :md P. li:u!riio!L fJftiJ ~ of CNn.i.t:d rfirP*ripC'. ~ I!!IL S~ 2.
Mcamw-Hill ~ ~ 2006: JL R.!Pm) and D. ~ JWry& ~ E~m ~" "hh &L Sa:;_ 6.
~JfiJJ. NC!W York. J99J.

,....,
J ~ ~ ? ~
~ e
DI -
t + 'li
d-
v.
~
Ot "''
Jr
j
~
6
=e ~ ,I_,
~ u
i
U}
rl <i
~J
l
i!lJ a: s; ~
irn c
+
8
e
~ ~ i
ri::

s -
[J
...<d:: 1 ('\1
w"'
(.D
"""' -~
!Ill
~
+ ~
<1
I
...
---
.::
~
<1
+
1!<11
~
-
w~
~
I

'a ] =+- ::::
~
_,.....,
a::IJ u, ..,.,..
.._.,.,
l'ill;
..____,
od
-
..,~
l:.ti
<j
"- ~ -
~
,.....
-
~
~
<:;ri
I
-
N
N c
~~
/t.J -
N
V'),
c:..o .:!1
~
5 ME:
~
.,:Q
0
I .....-...
~ afJ
'S
;
~
-....l'
W._
:s
-~
....a
0
<]
-
.
~~
-~

I
.....
........
4:
-=
n:
.. - ._..
t
_11: . ~ '
~ c.";
-
<;'II
~
e <J
0
Q
+ ...
:I"
d;:; .....
~
~
~
~
~ - -~
"'13
~

The fiuodamentlJ property relot.lon a~ m this application k
dH;; TdS', V dP
Jln addition, tJ:lte specific \>"'lu~ of the ltutfd may be colt$idtn:d il fuootiQn of its eouo,py Md
pmssme! V,.. (S. P )~ Then.
11\'~ e~t ds~(:~t <IP

Tms. J;Llllioo put into ~JJ~~R eom'mient fonn throufh tlbe malhntatical idEntity~
(av) ("") (ar)

as , = IJt as ~" p- .
Substituting fur the tav padiaJ derivativa oo the~ by Eqs. l.:Z) and (6.11) giVl!S:
( ~)
as
=~
cl' p
wlxP: , i the ..,-olurg; e'!tpamMt). Tbe: equation derived in ~Jsics, ror me speed of soand c
ill ~ fl_uid is.;
ell:% ~v~ (ap)1
av , s
or 1(av)
aP s
~ -~
~
Sohstitutmg for (be ~-o p.1f1ial dCTMitives in the equmioo b dV now yieJdS:
ilV f'T \1
- ]:::> --J s """ w.;;d p
\' Cp C""
~ (1..3).. f7.4), (6..8). UJd (7.5) tcbtt the~ diff~utial:5-dH, du .. dV, J~t. dS,
.and!d P . Wi~ bm foor eqnatioos. we ~t dS i!l!.lld d A '"irnd~.-DIIIenf, i!Dd dM-1op rqDMic;~~:~s
tbal: ~ me r:anaining difif~ as fiiDCtiom oftbcse two. fim~.Eqs. Q.J).md 16.8) ue
CODlbifiett.
T dS + V dP ~ ---utlu r(7.6)
Biminalling d V und d11 fmm Eq. t{1.4) b)~ Eqs. (1.5) and f1 .6) ~ upon rnmmgt'IIIClt:
(7:7)
wbeJe M is me M1acll rm..mber.. ddinedi M me mdo of me spetd .of me fiLtld in Illite dLICI.to lbc
w
spsed 50IJIJd in lhc lluid. ujc. EcpiaDoo (1.7) rel!atB.s JP to JS and dA.
l!'qulio.DS (1~6) and (7..-7) IN combined to elimin-ate V dP :
1(7.'8)

258
~ ~___tivo ~~at~ du. to d $ ~nd .d A. CQmpUJgd w.itb Eq. (7.3) it R"tlle5 d H 'to d S and 4A.
ond ~m;:d wilb (7_4)il~dV tb~~ei~ ~~-
'lbe differ:enlinli in the prreceding eqn.31ions ~sem re~ in me fluid! as n mi\"e::'8e'S
n ~ kogtb of il$ p;!l1h. 1J(dm ~ i,.~ h., d1m ~of tbe ~of Jl~~ amy be
divided thmogb by dx.. Bq:~oos (1.1) amd lJ .8) lih9 become~
1
2 dP fJri
(
Vf l - l\f-1--- + T l + -
) dS
-- ~- =0
.,1- dA
dx Cp d.r A dx
fJtl ~
du _ C_, - = t1S ( t ) fl.l d t1 _
"dx T ~- - tb: + l - ?rP A d:r ....
0 0 .10)
AoeardJng to abe second ~:rw. the ~"biJities doe 10 Huid frictioo in adiabatit; now l~
an C!lllrOpy ~ in 'die fluid in the diRUiGD of flow. m~ limi1 as ltlte Dow ~
~~ilily. ~~lis iDrn=ase ap~ m-m In ~saL ~
dS:::. O
d.J; -
Pipe Flow
For the c;ase. of ~~-sute wbal:ic ft of eompressibl~ fluids Ln a bmimma1 pfpe .C)f ron-
Nnt ~nal ~. d A /~ = O.llld Eqs. t/.9) and n. tO) ~ to:
For till.bsonic lilow. J\tl < 1~ all terms ~oo ibe riptt sidles of these rqwnkllh are tbcn po.url'\-e,
nod
!!.<o
dx
nnd !!!>o
.tLT
'Ibm lfhe pressure~ :md me \'dOdty lncreilses iD the direa.ioo ur ftpt~ }I~ d'll
velocity amJKJl ~C mddinilety. If the \''Cl.ocity 'i\'\Ue lO eK~ cDe :woic ml~ lben me
~ ~tlllliU~ \ti.vold JC\~. Sudi "tf<lfisiti0n is ~ ~le m .a pi~ of oo tanl ~,.
~tmal area. For suhson:ic flow. me J:D!OOmum Doid Rloeiry obtainable in a pipe of C01lS.tt1.M
cros5 scctioo is: the speed o'f wund.. wad lhi:i wlvo is maehcd aallbc ait cf the pipe. Al this point
JS/ tb. ~ iJs Umi~ va.tuc of um. Gitieo Iii ~e pr:tssorc:: l\f'N moup for dl flow
1
m bf:amJe wuic. ko~~ tm pipe docs l1!0t atter dlis re._~r; me mtW me of flow <lecrease:s.
SO dJat tbe. SOilfl! velocil)1is ldJ obmi:tred M dJe oufla of 1be lengthctltd pipe.
lbe eqwnions for pipe ftDw J.odicar~ 'd ial when Ocl\t is supel'SIOoic me pressure ~
Wild lhe ~ty dec~ in tbe d~~oo of tiJ.W, Howe'"Cf ~h a ftow ~p:gc B u~k\
and wbeo a !illpersonie 8tteam emm. a pipe of' oomtml ~ lliCaloo.. a am~~nn shcxt
oams. 'the rcsuJt of wme'b is,ao abrupt andJ finite inc::mtse in preswre and decreau in '\-e.locilly
to a Ubsenic _ue.
Example 7.1
consider the st&ady-slate, aclabatie, irrever,d)&e flOw: Oti an inr:ornprt#SSible Uquld b1 a
hof\Kzofltal ~of consumt croswectional area. Show 1hat
(a) The velocftv is constant.
(b) 1be tempemture tnoreases in tne olf'Eidion of'ft(JW.

(c) The pressure ~ im the dheclion of ftow.
Sohn10fl 7..1
{a) 1bc Cl:ltltrOl \-mlumc ~:iii 1i_mpl) a. finit~: lkq,th of horizootll pipe, with
entm~K7e l!fid ciit ~ i&!ntilied .as I and ~ lBy tbe: wmim:rity ~
:Eq. (2.27>~
-Oiiiiiiiiii.-
,ri:!A2 u1A1
Vi - tJt
HCN.-e"'Cl'. Jb ~ Am lWD5Umt cmss..sectiooal an:a) and V1 ... v, (inoompressible
:lilufd}. li'ellce.,. .u2 ~ illl.
=
(b) The ~ub'Qpy bdaDCC cfEq. l~i.23) helle becomes. s1mp~ So Sl - St. For an
rfncn~l- liqp;id with ~qptclty C (5 ~ 6.2 pp. 203-204)~
rz dT
SG: ~-Sm = /, C-
_T, 1
B:tn Sa 1! pctslli~ (flow is, Un;\>rrtili!c) ad b!mt:t:.. (Jy tk: lut eqwlion... 1"'! :> T~.
and~~'~ in Jhe ~dimction of low.
(c) As shown in (a ), 111 = u1 . and lherdorc lbe cragy baila:nce, Sq. (1.32), mdUces
fur the s:taml conditions to ll~ - H1 !!!!!! 0. Combinin& tbitt wdh lb: in~ep:cd form.
QfiSq. (A oflk 6.2 applied w ao inwmpteWble liquid yielfi:
As 5bDwn .iD {&)~ Tz > Tt:. lilu8 by the. f_asr ~ PJ < P 1. aJld ~
~ io lhii! direction offtoa~
Repeating drls ~txample fot lht case of rrt."errible ~~e IO~J~~W : instn~ctj~
lDJ dJii case ,11'% .., 11 1 as befon:.. btl1 Sc; = R 'The emropy balmre dEll ~ 6111
1i ~ T1" in wbidh case diet eamgy balaJlce yields 1'}, ... P1 Wf: ~tude ~hal d~
tempemnre ~ of (b) and me prts$U~ de.cteas-t: of (d orig~ from 8ow
m\i'~!bilities- specilicaDyfmmtbe ~lllti~~.d widl Raid friction,

~ limitatious ror flow of m~~ ~Bids in pipes do oot e3mnrl U> pmpcrly
~n-ed
~ped nozzles. whim lYing abo-ut lb: intert!hanp of internal ,and tmetic energy of iWd
as the fCSUbl of a dlan~ oro.ss-ktiom1J area a\18[_1ablc1h Rom~~ 1b: r:dudwJ bet~<een nodle
~ rum ~sectitJDal area lK DOl ~('lll'ble ID lhelmodynu* ofiii3JSs.is. bu1 h a pmble9D
in lfhrld medianics. 1o a pmpetJy de:signed n~ the am~ cbanges wilb length in SLJdl, a w.&y
ttt .make the :Oow oearty fricticolcs:&. In lhe Jkn___jt ofm~le fto.w, tke Tt.to of clltJ'Opy increase
ap~ ~.and dSJdx .. o. 1D dtis ~t&p. (1.9) and fi.IOt becomr.~
~ ~~ .,f Oow dq'Mmd uo w~ the: Dow ics ~ I < ~) Oli WflC' tn.iQ
tl > l). The various eases ;ue IID:liiJI3ri_zcd in Table '72..
Su'bstltlic: M 1

~vging Dh-nging Con\~I D.h:axftag
(JA
~
dx
- + -- +
.dP
-tiJ: - + + .......
do
-dx + - - +
~ for ;ubsooic tlov.r iD t:t amve-rgia:g ~ lbi:. wcloci"tY

and the ~iDe~
do; ~~ ~~ ~d~, ThemMit~mm ~~ ~hJ.id 1r-duclty ~ ck
:!lfBd of sou~ rerrcbet1a fbi: extL Bemuse of Ibk. a com~g subsonic i'lQQJe e-m be used
ro de,tim-" a COMtant fiowmte into a nagioo of ~e ~ Suppose a com~bfe flu~id
"'tus ~ QlQ\~-8 ~.fe ~ ~ PJ snd disd~Jut~ from the Dm%1~ mro a. e~ of
wrillble preiSUft! J'l. Ibis disc~ ~ de:crea5es below Pt. tbe fiowTate and wloeity
~. Ul mcJ)r, ~ ~ ratio P!l P1 ~ ij Cfil:L(::d l'UICJe ~ v.itid:t.lbr. \.t"J~iry ~
1ibe nonle em.~ SCJnic. IFurtber Rdoolion in .f'.! bas oo ,effect on me eomfui~ mthe oozzle.
The flov. fCIII:Iiwi co~DtUDt. :md the velocity at d:Jc ~ ~L i5 snt.rlc, ~ardlcss of the value
of PJ./ l-'1, pt(nthled iJ i8 iii-ways ~ 1fum lh= IX:irtnd 'Wllbe. RJt .smun_ lhie crllieal \'fiJal:e tJf tlilii
ratio alxJut O.S.S at modlemt.e lemper~ ;md ~-
Supcrsaaie ~ru me mtdJ.Iy _jtblioed iD the di~g scmon Gf ;I properly desi~
G<~~D~_gltfrt~,@ mmlJ:! (fig. 7.1)- Wilb -ookc ..--eJocity ~bed ut dJ:c: lhmat, a f l1i1hct
illceas.e m vefocDy and ~ in~ ~es Ill increase m, ~~ area. a
dh~g ~iw to ~ounodldB in~ing "o1WIJC of dow. The tr.m:Pcion Ql.'Cws. l,l1 the
'lhmat. ~-ben: dA / dx 0. 1'be relliiiuMhip& benwe:il velocity. :Jrell.. mul pressme in ill .coo.-verg
ingl~g nou.le ~nt ill~ m1mamdly in&. 7.2.

261
Jltuft7~!
COIO\~~g
~
The speed of ~wtd ii ~ atlbe tlttuat of CWJ"~g/dh~ mot.zlc Only wbeo

the pmssure 31 the lhroat is. lowMOUgb that tbe cri.timl Wllueof P,.f Pt ~ ~ lf ~
~ ~ i$ .wailallL! in h nozzle for lbe wlooity lD ~ ~. lbe diverging section
of fbe I'IDZZI~: ,n"tS n ffrffnset~ Th$1 is. aftct dut thmtl i~ rtac~ m~ p_~~ rises and the
mocuy rs
decreases: lhis the conventional bebavillr for subsonic How in di\~g st'CiiOo!i.
The RIDlon of ~~J-ei'odty to press:u.re in :an isentMpic M?-Zle can be sprrssed a.naJyti~By
rf lbe D\lid bdl:a\ a" an idcaJ ~ v.,"itlJ eonstmt heat mpacities. CombiDalioo of Eqs. (6.8)
and (1.l) for isam'oplc flow gh~:
udu = . . .\fdP
IIi; - ui = - 2 ~~ \1 d p = 2 l't Va
.. }Pa y .... l
[t -t(!1.)(;y-..l)f7]
P1
~ tba 6na1 tenD ffi obtaiDet:l upon d.imi.Datico o! V b.y .Eq. (3.3~). P V r _, cou.
Equa~ioo ('7.] 1) may be sd~d f'w die ~ mio I'll Pa f<B" whim ill! rea.dte5. me
speed of :SOUDd te..~ where
(7. 1'2)

Example 7 ..2
A hig~~Jodty ~ is. designed l:o 'OPerate witl1 steam at 700 kPa and 30tlr C. At
the m22le fe1: lhe \leJocity is 30 rm s~ I , rCmeulaie val'ues ol the ratio A/ A (where A f
I&the~ aJM of 1tle ~me imet} tor tne seet~oo$ \Vhere tna pr$8$u-:re is
600, 500. 400~ 300~ and 200 kPa. .Assume 1hat dle nome operates isentropicaDy_
Solution 7.2
11l!e nqllired area tatlos are given by Eq~ (2.27}. omd die velocity u is foand from
lM inle:graled bm rOfi l!q. (7.J);
locit)r onirs ef m ~ a ~ Jii bas the uniu.

Fnr or
&- l. Units of J kg-t fm H n:re
~ _ .uh~.J~se I J ~ 1 kgDY "" .. w~ l J t,g- ~ J m: -l.
2
lniUa.'l ,.~fur ettJnJP:)~ Cllm:filp:~.. uDIJ ~c \J'Oiwne from me m:.am. mbt~:
s, - "1'.2'R1 kJ lg- bk - 1 Hs :;;;; ,0591. x 1ol .J kg- 1 ~~~ :;;;; l7L39 em~ g- 1
A 30 ) V
(
A* = 311.39 . -;;
t.f 2 =900- 2{/f - ],059.8 x lCl)
Be..,
"apse t'hl= ~on is iscmttnpiclt s - s~: stca:m-tnble 'II'Ult.leS ~ 600 lkPa arc:
S == 7.2997 kJ t,g- 1 K-~ H.:=! l ..Ol0.4 x lfrl J ~q;- Y :=! 4 l8.2S em) g:-[
F10m ~. (B}.
B)f Bq.(A). ~ ~ ( 30 ) ( 4UI.25) ~C. llO

Al .311.39 282~ l
Area ntic;~s for other ~~ ~ evalwkd di ~ WR): and the T~ ~

sum~ in lbe klllo.~ing rablt.
PltPa Vlcm~ g- 1 tdm - I A/ .lt.1 pJkPa v1cnr g- ' uJm s- 1

1\J."\ t
700 3"7 1 ~3~ 30 1.0 400 511..23 523.0 0.018

600 418.25 282..3 OJ'20 300 7H.93 633.0 0.09!
soo 48 L..2b 41 1.2 0.095 200 910.04 752-.2 0.104
1be pte$SU1e ut tht thraat of ~k nome i about 3.80 kPn.. At l<M'et pm.$UteSi
the BM'ile cle:arl) d.ivefges.
~ wil ~ (O'M W..1~ II (Sra~)- l tilii\11 be mti~ t~y 173.]61 fl ~ lf8 }- 1 llliltl. l'l)llhl!: ~~
0011~ ~ == )2.1 "xtbr)- [b)--

Example1.3
Conste~er again the noz.de of e,c_12, as&~g IOOW that steam behaves as an ideaJI
gas. caJculale:
(a) Die crmcaJ pressure nuio and lhe velocfty atihe rJuoal.
(b) The di5Ctrarge pressure lor a Mach number af2.G at 1he noate ~
Solllllon 7 ..3
(a)' The i"idkl o.f $pific hem f m:am is ilbout LJ. Subslilnting mF'..c:t (7. 12)1
!:J._ (
Pi --
2
l .3 + l
)t31 1.:3-l) -
-
.-
o.ss
The velocity m the l!bro.U. equal (O dJe ~ of wun_d, is round &om Bq. (7. 11 )
.,..iDcfi conWn$ tim (lllJduct ,-, V1 , ~ s tgm. u an ideal ~=
RT,
fi u I(8JI4)(513.1S) "i~ C:l' J" 1 -"''
= ----. =
.r I " ~ = .-v-r.,..; m- .s "
M I8JUS
l1n tiiii equaoo Rl M bas the unib;
J Nm k.gms- 1 m
[QK = kgK = kgK
Thus RTfM, tmd~ PaV~~ is. tin nt2 - 2 , ~un:ilsdwloritysqu3fed.. Subsb-
tutiou mEq. n.11) gL'ves:
ll2- . ;:::;: (30'~ + (2)( I .J,Hl64~ [ L) [1 - (0.55)(f.J.. I)/I~] t= 296._32.1
~~L 'l l.J ._ 1 .
u~ - 544.33 m .... 1
..
This fe5Ullts mgood~ wffb the v-itlne i,ll)l~ in 81. 1.1.. ben.-ns ~~
31.1bc'sc eomliliw: d!o5eiy appnJximates .; m ideal gas.
{b) Far a Mad! nnm.beror2.D (~on lb:e v.~ty of soumlai dJt: nauJc lluual)
~ ~ wlocity is;
2u!bN1 c (~)f544.33) ~ L.OS&.7 m ~-I
Sn~ of~ lit'~ in E.q, (1. 11 ) nJ~ C~~Jculi:IWP Gfdle ~ mtiliJ:
n OB87l:z - oo~z = <ZH1.3~C264.51 t>[~ - ~(~)~,.)- )JJ~]

' . LJ - ~ Pi .

Thmtfllng Prol4
'Wbcn a tbdd ftO'NS Uuougb "'~etiJJIJ, such aD orilio;:. a p:udy closed wllRw or a porous
Pin& wflh:om .my i\~le ehan~ i:n klloetic or~ ~. dJt- pi:Jnwy ~~ tlf lhe
~ a Jl!RS.-~ drop in the ftuid. Such a drm111ing pmceu. prodw:es oo shaft Wllf'k.. ODd
in lh~ a~Jsci::ft of t.r~ tlima.s.rer,. iq. (232) redUl"U 10
'The proceg lbe~ occu_r5 at~ enthalpy.

lBet'allse ~ entba'I.P:Y of ani~ gas~ on t~R ooly't a dirdtliug ~
dac=s DO( dmnge 1M ~ of an ideal pss For mo:il mal gases ut.mocltrate ~ns
of~ and~.. a mlliCtkm in premm: at Cllmlalit eolhllPJ results in 3 ~nme
in fl:em.pet'ldUre.. FOr example, if ~m ut J,0 00 k'P.a and l(llf.PC is lhrowcd en U)l -325 Wa
(~~~).
.na s. :1 lJl52"'I u t8-
b1tqpoliuion in tlte ~ qblss IQ ths ~PY ud at a prcswre gf ~01 .325 kP\t iodicllles a
downmeam ~ of2SI..8WC. The temper-at~ 1m!t ~bid tbs df~ is small
Throttling of wei steam to sulicleml} low- ~ im)' c:mLiie the: l~d lD cvapom~e
nndl ~the" p to~ ~pc~ T.bus if "!fl!'.l 5limD at 1,000 kPa (t ;;;; 179. 0 w1tb a
qoality ot 0.916 is lllmaidM 1.0 ~01.325 t.Pa.,
Hz .. H J _. '(OJJ4}t7&2_6) + (0~96)(2.116..2) c=: 2.._695.7 kJ kg- t
ru 101.325 TePa~ with this.an:hatpy bois a ~rn of 109

C: .it iK lheref~ ~
~ (1 9
-= I C). 'The ~~ ~re drop bae ~uhs from evapormoo of
liquid.
If a n1mtal liquid ~ llhroWed to a ~0\\w JmlSS~ some of the liCJOidl ~ or
~. ~;ng; ~ ~of~ ijqllid and~ ~a\ tho lww ~
'11ms. if sa.turmd .liquid wata- ar [ ~aoo kPa (tw ::1 ~ 7~.8 C) is fta&bed 1.0 10 I .J-25 kPn (l~ =
t0CPC1
Hz = Ht = 762.6 kJ q-~
At ~Ol.J2S kPa ~ qu:dity of'dlc rcsultiDJ steam a!S {OII.Dd from iEq. (6.1Jat Q.'!im AI c- H :
762-6 =o -J:J (4l9.n + x (~616.0D
c:: 419.1. + :r(2~,fi76_0 - 4~9... l)
X -0. 152
Thm 15.2i:. of lhe m18Jina.l liqt.Od ~R'S in tlE ~- t\;ain.. ~ ~ra~ r.Wp me
resuks from ewporanon of liquid 'llunming ~ find fie~ applirolioo in ~m
tiOQ(Chap.9).
"'be lfoJ1owlog e:xmnple Illmttmtes use o f ~ito!l ~~ions in cal~latiom (Qf a
diJottling process.

example7.4
P,ropane gas at 20 bar and 400 K is lt!lronled in a ~state flllw process to 11 bat..
Estimate the fma11empetld11Ire ot the propaJle' and its entrq:JJ change. P-l'qJef'ties ot
propane can be round htm sulmble genemlized ooff&latiollS-
SOlution 7~4
Apply Eq. (6.93) ro Ibis amstattt...Dlhalpy PJIOCes&:
AH == (C),8 )11 (1l - 11 ) +f . . . nr =tO
If ptOpm~ in it5 fin state a1 ~ b:u- i a.uu:med mbe an ideal~ tben Hf -.. 0. and
me~ eq1lillion. soi1ed fcx T2~ hoc~
nR
T2!: _l + T1 (A)
{C~B}H
For p-Optlnt.. T,. = 369..1 K Pc :;;; 42.48 bar w =0.152
1bm fur the irnitial ~
400 20
r~'~ :: 0.471
;:::
369 8
~ c:::: ~.og2 pil'a
-.
~ -
42..48 -
A11bc$e QODd[tiQ~ 'l bt gtnetali,mi ~tllldatioo based ou steODd ~irial ~
is ~TY IFig.. 3.14). and calwlmon ,o f u,~t by ~ (6.87). (].65). (6.891
(1.66)1 and (6.90) is flitp~ted by 1(S,. 6.?):
HR
R~
47 HRB1 .082.0.471.0.152);;;; ~0.452
:;;;
Whence~ H 1R =(8.3~4)(369.&)(-0.452} ~ - 1.3901 mol- 1
The onl) mrnaimng qttlfitit~ In Fq. ( A) 10 be~~ 1 {C!1 )H. 'O .Ilx
~from Ta1Jie C. I provkle lhe bea1--c~y eq~
cj
; ;;;;; i.213 + 28~71S X l0- 3 T- 8.824 x 10~1
For nll ini.W ~CltlJ!ltiOD. -~~dtal (C~8 )11 PP dw v-alue of C~1 al the. iJma1
temperature of400 L i.~. {Cj.6 )H e~ 94JJ7 J mor- 1 K- ~.
eteari), UJc. tc~~dw:Jp: sma11 .cl (C ~1 } 8 is RevalUated (Om aeellent

approxim;aion M C~' at the ~C- mean ~pt"~-,
TAm ,;;;.: 400 ~'3&5.2. = 392.6 K

266
Titldi !lives~ (C~.r )H = '12.13 .J mor 1 K ~

andl ~mtlalion of~ by Eq. ,\) ~ields lbe final \1~00: Tl = 5.0 K.
The entrop)l cbang of tM p~ i gi\1!!0 by Eq. {t.~94)~ t1rhich heflie beoo~
T2 Pl R
S == {Cp )r lD T;' - RID Pt - S n
j
B~tU ttu; ~rntwv cb:ao,p 1s !\Q Sl!IPJI. rt o llD a<:~UeiU .approtintatrM1.
(C~'~- r: {C~')u a 92.73 Jsool- 1 K- 1

C~lot.lbti(ln uf Sf b}l Eq&. ~(;.SS) doough (ti.90) i 1epresenu:d b_ ~
R
f =:l. SRB(il.082,0.411.G.1!S2) .., -0.:!934
\Vbl.mce. sr ~ (8.3,4)(-0.2934) = -2. 4l9J mor 1 ({- [

:md A ~ 92 731n JR,.O l
400 - &.J J.Un 2() + 2.4)9c: 2380J roo] J K- i
The rns1tiw \-;:d,ue ~ 1be irrc~Jfy trf tbn."Jniln.~ pnx:~.
Example~ 7.5
Throttling a reaJ gas from coodftions of moderate temP&att.Ire and pressure usually.
nt$0lls ma temperature decrease. Under what comdttioil'\S woufd an Increase m\em
perature be expected?
Solution 7..S
The ~gn oF the ~ cb:m~ is dtue111lined b~ th ign of me c.kril . rve
HiT / i1 Phi, ~kd l:'b,c J()U1dnrmJuon ctNJ]icicra JJ :
~~= ' ~T)

(-ap - ,
\Vbeu p - ~~ CllmttUng rt."SI.llh.s in a lrullpttalure ~: ben n:egatj~ rn
3~ ~.tilm~ '
BncruJSe 11 !02 f t T. P'J. me o1llm..iag ~ Nbta lht- Joul~1h0n
l'(k-JiEK:tem 10 otbeif th~modynamic propati
(PtlT). ,fl c -
(8T)
H
(8,.pH) r
P = -
(aH) -'(9
if P
11)
iP 7

261
Fipn 7 ..2: l!wasiu!Ji ~~ fti

~~ ... De
~~a kiL~ ofpoims 'fu,
M1Jdi 11. = 0. &1.lid. ~is
from ;t dfim ~: disbed
~~-, from 1M RNiidJ:IKwt.q:
~OD. A~~
rr:5lllca from lbrottljng ~m
~- \\bcfe 1i is DC~
8
P,.
Bee2Qlsc Cp i$ ~sadly ~-e. the sip of u, i8 dclamined lby lbe si~ of

(o HI ilP)r ~ Him mII..Lfll it' ~red to P VT lbdl_vior.
aP r = v . . . r(!!)
( ~) ;,r , (6. 19)
Beenme. V ~ ZRT/ P_this ~OPJ m~y be wriuoo more coocl~y as
r(iiP'
~)T = - ~
P
(~)
aT p
wbere Z is lhe ~'bl1ity fator. Substnution iiiiD Eq. {A l gh:'es:
ttr:
p. = ~ [
!
c,P ar
(az) ~
~"
~1 (iZ{8T), a:ru1 11 have- 1d)e same sign_ 'When (a2 /8T)r is~ as for an
ir.kd ~ tbe:o 1J. ;; 0. and oo (anpel"illllre cbmge i~~Xtrmp~ ~-
Th 1)1]~ (3Z/8T), = 0 m 1)1 obtain LocaUy for rtal gases_ ;Sue.h points.
,. t - , t ; _ the J~ i .
~
.. .
pP.'eJI'Jllill't ~ UM01U -r--
-.~-...:....t.. ~Tw!tfte. 111..--
1J from dmt uf ocgalin p. Figu:e 7.2 &bows "ilucr4 ifi\'CI'Slom cunu givin,g lhc
. -~ .
UJ!I; ~ Ul pl1SI
"ti\."'C
.
=
relidioo bft\\r~D T,. and P,. for a."b.icll U 0- The ~tid Line correlaies dalil fot' Ar.
'Ci-L:. N,:. CO. C~lL:~ C)lls. C02, al'lid NH1-~ The dasb.ed Utr ' ~frOm
!be condi~ (81Z/of,)p, = O~ed to the Red11ch1Kwoo~ equation of State.

268
7..2 "JiURBINES ~(EXPANDERS)
1be ~of a ,p in a oonr&- m prochla: ~\~icy SVco~D il ,:JJ ~~bat COO\'l':ltl

immW energy iirto tinetic ~'l wb.icb in tum bi rom'ated into i1lttft work wben lbc. stream
impiD (Jt) blade$ ~ nacbcd iO B rot:atin& aft 11J.ma, a futbiQr (Oir~) ~Of a]_
tent~ ~ of I'IOZl!fe.s and mtarlJJg hJades lbmup a.'blm wpor or gas Hows in n suad~..s;mte
ap;msi.on P~'- 1kowaub ~Jt lis lbc ~11 of the in:tem~ ~rgym a bigh-pNSsun:.
5trcam into shaft wcr '\Vben _am provid tbc motive fCXDe ma powu plant. tiDe device
is ~ a tut'bl.lte: wl1nl il is a higlt-p~. gas. :5Uth ailillllOttia etb)rlene in a c~cill
or~ pla~IL the de-vice is called. ;m C~Kp3Dde:r. The~ is mown itn fig.. 7.,-] .
I
I
I
1
..
lllpN 7.3: s..ear.J} JJow 'l.hmu,p ii.
o,ut~lJm 011'~
fE4uatitlll$
:md (1..32J m- appropriate ~ mlattom.- H~w~ lhe pormtilll-
(2~11)
~tam ,can be emitted. because there .is llide dlmge in elevmron. MoreDA-a:. in any
prupcdy designed ~ lbml tmlSfu ocgll,J"bk nd lhe inkt :md exit pipe'S are sized ro
~ fln_ld "~~fbc& ttJ~~.tgbly equaL f.qwi:fion& (2.31}I and (232) 1haefore reilm.-e m~
Usually, the i.olet amditiorrs Tt and P~ and the diKdtarge ~ P: n~e hed. Th1.&8 in
&q. n .l4) oo_jy H1 ~ bJow;o;. boO) ~~~ md IV. ;:ge uokoown. aDd dx me:rgy ~~Ption aJgoe
~ aot allow ~, ~ul~oo. Howe\"t"r~ ilf me OUid in U. ~ ex:p:mds ~e~b(v tmtJ
ttdi.tlbtHktllljrlhe process i Ssenll\lpi~ ;md SJ !::1 s\. This ~ reqWIJion fixa.lbe inal Slmt'
arlhe ftuid ~and~ 111.- For this ~;d ~WI i5 Jiwn b-y Eq. Ctl-1). writlal:
W~ f~ll1topic) = (AH}s (1JS,)
~ matt wort IW,K~) the: llltiXI.#IlHilllhtll am be o~ from 3n adiabatic
tutbine vriti 1ivtn inlet ~:oo ; d gi~ arsdtaq:e ~. At~tual turbines prod~ lb
\Wil'k, ~die~] expansion pma::ss is ~le.:. -~ detioe a rul'lliM glftclem.~ ~=
w,
l} """' W (isemmpic)
where W is lheaaool Wft "wk. By Eqs. (1.14., 3lld! {1J5)1,.
AH
"== l6H)s l1-t6~
uoras proteg1das por direitos de autc
269
Values of 11 uudly range from 0.7 to, 0.8. 1lJe HS ~of Pig~ i.4 sbow's all~
~in a biJ'bme and am~ apMI!ion f.nr ~ ~ i:nm.te ~~ and lhe tWne
disdtup ~ 'The ra'el'!ibk tpmb is abe dashed 'VelticaJ (cm:SCIIII-eJ!III'Uf')") line from
poim I :ill in~ ~ P1 lo point ~ at~ pi'e$$DI'Itl 1'2- ~ dd line. shtJ.win~lbe
Klmt1 ~mble p;niL sum at point [ and (e!rminaJi poim l em the i o1:tat tor P}.. BCQL~
the process adiabalic. ine-wem"'bilities. cause m incnme mm1mpy of~ ftuicL and me p!Ub
is ~ lOw.ald :iDcrea.._~g mJropy~ 'The more O:rel'm'iible lhe pmees~ me furtt~er point 2
lies w die ngbl oo die pZ ~-Wid~ lowtr the ~ey 11 Qfdlc ~
B
ri&Ub 7..4; Adi:alxdic ~~~ ~
irl.a~or ~~.
Example 7.8
A steam turbine With 1rated capac1ty oti56,400 II<W (56.400 lkJ s-) cpera~BS With steatn
1
a1 rntel conditions of ~600 kPa atKJ 50frC; and discl\afgeS into a condetlser at a
r;Kessure o11 o kPa. Assuming a tulihlne efrw:iency of o.75, delermifie lh& state or U'IB
steam
- . ......
Cl!4 (lscha - 8l'L
- -- - 1'98' - d ..,..,_ . ra.e
~rlll:!l fnass ~ 0 if A - u 0 f .._
FNY'II --
ume S'i~JIIII.
Soludon7.8
At d.x inta ewditiom. of ~600~ kPa and 500!7C (be~ tables pn.wide:
lf'lhe ~1cn ro 10 kf'a is~ men. = s; s. ~ ~6.6858. Steam v.-ilh llOO

CIJ.l)Uj)) iii 10 kPa ~ ~ and Eq. (6.82.b). wiih M :a S and x c: xj- y~e~:
Si = ~ +xiCSl' -~)
~ =0.8047

'Ibis is tbc quality (&action vapcrotlbc ~ 5lream a1 point ~. 1be ellU:Ialpy
H; . ar gt\'ett by eq. (6..82bl wrinm:
Hl = lfi +4Vlj - Hi}

~ II~~ 19L&+ ~~.8041)fl.SM~ - 191.8) = 11T1.4 kl tg- 1
(AH} ra: Hi - R1 = :!.117.4 ~J.391.fi-- -1.214.2 kJ q-1
lmd by "Eq. (7. Hi}_,
Jl.ll ::: r)t lli.ll).s !!!!!!! (0.7Sl(- 1.274.2)!:: -9SS~6 tl 't 1 -
~ Jh ~ H1 611- J,391.6- 955.6 ~ 2,436.0 tJ ~~-
lr;z -0.9378
~ ~ c o~M93 + (0.9'l7S)(S.l5 J I - '0.6493) ~ 7.6146 kJ q--1 K_-L
1'bh val~ may be com__pued wbb die mitial YB!uc-of s. =::: 6.615 .
~ !iteanuatem isgivenbyF.q. (1~13). :Far-a orkr..tt~of56,.400kl' -l! ..
~v., ; ; -S-6.400 ;;;; m(2.436.0 ~ 3..391.6) ~ ;;;; S9.02 t, ~ - '
E:J-k 7.6 i:i ~h'SCJ widJ dam from b Slaml ~bits.

\\'ben I ~pm'Ub'ie ~d of i!ablcs
b om nvaltabl~ f dlt ~wtiDg it~. ~ ~~ ~ of Sec. 6.1 may be used U.
eonjunetion wilb.Eq (6~.93) md (6.94). ~ llltl.lSU'ated 1n lbe folh~wing cumpte..
Example]7.7
A :sveam of ethylef\e gas a1 300 C and 45 bar Is expanded ad'taba1ica))y in a Wrblne
to 2 bar. Caladate the isen1ropie 'WOllk produatd. FJnd fhs proper1ies of ethyfene by:
(~) E(tuatb't$ b an ideal gas. (b) Appropriate generalbs(l oorrerat1on&
Solution 7.7
(6.9))

211
( tr}l mf em,leoe ~ ~ an ideal gas. mea ~ll residual PfOI'CIIJCS we zero. a.od
lhe pecoeding eqmdions reduce to;
(A )
EquaOoo (S.17) povides m a.~ ion for ~c~ >slR. ~mdl tor ~
firma! pc.t~ i$ ~by~
(C !Js "' MCPS(513.1 5,T2;1 .424,t4.394E-3,4.392E.a.M)
whsc the ccDSWJts for eUL)'lfeoe rome from Table C. 1. Tc:llii:PJAt~ T2. ~ fwnd,
by i~fad(lfl_ J\S$Ume an in~ value for ~11l)umiun (If (C~ >sfR. Hqualion (.A}
1
Ibm proviOO a De'\\f wroe of Tl from wruob to :reroompure (C~'>stR. and the
prcndare ~am~ 10 ccm~ ao tb~ 1Wal wJue: T2 ;::;;: 370'. 8 K. The ~'~
of (C~.! ~n /R. g.\re;n by fiq. f4.8). h for oompotatiooal purposes ~~ted by~
{C'")
' ; II = MCPf-1(513~ 15,.370.8; ~ A24.114..394e4.-4~~39-2E-6,M) = 7. 22~
'Tbetl W.s(~c ; (.a Hb : ~C~1 )H(T1 ..... T1
Wi.(isemmpic) ... (i..2214)(8.l l4. (170.1....- ffi.IS) ..- -12,JS3J mot- 1
(6) For e:Ebylene..

T. =2~1.31K P~ = SOAbar
AI rile; initiul stale.
r,.. = ':~ = 2J)l0
~ tu Fig. J.J~ lb! get~a"llfi2.ed ~ens~ on 'second wwcoeffi-

cients Y:toot1d be satisfaaory. The complltllimtall l.X'O'lX~ of~ f6.1i)t., ('6.88).
().65), (3 .66)~ (6.89) and (6.90) am ~Dtc."d by;
HR
R~~ ~ HR9(2.030,0.893..0.081) -= .....(1.2'34
1

27l
tsR .::J s~~2..000.o.m.~o~087) = -1.097

Hr = c-o.~"'t4t( J~J)(282..3): -S49 J mol- 1
sr ;;; (-0.097)(8.314,} = - O.:BCJ6J md.l~~ K-A- 1
For dO. Witlnl esfinlal~ of sf.

m pm (a)~. Tb:n,.
2
P, := -
SC
)_4
=O.twl
and Sf = (-o.OJ39H8.314);;;;;; -O~ l16J moJ- l K-

U ibll: ~on procesl i:s lsmlfOPk l?.q. ~(6.94) becomes:
~ n . 2 . _
0 = (C p >sin S1l.lS - 8.314 ln (5 - 0. H6 + 0.806
l''j'J - 26S16
!In .. = .
~7J.t~ ~c~')s
1~ ;;;;;; 365.8 k 1'1 = 1.196

With~ aloe ,of Tr: lUid w1th P~ t=f 0.040..
-~ SA13(1 a298,0.o40~tl087) Cl -0.0144

R
~ S:;; (-l)J)144)(8.ll4) ;:; -lltJOJ moJ- 1 K- 1
This msull n :SO Lllfle e~d WmidJe ilmiaJ e.sOmate (bat nodla'~lllmion ~of
T2 ~uno~. ~d H;:.ll i$ ~~ SJ die~ tundiiiom it* cS~bli.~td~
11
R~" ;;;;; HRB{11.29SJOJJ40,0.087) .... .....0.0262
H2R =(-6.0'>..m.)(8.3L4)(182.3) ~ -61 J mol- 1

8) E4 t6.93),. (CJ.H)$ = tC~-'}H1(36S.8 - :S73.1S} - 6L + 549,

273
E\~WI'fioo of (C~ )H mp:ut (a) wilb 1'1 c 365.8 K sh-es:

{CJ~')11 c: 59.843 J mol-l K_- t
t.AH)s :~ - 1V)20J moi - J

\1/~ti..il\enll\'Jpicl = (AfHs- = ---II ;9201J mol- 1
3 COIIPRESSIONI PROCESSES
7M
J\181 as expansion p~ ~<Ult in pressure redtlldioos in a tltJ~ing 'ftuid. so coiD~(XI

~ bring .about pres-sure i.nm:-ases. Com~ ~P-' ~ bl~~. _nd va~
pqmps 3re aJJ de:ric~ 4ksi~ ror
~u JlllJpl).'ie- l'br:y Me viw for rtbe I~ of Ou.ids. for
ftliiHmtitm ot pallielll'alc ~ for llrifiging H~ ro lbe proper pres:swe fo:r r:eactmo m l1fO"
ceWng. etc. We ::ue cooc.m1ed bew oot with the design of such &no~. 1m with specl.fietttioo
fHIIUJJ m::(Uir~~ fur ~teadly~ ~il mwin,S un ~t ill ifh.lid press
C~pl'fiBWS
~ CimJflll ession of pst'S may he ~~al in ~nl Wllh rotiJling bl!a_ditB (tie 0
mmine ~ in re~) or in ~ witb reeiproeating pisms. Rlllmy equipiD!.mt is
II'SCfJ for bi.gh'\o;a"JI~JBE flnw wlnttc tbt: disch;qc. ~rc i$ not r~ hifh. Foe hitb ~
~ ,..~ a.re .required. The eDeJIDi' eqmuit1m are indepeodmt of~ l}l'C of
equipment: ~ they are lfie same as lor tum~ or e1paode~ bfcaus:c bert lOO pntendrd-
~ kine1ic~efiD' ~ .~UC premmet1 ~liglh'le6 11:ru&. F.qL ('I_~ 3~ lhroogh {7_ 151~ apply to
adj bade oom~oo. a~ rep.resm~d by Fig. 75.
2
I
~7.s~ ~r-~
~sicm.~

I
1

274
In a compressioo process. lbt: - tropic \1-m gi~ by Eq. n . l5). ~the mininwm
dlaft work required for ~ of a ~ from a gi\-en initial tate m a giwn di.sdbarge
pcc:ssu~. e de a~ eftic:iency
(6.H)
115 (1. 11 ~
AH
Com~ efficiencies aTe usually liD the nm.ge of 0.710 0.8.
II
The camprc.\..~00 process is 5hown oo on H S diagram in Fig. 7.6. 'fbe \~l dashed
lim ~from point I to paint '1 ~ lhe ~ru"ble adiabalgjc (constmt..emmpy loom-
pression pmces! from P1 ro ~. Tbt aclllal im:~ct!tihl'c- comp~ lion ~ follow the solid
line from pni.n 1 upwmd d to the rigbl in tbe direaioo of in~ en~. lcnllin3tinJ
8l point 2. Thr mare irn:\-"a"SJDk tbc pr lbe funber this poilu ~ {0 the right on me ~
isol)ar. and the 1owet m~ tffkieoqt 11 of the procr.ss..
!Example 7.8
SaSu:rated-vapor steam at 100 kPa (r ;::: 99.63;-C) s compressed ~ to
300 kPa. Hthe compJBSSOr effitiefl1lcy is 0.7:5, what is the worrk required and what are
d\e propetties o1 the discharge stream?
Obras p o eg1das par dn e tos de au c

Solldlon 7..8
fw~5Gnlnlptc eo~o 10 lOO kPa. ~ ~ S, ~ 1.3S98 kl kg-~ K - 1 . w~

l.aboo in the mbles ror .wpethe.ruerl smam M 300 kPa sbows ~hat Slemn wi1h this
enr.ropy lw the enrtmlpy: H~ - 2..888.3 tJ q - t.
"~bus. (i!!J.H)J ; 2.888.S- 2.675.4;; 2l3.4ldl ~tg l
By Eq. (7. 17~ AH' ._ (AN )s .. l~'\.!1 ... l14.S kl ~- I

q 0.75
Wbe~ ~ ;;:: Ht + A H :- Z-675.4 + 284.5 == 2..959.9 kJ ks-
For :supbeated steam wilb this eo_d!alpy. ioterpo.lalion yields;
T! ... 246. l cc ~ = 7.5019 tJ kg * IK.-
Moreover. b)! Eq. (1.14). the woduequired is:
W ~ AH c 184.5 tJ tg.... l
Tbc c!liJa:tappticalioo (Jf Bqs. (7.13) lfu'ouJh (7. l5) ~ tbt: a'\.1111ablliey of rabies
of d'aln or an equivafe.nt lhernmd'ymnnic ditagmm fut lhe 6uid being compN:SSed. Where sudl
iof011'1l31ian is, not a~Me. tbr: gen~ oo:rmlatioos ofSee. 6.1 may be u.wd in conjlmCtiGI'I
witb ~ (6.9)) ,PJld (6-!M). ~as 'iJ~ ill Ex. 7.1 f an~ ~
1be: twlmlplioa of ideal~ leads mequmions ofrelntive s.implk:ity~ By IEQ. f5.13) {or
liD~~:
TJ
AS= (C,-..)1 1n - - Rtn~ ~
fl
r. Prj
where for mplirity tbe wperscript. 1-Lig"" bas bcc:Q t.QDitt-td lit.IJD t~ meam beat ~Ly. Ifabe.
compres:iioo ~ ~ .6-S ~ 0. and mis 'CCJ0WOP bcei:G~
,... Tt ( ~Pz) B/(C",.Is

11 (7.18)
wibeR T~ is.lhc tempemm:re dr.:u J'eSU1ts wbcD ~ from 11 andl Pt m P2 6 Cunmrpic

aodl wba'e: (tp)s is lbe mean beat~ fm die tmt~ tanF &om 'Ti toT;.
Appticd 10 isentJopiC ~ on. !'tl~ (4,. 9) here~;
( AH)s = (C~)H (Ti- Tu)
hi~ ~itb Eq. (7.. l 5). W (isemropie) c: (~p> (1] ~ TJ}
11
116
Thi rcsul~ naAy ~ combmed w:itb lb~ ~ d'&icocy 10 li1r~~

w, = Wi (tiellOOpit') (7.20)
I. 'l
.Q H;::;; (Cp )11;(T:! - TJ)
AH
r, = 11 + w w ..
"' ('~I' }H
wt.re by Eq. (7.14) ll.ll -= IV,-. Helle (C~)r~ is dz :mean heal-capacity f()(' rlbe temper.JIID!e
nm!:e fmm T1 to 12 .
.For die specinl CIISf: af an ideirl gus v; ith CODSbmt be:n apaclties..
{C'p )ll = (C,p>H;;::;;; {C'p)s = Cp
EQuatiOPS 0 .11 ) Wld (7.l9) lbtJt:foro bei."opw;;
~ning r~e equadOIJ!i gi\-~:6
W,(J$CIIInlpi<:) =. Ct- r, [G~r/Cr -J

I
For monatmn~ ~~ ~ a:rg-ao and lk!1i~ RICp - liS= Ct4. For sudl diaromic
gases ~ nitrogm. ~ air u ~ ~ Rf CI' ~ 1{1 = 0.18S7. fu
~ of greUtu molecWar comp ~xitY ilie i<lhl....- ~ ea~ depends mm strooJir ~on
tempemmre, and &i- (7.2l) . lr tiktly lo be solUble. Om: cmi t-~ly !tho- 'dmli lb: ~
tioo mconslanl hl:at capacities al~ tead's to the resnh:
Example7.9
If m(flha.rne (assumed to be an idea~ gas) is Qllmpressed ~ t~m 21l"C and
1140 kPa to seo kPa. estimate' the work req-utremenl and (11& clsc:haJ'ge temperature 0f
1
1 1
tt1e methalle. The o~effidency s 0.75.
~ ~ Aj(~~)- )"-
rRTir [[ (~)t:r-l~l~ "'"' ] Aftii~IIU$ is !be fOtmti)JQJtJCMl).< eu>#~ed.
~ ~~.
Sq. O'.ll) n~ _. . ~

Solution 7.9
Applieatian of~- (tl8) ~~ Cl'aluaticm of1he ap;mcot ll/{C~)s~ ' fib_b i
providrd Eq. fSJ 7). \1/bkb for tbc present rompotwioo i5 ~ ~=
~) .
; "S -. MOPS(293.1S.T2;1 ~702, 9.081E-3 1 ~2J. 84E-8~0.0,
whae the eunstlmts or methane are from Table C. t. Otoose a \'alue :fur ... r.:
SQlJIWbBl hi~ than ~be iuiliall trmptr:atur:c T1 == :&l-IS~ "n!c ~in
Eq. (7.IS) is the i!mipmcal of < ct >sf R. Wllh P~J P'] - SfiJ/ 14fl J!:! 4.0 and
11 ... 293. J5 K.. '6nd a It~ value of 1'~~ The J!)IOOCldure: is repe:akd until ,I!W fwtkr
m~nt change~ io the \"BJotorr;. Thi ~.,~the yaJoe_~
nnd r;, ;;l91.nK
{Cr) . . --
pH ~ MCPH(293.1S.397.37~1 .702~9..001 1E -3.-2.164E-4Ml.O) :.-45114
R
Wbenee. {Cp )11 liiil r(4.5.774)(8.3J4) .- 38.056 I 0101 .... 1 K~ 1

Then by Eq. {1J9)..
W1 (isentropic} - (38.056)(397.J1 - 2-93.15)- 3,9G6.2 J mo!....1
3,.966.2 I
w, :::%
0.75
= 5.2BS.J J mol-
Application of Sq. n .l i ) ror the cttkut.'tt:ion of T1 gn-es:
Beam;e (Cp)11 depends oo T3. we ;again iteme.. Witb 1i 3!1 a slal'ti.ng Qlue,.lhfis
~ to the results;
T1 = 428.65 K
ami

218
Pumps
llJquids we wwdly maved by pwnp FnaallY mmon,s rqu.ipmrm_ 1M 5alliC ~unb115 apply
10 ~ pumpi toadinb3tk eompresson,. I1lus. Eqs. n. 1:n dlmup f1.l5) JIM Eq. 0 ..1Tl
.DR. \'Bl'kl. Hml."e\,._ ~D of Bq,_(1'.L4~ fm- dr <:akulruion of = AH requinl: vat~
or flhc leotlmiPJ of~ rooled) li~ and rlhese 'fdom l11113ble. Tlu:
fvndmnmt!JI ~ Rlstinrt. &t- (6J). ~an 1111~ FiQr n ise:DII'opit ~.
d II ;;: V tl P (~C'GIISl S)
Combining aha wilb Eq. ftlS) Y~-
W.ti~utlnpic) = ( N)s~ f f'! Vd P

If.
"De ~ fw Inqwcts rat eonttinmn, ~'"ell remu'~ Jitnm lh: aitigtl point n chw ''
i~ illllr~ of P. fn~prilm ~bro gi\'"CS:
IJIIf(ti 1111ap ).., lAH )s = VfP.l' - !111 ) (724)
Also IHdul m:t die foUowin I!IJIJ:JI-rions &om~ &
Jll = Cp.JT V I ~ -T)'dP t6~,) dS .;.Cp~ -JJV d'P C629)
\\'~ ~ m~ mp:tmil'ity ll ils de&nm l!Jy Eq. (3~.2). &arose ~mporaltl:re dmng~ in lhc
pumped lluW are 'm )' mmn and becznu;e. abe pmperties or tiiJIIiW. .lire insmstli~ rto pre!~.~
(qain ~l ~ ott cloie' IQ dl~ critical PQin.n. lbese equatiom are ~l)' int~ml on
me assmnpti:cm 1hnt c ~. If. 4Dd IJ Are L"'OlliUill,. usll:llly at milial \U5. Thu.~ 10 ll Ulld
appc~n
Alf;:::; CpdT + ( I -/JT~ AP
Example 7.10
water al45cc Pld 1rO kPa entet& ~an ~ pump and is discharged at a pressure
or a.eoo kPs. Assume the pump' Bfficieney to be 0.15. Cak:uta Hrtel Vi!Dfk of Ole pllfl1,1j
the temperalwe dlBnge of the wat~ and 1heentn:~py change o1lhe water.
Solution 7.to
The fO:II~i11; pmpmi~ for ~ratr:d liquid wat:u at S.. _C ~ll I8.. 1S K~:
Obras pro egtdas por di r r os d autc

279
D)' F.q. {1.24)
lVs (isemrrqpie) ~ {AH)s :=l ( tOIO)t H~-600 - un c 8~616 X l~ .t h cm3 k~ I
8~ I U- toG k:Pd cml.

w,.(isentnl;Jpic} ~ tJlH )s ~ 8 .61'6 tJ ~.;g- 1
By Eq. a. rn. ~ H = (~II .s :::: 8.676 = I LS1 :U kg-1

9 (t75
It' BAH z U .S7 tJ ~-~
The~ c~ of~ w.:tter du.riog pmnping. fmm Bq. (7.2.5):
U57 ~4J786.T+ 1..010[1 - (425 x IO~I(lUt~5)) 8~

- olution for ~ T giva:
aT = 0,971C Ql
Tht; rmlnllp)" clum-p of ~ 'W:I.tCr i, ~-.;n br IEq. (1,26}:
AS = 4. l781n ~~:~ :~ - (425 x 10~6 l(I.OI0J ~~: = 0.0099 kJ ktC 1 K- 1
\
Flpre 7~7~ ~~
~-
I
Ejector.
.E"JeCWl"S remoe gases or ~ from an ~edl 8fXK'C ,and ~ompress lbem rmr
dist'lblqe
at aJ higber pr ~ Wh:ro ~ of the g&_~ or ~':!}IQJ5 \\lith the dri''ini fluid is :d~~
ejectors i~re m.will.y lowa" in tiM COM .I.IDd maincenam:c ros~A tbwl abel' r-ype& of\~ pumps.
As illUitnt.OO in F1g. 1.1 e:~ ~OOS!i.5n of an inner ooovc.Tging/di"~ noule tluoo.gb

280
wfDdl dJe Cfriving fluid .cmnmonJ) fed. aDd an aut.cr~ luger oO<ZZle lm.lugll whK:h
IRm) is
both lw. ~ ~ ~pun; and lbc drivinj HWd pass. The fllOniOOlllm of the hJp~
~ tluid Jet~vin! tbe llririQ nome is 1pmiY nmfened rto the o~ gases or w~ afid
liE Jl:Jd~ \1tloeiey is ~ ~ dmn tbat ~or me drivini fluid leavmg the smaUer zzl~
1~ is DtNenbeless highs lban tbr spmt of m.tod; mid tbe iat.get" amr_lc d'lmf~ acts as PJ
con~p.tivaxing dlfl~r in wbkb the. pressure ~tises IJid the velocity deereases. pMSing
d~ the ~ ,o f $(.1llllJ)d 111 ~ 1Ju;Qat. AJdtougb die usuaJ emq:y eqgatio for nomes
appi)\ tbe moons process .lai romp.l~ tmd as a resull ejl:c:IM ~ rs ...y cmp[ritul7
PROBLEMS
1.1 Air e;;....--..,

~~nu"~ ......t:..""
!111.1~. ....:iall
___ y .............,..., i!_ ..................
q.I.J Y!.l.ttH ~ n~J~.n ~a "'1'i "'-te 1m
_ TIC::~Jlu r-1' YeUAltly
"niIlia ~ .. W a 11'!:--,
.J'lljlj
'~} of 325 m .... ~. Wb31 is me remperat~~Je. drop of 11te- nir1- if me is .IL.~ w be
W1 ideal _p ror wlucb Cr = (1/ l)R?
1.l. ln1&, 1,S an c~~.on i;s foWJd f(Jif abe Joule~Tbomson cwticicot 11 ;; (31'/fl fl) ~
lha1 rcb.tCS iJ [0 El heal CS~fi~
r-"" i .lltJd ~n<U"- .....t_S!lllle
-,,_........-v.. ~nt1-ft4 ~
... m~ F,_,.'l_ 1- -
~-v,..HJp SUii!J.MI!
!A.IllQD..
1 "
e.xp~ tor the ddi\"ilD,.:es.:
tat liT/a Ph: eb (aTta v)'t~

Wbw. an yoo say , hom ~ ugn.t of t1rese derivath-es? Par what ~ of~
mj_gbtthes.e daJl..,..di-va be im:podont ~quantities?
~ V ~ ~r ""Q(pmc: and \1 iJB ~IT ~ -1\) wbn ~ tiU ~IJeRII muit

~for. (a) A!D ided gas? {&)An inca~ l:iquld'? \Vbal: do lbJ:sc raults
suggest qualitaan-cly aboutm~ sped of ~odin li~ Jdlniw lo gases?
1A. Str4nl ~:ems a ncak a~IOO ~and ~C n1 nqti~ible ,.'doci'ly and~ at a

P.ftBillfC of 52S ~ ili\&!.LrnUfiJ isemmpi:c ~~~n or 1bc ~ in lbe ~1.) wbfit
~ llle e.~1 ~~ and \ll'lm1 is me c~sectioonl area a11be DOZile ail for allow me
(J{ 0.75 tl!g ~ ~ '?
7..5. Stmm mtrn oom~g ~le 4l800 kh mel 280-:;C widJ qeg.Ugi'Ole \-elocity. U
expansion 5 isemrqpic... what L tbe minimum pre:smre (bat em be reacbed msuch a
n~:e and wlua is, the crou~ond ~ t b nozde thmat at tm ptl'StlUI'e f t\
flow l'tlte: of 0.15 kg s- 1 ?
7 H. lbr)' D. Cirttn. ~H'.:Pirw.lit'od ~ ' HiJI:Jd/:rdtli!t,. 1t:b ~. pp. IUc-:s&-l0-57. ~~-Htn. Ntw
Yoi\..1CJ'n,

1~ A ps mk>;Ba CODW~ DD'l:dc a1 pra..~ Pt wim ~iafble ~-ity, ~ds iien-
tropically in die ~ and d- fwxes inlo a dlanWer ul p~~ ~- Skdeb gf3ph:$
shm\'ing me wloclty ;U dw: throoi and rtbe mass flowrue as iliLmaiom of lbe pre.ss.11n:
mlio~[Pt .
7.7~ for isentropic exprutsionma e~~g 0072Je. wirb neglip&le mtmnce

~-elocity. ~ graph$ or ~.Pal fkrwtaJ~ m. ~tooiJY ~' ~d ~ r-.11do AI A. v. ~ cbe
preDltJJ'C rill:iv P1Px _ Here. A i8 lhe Cft'JS.tsediooal area of me oozzl.e at ~ pomt in
die DO'.l.ZJe. V~ilae tM JR5iSU1C is P, md wb5aipt l ~ 1bc nO'l.t.le m~
1JL An ideal.- wi1b ~ htm Q~ti - m~ a C()~j/d~g 11~ wilh

OCB)igiOlr ,~(!dry_ If it CX.ps:!'l& isentropkilll~ wilhin d'le ~ ~ ~t lihe. ~
\retoc.it.y g gi:wa by;
z yR1t ( 2 )
Jl1ibnm ~ T , +~.
\\bt;:te T1 ~ 1!be ~ of me gas emeriDg lbe DO.ule, r1 is me JDi01ar lll:iln. and
R ib lbl: mob.r gas amstnnt
73.. Steam expands ~cally in. 1 coov~~dh13ging ~ ft<rm illkt ~itious

of 1,400 kPa. moe..llt)d ~ibb: ~lly (041 ~ ~ d 140 kPa.. ..u
i[ be lhmal me ~-seaiooal mea 0 6 ~. vr
Detmnine the JD&S.'S ftowme tbt: smam
;a d the state of the i1mm mdJe cxlt of til: !BO.ttlo.
1.1 I. Air dis.clwges from un ddiabiujc rn oule at s~c witb a vel.oelry of 580 m s- . What
is wile ~ :.~me en1ranee of lbe: nome u die mtnmec wJocity negligible?
~ m
Mbe an ideal cas rw "'
tb c,. :::: Gl 'l)R_
1.11. ~water f!l 15C is atuoltled fiiotn 5(rum) to J{Mm), ru; in a kitchen~ 'Wb:lt is
&he temperamre dtrulge of lhe wmer? What is the l~t work per kiiogr.un of \VatS" fur
lhi8 e\W)'ay houselwld happening? At 1.5~C and L(:atm]l. the ~ ~ ~ fJ
fur Uquid wata- is abcut J.5 x tcr=
K .... 1 1'be ~ ~raue T, :is 2.(PC.
Suw carefully any asS~WJ~~Xiom ;yog ~ ~ ~ .. ..e:s; ~a ~of~~
1..13. A pS at u~ e:ofldi~ (fl ,Pm) ~ ~ lQ a down~am pt~ elf I Ll hill'..

U~ the R.edJidiiKVt"OOg equ.a1ion (D estimate the do.mue~ Wllpcrall!m and 4 S of
tbc- fw one of die fQl~_ng:
(a) Oubon dio}l;ide. with T1 : 3SO K and f'~ ;: 8D bir.
(b) Elhy.lmc, with 7'1 ~ :uo K mJd P 1 -= 60 baf_
=
(d -i ttoprt wiJ:b 1'1 2:50 .K aml.Pt = fJCUm.
(d) Propane. widl Tl ~ 400 K and P'1 e 20 bar.

1.. 1~ A gas'" 1!~ ~d:itWns givat by ooe of b pats of Pb. 7.13 ~throttled w a pmr
5W'e of 1.2 bar. U:Se ftr ~di/Kwwg ~aooo ~ C"Siimute die ~~~
temperatiire and AS of me ,p ..
7JJ~ A gas at ~ amdilims gi\"m by one of ~ ~ cf ~ 1, ll i:s ~ed 1Q

a~ or
1.2 bar". llseJ the PengiRDbiJison equation 1D estiJUale lhe ~
temper-amre ilDd AS oflhe .~
., .16.. Fa. a ~~ eqwllton or SI'1J.t. "PJ'''Iie that dJo. Joul:enbompsoo. im-ersjoo

cun-e is libe ~of~ for wbicb:
T (!!)
ar , = (!!)
. &, .P
T
Apply 11m equation to (a) the wn der Waals equation; (bJ the R~ldt/K"' ong ~(m.
llisc~dle~
7.17. lWe one-~ rmb. ,o f rqlis;iblc beat capacity and or equal volU111e [nia:.iaBy
onnml:n eqmt .~fiea oftbe same ittil p .M tlie~t: T Wid. p_1\nt A~
tc tbe atmosp~ tmwgb a small tadrine in which lfle gas expand~ ismuopicatly~
r.an.t 8 discharges. m ~ annospbe dtmugh a porcxu pl~QK. &lb devi~ opera~ wtU
c:lisdmrge ce~.
( tJ1._, Ak"'....__.. ceases., -I !W'IIii
When ~6"1' ~Dl!te
d.... --~"1""'~- __ - __ bl\o n_. 1
Ul bn"'- ess ~-- ...~~,g.~ OJ' giea~er
IDililli,. C'JUm ~.
tbm.tbc ~ iD tank 87
(b) Whrn ~ ~ mbot& ta na"--e fallk:n w balf tate mirilill p:refl:!ure. ~s me
t:empemllll'e of rdte gns ~g from me ~~ lC$$ ~ cquar ~or~
t.baar..._ rAtllpmllllK of tbr J1U dL~ from die porous plU,g?
(c) During 'lbe disehaqe pnx~~ i! 1M ~mrc of rmc gas k.a\-iU~ the wmme less
ihan..~ 10.. OT p!attf llban the lcmpcmlme ofthe~ ifea'tt,.g, mnl A m 1111: wrne
.imt.ant?
{d) During the~~ is the tauperamr.e of~ gas le.a\ing & por-ous ,.ug
tm ~ ~ m. ~or~ Wan dJe. tnu~ of die~ lea\'ing tank B m the
&:IJ'I'Ie inBiant?
(t) \Vficm.,c:fisc.bal'ge a:ases, .is tile 10088 of gas remaining iD tank A less ~ a:pW ~
or gtealtr than the ltla$5 of ps ~~ in tmlk s~
stt2m lDr1iini: ~res adl.abo,ically at a~~ level ofljOO k\\'. Steam mters die
7.18.. A
~ at2.400 kPa and 5(gC r.md ~from me
rutbine as ~ted vaptx aJ. 20
kPa Whm i.. dE $laQ!l fate through the ~ aod what is tbe 1Urbine etlieien.cy?
'7..19. A Olfbtne operate& ~mlly wilh ~pc;tlated ~earn ~ug 31 Ta m P'1 witb a
ma fiPWiilte m, The aDmst ~ ~ ~ and me WJ'bine dlki~ is TJ- Fo_r one of
the fuUowiJlg set of f.'Jpe.mrinJ coodiliODSt dctmm1ee me IJO'Iat:'a" mlt;pul of the rnmioe
and 1be en1ha1py and~ o l lb:e exhawui s~
(~) ft :;:::; 45CrC, f'1 :;; 8f000 it&. fit ;; '8C kg s- ~ , ft - .30 tfla. 7} -;:;: 0.30.
1

28J
(b T1 ;: SWC. 1\ : ,,000 tPa. m=90k.g - m, & =20 tP"a, 11 ~ 0.17.

(c~ T1 ~ 600"C, Pt ~ 8,600 tPa.. .PJI = 70 kg ,-1, 1'2 ~ I0 tPa, 'l' ~ 0.82.
(d) 1i ;; 4tl!YC. " = 1.000 kh lJi = 6S Q. - ' .. P1 =50 kPa. n - 0. 75.
(tJ T1 = 20:)9C, P1 . . 1.4()0 kPa. til - .50 kf s~ m! Jll, ;;;;; 20o ~ ~~ - 0.1,. 1
(/) 1'1 ::: 900("F). PJ = LIOO(psfu)~ m: lSOObm)(s)- 1 P,. e l(psfa)~ 1J :::l OJto.
<r T, =soorn Pl = tOOO(~ia>. m= tOO(IbuJ( )- 1, P:! = 4Qlm). '1 =- o.1s.
; .ze~ Nitrogeo ~ imtia1ly at 8.5 bar expands i.sentropicaliy to 1 bar and tS c. A..~
ni.trogm to b.l an jdaJI ~ calallate lb: in~W t.anpen~ nd the wrl p!Odutal pet
mol~ of~.
7.21.. Cootblw~Oil prodllcu from a hum~ enter 0 3M IJlJlbine ar 10 bar and 950 :and rdis.- c
ma~ ,; n J ..5 bar. nm tu_rl,inc ~rates ~y with an rc ftk\mcy of n .
t!tl---
.,liOUJUJ.S do....
~ ...............
wua~ 'Lftlir .,... be 8ri. ;dw..Ln."' --l. t.ite ~ l!i beat c;a~ ...~
.,..,...,......,...!!"'
~............... W' " _ <P.H ..--.--~- IUj _ _. ''HJ!.I.. . _ . _ - 1~-,:r "'Ji
l2 J mo~- K-l wbaJ is the wort ompw or rme imbine per mole of Ia&. aru1 w:r:w i:s
1
tile r.e.mpem.lil.1re o f me gMe:8 discllarging trom me trlll'mne1
7,. 21 J80b~ c:-,xparul.s odidr.ui'eflll:y in a llilbint from SJ)OO tPil antE 25t:FC too :500 l:.P-.11 at
dJe me of0.7 Q llll01 :s.- 1. If t:he kubine efficiency - 0 .. . What~ dJe ~'a' OUtput of
b! tu:tbm~ and What is 1he ~Clillfl!O il);IUI or ihe iSiJbuiaoe ~'Viq abc turlJine"?
T~. The steam rate to a tnrbiM for variable outpn is comroilled by a tmmd l!3i in tbe
in_let line. S~_m is supp'Md to du: dJrouJe l!UI 1 ~ .700 k.PaJ and "'S~C- DuJ:inJ ~
~ nm.. tM: ~ 11 tk ~~iqe inkt 15 J,(KIO kPa. dlc ~wst5Ctaml at l 0 kPa b~
ill qaality of 0.95,. r.bc stram ftuw r<~~tc is 0..5 q -J ~ arull w power ou-rpttt cf the mibinc
i<S l:80kW.
(,u ) \Vbat are die~ l sa from the turbine?

(b' Wbal would be the po'Net" output if lbe steam supplied (O die t!hroUle \-ruJ..-e were
~dlafl ism.nupi~ ro the final ~Jressunti
7.24. Catboo dlo ide p.s cnten an adiabadc expaodct m 8 bar and 400'C and d'isc~ a1
1 bar. llfth IUJ'&ine efficiency is 0.75. \\lbat iB. tb.e ~ tempeJ'.Itm'le :mdl wlm is
~ wmt OUipll per mole of C0}1 Assume an b) be an i.dJ!a'll gB5 at ltbem eooditi.om.
725. Wests o.n aD adiatwil' gas, OlJ'bi.rle (e~dcr) yield "'rues, fa. iJdet ~ (1"1 ~ P1)
nnd outld coodiliom fl"l ~). ~-uming ideal ~\With (.',Q8SWil hem mpacities.,.
dtmJdDc d:1ie ~ .dficiGncy foro~ or me foUowiog;
T1= SOO K. Pt = 6 ~ T1 = l7l K. PJ = 1.1~. Cpj _R = 7/2.

(-Clt
(b) T1 = 4SO JC. PJ = S hm'.T1 - J7o K. Pl- 2 bar.. Cp / R - 4 .
(c) Tt - ,5.25, ~ Pt;;;;; 10 bar. T1 c 4j& K, 17, r:=. ], ~ Cp/ R c U/ 2.
=
(a) r. ; 475 K. P~ 1 bo:mi, Tl g .r n
Ka PJ t:: l.jk\1, C:pJR c 9/2
(eJ T1 = 550 ~ Pa ~ 4 03r, T2 = 403 K. ""- = J.l ~ CpJR = S/2

"1~ 1bc cffidcncy Clf :a pani~lat series .( ( ~ ps ti.IIbm (expZIDClm) oorre~ates
with power ODtpUI ~iltg to~ empb:i~ ~~ 11 = 0.065 + 0.080 bJ IlVI. 1
~ i WI is ltleabs001te value af t1m tlCtiill1 pmver ootpm mkW. itmp gas ~ lfO
tx qpaPdrd 6um inlet.~ ,o f SSO K md r6 bar to an owlet pJaSUie of 1.2 ~
For a molar flowne of 175 mol -~ , l:tai. ~ lbe .Wt\"~ Pl'Yf'Cir iin k\\'1 wtmt is We
e:ffieieney of tbe twbine? \\fb:lt is lhe ~of eliUUPJ ~OD SCi? ~ ni.tn>gcn
to be an i~ ~ it~~ c P == <(1f}JR.
7.:&1~ A lmbioe.opemleS wahalieally w:tm ~ ~ emering at4S ba!: ;lDd 4WC.

:u: ~ ~ ~ mu.~ ... "dry w&at '. . minimum allk:rwa111e c:xbau:st ~~
for a tDtbine dicimcy_ 11 = 0.1S? Snpposr. dtc eflicicncy \\"al: 0..80. \\~ulcllhe
minimum e:dwlst press:ure be lower or hi,gber? Why?
1..&. Tdlbio am be U5dJ to ~;a mergy frnm high~ liquid~. H~

they IR JlOI um:l W-'btal ibr bf~Qre ~is ai ~ lMp;dc1 Wby7 ruustmte
by ~~ me ~str'Qm state for i.seDJlt)picexpawjoo of~ Uquid wakr
S bar 10 a fimd pJe.ssuro of ~ bu.
'7-19'.. 'U qutd Wmct tilkf'S NJr adli~ h}~ &( S(atm) and l S ~ and WalJS'tS ill
0
l (atm)~ Estirmate m pm\l ~" cOU.tpUt of me rurbme mJ kg- 1 of watet if i . ~

'l ~ O.S:S. \Yiba1 is 1M oudd ~ of die vr.ner? ~ wmer mo be an
i:oeom~le Uquld.
7..30.. An etparule'r opermes adiabatrcaDy wilb nitrogen mlerin~ at Tt aad PI wilh a liJQI:ar
now rate fl. The ~ presso&'e ~ ~. iilfid tbf: cocp:mdtt~cy .is 'l- i;stitniJ,b; tbG
~ ouqJm of lie ~l'ldel and ifFJb tctuperatm"e of the eXhaust S'tream for Olle' or the
ro~ seiS of operadng coltdilitm.
(a) r, = 480~ P1 - 6 bar.li = 200 mol - ~ P2 = l bar~ , -= o.to.
(b) T1 ~ <JlC, P1 ~ 5 bar.ii ::~ 1SO IDQl -. Pi. ~ ~ brall JJ == 0.15.
(,r ) Tt a S<lt*C Pt ~ 1 w ...fi ~ 175 mo1 -J. ~ :::::1. l bar~ 9 e 0.78.
(d) r. :;:; n
4So~c P. ::;; 8-biD". -=:: 1.00 mol s- I Pt. t::: 2 bar. , :Il 0~.
I
(,) Tt :::; 900( 0 fh Pt :; ~(psia)~,; = O.S(ltb mol)fs} t ~A.= IS(pw}. tJ ':::! (UUJ.
?.JL Wilm is l:lk- kttal~wmt: om fm ~ ~~oo J!i~D(~ cf Ex.. 7.61 Wbat is 1k ~

dyo!llllic dticimcy of the p~? Wlmt is tbe rate of entropy generation Sa1 Wh3t
is ~ ? T-aie T.,. = 300 K..
1..:tt. Exhaust gas at 4tJ(ff; :md 1 bu from intemal~oo cn~i H~ u the-1111C of

12$ mol .-l into a~ lxri.ler whae: ~steam is gcmeraled at a pressure
of 1,200 kP'~ Water-~ ~ boiller ~ ~C (T~). fmd ~ ~J~aust g a_re cooled
to urilhin ~ c of lbe. steam temperumre. Tlle. be3i ~P=Wil}' of me ~ ~ l$
Cpf R = 3.34 + 1J2 x ~ JTIK. e ~ ~ mro an adiabalic turoioe ~nd
~ ca u p~re o f 25 kP.t.. If h t:i:lrbinc c:d1iticmc:y 11 is 724.
(6) Wbal b W, . ttlt ptJ'WCI' ooqnn of the ~?

285
(bJ Wlbal dJe ~efficiency of the boiJcdturbi:oe OOlilbilwioo?'

(c) Determine ,StJ fOf fbe boffn' ond fm- lhe rurbit~e..
(dt ~ ft't0i!01(00iler) and W'mtU:wbme) a fractions of I~tr-tdr.IJ,(. 1hc ideal WOJt of
the pn;w%$&.
7.33. A smaJJ mrstmtic ,aif 4t01JJP~ l$ ostd to pump t1ir imo a ~ irut~ tank- 'lbe
milk inhially eootains ru:r aJ 254fC awl 10~ .J:l ~~ eutO)' ~ oondiitio:rts tU whk.1b
ail' enttrS the oompFeSiOf. Tbe pumping ~~ oaotin.- Wltil lhe ~ in the
tmk reac:M-~ 11 JXD t~- If me ~ .is atftabatic and if cc:om~irm i8 ~
wbal is tbe Sbaft ~:rt of lk rompressor? A&mme a:ir lo be em ideal ps for Yibich
=
rC , <7/2)R and Ct, = (S/2)/l.
1.34.. S~ted deatn at 125 kP"~ is ~ adillbaticdl)' in ~ fu.pl comptlre$SOf to

700 k.PCII m
1 me
r.att; uf 2..5 leg - I . TJite rom:pJeSSOr effideney is.1g%_ What .is the power
rwquirmJCo' of the ~or and wbat ;m; tho rm1batpy and entropy Q( the tam in
i~ ~] sr.ue~
7 ...\S.. A compress~ ~Y "'ith air enterin,g u T1 and P 1 rib .UJ mow flow
tn.tte ri. The dL~IImp ~ i ' ~ and die cvm~ efficiency i q. Fai_mato the
~ ~ftJrUitemt"o&t of dr co~ and ibe ~tutt c~r tlr tJ.i!ichatgc stre-am. for
ooe. of die foDowini sets of opetaiing oooditiom.
(a) = =
2.5"C. Pt Ir01.33 'tf"d., .ri lOO JnOI s- 1 , I'}= 17:5 ~ ll !!: 0.75-
T11 =
bo) T1 = C. ,fit _. 375 kf'a.. n= I00mol 1 1\ ;:;:; L 000 kP't~.. 'I - '0.70~.
(cJ Ttt = JUC. Pt =
100 iP.~t. ri = ISO mol s-.
Pi~ 500 tp-~ '1 ::!:1: O.SO.
=
(tiJ f a ;; .llXrC. P1 ;; SlXJ kPa, .Q = SO mol s- l ~ 1\ ;:; 1.300 kPa. fl '0.75.
(i!) T1 c 80 f).. ~~ c 14. 1(psia). ti c O.S(DJ mol)( r"" PJ =r SS(piia). t~ :c. 0.75.
1..
ifJ r, = 1.S0t f), P1 =SS(pria\- ri =

0
0.50b mot)(sJ- 1, P2 := 13S{psitl), 1,r = 0.70.
7:J1,, Propyl~ w ~~~ly from ~~..5 b3_rand ~Cto ~~~~UIIeli$of

II kg mull - t _lhbe eompressor effidt"!IKY is 0.&.. what is rile poweY reqniremem. ot"tbe
em1pre..~ mc'J wmt
is dJc discharge~ of11be prop)'iene1
7,3'8f ~ ~ oom~ udl~~ in a pipeline pumping~ ~J-'00 kPa and

J5~C to 5,...;()0 kP;i at tbe rn1e of 1.5lg Dl01 s""" 1 lfl:be oompressor eflici~nq' is O.?a
""..._ i~ lite pow~n:~qui~eh!J.e ,c_oql~i\Of"~ wbat, i;s lbe~~tute
of~~tlw~?
7..39., \VhJd i~ b ic:kW wwl for lbB ~m~m PI~ o f lb.. 7.91 What i ' lbe ~
roamic efficiency of me pmL"iie"SS? What are So ami W~? Tam T11 - 293. l.5 K.

1AD. A/an is [m e.tfecr) a ,gill! romp~ wbfch IDO\reS latg-e \lm~ of air at low~
ae<$5 man {J to l ' kPu) ptreS5UJC ~-s. 1Im u:;ual design equntion is~
W~! ! ! JiRTI AP
;,Pt
~ 5'Ubst'ript I ~ inlet corulilions and Ji .is the etlicieoey wUb reapect ro ~
Q'Opie operatioo DcvdOp, dd~ ~~ Show also llKJW it follows fivm dJC ~
eq~m:t~on Jot o~ or W'l idleiJl ID vritb1~~emu~~,
?AI. fora:a ldmbDc gas compressor,. the~ with~ to .isenlropie oper.anou i'JllS
a mr-+JSJ~re ofimemal ii'RWClsibitilie$1 go l! ilie~nsionlc:;s rate ofmtropy ~on1
St;/ R Sc; /d R. ~thai ~ 8ti k Wcn1 wiib COfistiPlt bcaJ ~es.. 5obo'W
lbat tJ BDC1 Sc;/ R' uc Jclan:d tflmugb tbe ~~
So c,. .
......,.~~ Jn.
(;q + 11 - J)
I
R R rr1r
7.42"' Air a1 l(arm) d lSC is co~ in a S~J~ged R~Cip~ wmpre.58()r (widl in-
L~g)~ ro a fiiW ~of 50(atmJ_ .!Fot Clidi ~~tile i:Girt p'i ~ is
lSOC and tJx: mui:J'IUIPI.aUQ\VQk ~ taJI.pcmlUH is ~C. MeehanJal power i
1
the same fo:r- aD &tageS, and isenb:vp.ic ~efficiency rs 65% for ea:b ~- The \'tilumotric
ftownuc of air ' O.S m3 - I al tM inkt 1.0 die first :stage.
(a) How m.1ny tlg.t$ are requQed?
(b) What is dJe mecb~""PJW~ '~ per-stage?
{d Whit: i5 die beat eM, for eada ~Jeil
(d) W4tet ' tbe I))JUJt f lbe ~1$, Jt cn1r:n at 2SC IIJd 1~""-es. at4S~C.
What is Jtbe ccoling...'W'IleJ me per i.m.en:ooier?
~rmlJp(: air~ itO id~ V4 with CP = (7 /2Ut
1.41. Dane~ lbat ~ pgwcr requ.irwmleDt for compressing a gas is smk1iler. (be more
("OJIJPr~ tbe p.s. J\$11~ ~bed valut5. w,;., . 7t Pt. and PJ., Mid that the gas is idea]
with ~con.q;mt heal capacities.
1 At. Ttsm oo ru~~ ~tic ps ~ yiekl '1/alues for inlet 'konditiollS (Tt. P~) and ()Ql-
kt eoaditi-o.ns ft1 . P:!). ~ideal gases mil constant lleat eapxitle.s. deteroti.fie
~ rhrl"rfii:P~ .,m.....J...~ ~- - - nf .t........ " .til~ .:
. --,.-..--- 10<l~!ii11Wy JW Oli1e "~~- ~....- ~O~IYII"'lillg:
(u) Ti -.300 L P1 = 2 bar.. Tl = 464"' Pic 6~ Cp/ R = 1/2..

(b) fi ;;;;; 190 L P 1 ;;;: l .S bar. T1;;;; S4'i ~ :f'l ~ 5 tmr.. Cpf R '=' 5/2.
{c) T1 = 2t5 K. P1 ::::; i .:1 bar.. T1 ;;;;; 4SS K, ~ - '6 bar~ C pI R' .. '9/2.
(d) T1 = 300 K.,. 1\ ~ L ~ bar.. T2 = .S05 lt. ill :; IHrar~ C p{R = JJ j2.
(e) Tt ~ 3D5 ~ Pl = 1.3~. T2 =496 ~ Pz = 7 bar~ Cp / /t = 4-

287
7..45. Air~ O(}Rl~ in3 ~y..ftow compressor~~ at I.:lim nod '300 K ud leav-
ing a 5 bar al1id 500 K. Operntioo is nmtadiabmc. with beat~ to i.e~
at '29.5 K. For the: ~U~X.dmnge mstate cftbe am._ is b ~pgwcr:req:W~
por mole cf afr ,S Jal w b for llumdiabatie lhan fur .~ operill.km? Wb)fl
1M. A boiler house pmd1.u:es a laJp- ~cess of low..p~eSSUK. [5~g). S(F,~)

~. An ~ k proposed- that ~-ootd firn:t run die low~'lJitC ~ tllnlugl'l
m adia'balk slead,.fto oompres.sor. producing medium-~ [ l5()(psig)] steam.
A JfOaJ18 e.nginee:T e_xpresses ~co_mcem mat com~on could resWt in the formation of
liquid wmr~ ~mgthe ~r. b ltbsre ci'IDe for OJDCmJ? s._esti~ Rde1
Go the M~diaplm ol fig. 6.4.
1A7. pump oper-dlts adiahatk:ally v.illh liquid ~ anering m Tt and P~ witb a mass
Dowce Iii. lbe distbarp prasme is P1.. mil tbc pump dliciency i5 f'J. For cme of the
ft~lfowirng Sl't~ of operating cnnditi~ d~nn_-Q ~ pow.~~ ~eru of the pump'
and.tllc ~of~ w-~ ~~from rhe pump"
(a) T~ ~ 25QC-. Pa ~ UlO ~ m~ 20 kg -I_ P2 ~ 2,000 kP:4 1J ::::l! 0.75.
fJ -251.2 x 10-~ x-. -
fbJ r~ = 9t1'C. "~ = 200 ~~:~ ~~r = 30 tg :s-~. ~ = s.ooo lPL, ;;;;; o.m.
fJ = 696-2 }t li6.....(j I{- I.
1
cc) T1 = 60~. Pi = 20 kPa. m= 15 k8 -t, ~ = s~ooo t.Pa.. ~ ~ 0 . 75,

JJ ::;o;;; S2J.t x mo4 K~.
{d) Tt =1orF.h P1 ... l(mml. m= SO(ibmXs)-~" 'P} = ~n1m). r;J- 0.10.
1$ = 117.3 X lO~ g-i.
e) T1 ;;;;;;- 200{-f-1, 1\-;;;; ISfpial, m;;;: Qlba.,)(s)- 1 ~ ~;;;; l~W:pRa), :q - 0.75.
p ~ 1 14..3 x 10-6 x-.
1A& Wbl~ ii 1he ~ wod fOf ~ pumping~ ,o f&. 7. 10? \Vha1 is d1r: dlamody..
oamic efficienqr of the~? Whal.lis Sa' Whal is ~~ "? ~ T0 = 300 K.
7M. Show llllil.E the poin.t5 on lbe Joulellbomson inve:morH:urve [for wbicb Jl a (9TJB P ht -=-
0] aK aha~ by ,; acb of the fuHawing:
fal (~),. =0: lbl (!~t = ... {t"J (av) v

-
iJT ,.
c::t - :
T
ld) (avaz)
-
~"
cO~
le) v (:~)r + 1' (!:t ~o

7:.50. J\C.(Q1J~ 10 ~ 7.3. rot d1crmodyoami 5Vund $pCCd c ~ onlflc P V T (wooo
ot mn:. Sh~W~Ibow ~Ill SOWJd. .spcedl ~ g.o be U&cd L(J ~i.lmtte l.bc
second vlrial coefficient B of gas. M!ome dw F4 (33Sl app~ and tbru. the ratio
C~I Cv ~ gjvm by jtj rMbll-,ps value.
1..51. Real-gas behavior fw~ is somd"unes e:wpiri~1J ~ Ehrou-gtl

lhe ~t't!S$5oli. W~ <Z) lVI~~.. ~befe Wi.r is lbe ~~ m~ power wx1 (Z)
is some suitabi)' defined aven;ge vat'ue ,o f me compressibility facror.

2S8
(a) Rationalize this ~on.

(b l>e\~ a tmbiur cump&c incorporating Ral.-ps bdtavior v'ra residual pvpetties,
amd d.erttmint! a ~value of {Z} for tho example.
7..52. ()penlling cbta arc mtm ou an air aubinc. For a paniaalar ron.. P1 =: 8 b..-tt. T1 ~
600 K. and PJ =I ~2 bar. lfowe\e.r.. ~ .recorded oo:tld r:er:rrpcT~t:QJe is only partially
legibJe~ it could be T~ == 31 &. ~ m 398 L Which ln1$ ia be? Far the gh~n cood'i
tfo~ zssumc. m to be am ide.01l p with COO!Stant C p =
(7fl)R.
753. Liquid benr..coe ll25C ~ l.l bar is QXNelted tc YapOt' at 200 c and :5 ba.r m a lYt"O-
&te;P s~y-flc,w ~Ali: ~ODip~n by a pump to .S bar. followed by \'D.J)Orizarioo
in Ql cwlltcr~Dow ha.t ~ Detennioe lhe pM'a requirement of mhc pump and
lim dUI)' of tbe euban$ in kJ JDbl- 1. ~m~ a pmnp eftictel'lcy uf ~. ODd l!n:at
benz.eDe vopor d.! an i~ gas wilh ronstal1f C p =
I 05 J mo~- K- a.
7.54. liquid beozefte ~

2S.;C and 1.2 bat i.s COJ'.I\Ierted lO npor at 200'-C and 5 bar in a
t'&'o-slq) stcadyHo process: YapOrimlioo in a.cou:nter-ftow he-at Q~Jd 1.2 bar.
foflowed by compres.~ sa gas loS bar. Detamine the dwy of the aclmnF ::md lhe
power ceqniremeDI of Dr ~~or mk1 mol 1_ AsSIIIDC a compressor eHieieney of
c
75%. :md 1rel_t benzene va:p<r as as an ideal gas with COOManl p = I 1 mot- [ K -.as
1..55.. or the processes proposed in Pbs. 7.SJ and 1..54.. v.'hich \\'OU!hi you ~'? Why1
7.56.. l...iquid!s fadentilitd below) at ~C BR COTI'Pidcly vaporized m l(nnn) ill a munrer
cUTCaJt heat cxc.ban~. SamratEd steam l5 tbe he-all~ medium. m,~ble at four ~
mre:s: 4.5. 9. n~ e.nd3l bar. Which vmiety ofstcam is mostappropriateforeadl c:a~?
A.miJne a minimum approach t!J. T of lOPC fut heart ettbiin_@le.
(a) BC"ni.cnt:: ~(v' n..Jflecmf-; (c) Etb},kne glya>l ; (d) o .. XylcDe
1.57. ~One bnndred ( lOO} bnol hr-1of ethylcnt" i.~ OQillpresscd from 1.2 bar and 300 K to
6 bar by 3J'J clearie-moror-dn"ven compressot. Det~rmine. 'th~ ci!phlll cnst C of dJe unit,
Trea1 rthykoc as an ideal ga5 whb comtanl C p = 50.6 J mol- 1 K- 1
Dan '1 (cornpn:ssor) ~0.10
C(comprc:ssar)l$ = 3,040(Wslk ,_,l
wbcte Ws s isl!llfropic pal\'a requircmeflt ~the ~
C(~)l$- 380(1W~JikW)O.US
where li'e thliv~nrd shaft power of motQ.
1.58. Few' different 1)rpes of dri\.~ fur 8.iL'S compreSsors~: d~trlc 1110fnrs. gas C;(p;mden,
team ~ and interoal--comtmtioo fttgilta. SUggeM \\ben C3dl Jnigbm. he appro-
priiiie. How 'WDUkl }"'U estimate ope'l"idins cost for act. of~ drivers? l_gnore s ueb
8dd-oos as nWnrennnoe, ~ng 1.11bot, .tmd ~mradl
759. Two scbemes are ~for thr reduclioo in pre ure of ethyltne gas a1 375 K :md
181xsr to J.2 b3r in a Slddy-low ~:
Obras proteg das por dire1tos de autc

t) fass il tbmugb alblottle \WiVe.
{b) Seod it tbrougb ,; m aditibatir expander of 7~ eOkieocy.
For each~~ the~~ and tk rm:c or mlmpy
pucqtjoo in Jl mol- l K- . WbBt i:s diu pgv..u outp~ far proposal (bj1iP kJ mol-~?
Disco.ss It~ (Jli'(JS and cDJU of the 11'" )m:lpm}s, Do nnt il.~t$UJPe i*d ~
? M . A HJtlieam of .b ydl'oalrbon gas at SOOCC ,is coo4ed by cnntin.uOW!IJ ~eomtrining it "'itb a

$tft',3JJ\ of ligllt ail in ,a n adi~fjq)lK: lOwer, 'De ligbt oil -~~ Q li4_tiid at 2SC; die
combined stream leaves as a ~ at 201r'C~
{ll) Omw a c:u.eiul!ly bbeled flOW" dlagatn ior die pl'(Kl-ess,.

tb) Let F aod I} deotft respedi\-ely the mow tml& ofbot h)!~ ps and Ugbl
o il Use data givm belaw l0 detetmine a nliDterica!l b.e. .ror lbe oill---ro-gas mtio
DIF- &plaiu yot~ arml)'ti -
(c) Wbal is me atl~rc to qlltt'lclllDg die byt:;imea.tiboq gas with i! Uquitl rathew 1batb
with aJlGiber (~) p? Expbin..
lJattr, Cp(av,e} ;::;;; ISOimol- 1 K- 1 forrtheb~g,as.

C p(ave) ... 200 J1 JIM) 1 K - 1 for !too oil v:apo.r.
aHii'(oil) = 35.om J rmoJ- 1 m 25 c.

ChapterS
Prectuction1ef Powe,r from Heat
~ rm lliiCiear power. me sun is me wtimare ~ of aU Ole mrcllanicil f!"~IY used

by maob"'nd. The total r.lte at whidb enagy ~ lbB eanh from the on is ~~g:.. burl
1M rote ~ wbidl it fal.ls oft ~ 841Lmfl: ;lliC'r of~ i! m~dJ.. !BHCq)r ~ over a L1.tge
~~va is~ to make pmctical. ~me in any~ prodnruun ,u f WOIL e'\~l~
~~- phuiovotlai QeiJs, iJe n$Cd r(l(c1tric (JO\RJ m mall~ special applieatioas. Solat
n.diatioo als-o finds dlJed app~~ for beatin,g wall:f and btdk,fin~ ti)r g~r111iw (If high
~~fiE'S m mddl~ ~plieatrom (solar furnm:es:t and fore-:~ waEel' iD ~
pmd'Btlion of SiiiL
The tine1ic enam' ass.ocia~M wm ~ric '\rind.i r.s ~hj)y ~ io fa\1fJnlbw
l~ions m prgld power b)' I~ \\riOihnilb. 'The potenti_al eneq;y of tides. is~ po~le
soun:e of power.. but pnxtw;tion fm these stJ01"'U Mllbirns ~~~ ~ ~u wi dJ ,.'Qdd
dcmaDds for aiCQY. Evmtudy. adJ altemati.ves will lbet:ome essenruiL
Sipifkaln by~ric IJIO'WCf i5 pncra__ted lby com1Cnitm of tbe poteotird enefgy of
'~ iinm :odt..li ~that can iD printiplc be aii~ wid~ an ~~of IIOO'l-.
~~r.. by [u lbe. Dl05t inipJJt:mt. ~-of power aR the ebemi-cal (mo~} ~ af
fnds W DEICJeitr ellCJIY~ l.Jlfle-~ale i_~alio:m {Of' this ~ depend OD rtbe evoiBtioo
of beat and ii~ subsequent pat1ial COO\'ei"SioD into w-ed. ~ ~Nte~ in equip~
de.~ the cmQe:ney of CQ~Jcm dOes. IU# ~ 1009-. This is a CilliiBeqlleJlCe of me
second law. tbeeflkieoey of OOIR19llioDal ftmn-fnd ~ pJBtU$ liUl:ly ~~ 35%.
H~ didmcics geawr lban SiO'.i- am be J."e.lllimd irD com'b~de pbnb Y~ilh dttt!]
pmrtcr~
FJUtn.adwoatedmology ps ~
f'Rml ~e.r cydes opcraring. on Dca1 ~ovtfitd ffiorn bot~~~ pses.
A wornmon fk\,b fur h direct con-.c:rsioo of cbmniA11 rel'lel!Y info eieettmll eoergy,
wiibout me fnremterdiiite ~or~~ is ibe ~ed ~!I~ e.g... ::t batw:ry. A rc--
~ dPiee: 1be}itn cell. in wbicb: reaaanas are mp:pUed conlimmu&Jy 1o !he~. The
~ - ,II a:D in \\ilk-b IJ,,.troge~~ ~'1$ -.lib ~ypo 1:0 prorlun \\~ dlrwgb deeuo.
dlmDe-at. ICOJl"imi.on. 1lle. resWti.Qg ,efficiency a.n be as great as 15%. a oom!det'able i:mpro'D*
mcnt o\<"a" ~ tbaa fim ~OI!iW'if ~I eneliY inm beats This~~ has poteruiaJ
.a.pplicalioo m~ and may well tim odl!er IOS~l' lh ~l ~is coasidcrc:l
ill Stc,. il.JO.

B. I. The Sre.un Powec Pt:anl 29)
In a oomrectiomil p.l'Wet p)mm ~ molecuJar eo~ of flLel ~ releaw1l by a c:otllbustioor

~ '115 t1maioo of tlho wwt~ dc\icc i Lo WDl"m pu1 of l:bC" beat of w.m-
~ mtD ~ical et:ltfg1. Jn a rt mc;lear pown- pltmt W issi:oo. ~ fititaliCS ~
of lbe nudeus of lbe .atom as bem. whk:b ~ lbeo panbiJy QOOY.med into wurt. ~ ihe
tbermodymunic anal of~ m,gi:n~, (JRWntcd in this~- ~phJ ~ty l\--eU ( Q
com.-e11Jklna1 (fMSi.l*fdel}> ml nuclear po!'Au rpmms.
The S1Rm pg'\vef plant i~ alarp-5a~le h;a1i engine in wbicb the workiJ,g flgjd (.EhO) is m
~y-s_~nre Dow sm;a:ssh1;}y lbroogb a pomp, il ~~ a 1IItibim; and u ~~ lft .a cyclic
~ CSec. S.2). 1be oriking ftwd is ~dlfrom l1le beat .soUNeo. and .hem~~
acttJS a pbpic!ll bmmduy. ln _. f0$$i1-r~I-tircd pbrrlt111~ combL1 on~ a~ sepan!lted [rom
dlt: ifcrun,by boile:r--tidle w. th. 1
The iJUemal~on rengine is ilil01ber fonn 01' ~ m.gine. wheR:in bigb fm}JK_ra..
are auained by romersion of am co~ etagy of~ fud diRctly into ioJalla.l ~
tui'C8
wi!bm tbe \\~producing device. E:.umples are Otto and Diesel engines and lhe gas 1urbine.1
~ eba,pter ~ de oted m the ~}'8is ro f Se\efi~ OMliiiDD heiil-etlMi.ne. cycles.
f
Flpn 8.1: Si~
~~plimt.
.- '~ (pumJjl I
[8
A .. Cootnwr 1---
1.l. -
8.1 THE STEAM POWER' PUNT
The rCaJoot...engi.ne qcl~ del!a'ibed in Sec. :5~ opermes m~ and rom,~ oftwo isofber..
mal 5lep5 eon~ by two lld~_k 5fepS. In lbc i5alhc:nnal 5tGp at hiabef ~ 1n.
beat J{2-,., I is ~~~ by tile \\~ llukl af lftc mgi~E ilfid bt l1.lic ~liii:al Slq) al kw/et
1Dc:lllib or s ~ a~ nqiKs ~ ~ rn e. B. WCJiQdrnff, H.. e.. l.limi!MI'J;

:lDd: T. S . t.anm~ 3Jmm P!mtt ~iiJII. ~ ~ lwk<'.q'-Hitl ~~ YOit. 199~ R C. f. ~1QJ. 'Jil~ J.rr~
~ ~ m ~ itJJJ P.ratticr: 't.JitmMJ~ fiDf ~ITt!~- MJT~ BlliltJH.. 1

292
temperature Tc , IQd is~bydu:Ouid.. Thc\\IOikpodtx:cdi~~: W' ;:; IQII - Qcl.

nd the thctmal dfiamcy of tb Camot engine is:
JW1 =1 Tc
IJiii - - - (5.8)
IO'H l TH
Ckarty. 'J iocreases TH inaeasesomd T. ~- Altbousblbe~of~
bear rnJines are t~ by .irR-u is still true th31 their ~ies .are int~d
when tbc: ~ 1CIDpCI'tllure at which ~ b i:tlc:reased afid wbett tbt _rauge
tdl'plrafUir a1 ~hich beat r cjcdal i decJeaSed.
1-"igure &.1 ..ibow"l a simp]~: steady-slat&: Ready..flO' ~ iD Ytthroh sream ~b:d m
U bot'ler J ~ m an lldidwic wdJint I Q pfilducc WJorik. 11be discJlgrgc wealD from lhe
Ulrbi.ne- s to a condensa fmm ltkb i1 is pu.mped .adiabakical!y bad ~a tbe boiler. 'Ibc
pc.w."e.r prndue-cd by the blJ'bioc ~ much pe - moo the pump teq_uite~D~eru.. and tbl,; t'll1 pml~r
a
oaq;xrt ~equal ItO l(be dllfemx:r bet~ w rate or bt:at inpm in the bolla I If ' md the tiUe
ofbeaJ rejection in Ihe condemiel' IQcl.
~ fliOtt$Sd mat OC:etlf M lbc wartiog ftuid fl~ around the: cycle of fig_ 8.] are
~ by lines oo the TS dagmm of Fi!- 8.2. ~ quon o f liDC$ sbown Qon(onm
to u CantOt cycle... Step 1 ~ 2 is tilt vaporiz.atian process tnkin,g pl3ce in the. boiler. l\'ilcrrin
~ llqoid et ~ ht2t at lhc OORSianl lm'lpr~Uture rn ~ and ~ -
npar. Seep 2 --.. 3 i~ a ~e. adiab:nic ap:msiOIJ of urnted Yapotr imo the ~
rcgiun lO pruc:iuce a mixlute of santt.atr.d liquid snd \lapOI' Tc. This ntropie ~ is
~ed by " \'el1kalline.. Step 3 _.. 4 is a partial rondetlsation ~ wbetei_n hem i~
~ l"c . Step 4 -+ I -_ tile cyd~ bact to itli ongin. prod'Oeillg uurated-liquid 'Willet
a point 1. b is an bi'Opie compre:ssioo process rep.e~ted by a \'eftical lint.
Thl:.lbt:nnal tfticiene~ Df the-~~ cycle jus1 dc.\eti't~41 ~ gi\'a~ by Eq. (5.8). As a re\'ersfble
cycle. iJ could seA-e as 1 standard Df comparisoo rat actual n~am power plants. ~W'i't'J,
~.ere practical dif&cul!ics deW dx opm~iitm of equip.IDI:_nl intended to auy out ~ 2 ~ J
and 4 - J. '1Wbint' th:4 tilke in $8DlfMCd ~ product' an ~ha~ with high liquid contaiL
Ob as pro eg1das por d1re1 os de autc

wbi'cb ca\liles ~~co problems} E-,..om tnoJitl difficult utx <t~ of a pUmp 'dial '
in 1 mix.turt of liquid 2UJd vapor (pOinL4) rand ~ a satma~ liquid tpoint 1). Rlr the:$e
n:wlOll~ 011 :altanative model cycle is Ideo as lht: stAndard, at lellst fur fussU..fucl-bwning
power plants. n is: Cll.led die RtJn.tiM t:}'t:k and ,diif&r.s fmm llbe cyde of Fig. 1.2 in a~ lllAijor
r
r~. F'JJSt. lhe- bming itep l -+ 2 iB cmird idl be)IOOd \-1I_JJOI'izatiOIL so as. to pnduce 1.1
~~vapor,. and 5CWild. (he cwtiog step l .- 4 ~ about cump1de eoud~
y~g mttmitcd Liquid lQ k p:rmp;d to~~ Th ~ru: ~e ~~ u~ QJ
the fmD" steps shown by IFJ,g. 8..3~ and described as tbOvvls;
~ ~ 2 A C&mSbUit-p~!iU:IE hcarillJ piQCl!5S in a boikr. The t.tp li " aloog 111 isobu
(lbe ~ of the bmler). and eo.ncsim of lbllee sections~ beating of subcouled liquid
water to its saturalioo tmlpenlw'e. \~on at c omant tempc:mture and pressure.
aDd upe~ng of dl ....apor to a.~atup; ~n above it~ utumLion lmlperatUM-
2 .... 3 R!e\-'ei'Sible. adtabalic tisemropkl ~ of wpor In a tiJJ'bl1it Lo die~
o llht: coodenser. lbe step oonn:illy cros~es the sarnration etll"\"e. pudiK:ing aJ we~ ex-
~s Htm'CVGT.. ithe ~ iiCC'OBiptisbcd mstqJ 1 ~ 2 shifts~ velit:icalliDe fill
eoough to 1be right on fig. U lha1 tbe m~Uil:i oo'*ot M~t 100 brg~.
3 .,...,.. 4 A ootm:mt.-presmre. OOMIMl-tempemltlfe process in a coo~ m pnx1l'ooe
5&1)unted liquid at poim 4.
4 ~ l ~ible,. odiabillie (~pi.c) pwo.pifig of~ sawmred liquid m 1 rht; ~urt
of the boiler, prnducmg oompR&"Sed (subcooW) ltquidl 'The' vertieal tine fw~ Jen,gth
is ~ in ..13- 8..3) ; very 'bon, bcC8USIJ the ~ rise assocludl with
oom~n or n liquidl is mun_
'I fltun lA~ Simpk

patlcul f'll~r e-yd_e..
l?bwer plants can be buill to operme ou a. qde 11m: *pam from lhc Rankine C>~ sutely
booause of thG irm'Enibilities of the work~ing mdl wort-reqolri.n,g steps. Figure 8.4
1
Hnuthtlblr... prt:ii!M. .) trudellt pr~ plallfS J!;mletlW' ~ ~ -~ ope.rar.e \lrifb ~ deslpd to
~ liquid! \'llit~ SUI~ o( ~C!IL

~ the efmcts ol mese
~~. on steps 2 -;. l i1Dd 4 ~ 1. ~ l~ me PO
laojet ~ but laid in die dBecUnn ol~otrupy. The tw:bine exhaus is motmJllly
stiU ~' M Ions s tbe ~ ~l iJ 1h:m alJout 10%,. crns.ion problems are
not saitm!.. $light~ of n ~in rhe ~ iDIIy ooau:, bul the ,e:ffcct is
~
11m boiler rvcs to bm!CI' beat fmm a baming fuel ~or from a oueleiat rm;;10r) en tht;
cydcw and tbo.OODI~ ~fat ftom die C)1dc to the~ . glcdirng kineQe..
ODd potential~ ~ ~ ~be meJD ff]l\1i(ID - Eq . (2.31) t~Dd (232). in_ eilthGr
~Jto.;
I
@ 5
(11.2)
Exampte8..1
Steam genel'ilted In a power plant a~ a pressum ~o1 8~500 kPa and a temQendure of
~C is fed to a turtlifte. Exhaust m:wn the twblne enters a condeftser at 1o ~
where it is condensed 10 sawmted lkJdd. wl*!h i&lhen ~ to tlle ootler.
(a) Wnat is the tnerRtaJ eff!dency of a Rankine cycle operating at these condi..
lions?
(b) What is the 1hermeJ effleierq of a~ cycle operattng at Uxtse conditions
It the~ bn'bJne efftCfency am ~P efticiency are boll o. 75?
(C) If the ldng of th& [pc'Nier cycJe,o1 pan (b) is ao~ooo kWi wha1 is me .ste8JT11 rate
and vmat are the heat-transfer rates Ill 1he baiter and condenser?
Solution 1.1
(a) 'fhe turbine opemtes under llle same roodi1iom. as 'lbe turbine of H.l. 1.~
~ (AH)s ~. -1 ..214. 2\'J k.g,- 1

"flws W,s(~D:) = (ll.H b = - l.l14.2k.J q-1
lorem~ the edtdpy mlthe end of iseotmpic'e:lplfi$iOD; 115. in l!x.. 1.~ i ~Jete:
H~;::::; 2.111 1~4 kJ ks- 1
ThemthnJpy of nmned liquid at 10 kPa (and , iJ.C ~ 4S.83"C) is:
H: ~ 191.8 kJ ~cg-~

1'111.18 by &J- (1.2) appli-ed to ibe ro~t
~Q {~n~') ~ 14 - H) = 19t8 -l.l17'A = - 1.9!3.6 u ks- 1

where me minm 8igD ~cs that he3t 11oM Olll uftbe. sysem_
The pump ~ rundu r.ssrntimly abe im~e conditions as :tbe pump of
Ex. 7. 10~ \\rben;
W~ (~~) = (AHJs l::: 8.7 U kg- 1
~whence. H 1;::: ~~A, (~H)s c::. 1'9U~ + 8.7 c lOO.j u lkg- 1

The ent.balpy of snpetbeated Steam at ~600 kPa ~ SOO"'C i~e
H,. = 3.J91.6kJ ~-
By Eq. (ttl) applied to the ht)ilot".
Q(bollet) ~ Hz -= H1 = 3,.391-(),.... JOO..S = 3,.19tl kJ ka-~

The 111e1 work of me IRanJdne cycle is 1he rom of r.be ~ wad:: and lbll: pump
a"'Ot:
Ws(lbnldue) = -- 1,.214.2 + .7 = - ~.265.5 U k@.- 1
'Ibis result is of ooune BlsD:
W.. {~kine).:; ---(?(boiler) - Q(~~)
= -J.I91.1 + t i9l5.'6-== ..... JJ.65..5 kJ kg- 1

1b:e tbennal e:Dieieacy of fb~ eyde is:
_ J W.,; (Rukindl _ ~.,26S.5 _ O~~
IJ - - - ,-1 ::nJI!IJI
Q(bQilft") 3,19LJ
f_b) Witb a nubioe dliclcocy of 0.75. dlcn also fnmi 1:11. 1.i!
W.t(l.utbine) = llH = - 9SS.ti lkJ q-
Whence HJ ~ H'l + ~H :=1: 3,391.6 - 9.5.5.6 e 2.436~0 ti q -1

For the c:oodenser.
Q (~~) = H.., - H.' = 191 .8 - 2436~ = -2.244.2 tJ kg-m
By lk 7. ~0 f1),r di~ JPU~

W, (pump) = AH ~ II,.6 kJ kg-~
11:1e wort mthe cycle J51berd(n;:
W.,(oel} sa - 9.55.6 H .61!!!! - 944.01Jtg-1

Wid H - 11.4 + llH ;;;;; t9L& + JL6;; 203.4 tJ 'q - 1
llr:nt QfboUer-)::!! H1- H, o 3,191.6 - l0.3A :c 3, 188..2 kJ tg""' 1
be~~ dficre..:y of the cy.cl1: is~~
"
:c: J\V,(net)l ;;; 9-W.O_ ;;;;: 0.2961
~ Q(baile..r) J, Ut8.2
~ ma)r be co~ ,.idJ the :msul~ ofpa11 (a).

(c)' 1\lr a p)WI!f" nsting of'S\1.000 kW~
lbeD by Eq. 1).
Q(boil~r_l :=:; (8-t75J(3.18&.2)!!!!! 270.1 x lfr' tJ s-

Qf.~J = ( -~15H-2.244 . 2) = -J 9C).2 )( Jol :U s-1
1be Uwmal efficienc:. of a seeam ~w cyde is ioemased lim

the: ~R aod llcla lille
'liUpm.imtioD lempem.tnre irJ dJe boiler is ~ Jtl U abo mart\5d b)'~~ SU~
iD m boileL Titus.. bigb OOilbr ~~ and ~tuR:S mvar
bigb eftltiencle:s. However;.
lhele same OOirtCitiliom riDcrease the~ i~ mll be phil, bceausc they n:qnm: ~cr
~ttion ,f!Jld Ql(lfe cxp:-m.""ivr ~rials or<:-on -f.Udion. M~'ei'.. lbese COSI:.. iDcrease ever
~ F~'j liD motr ~ JJditiD De irnpose~t ~ mpJ'adtice J10'Wf plmJI$ ~
~ .a1 ~'Uf'eS mllt'b abc:we tO,I()(I()tkh om- teotpefalurtS moob ~ 6()0"'C. ~ thmnal
dE:dency of a,pov.~pb:Ht ~ the ~and bence me tempe~a1me in die:~
Is rntoa.-d~ H~. ~ rondensAtion temper~re mus:t be higher thant dis ~re o
ILl!;
....._t:
cooung ___.. , usu~,
mc:unJm.. . - ' ,, u
., .._, ~<~ ..~or
-...... ~ :.... ,......Y~.......,n...r '-r tr- . . . 1 .~ions or c-l.in'lare and
~AU ~ ... ~n.n,J~\S YJ UIA,Odll
geography. Power plants Wli\'~Y qperdle wob conden5er ~~as low as pr:Jdieal.
'Most ml:Jdem power IP1 O~ ,g_g a mod~ of abc! R~ntine cydc thM illlOQf(IO-
TG.tG ~dwJ:tCI" btt-.th.~-:8... ~.. 1fu.lm l.be mod~ llitMr dum being pumped dll'ectly Mok lO
lbe boil~. is Jim bemed by ~eam cx~r:~~:tcd fi:om the l.W'bine- ,.,... Jro:mullly d01te in~~
~ " rith -~ itu,k__.CII tmm the Qtrb.Eile 'ill srYt!rill ~ .s.tar.a of exprumoo. An 31'
r.rb.;gtmcm "atitb fum~~ lrilll=r~ a dlowo ~n Fig. S..S~ The opemting conditions~
oo this figure ond de:sm'bed in the following ~ m:e typit:d. and UJiC the basis 'f'(lf the
illu~ adc:.WQ.!ioos oi Eh. 8..2

p
-~ --
kPii ~---
g Oi'W!II
---- --
1k cgnditjQI]$ or -itta.m gaamtroo io l.bo boib ill\i me 'a.nK m 8.1; .JJOO kP1ll
~d 5000C. '1lbe ~ ~of~ tmmnt., 10 ~t u a.ho ~ ~ The ~iotm
tetnperaiUie of tthe e.:tllaBst steam is lberefore 4S.83C. AUowin@ for sliPt subcoolJng of
a. ~te.. 'i\""e ft:t tbe ra:rt~nue of 'the liquid ~ ti"om. d1t ron~ 31 4 C. ~
r~2.ter pump~ whitb ~ tlDilet eDCdy tbe C(Qiilions of rbe ~P m &. 7 .10~ ~
a tem:perature me of iiOOut l 'OC making itbe ~ of (be ~ emcring 'lhe series
of~~ Co 46C.
The salurafion tempen.tl!re of ~team at the boiler pre:ssure ,o f 8.-600 kPa is 300.06' C. and
the~ to wtricb the feedwal can be miscd in the beau is certainly les. Tim f m
perlllllte is. a de:sip ~~ \1lbidJ is~}' ri led by~ C'OllSJdctmiom.. ~.. 01
m~ must bG cbosm bdOK any lbmnodyuamic cabdalion$ c.;m ~ ~. Wt have tlieicf.-e
arbittaril.) specilled ~ rempermure of 22c.6"C for the r~ stream mtering ~ 'boiler'- We
~ .:dso $pcci6~ ttmt !.1.1 four fecdwat.c.r h~ aeoolDpliiflh the~ tem;pera,tu.ro rili!e. Tbos.
the rom:d ~ rise of 226 .... 46 ~ ~800<: .is divided imo rwr 4.5 C d1crtmen~&. 1'b:is
~std)lidJes all in~ feedwata rempmnmes at die valva si!K.m'D oo Fig. 8..5.
1h smat supplied ro a giva ~ftlwater ~ nm tr m a~ bifb enough lbat i1ls
iifnrmion lmlpe:Rrtllfie 15 abcn tba1 of the ~stream leaving Ole be;der. We haw kre
~med a minimum ~~ dl~ for llt!ut U'allder oflliO bs dla...D C, and have
chosm eDI'aaioo ~ presswres such dlat the ,iat vallles mown in U-= feedwarer b9.tm's are
al 1~ sc yeatcr than die- wt lemper;l.tUfeS of tbe f~er s.tremm.. 1be ooodmsate fiom

29
eadl.fcOOwat,heaftr iis flmttat ~a t:llroulc v:-a:k"O" to the~ th:c ~ .lol\ia' p~

m
znd lbe coll!ectcd ~ lbe lin3l bearer of llhe ~ :b tb(bt-d iiJ]br the: COOdrlfia. Th~
aU con~~ rrom ltu: ~ 1D die boikl by way of dle feed\J,;'aiU b=tas.
TIE plllpOSI: of hcati-118 die ~w4fer ill - w ~ m ~die av~ lempernlure
'which beat added in rue boiler. 11m~ I~ tb:amal dfieleoq of me plant,. wtridt is
said to opemre. on aJ rf:R:J!1leJTJ1ilr:e cyc11.
Example8.2
Oetermine the 1t1ermat effid~ ottiM pDitY8f plant sho-wn in Fig. 8.5, auum~ E~Jr~
bfne and pump etfidendes of 0 .75. lf its power rating is 80~000 kW, what iS the steam
ram lrom the boller and what are the heat-1if'anSfer mtes .rn the bOil'er and co:m:tenser'?
'SolUtion 8. 2
Initial cablations are made on lhe baiU.s of ~ q oi st~mn eotmng me l~
from me boibx. Tht lUibioe is 'in effeet divided iniD live seelioos. irldiared in
Pig. ~.,.. ~ e.101 i Cl~J*;t11 at tb$ end of Qcb ~b<m. rtbc Bow me in ltJe
IDl'bme ~ &om one- sectio,. to lbe: DQ1., 1'be ~~ of stc'm ~d
from die fii4it tour ~s are determirned by eoergy ~-
This roquires emtbalpjes of 1he c~ ~o\ta srre.ams. Tbe dkd or
~~ ut c~ ~ rl lQ a liQQid is ,Ki\'m tby l:q. (1.25t:
6H = V'tl ._ I)T)Ar (coMET)
s
.F'm santt-ated rlquid ~ at 226-:.c (499. J Klt the ~ tablel JHOvid~
p - = 2.598..2 kPa H = 911.5kJ q-1
lTi ;a&Ji;lion, !11bi$ l~

11 c L5R2 :.c 1 ~ K- 1
Tbu ~ for a~ dllnge from tbe ~~ m ,61)0 kPa!
6H;;::: t2Dl[1- (l.SlS X Jo-1H499.[5)~(81J00~.2$8.2' c 1.5 kJ kg-~
and H =- H (saL lliq.) +~H.-. 97t.5 + 1.5 c: 9-73.0 kJ q- 1

SimiJnr cakulatioas yleild ~ mlbn1ples .o f the fetdwt.ltN :l1t Q4bu item~.
AU ]Xl1incot values a:e ,given in the fQilowing lnble..
226 1:81
HM kg- 1 mc\\-aTer .:u..
f and! f' ~ &.6(X} kPa m ..o ni.J 517.4 38"i.S 200.0

299
~JJI)
f MOO~
t- ~
H -. l.3!ll.IG
.S !
FipltUi
SmiQnlof
lm'binr aod :firsl:
reect..-er heoUer~
n -~
Comider1be Drstl seftionofdle tuJbine and tbehscl feed'water beal:er. as mown

by Fig. 8.6. De enthalpy and mropy ofthe s1eam mtcrlng die twbint lllC fowd
fulm rr ~ t:l\b1c$ ftlr ~~ ~ 1'l':le mption of ismm,;pi:c ~~ of
srerun in ~oo I of me bllbin~ t& 2..'900 kPa leads 10 th rem~
U' we _ U(tJC '~.bin llhe 'Wtbinc efficlcoo)' i:s i.ndependem of the pressure 1n ~him
tbe steam~ then Rq. (7.16) giws:
A.H ~ J1(.0.II)s ~ (0.75){ --320...'5) !!!! -240.4 tJ tg- 1
By Eq. (? .14~
!In addiliolb the eu&balpy uf Bam~ f.rom itk' SCiioo of tbe twbioe 0:-
H ~ 3.391.6 ..... 240..4 c l.1SL.2 tJ kg-L
A. $imple ene.r:gy bat'!Dl~ oo me roodwater heMet res-tiiU ~Min me MSUI'I'II"

lion that ki.nerlc- and ~~gy changes are ll'llegUgible aDd tiom the as gn-
mems.. Q;;;: - ~;;;; 0. f..quation (2.30) thea ~\:lttS to=

~~~ tJ -kg -;
~ i:J _ _ , K- '
f1lure 1.;7; Secdon H

~~:ad~
fccdwlcr baler.
-
1bi5 r~!itli!dion ~es matbcoutica1 apressioo to me ~nt 1hal me l(ltO!I e:p-
1halpy e.banp; foe the: prootSS bt uro. Thus oo ibe bam oll q of 5t=m euteri:Bg
the IUrbiRe ~~- 8.6):
m(999'..5 - l ,]Sl.l) + (11)(913.0 ~ 111.3) ;;; 0
I ..... m c 0.90626 k.@

On tbe - af I kg, of ~m enttd~ lbe ~ I - m is the mlU1 cf ~cam
'Rowing into ~OD Ill of tbe lurbi
SlsWI(ln u of lire uabjqe m lht: ~ ft:rdwatt:r Inter ;m:..sh:Jv,n Fig. 8.7. m
In doing the 5.i1llle cOkolaDom as rm sedkm L we ossutue rthat caclJ kjJo,pim of
~ IC*Ving ~on U ~from i ~ allh~ rurf1w cnlnmt:r to lbe exif
of section D \Vit.b wt'ef"lidency of 0.75 ,l"Om~ widJ i:si:Dll'Opie ~:OIL The
anbalpy ollhe steam leavins itioo D found m llbi!i ay is~
II ;;;;;; 2,987.8 kJ kg-
Then no lhe baiis of I kg of~ entering 1be UHbioe.

W1(Q) = {2-.987.8 -3.LS1.2)(0-90026) ~ - 143.08k.J

301
AD ene~JY b~ on me r~n- hcatt:r (fig.. 8.7) gi\le$:
(0.0C)'l74 + m j{789.9J - (0.00'74)(999.5)

- m-(2,981.-8) + U)(Ti J.3 - 571.4) = 0
Noce mm1htolnl[ing. me '~ns-.ate me.am does ooc dwtp mcruhalpy.

1Jbese re8lllrs aDd rho~ of lfimilru- eill~OM for tbc ~a;ifii.ng ~lb. of
the lllrbine: an: llL~ in the aceomp;~nying table. From the results sbowtL
.m ;l
HAJ kg-~ W,JlJ ti~Cat m/Qof

illi~OO forseai.oo seL'"IiOO Slant
exit em Sn\te e:urad.ed
Sec. I l ..I.SI.2 -240.40 303.65 Supe:dx.ad O.&Jl74
~
Sec. D 2.981.8 -141108 212 48 ~m o"o-7928
vapor
&c"" m 2,827.4 -13'2.65 Jll-84 Supnbeed 0.06993
vapor
Sec. IV ~6S, J .3 - 133.32 %.00 Wdwpor O.G6257
.. = 0.99[9
Sec. v 1.4j5.9 -14~..59 4$.&'3 Wet vapor
X ~0.9318
Thus for every ldlogr"-.rm of ~ RIB tBtering lbc mdlhlt,. the work prod~ is
804.0 kJ, and 0..30$5 tg ,o f steam is ' ~ from the IUfbine for 1M feedw'Dter
~. The wmk ~by me~ is ~Jy ~ 'llwk ~ rur ~mc
pump tn Ex. 1~ 10~ mat is.. 11L611d. The na wor.k of l'he cyet.e M lhe k&"k o.f 'I tg
of 5t:eam ,gc:n~ in lhc bulla iB thae.fwe~
w.llld) ;;; --104JO + 1 ~ .6 ;;;; -19~..$ kJ
Q(boiler) ~ liH ~ 3,391.6-973.0 ~ ~418-6 U
_ I W"<naO I _ 192.4 _ 0 J"YfA.

fl-
Q0:10iJtt) - . -
2.418.6 u r
This i~ a S.,mfiamt ~V1:IDCDl over tM value 0.2961 w:E.x.. 8. l.

~
., Ws (~) - 80,10J lOO tW - I

m ::::' W., (net) = - 792.4 -- ~ ""kg
1bis is the steam mte to the biJbine;._ ased to calculate . - ~QII'3BSf:e.- ...ate in the
boilM:
1be be t-11ilDSlet rotc to the coofing v.'tler in the oondenser is:
Jl(condenscr) ;;;;. -Q{OOiler) - W, (na)

'=' - 244_2 x 1-0'- (-801,0 x toJ) = -116J.2 )( loJ kJ -I
Abhmglll& stmm ~00 rat~ hi hig~ tfum. lQS fuuud m. lh. 8.1 . die heal
tma._-defra m liM builer &Dd ~are ~Jy ~ bause dJeU fuQc-
ri . Me Pfltti)ltdeu ~r by du: fced..,xr ~
[n a ~cam power plam, the ifeam is ZJDioen medium to wbicb ~ is 1ramfetmd ti$m a
'*llDng fml Of froiQ ~ not'lew ~OJ. It i5, t.bcti;fore ~krized IDJ large heat~er
mrfm:es: (I) mr ilfl:e absorptioo of kat by me Steam at higb temperttlute in ~be boikr,. and
(J) f(llf tbc rt~P ~ brat from tbe st~ at a n:~~Y krtlt wnpermure in the rondettser.
l'be dis3dwnmge is lhtn wbeo beat ~ ~ ~f~ ditm1g1l W'Jils (as dm!ugb lbe. metal
waib of boiler tubes) me ab1ilily or tile wa.lls t() \rithstwd hi~ t~b.u'es OJJd ~
i~ a limit on d:Je lmlpcracure o.r !ben ~ ln m iin~oo m~c. oo
lhi! otbi!r blllltl a fuel i$ bt:nned widtia the en.gigc itwlf-.. and t:bc comln:~scion p.roduc$ n.'e
as the. wortin1 ~ acting for emmpfe oo .tt pi8too. in il cylmLfc,r, High t~~ ~
i~ tiJd do 001 un-olTC heat~ SUI~
Bumitng of fuel \\oilhin rdJe. inJem:d..wmbustron, engin~ eDmpltcates ~mam.i~ ililliJ.
:f5b.. M~. fuel aDdl air ftow ste3dily im& an We.milll-cOillhWiiJoo mgloe and ~iBn
~~ ft(iW ~y 0\11 ol'it; oo "Ofltio.g I1ICdium ~a cycllic ~- :IS does~
In a 5team po a planL H~. for ~g ~ mud~, ,Oge im~IIQ C)"Clk: a~giRCS
with air ta the Y~u:ki:DJ ftojd. tmd :m= ~ in pnfoJ"''rum!Z to ucnaa1l i:~mal~,'Oil'lhu3lf:on
~g~ bJ ~ lhc OO~tioo ~q> ' rt~d by tm addition to 1he. air of an equh<alenL
:m1oom ~ beu. In ~~A't.;u foll~s.. t3dl ~--a-,m~ioo ~ is illt.rtlducad by a qu:di 8
la.tiw. ~ This is foDov;.'< by a qumtiwi\-e anal~ of ao Bkal cydc in wbJch iii~.

~ B! a ideal ps. wiQ ~r.;tmt he:at ~ ~j; cbe working mediu.m.

103
The Otto Engine
Tbe mD$t t0Mil101l ~~ ,engine~ its ~ i:n WJt(jjf}l)biles. ~ the Ono

be(';iiiOC of
m.gin~. lts cycle alm:~ ,o f our ~and S'tmS 'w im aD tiBmke stroke at essenJiafJ:y CODSIBDl
~. duriQ whidJ a ]risWD Rl!IJ'~Ill Q~Jtward ~"$A fyd/WJlli~ intO" cy~ 1'1Q$
is replC!ented b'y lime 0 ~ ~ iD ifi~ 8,8. During lbe. seeo_nct ~ ( I ~ l ~ 3l, ali valVes are
do5ed iiOd'lhe fueliaiT mi'WKis ~ ~~ ~y ~~doug line~'
J -) 2.; ~ ~ttu:e u 1ht11 ipjttd. and ~~ron ~~ $0 ntpid.ty blt~ YO'Iwfit ~.ns
neatly OOGSUit'll .~hife. the pressure mes afOO@ Line segment 2 -+ l . h is ~ 'b dtiJd
scrob (3 ~ 4 ~ J ) that "''A is produtal 1'hc ~~~~~ of
w~ ,..,and~ a~el)' ldi bltii:ally doog ~tine ~ 3 -.. A ~ 'We~ \o-al..-e
l.bm opens :mrJ Ole ptes:.mm fulls rapidly i\1 neatlyCDMCUII YOJu.me oiODJ lin!= &egrnen1 4 -+ ) ..
Dming the fOUJth or em'WSt ~e t{line: I ~ Ot, die :piston puihes the ~ ~otJJ
~ (Qctpt for tfle CQO~, of fht: ~ volume) r-ro:m dJe cylinder.. '1."he 'iOJtJJ:De: pl01.1cd
to Fig.. 8.8 is:~ totaJ 'V01'nme of gas Clt'Dained in lfrle cn.gint berwecn 'dre pistoo and lhe cylind=r
bead.
The elifec'l of UK:reasiog abe eooJPMSSion raDo.. i.e.. 1tle r.uio of the l'Olu.mB5 at tbr qin..
rnng agJ md or co~siw ftvtQ poinl to P1inl ~ t& 1(1 illa"ea.~ tbe efficiency d 1be: engine.,
t..e., w ina:'e38e lhe wort prodw:ed per umr qwmtit)' of fueL We d.emon.wa.te' Ibis for' an UJe..
aJizcd cycl~ <C1II1ed dJ& m~ OUo cyclt.. dJowe itt fl,g. 8.9. II cw "'. uf rf ii o ~tic
wuJ tWOlX'ml'llttl-voiUIJX: ~ wbii:h COIDf.Xi!.e a heat-engine C)'dc fUr whidlJ me 'orlCD,g
dntd ~.air, cotmdered an ideal p with oonsttmt heat capacities. Step Cb .a f!e.OCB1lle ad_ia,
balD: cv~~ fo~ by ep DA.. in \VhidJ ~ ~ i! ~by fbr. m lrll
~ \.'U]ume tu tillsc m re~ wtd ~to the \'iillles ~g frcm cODlblh-,aoo
in a.n-.:tua1 Otto~ Then themis ~~J" and ~bty (~liB). and
~ '!.! ~ ml~ (~ BC) tu (he inibftl -:cat C.

The tbemml e:fficleacy ~ ef !he air-standmd ~~in Fig. 8-'P i :simply~
- IWt Dd}l -
"~ Qolt ~
f2D1l ~ Q,,
QJJA-
8..3}
FW 1 mor o1 mWith cormJWt r:-t ~]Jicl~
Substituting.~ apre.~ions in Eq. (1..3) IJ"vf:s:
CfT."- Tnl + C\f (Tc - T,a)

Jj1 =------------------=-----------
C!r(T~ - Tp,)
T1 - Tc
or JJ c I-------
T;t .... TD
Tbe dldmal efficiency is litlard. m-a Mm,pt:e wa,r to dliC compl'tSSioo mlu, r l~c I Vo.
&m ~are ii-n :Eq. (8A) is, repilD:d b) on ~opriatc- ~ fiV I R, in aceord with IJbe
ideal-gas eqnaion. Thus.
~ Pc Vc
c= k
TA = P,- V~t = PAYv

R B
Svbsti!Qtiug Wlo Eq. (L4) ~ ao~
fl =]- .................
Vc
Vo
(Pa -Pc )
P!t - PD
:; l -1' (PIJ - Pc)'
PA- PtJ
fQr the t adiabat~ rt,~ stql:S, {IVY -e ~~ HelKe:
P,.V, ~ PBVt
PcY/ _, PDVb
~~- a:retmbid mel~ tbc ~~

'PA PA. 'F'w P.~
- - ..-.- w tliee - - .... I ::; - - 1 Qf
Pc - Po Pc Pu
f 8.6).
This~ shows that the ~ dficitot-y ~ npidly with the c-~n nmo,.
en :low~ olr.. t..u fl1lliW dow1y m ~gh com~oo ~ 1.bis ~ Wi'tb mt ~ of
OO{ilDitf$1$ on 0tb) eng.~

The,Diesel Eng/118
Tbe fu~ diff~I:'!Ce betw"n 11tt Quo eyt~e and ~ DJeseJ eyGle- is llhiii in the Di d
cycle me~ u OJe Md or ~m ~& sullideru.Jy Ngb dim: comtm1lioo is lnbia~ec~
~y. This bigha' mmperam~ i'e!il!lll.'! beat.~~Se of a b.i,per com~oa ratio thai
~ lbe compess;on step to a b1gber ~ 1bc fueJ is ld mjUd unUi tha cmd Q{
~ collJI.IlQsivo *P~ ud tbe:n is added Jowl) ~ooogb mat dJe comkrstioo p~ ~ u
a~lmately coo.~~aru pre~.
For dre same. mmpression IJ'alio. !he Otto eJigjDe h:ts a higher dficieacy than the Diesel
engine. Because- prrignitioo limits c.bo W~I1D ndlu a;tta__im(bJt mtbt OW, en,gine, k
Diesd engine ~at J:rl~ eoo:tpretifoo mtim, Mtd ~uetrtl~ at h.i;g'IBY efficiendes~
Example8.3
Sketm the air~standatd Diesel ey'de on a P\l dagram. and derive an equation giving
the t:hermaJI effid8ney of Ulls cyo1e Ol Jfelatiofl to tne OOmpreSSioo f8lio rr (r&fiO of V()l..
urnes l!d the begiming and end ol'tt. oompr$$$ioo $ff)p) and me (9plllti:Don mHo ~"<t
~ratio cfldumes at U.e end and begtnning ot the' adiabatic expansion step)~~
"''1lc air-~ DJcsd cycle is die same as ~be air-sUUKbrd Otto q->ele. ~ l!mt
lhc hcat..absoqni<m ~tep (~g tothe oomlxL~oo ~ in roo actual
~D,gloe) lis 4t coosiam ~ .:u mdlc-~ed by lme D" ~n fig. 3. I 0.
I
a..
On the tmD. of l1 mol of air" causidacd to be an ideal p.s with ~ ha;t

~tics. tlr heat qtfJintil:ie$~ in $tCp D A and ~ in s~tp BC Hnl!:

'1- 1 Qsc ~ l + Cv(Tc- T) = 1 _ .!_
QoA C~t CT..t- To)
(TB- Tc)
i' TA- To
{A)
For .bJe. adiabltic ~ (~ AB) aDd n.-ve~ ..diatr.ltic oou:rpn:s-

sion (Sfq) CD) .. Eq_. (3-t) tpptics:
TA VAy- l -
-
"]" v y - 'l
<LB 1
7'
D D
v,.- - ... l'y-1
c
-~ c
By dc.tinitioa. ~ ~ JUde is r
rtWO i clefined r r := Val VA. 1bus.
~ . ,. ..
Tc =To ; ) (
Sub.ltlitutfng t~ c . into P.q. (A) ~:
l. [ TA(l f r,)J-l - To(lj r )Y-l]

n-rt - - (8 )
Y TA - To
A_b PA = Po, and ftom 1bc ~ equ&oo.
and p,._ V.A = RT~
Mateo\ e:r. Vc - Va~ and tben:i'OI"e:
To Vn Vo f Vc T.-
T; ;:; VA :::;;- V~/ VJJ ~; 7
11ris relabo.n eo~bb.ine!. wl1b Eq. (B):
.
J? = [ - -
L
i'
[Ufr~J"- 1
- tr.-Jr-Hl/r)r-~ ]
l - ,..,,.
or 1l = 1 _ .!_ [ Uf r, )Y - (1/ r
)" _ l f r#t- lfr
r] (8.7)
The a..-Turl.tlne Engfllfl

Thr' Olto and Die.~ CD~ ex.em:pfify direct use of me ~ of higb-tetnpefBl\Q'e. bi.(th-
~~ a&tiDg on a ~ witbiu cylinder; no heat trmsfcr v.i dl an exremall omee ~
n:quj mil Howe\.'el'. lurbines are .tDOl'e efficient rban rtd~1liog eo:ginca. nod ft $d~t!$
00' uuem.aJ comt..aStion ~ ~d witb those of the l\.at)ine in me gas-turbine- mgime.
Tbe gas JUllbine ~ ffn'Ven by ~.e:mpen.ture ~ trom1a c:om~on. ctw:nbt.Tw indi-
can:di in Pij. 8.1 t. The cnt.erin;g WI' ~ cclll)JMSSed (wpercb3argedt {0 fl pre.!b'Ur'e of :se-~ burs
bd"tft com.flu,.-.l.!ic.n. 1lu= t:curs:l[upl , ~ur O,pCnU on the same sbaft tbe twbiae.. and
put ofae ark ,o f lihe OJJbi.Dr' set'\~ co dd ~ ~ romprrAS~X. Thr biglrr the tmtp:rat'ulr tbe
Obras pro egidas por d r itos de aut<

301
===== . -- Full
~gases entt_~ tile wrblner lhc higher 1he efti:cienL1' of the wt~ le...lhe- .~the
'WIOik pt"'ddlced per onn of :fuel burned. 1ibe tlinillDg temper.ati~Je is determined by rthe smaglbr
of tht: ID!tll' tuJbine bladS:. and is much lower than rthe ~ ftarne tMI(llmltute (&.. 4.1)
r4 tbe f1.11e-L ,snmrie:-ot ~~air :mu&t be supplied to keep dw: e:omhustiDH. rempenm~re at a~
few~.
11ue ~of..._
. .- mril-mfbi.l:ie CIJ&I..._,
. "'~ cr- .. . . B-raylOD ~~le.
,,.... rolled~ ~i! diM~t!fi
"""- a....., . oo a. PV
diagram iu Ag. & 12 The wom:._g 'fiWd is Clken a8 ~ considered an ideal gas with constmt
beall capacities.. Smp AB is ar~ble adiabatic ~on from PA (.a_tiiJ:OSphcric ~)
hpn ~ ilmleyclt fur ,-as-:~mgine.t

te.. dtt 8 r.~)lt.M cyde.

308
to 1'~ - In~ BC be3t Q,.c, rep~Dtitl! ~ u ~ m cXIftSWH ~ mmng t:be

atr temperamre. A work-pmduci:ng isentmpie ~of die air roo~ lite ~ from
l'c to Po (aill'lOSphaie rnc:sswel Step 0.4 ~I~~~~ tb;rt merdy
COMpli;&es due cycle.. 1bc ~ effieienq' of llhe ii: er
q ... ]'W(lndll -- JWcol-- WAIJ . )
f11JC Q:sc
where ream energy quaolity is !based en ~ mol of air.
The wort don~ me air fiW ~h ~ OOm)JIC il ~ by &j. t 7.14l, md fotr
,tiif . an idr..al gas wUh oonstam heat cap~~
tf..\B = Hs- IIA. = Cp(TJJ- T;)
Sllbslilutiq ~equation into Eq. ( ~) and~ bdi to!

TD ... T..t
t~~ 1 -~~ (8.9)
Tc- TJ
B=nzg: p~ A B' and C D are i~opic.. the tem,perarures rum pressures are rehwld by
Eq. t l.30b):
(8.l0)
TD
-~......-
( ~'} b- 1)/7 ( p A) (J~-1}/7'
..:!W!I!I!Bft [ (ltUl
1'C' Pc P8
With d:Jege eqnarioo, Tr1 and TD llli1., be elimim:ned t.o ,gk
{8.12)
Example8~4
A gas--turbine engine wtth a compression ratio P,1PA ;;;: 6 operates with aJr entenng
the compressor at 251)C. If the mbir~Wm pellfliSSibl91eftli61'8lUM mthe tumne. is
~c~ determine:
(a) lhe ceffiolency 11 of the ideal air cyde for these conditions H r c VJ.
(b) The 1hermaJ eftlcferu:y oJ an air cyde lor he ghen condltioM if the ccmp.ressor
and wrbine opar:ate ~but intnr~JJStiy with eflicfelilcias 'It - o.as and
fjJ ~ (1.86.

3()91
SOlution 8.4
(ol Oiled substlitution io Eq. r8. 12) p 1be ideaiC)'4;.-i'e efficiency:
11 = 1 - ( 1/6)(1.4-0JLot = I - 0.60 = 0.40
(b) Jm:\.--ersihilltms m liolh me rom~ .Wid wtbir'E recttJOC. dle ~ dfi ..

~ of the eogl~ became 1m: llet \\"'ft is tbe d)~ between rthe wk
mauntd by the compNSSW wxJ k ~ld prnd:u:cod by tOO turbmc.. 'The cema:au
hlrC of~ air eructing mr .tvmpt:5Sur r..~. and dw tnn~ of e nlEriog
the rtuJ'bioe... me spedAed maximum for T. are the saJile as for the jdeal ~.
H~.. tbe tom}i.aaturc' ~r ~blr: com~ in tile ~r Ta is
b-
bigher 1han me ~~ramre aftm i.stnlr.opic ~ 1~ ' and 'tbe lt'mperc4tl.lfe
after ~e eApmsion in 1be tnr~ To is bigber ib>1a lhe ~ afta"
~fie exp;msrio:o r;,.
The lhmn.'d dlicicncy of Lbe engine- is givm by.
IW(turb)l - 'W(annpl
flC Q
The tvM wolk 'l fftm Me foond. from me ~0118 for isetttropic ~
I W(urfb.JI = fi;C,.(Tc- 7'J>)1
W (~);;;: Cp(TI - TA)

' A)
l'k
The ht absctbcd to siirmknc corolmstioo
(? ~ Cp{Tc: .-.. Ts )
~ ~eq-uations ccmbine ~l) yield:
'1;:
ft,(Tc - T[.J- (!/'1cHTi - TA )
Tc - fa
An illtentaril~ a:pn:Woa fQf the~ work is':
W (comp) = C, 1B- T...,) (B )
Combi.ning Sqs. (~)and ,f B) and usiDJ cfie 1result to e.limiruue TJJ from dle eqwttio111
for if ,gives.affti" sitnp~Oil!
~ = lJ't'flcifTc! TA- T;,J T")~ ( fB / TA, - I ) (C )
t~.:(Tc/T,t ..... J} - (11,/ J:-\ - l)
"~"be mtio ~C / rr
fA .UlliO'pcR~,g
a-. - - ..... t)Q ~
~~:.:.""' '
\.V,Uiii___IUl_l(IS.
wn..... . T'
J. l-llll r.lOO - B I !1-
I A 15: R 1--..1
llll,j:U lQ
lbc pes.s~ emu :b)~ F.q;. f&. lOiJ. ID. view of Eq. (8.11), lbe rut:io Tb/ T~t 'a m be
~as;
T~ _ TcT~ _ ! (P11 ) (y-~ t/t
TA T4Tc TA ,B
3t0
s~ ~ex~ iD Eft (Cl yic~:
lfll JJct1'c/ T,~~)(I

- 1/ a)- {a~ I)
'J = ---=---~-~--:---.......-- ~8.13)
- Jk(TcfTA -1) - (tv- 1)
Ct :::. ( Ps
p~
)(- U! y
Otic con
in~
oow 0, &}.. CSJ 3'
11Ja diiC l~ cDic~ of die pHorbine: engine
the ~ td' lhe air entfting dJe ~ (fc ) i.ocreases. and
~c: enm~ and~ cflicim:ic:s lk and 'll1 ~
1ibe gl\"eft efficieOO)' ~Values 11R' ~
Tc- 16G + 2,13..1:5

T; = 25 +271~~5 ~ 3"47
0' ;;;; '{6)fl 4- U/ L4 _ ].67
~ dleie qua.n_dt:ies HI Sq. ~8..13) giVdt
c (O~S6J(O.S3)(J.dl}( l - I f L61) - ( l.fa7 - I) = OllS

" <o,SJ)(J.47 - n - <1-67 - n
11lis ~ 1bmw tfmt. even wilb a com~ and 1tln'bine of .mtDar high cffi-
ci~ die tbmn;d ~ (?J.~) is comider-dbiy :redooed from me ttll:al-
cyd~ wlu~ or 40.g: -
8.3~ JET ENGINES; AOCOT ENGINES
In 1be power cycles so far oonsidel!ed l.be.lrlgh.-.~. high~- e~~ in a

lUlbine (~ paww p1Gill. gas ~rumme) or in the eyfint~en or an Otto Of Dk.sel m,gme: ~with
~r~n; pi tom. In eidJa a. d1c ~ ~~. availabl-e ~ 11 rolalin.g_Bibaft
Aoo~Jier ,dmee for exp:mmng lhe ~w ~is a nttme~ ~the pmt."a g ~bl~ 35 ~c
en.qy :in the jc:l vf ~ pses le:a:\<ing lbe nozzle. 1'be e'iDtire pow plwn. consisting. of a;
~M clc-vk.e and a~~; ~ wd.l as~~ i~ bKR'Iln a~ ~je1 eo~
BcL'3'WS the ltinedc energy of the ~ ~ iJ directly :n'illlitbk! for pMp(~lUng ~.be' engint:
i~Dd.lic$, atrt.~.tJuhems. jet tgincs aft: IOOst commoul)r QSd to :powa" aircrnfl. TheJe are sevmd
t)"peS of jet-propols.ro11 mgines b~ ed on d1 lTe.rent wa~ of aa:ompiWMg chr Mmpre.S$i.on :llld
~n ~ Becau:se tbe.m A:ritiugdte enp bas tiodic-energ), (wi~ respea to the
~h u prcnwr t:LUJ be ing-ca~ in difr~

311
The 'urbojet en~e {usually caUedl siml'fy 3. jet engine:) il.iustrated in rt&g. 8. 13 !takes ad~
l~ ofa.ditfuserto fed~ b- wort of compR:Sl.iion. The zmai-ftml ,com~W' QtiOlplete.s
the job uf ~on,. and lhen lbr flllel is. injcdcdJ and l:tumtd in i.lw ce~iuo clmmb7.
The hex C'Oillbustion-prod'm:t .~ mt pass moogh a 1.iWiline whee the expansioo pm"ide:s
jus:~eiJO~lJb ]K1\m'tiJ drive me~. The~ oflbc:eJjpmWQD to~ edml8t~
~ ~ ~lisbt:d ill lhc ~- Hm:,. tbt: \~of lbc ~with~ lO tk e:~
~ ~ lD u le\~1 abm-~ IbM uf ~~~air. "lbi5 too~ in \~1)' ~ a tb.rost
('mrce) on d'te -engine in the ftli'\Wid direction.. If 1ibe compmmoo mid ex~on :pmc:esse,-s
are ~~ ;md fe""'tsible. 'the turbojct"'=D~ cyck 1s ideWeal m dle ide:W .~ ~ C)'de
shown in fig. 8~12. lhc only di~ .are ~ physie{i.(J)~,_ the ~o~on and ~paosion
seps Me carried 0111 m~ 10f dl:frtwlll: ~
A nxlc:el ~ dilJe:J$ from a jet~ in tllat 1t:re oxidizing apm is earned vr.'ilh tbe
engine. loitead c f depending on dJe ~ air fur b.Tmi~J~ lb: fuel the. roekel is selfr
~J:aincd- 11rls RJeall$ rb3t me
I"'('kot OUJ opentte in a ~um socb 4S in Oldd" :patr. ln1
fact. ~be perf~ is 'beltet in a. \'atl~Um. ~ oooe of the.lllfrltit is required to O\~me
friction f<J~U&
In rue~ ~ Liqmd foets. die. oxk~Wn' ~~m (e:.g... llquid ~oxygen) Is pumped fiomt
~ mttJ ttb~ ~liop ella~ Sim.ul~ly,. fud (~-g_, ~ lwrosroc) ~ ~
into die chamber and burnecl The ~on btes ph~Qe w. 01 eMtSianl biJb ,( RSSore and pro..
due ..,~....,~.,_.,AI\'_~ ~ -
_ IC:5 o.u.&"" ~~~ ........ -
. .,
+l..ril are nd d .. ~1' :-.;.A:_._...
lti.W~ ~ _ e.-qa e m a ~'e. IUI!UI~ m
- fii 0o. l4~
In rocb:as bum.ing w1id fue'ls abe Cue~ ,(~ poi)'IDEIS) and mlidizer (e.g., a.mmoniumt
parhlorme) are co-..ine!d tbgfthl!li in a w tid I.B8'"x and snm.-..1 01 tbc lf'tnt'ml!l end of the oniD-
bu!tioA ~~r--
Io an Ideal nr~.et, lbe ctJDihustitm. and e--Xpamion reps are the :same :u dtose ror on id.c:tl
jet engine t'fig..l. J2). A licf.fud rocket~ no~ WOJt. and in a 6quid-fLldl
tocketlll~ Hn~on t~ is $1\Ulll ~the bl iliad rmdi11rct ltrt ~ as liquid.q.,

12
1.1. TheN: ic qq;l rw ~~ pt.a.m i bown b); Fig,. 8.l. The unhiue u~
iabarically with iukt Sleam at 6~ kPa and SSO'JC D.Dd abe eWusl ~ t:n~Ln rbr
co~ so-c wllh a qual:iry of 0.96. . >turoled liquid \Ttlta' tea~"ti the eondenser.
and ~ pumped to the boilet.. ~ pump ort. and lk:indi - lind pglaltial-mcrgy
clwt~ ddcnn:i:Dc the tbemm.l efticieucy of me cycle and tbt tl.ifbillc efficiency.
I~ CUmat eapr with lhO as ll1t w t1Jihli4 opct1lttS &be cycle. lD fig. 8. 'l
'1'be H~O cimtlAI.i talC is 1 g -I. Fur TN 475 K and Tt" 300 K. detaminr.
a) Tbr ~ .lllaf.eS 1. 2.. ~ IUld 4.

(b) The~ .x iii SlaM] amd4.
1
(<') 1'bc mtr af ~ udditJpn.

(d) 1'be II'IIC of beiJ1 ~-tiont.
(~) 1bi! mh.micn1 po~ for c:dl ohhe four lrp~
(f) Tbc thermal etlictency 1J of ltbf' cyele.
1-1 ~mu ~ plJint opmakS on 1K C> fc fig. . . Rlf' one f lhe foU rm! ~
opera:ting conditio ~ l..be starn rule. the tr.It-tramfer nues in lbe boiler and
colldenscr, and the dH::rmal eHidaM:y lhe plllnL
(o) Pa = 14! = 10 - : T! ._ fJOt C: ~ - P4 - lO kP-a: PJ(mtbinc: - O..&k
=
Jl(pump) = 0_7S: pt:Mtt I'DI:ing 80.(0') W.
tbJ Pa ;::: ~ = 7.000 kPa: Tz ;;;;: 550 C: P) c: P,. =
20 kPa: q(nrrbiueJ ::: 0.73:
l}(pmnp)- 0_75: JlDVIlT mling ~ t kW.
d Pa ;;; 1'! = kPa; T: ; 600 C: P = P. - 10 t.Pa: q(lu:tbioi: 1 (110:
IJ(pump)~O.~ ~~=70.000 v..
(d) P1 - P1, ;:; 6.,500 kPa; T2 = 51S C: ~ ~ P~ ~ I01 J.33 kPB; q(fil(i,}in:) ~ 0.78;
IJ(punp) = 0.15! ~ natiq = su,ooo w.
(t) P~ - P,2 ~ 95p.-iDJ: T1.=: I, 0001 f); PJ = p.._ = l-1.7(pslll}! '1(turbi:nJ::;; 0.78~
IJ{pump)l = 0 15; ~ mtmg = 50.000
(f)1 P1 - P,. ~I, 12S(:p.sia); T2 ~ JOO(L P~! I'] = PJ = Upsiat~ q tmbinel ~o.BO:
q(pump); 0.75; povrer ntmg - IKUJOO t
Ob as p o eg1das por d re os d au
.JIJ
8.4. Steam enterS the tulbiJI~ of a pOVtw pb,nt O}OiWJJg OD lbe R1ml~ cyc-le (Rg.. 8-3) ,m
J)OO kPa and ~au.qu at SO 1Pa_ To 8bow OW.~ or ~g on lbe ~..
mance of tbe cyele. calwlale the lbcrma1 efficiency of the q"de and the tpmlity of rlhe
~ust ~ from the wroioc fm twbifle..mkt 5feiUII ~of 4S(ll, sso.. md
oso~c.
&5. Steram eut'eftl the mrbine of a. power plam ~g 011 l!be IRantim eyde (Pis. 8~) It
o600?C tmd ru~ lilt301kP3. T9~howtbc ~of boiler ~~On thepm<mnan~
&f me cycle. ~lMe me tbermaJ.e:ftioimey or me cycle Wld IE qudily mme e1haml
steam from the tUibine for boiler p~. Gf of S.<XIOr 7,500. aDd ~0.000 1 kPa.
1.6. A steam power pliant ernptoys two adiabatic turbines mseries. Steam eotem lfle: rust
lt1Itrioc at 6541-'C and 7,.000 \hand di~ fnml me
5CCood ~at 20 kPa "11:.
Y*m Is ~Did for equui power owpou fiDro the :t:~'O ~. ba&ed oD a l'W'b~
efficienqr of 78% for .mdr turbme.. Detmnine: dte tempenture ,amJ preuure of the
steam inr~~ intermediate st:Ue bcl'\l~ the twO turbines. Wbal is the ovcrdl dlicieDC)'
af the tWO turbine$ rogether wid[) ~ lQ isentropic eq1311Sioo of rtbe ste&mr ftOin the
mitiaJ m me firtal sm~e?
8.7. A stla.m power plant qpma:rin~ em a ~.nemtive ~-!r~ ru; iDm;flilllrd in fig.. '8..5, ill-
dudes jost one Ceedwar.er be4tet. Steam enJ:ers the tnrbme at 4,SOO kPa and :soo~c
and ~:~b~ ll 201 kPa. ~ fot the fttdwattr hta~a is ~d from ~ ~
at JSO kPa.. and in oondensing raises the tempemnue o f the fetdw.otet to wi1bi:n 6C
of iJs QJDdeDRtion lempe:mlllie a.t 350 kfa. lf the corbi:oe. and pump c:flidenaes :m:
bc:6 0.1&. wbm is the- tbcnnal efficiency ef lhc. C)~lc and wbat iiraction of die ~
en~g ft rtlJ:tbine is, eurdQal (t)r me f-ctwru:er bearer?
fUL A Sleam JK"\'W pbmt opcn.linJ on a Rge.~ cycle. as iJJ.u;stl'aled. i:n F'J~., 8..5 .. iiJ.
etudes just one fced~-ar ~ .Steam enrers die wmme m: ~) and '~F')
and exh30Sts att Jfpsia). Steam f~ the feed~ beater is e.'drad:ed from the ImbiBe at
SO(p~ ~d i:n mdea~g m~ tbc: ~tmpc'JOatLlllC of lbc: ~wattr 1o Witbif't 11 (Df)
of ii.S ~finn rem~ure .M st(psia). If rmc mrblne and pump d&it:llcie! ~
hotbr0.18. wbM is tbe: thermal efficie~y m lhe eycle and what fcu:tioo of dle s team
- IL- ~- ' --._..tr,r... d.- ~dw '-- " -?
~ Ul!i ~VJJVIIN :ui ~-.r~v .ti,IT Q_J,!Ii; ~ . !Jte:r ~
&9. A 51Cam JlO'W'f% plant opa'ali.ng on a mg~~ q-rclc. ~ i~ i:n F.ig,. Utr ~
diJJdes rnwo fe-cdwate.r ~en. Steam emcn tbe I.Dlbific at 6.50) kP:l illd OOIFC and
emrms,ts ru 20 kPa. Steam for tlte feedwtlter beaters is emacted from the mrbine
at ~ sucb tha1 the fcalVItder is heated to 1MfC in ~ ~J inaaoents of
~ptnture risle. with .soc appruaellt5 ~o thr $tl:aJn~ndensatiun tcmpeniD.I~ iD cacb
feedwmer Deater~ .nfibe IW\bine and pump d'ficlmcies are both OM~ wttar is the lben.nal
c:fficimcy of the ceycle mel "'hti &aetion d the~ enta:iog the. ttubine B 9~Ed
for eacb feed'wodmr beat?
8..10.. A power plrutt opearing on ~ rerov~ from lbe exbausr ~ of ~mal com-
W,.-qjoo ~ ust:S ~laDe as lbe ~~ mediDm ma. mocli&d Rankine eyde

314
in ' hidl the Uppet" preHUfe ~~~ i.& abore IU'Ie crilk'.cl) ~ Of. ~' TIJQ$ ~
~ doa. DDt ~a cllanp of phase as. it ~rbs 1'1eat pti\lt ro fu d}uy i:mo
tbe ~- JwbunLne vapor is bnted at 4.100 tpg to 26r~ and enters me
l.lit'trioc '
~b(:al Jfuid Itt d1tse (M_~ ~~it$ ita the lltf~ ~
supe~be-.ated vapor at 45(11lPa.. which is cooled and c~ at ''OMtanr prcgmrc:.
'l'liEi ICSIIl'ting: salUIIICd liquid ~ llJe pump fw rdUm to lhe beater. lf 1ibe power
rnnpot ol die Qllldlli-eil.Runkine cyde is 1.000 tW1 wh$. ~ rb imbll~ IJ(Jij;~ nte,. ~
flat~tr:msfa Nle.S in lhe bealm and. ~ and the dl!mnnJ elfif'ie&:y Of the C)'Cie1'
Tbe QPOf ~of~ .. giveD io Tabk B.2 uf App. B~
UL A pow;er pl&mloperatiog 0 0 beat rrom il po~ ~ ~ isob~

bg u.dium in a R:mlinc q"cle (fig. S.J,) . ~.is hti:::ned at 3.400 k:Pa (a ~
VJdr- .as_.
jliS! ~ li1tle I:Jd(lll( :Us m--ueat ~l m ., ~ of 140~~ .u whicll condi-
- i! emen me hlrbme.. ~ u:pmm'mn. m1M lm!biDe pmdl.Kies ~ted
WJX}f at 450 k~ wbidJ b woled aod co-Odtuso:J tO ~ted liquid and pwmpcd to
die ~:er. If l!be IIMmlle ol ~c ts 15 kg s- 11 " whM b. lbe iJl(P'\rr;.t o~
pvl of the Rmtkioc .cycle and \\rb:at,De 1be beill-llmlder rates mthe bemerlboile-J' and
JJO~j1$ef--? What i$ 11Je fbermp) dfi~y Of tN >f;yc, C'? 11M r.qKif jJ~SW"e Gf
~ til givent tin liable 82 of App. B.
Repeat abe:!!-= calndm.i~ for a cye.le m v.'hkb die twibiDe ami pmnp each b:n-e nn
dtit:ieocy of 8".
8..11. For~ of Diesel- and 0nf.l;ooeugme t:yd~:
fa) S:bnw lh:rm lbe tbm-naJ eflieiei!M:y or l1le mr.. llfindmtJ DEesrJ cyclle cmt be ~Pf~
rp:::: l - (rl')y-l rJ -
-
f(rt -
I
n
where r Hi die eom~o miio and r~ is die ,ei/IOjfmtio~ ~JiBed :n. rr c VA.! V9
{See Fig. 8. I 0.'
(b) Show dw lfor dE sart'l!e ~un t:i!itio die~~ cd'lhe .a&r-~dud
Olro mgme is ~U.n d:Je ~ dlicieue-y of me air-Siandard Diesel qde'.
Hbn: Show Omt me ftac.'ti:oo wiDoli multiplies ( [ /r)Y-- 1 iq dJ$ nbo\-o equmion 011
f:J ~ geater than unity by expanding r% in a lbylor series with Ole remainder tab:li1
. ~--
to me fir.st ~
..1--!..-~
nlR'Ifl 1.1.
(d 1f y == 1.4. bow doc$ lbe tbermtd dtieittiC) of :m :rir-.wmdard Otto cycle with
a ~Oft WiD of 8 00~ ~ me dltmJal eflicieocy of an ait--&tilrtldacd
Di~ eyde with dJe Sllllf)t: ~sion Gdi.g and a e:utoff raoo af 2? How is tbe
oo.mpari!ml (!;~' if lbe C\lW{f mtio i& 31
Ll1 An aiJ..stmt~ram Dic.~l cycle~ I.SUO l moJ- 1 of beat (step DA or Fig. B.JO,
wbi.di &i.mu~ . niili'oll~ii'lfil ami tem-
oombusoon). 1'lle !JL"...........,.~ - ilW'e'
. pna _. m . the~ - -in
_ "-"~-dl:n C.. .hr
V1 l(L..a..
.l ll;i.
~~on -stEp are I lh:u ud ~ ~ lbe- p~ mthe end tlf die ~mpre-~ioo
_ , ~ 4 ba__r. Assumina alT to k an kkal p ror whit"-h c,. ;;;
(7J2.l ll .aPd v - c
C5(J.) R'. wiJali are lbe compressiao miW and lihe.cxp:rnsitm nu:io oflh.ecyc:le'l

l15
&14.. c~ me efficiency for an ail-~ gus-~ C)~le (llhe 8raywn cyck) wp-
1~ v.itb a presmre ratio of J . Repeat for~ ratios. of S. 7. at~d 9. ~
y = LJ5.
ri.Jl5;. An air-,.snmdard ,as-turbine cycle is m001r&ed by iMtalladoo or a reg,enemn\e ~

ex~'l(lt ro billJ.'di-.r cocqy 6vm the. air Ja\iog the twbm to die air l~g the
rompresscr_ In an optimnm ~ercurrent en::h~Dlgc.r, the ttm~ of dJe ~ k;~,..
iog lhc: COIII'lJJNSSOI' is rai6edl to tbal of point D lin Fig. g.~2, and the tet~cftbe
gi.\ti ~8 ~ m:tbiue i.'- ClloJ~ to thtll of poi1n Bin. Fig~ ! .il. Sh()YM that the tbennaJI
efticieacy of dris, ~le i~ gE\:ell by
T.~t ( Pg) b'--- I)IY

'i = l - Tc PA 1
3.u;. c~.mc~er aD alrstnndardl eyc:J.e for me Oltbojet ~ pJant :!flowfi ~ P$8- 8. l). The
tmlptnUUr4J and ~ of lbc air en.terlng the wmpeSSDr we I bar and 30~c. 1'he
~ute rdti.O 1fi the COlli~ i$ 6.5~ .md. the ~IDpa'3~ at 1tbe curbioe mlet is
1.1 {)C)C. lf exp~ol!l in lbe oozzle is iseolropic and if die ooule ~ ru I bali
wbat ~ the prm-~ at dK: nozde iilkt (ttlllbine exhaust) .and wlmt is the Ydocily of the
air leaving the I!IUZlle?'
1.17. A.ir eorers a pHlllbine engiJJC (see Fig., &ll) at 30S K ~d l .OS bar. and i:i ~
~d to 7.5 bar. the: ftJel is me11wte m3D) K ~ 1..5 bat;. oo~ WKI mrbim
efticitnQes. ate ~n iO.tl-. Far o(lltl of the twbinc inlet t~mpe~ Tc given below.
demnnine: ~molar fud~tQ..air mlio,. rfbr ns mecbJodcal ,ov.rer ckln"lad lJ.)I!r mole
of fuel .. and the turbine exh3lm ~rature T9 Amlme eo~uplere oombusllmo of ibe
~. and.~.Woo mthe tuJbine to l(atm}~
{G) Tc ~:: J.,lDJ K; (b) Tc ~ 1,250 K; {c) Tc = IJOO K
&..18. ~f.()5;f clccuiall ~- io tbe tJI!Iited Slall s is poerated in ~scale power cycl-es
~~ oon:versiot~, of lltetn\al rei1C(!Y to ~hatli31 ~YT wbich ~ ~ ow~
to electrical enagy. Assume a tftamal eflicien.':y c0..35 ror ~on of~ 10
tJECbtmical ~, and im~ of0.95 fuir(XIQ'\'~OQ of~ 1Q re"~
energy. l...me losses in lbe distt:ilmtt011 system nm:otmt to W%. If the Q)Sf of fuel ftll' (be
power ~cle is $tOO GJ ~, ati_mat~ lbt= ~ of ele;clririty ct.ctiveredl to the CIIWJmu in
S ~ tWb:r. [pore opaating COSU, pmft.s. and tiXes.. Compare tbis number w.iJb dim
f'ouPd on a typic;d ~biD.
&19. lJqueficd natural] gas (LNG) .n; llruL~ m''eiJ lar,gg tinkers. ittlml as Iiqnidl m
~ with ia:; vg;pur at ap~man:ly ~pheric ~ If LNCi i5 essen-
uan, pwe me.thabe, tk ~ tt:m~ then iis a~;Jour 1~ 1..4 K.. dJs- gngl bJJilius
poi_gt of D5tbmJc:.. The eJIQJillllOUS aJ001Ult of cold liquid ea in prinejple s:ave M a ~mat
sini form oo~ bt-at engine. EnQ'8y di~ t()1tM LNG~ for its~~
don. lf me be:l1 ~ i:S ambielll air a1300 K.~ and if rbg:~ of a hiM rengil:re ~
61)% of itS C4IMot ...~ ~timate dJe ~~in moles vaporizied put.J ro f
power OUQJUL For metbane.. A H!" = 8.200 U mol.- I.
316
,& ,m '1b ~ wthe crepis ~~tAJ ~watertel1lp!filtlJN gradients.

J)epeDdi:ng on~ relil.til'e:ly consmru m~ dllf~ of ~5 t(ll!)C (l'QI
Obtain for deplbs of SOO IG 1.(!100 m. This )X'OVides dte opporrunity ror ~roM
(~p) am~rt ~ .-. Jteaf sint ZUlli wann (~J wata- .s a ~ ~ for n PQ't!l
q'de. 1be teclmology is ~known u UOTEC" (Ooerul11'1llemmJ ErDCrgy Coo\-enj(lrn).
(a)1Co:os.idu o location whete fbo. s.ur&ce IWIJpiXatm"e is l7=,c and me lempernlllR

;n o depdJ of 7S0 m ~C- Wiffi1 i_ $ lhe r{~ of~ 0mmt ~line~
~between t11ese mmperatare teveh?
(b)t ~ r:rf thc a~ of a~ ~"fde mus~ be L~d w-pmnp tbe oold wate.r to ibe
slli'face, w!tcte Ole cyde han!~ watt te$1~. U rht i:nbtttnt dJicicpcy of a flCUJJ .cycle
tis. Q.6 of me C.amot value, .and it l/3 of the ~et-db:d ~ is ~ fm mC'I.~i1!
oo!d ~ m the ~. wttat Om actnaJ effiaency of the c}-eler
( c)1 The ehtJice of wo:litLog fluid fur the cycl~:. is crincal Su~ som possibilities.
H~re, y.oo IIlla)' WWH to~wl a. lbmKlbotik, sudi as. Pe""I"'i tChemicrd Ea&U."F.J
H~vl!'.
B.lL Air..,l.afilhlrd 'power ~ we t;Cil\l'eolioo.uUy dixplayrd on P II diagra~. AP a.lu~m.

mre is the Pt' ,diagmm. StetcbtaiNiaDdard cycles oo P T cltagran_lS ro.r the folluw:ing:
la)1 ~ {;.-ycle; (b) Otto~~; (c) Diesd tyelo; (d) lB~rayh:m c;cle.
Why wouN a P T dUigram 001 be beJPful for diepicling p:rwer c:.yc]es invol\ing Liq-
wd/viJl)Or .~ dlaog-es?
&:11 A ~ pkrn ~ oulhc- eyclJ; ,o f Fig.. 8.4. Th~ ~me kveb are !'0 kPa and
~000 :k-.Pa~ sud ~ k-3\ies tDe UD:'bine as .&illllmlted vapor~ 'The pmnp efficieoc:'f is
0..70~ and the mrbine e11icieDCY .is 0.15. Detemtlne the tbermid ~~ of the. plo.tt'-
LZ1 DtMsl: a ~ scllemr b llnidyzi:n.; foLII'-step air-~titamJanll flllwc:t cycle~ 'Modd

eadJ cp oftbe cycle .as. a poly1ropic ~ de5aibedb)' :Eq. (3.J5c wim a specified
'fl*at~ t1f $ r ~ wbi(.iJ ~~!It() fiA.. partially 01' COOlpkt.dy. by w.ll!l off' ill.dfOI p .
AOO_ysis ha'e JDiC;IUlS ~lion ef T ud P .far initial cmd 1iDai sl'il1es of ~il step:
Q .nd w f~ ~ ~; !lllJ! ~ ~ ef&~ of~ cycle. Tho oyms should
aka incl~ ~ deteb of the cycle on a P'T ~

Chapter9
Refrigeration and Liquefaction
Refli~<m i best~ f~ ~ts ~ ift lbe att coodftiopittg; Qf bWI4iQ!~ and ~n rrbe. ~
'~on, and. ~mDR of foods aDd M~. b also ftods ~ l.mlustrial
.appli~. (QI" oumplo. iD the .m.uwf~ of i~ and die dehydration of~ App~
in dle ~trolcum UidU$1f)' i.nclude lllhtic.a1ing-Gi1 'PurifielitiOfit Ia -~ ~~ and
m
sepamtiDn vola:JjJe :b)'dmcm!~Kms. A rlme])y Jelal2d process is ps llque:faction. wmdb bas:
impommt CQlDIIIaaal applieatiQns,
Tbe :purpose of this cbaple: ~to pleSeld a thamoclymmic a:nalym ,o f rd'ri~n and,
liqudact1oo ~. HD'IR,,.~r, t~~t ~ail~ of JuipiDQlt <big1l are ld'l to~ bocii."S- 1
'The \\"'Od ~mliuiJ implies the IrnlinteDBJ~eC of a ~ bdfiW tb3t M' ~~ -ur~
~ Tl:lls ~ t;onli:tnmiL"i amorpt~ of l]r;tt w a lAw ~ ~ rl limll)'
aa:ompU~I by ev:lporWOO of a liquid rin Ill steady-sta DO\'Iif proeess. 'Tbe \'OpOJ funned may
be l'ctumcd 't o itr1 ori-JJimtJ tiqyid ~fat ~petatioD io ~"k (It' t\\"0 W9--J . MO$! ~b';
ir is simply coon~ and fileD ~ Al~y. b may lie absorbed by a liquid:
of I9W vokltili,y, fiom whicb i~ !ili~U}' ~ .u b:J.Pct prmDTt- ~ ~at~
ing tbese pnll!:iioal refri,genruon c:ycl~ we a;~dn-lhe CiiJQOil ~tor~ wbidl ptO\'idts a~
snrndard of camparison.
9.1 THE CAANOT REFRIGERATOR

hi il ~OS refii,&et-dlioo ~ ~ lllea1J ~ 01 iii ifb'w' tempcliltDre is~
rejecred ro 1he sum::dllldinp cu u mghel' rem~ Sadci.Qy~ a refrigerllli:om c:reJe is a te-
~ hat-o~ cycle. H~ u lniiiSfartd fwm a low klble v~ lcvtl to a. lt~ ~
~ 'rQ[hf. ~ law" lbi1\ RqUire& an exrernaJ solltf.'e ol eaerg~ The j:da1 ~gemt-or,
hE the ickal beat eog.iue (5-. 5.2). operates oo 1 Camol ~., ~in eu <Jf twg
isoLhcmm1 ~in wbidl bad IQcl is nbsoi'bed w the lo\\"Cr u:mpcmtun: Tc Wldllea! IQHI i8
rejected at rtbe higlw tempen11ure TH . amJ ~adiabatic 51q& 1lbe cycle J"f:QQIims the additioD
1.&..'fHR.4 H~ llLfri~ I'"~ FNFr~ 199:1: ll'-!AC $}-ttmm dfiJ. ~- &992: lfi'AC
~ t90l: ~SG:kt}' ot Head~~& h~dag mJJ~ Fe(~ kx.. A
' C1IIID!
lt
K. '-~b ~ .-j'Air~ mit~ fh/~~J~j,JdcGmlr.,HDl cw Vo!:k. 191U.
317 Obras proteg1das por direitos de autc

31
of ott ~om 1'. to rhe ~ ~ IJMU of the wolting Bnid is .wo for the cycle, the flm
taw ~
(9. 1)
~ ~ Gf dJe df~-mess. of li te_f-Ei.ptm' i its coejftd1U qf perjbrmlJ1tt:e 41,
4Zfimd
=
h~ea~ absmbed m: me flower te~ JQc J
(0' 'l)
(t)1
Del work
::1 -
w ?."""
E4 aaion t9. t) may be an;ded tby ~ Qc IKDd thm ~ v.ith q. (5. ~
__!__ ~ a~s l - l W ; ~ -l;;; Tn - Tc

IQd IQd IQ,cJ l'c Tc
(9.3)
! +21J. I~ -1
(d.;;; . . :c l l.b
(30 + 273.15) ..... {5 + l7lJ5)
1
8.2 THE VAPOR-coMPRESSION ICYCLE
"''be VciJPOI-compleWotl :trefrigemiian eycle !5 ~red in Fli,g. 9.1. Stia}wn on the TS diaii"dltli
arv ~ fnv ~~ of dJe pJO(:es~. A liquid evapoR.ting at eOOiUUit pres.sure (line ~ _.. 2)
pmYi*. a ~ for heat absmplitlfi at a low ~ ~tnptQ~ Tbe ~~ produced is
~to a higher~ and is ~ben l'iOOJed arul ~ with ~:doo of~~ m
a higb!:t ~re. lc~l. liq~ rrom
~ ~~ rcamn.s t'0 iJ8 original presRire by an
~ ~ In pindpk; his am be atr'im out in an ex.:pattdcr fiUTilJ which wo.k i~
ollJtaincd, but fm pnctical ~ is 1limfl) accomplished by throuling ibroogb a par:Uy opnt
valve.. The prrssure dmp in th ~c poccss resubs from lluid frictiiXI in dlc vtll\'e. As
bown in Sec. 1.1. the fb.rotttiing; ~ oc:t-tm. at ~~ e.m.halpy. (fi Fig. 9 .I line 4 -.. !I
~ dUs lfllvu:ling pr~ ~ ~ liJJe l --. l' iB the~ (Jf isentropic com~
(F-ig. 1.6}.l.ine 2 ....P 3. ~~,g !be aa:-ual oom.~ p~ :do~ i:Q lb.e dQOOtiQQ of
+..n-..- -A...,.;..;... .. ! . d . - ~--"'L.."C..
~jf.ll& CI!,'I>:!"'Jl"J!., ~~-~ H!IJ,I;oi~Jt UI~WI'HJUUJiteiS.
I r
lm me~ of~ mrll ma.u at Qlliflt * ~on" f(J( die~~ iP the~

amJ lk belH ~ed mlhe modem ate':
~equations follow from P.q. ,232. wbm the small~ in poteotW Mcllinetk rellerg)'
ure negJ'etie4 The work (Jf c~n i:s $impl): W ==
lh - H1,. atid by ];q. (9.2), ltiG

_ 3_
'I'
1 2
(9.4)
To ~gn the ~-f 0111~'01". ctJIIdmsa'., and u:rilia.ry JU1:pmmn one must
bMw. the ale af an.....mttoo of ret~t m. 1bis: u deWmined from tbe me of flat . .
sorption m 1he eva~ by !lbe equ31ioo:
th ~::: IQd (9.5)

HJ - 11
'tbe ~apor-compressioo C)''tk o f fiJ. 9.1 is shown Oli a p II ~ in !F".g. 9.2. s~
dilpu!Dl art: ~ Col'miJOOiy osedl bl timt ~p~Wo of reflisr.mdool ~es ~hail T s m-
apm~ ~ they ~ di:rectny tire nqnired enlhalpt5.. Aadiougb the evaporalicm and
~:n p~ are rq:~resented by constanl..-pressur:e piths, mu~n ~ ~ do
fJL"V beansc o.f iluid fridion.
For ~ V"".daes. or Tc md T, ~ die bif:best pomhle valii.le .of w. is, atmined fm Camot,.
cyd.e ~QRI:ioo. The low r.du.a ror lbe ~"~on crcl resull from~
" .i.--.olt- - -~ ,......._... . Jft"'-''ttfi'L1.. ,Nart~-inft_ """- !['...;~- e.amnJ.a.--.....ildJ5 iUI
C.'tpiDSJ(H} flD Q.ll.l.,II.Ut; Yol~U"'! iJUU Q _ -~ ..,._"""'"r"'"~~ a.- ~1\,11_._,,.. ..1116 . t"""'
JftV"FI
indication of typical values for eodliciems of pmontliUlee.
E.xam:ple 9.1
A refngemted space ~ I'J'l8intamed 811'0(0F), andJ coding watsf Is available at 70rFJ.
Re1rlgemJon capacfty fs 120~000(Biu)(hr)-1 The 8'l8pQ1or and concfenSer are of
'- ~ bsl Sr.a-Jei ran;mrioc ~ ~ eor:Dl )y ~ bltJIJS ef~ a Wllld ~DISh

2
ddbitdaslbttt~ m6c:nlll of Ll,cCJOOmtJ.U(llz)-~ 12,t;60kJ pmlbour. Thl:\ (ilii~*f!IWu.ximaklFto
IJI'
~ I!IK Cif~ ~ reqai~ 10 ~ l(-Hof~. - ~ JlJ ilt 32~ pet(bt.

Flpn u \ "ijllIC:li<IIXDf,ii~Mt
~I!).ODjf'N
ll
suffldent size that a 1Of F) minimum-temperature dlftefence for heat balls.fer can be
reatqed in e8Cil. The rebigetatit is tetrafiuoroethan.a (HF0-134a), lor which data are
m
gtwn Tali& 9.1 aJKJ Fig.-G.2 (:App. G)t.
(a) What is the value of a, for a CarilOt refrigerator"?

(b)1Cslcdate 0 and mfor the wpor-compresslcn cyae of Fig. 9.1 if me compres-
sor effidency is 0.80.
~utlon1.1r
(a). By !q. (9.3) fGr a evtwx 'f!OfriFdltll';
0+4!59~67
m!!!!! a .5.75
(BO -:-459.67~ - (D + 459.67)
(b) la;;wse HFC-~ l4a the o:frigemnt. tbi! Clllb;dp' for SGI1Us 2 andi 4 of
9J mJ 9.2 are li'aiiJ ~Y ~ lablc 9J. ~ CtUI)~ at ~0 - 10 ~ P)
:I:Dir~ lhal HFC~ll4.:a ~ in.tk c\-a,poramr m: a ~ore of lW . 162(psla).
.Its ~ .a sdtuared "~ lhesc CQnditiom are:
1he amy m 10 + 1a ~ ;sorF> m Tdde 9.l ~ ttmt HFC~ IJ.~a e-m~~ m

IO~ .l?(psia); i cmbalpy as a tumtcd liquid aLlbew eamlmom is:
fl4 ~ n .978(Btu)(OJm}- '

l21
[f lbe .oompre.mon ~is m"ef:Sl"bfe and 8.di.abatic (iscmro~Mcl fmm aturatod \ _...
por at ..,~ 2 to supedmil'led vapor at stlte 3'.
Si ;;;;; S! = rO.:ttS:2S
The mlhafpy from fig. 0.2:0 this. e:nlro]!))' il11d d g, p~ rof 10~ .37(~) is
about:
and b endmfpy dlruls_e is:
{AH )s ~ n;- Ill c 111 - IOO.Ot5 = ll .91(Dtu}(lb111) -
8~ &&- (7 .17) for u eontp-essor eflicleo_cy of 0.80. m:e adiJW enthalpy c'll:lqe fOI'
&tepl..., 3 ~
H, - II,.; (6H ~s ;; L03~~ ... 17.48iB1U)(1~l L

,, . ou
Beoa~ diie tbrottling ,pAX'e of ~ I -+ 4 is isentb~ Ht' = 14- The

Qleflldem of pedonnanoe :u gi.Ye.n by Eq. t9.4) dteretcre bm.mles:
- ~~~ - H. - 103..01:5 - l7 .978 ~ '} """'

.w - 14-111, - t7.48 - ~-(,;.
WKIIhe HfC.. I:Ma circubdion ram as gWen by Eq. f9.S) is:
. Icid 120,01ll0 l MS(Ib )n...)-'

m - ~. - 114, ;;; mOJ.OlS - 31,978 = . m
' qm I
9.3 THE CHOICE OF RefRIGERANT
As Ntowo tO See. S.2. abc ~fm.'}" of a rQ unm hem C_tl~ is ~~ of dte 'li\'Otk!Illg
medium of dle mgine. Simib;r)y, ttw ~ ~of PGrf~ of 1 ~ rdrigt:~Utnr is
i~n.t of the.~~ ~the. ~lliics inbmm iD 11\e wpolf<UIIl~
cycle~ r.be-coefliciem of pfGI'IIIIliiK'e ofpracticalr~ mdepend to PJD~t~otoo
lhc tefriFun~ Ne\~ sudl dJlltUEICrisi - as i~S mx_idty., fi&IGllmbiiilf, ~MI. ~Jon.
~~ un.dJ wpor~ lin rela"lkJo tfl, ~are of greater~ in lbedKJice
of ~t.. So dial ail caDDOt leU; into thG rdri&tRtitto tot 1hc wpor ~~of the
mfnp.pmt tlit; ~r tet:n~ $hou1d be ~than ~-pberk ~ On the
olber haod.lhe:vupor pR5SUiie the~~ mould not be: unduly 'IQ.IL beeat~
or d. inmaJ CQSl and~~~ of ld;gb~~ ~ 'lbesr.twoNqUMmems
lim:il die make of Mfrigemnt m relatively few fluids. The final se!ectHm lhwl ~ en Ch~a
oCJer dmraccemtics menliOi'Ded.

Tllblt9. l : Tbmnod:rnamkPropert~esofSaturaled~e
"\bl EnWipf ~
trt}'m.)- 1 (Bm (~j(lhsn)- i (RJ-
trf:J P(pm) Y'

'" Jill no s stt
-tO 7.U9 0.01132 S.1R ().(00 9'1~JQ!O C..OOCOl 02.lll.~
-~ ssn o.ou~ S.osl 1 91 0..52 l1.2.lQtt
-lQ g_iQ ill.OI ~4S 4.431 2.984 ~S56 0.00'1'01 0~
-25 "~, o.ou~ jiJQJ 4~ 9f.JOI:i G.DI~ o.n~
-20 12.&9~ Mll5 l:44S S-~1 ]~ O,l)l:.t92 llW786
IS 14~ Oi.OJ 165 3.Ml 7..Sfl5 Ulli'99 ~011ll 0":?-!114
-o 16.616
Ill 1
QOil~
0.011~
2..111 9m6
lo.e
LOL~2 0,01_07) 0>1W7
0~
-5 ~6 lctUSO 0.00409
0 2U6l 0.:01181 i)q$g 12..()!)1) JC)31)15 o..o'!!7.&4 o.2lS5
s 23. 61 Mll94 1,9-J..I tlCS UD.145 O..tCBOn (U..."l.i'iU
tO 16.617 QJOil('C I,13(). IS.UJJ 10+..471 O.QJ408 0.22.4Ut
lj ~.726 0101110 1_$61 f6.148 10Sd~ omm 02D10
lO l3.ll0 00l2L 1.410 fL"iU: 105.901 O..OS!l65 0.2l315i
36.ru l9~97
~
2S (M)IlJ6 106..6J'7 CLOI:l91 0'"113-
30 40.168 OiOUlS ~.~~ l1A!6 Ut7J20 OlJf7tS 0...2n-44
ll !.fn3 O.DtUl I...Q.:d lJ.W 10$.016 fletSOJS eul207'
40 49.714 QJOIID 0-~ 24~ lOS. 70S C1.trn9 0..22172
4j s-tm 0101~ o..86S M.3J-I lO!l.lt6 c..osm fi.22io&t!l
jQ 60.11&. OJD12il 0.1'12 !1.944 UOJJ58 o.osm CUlliO
~ 6~.89' G!Oijil O.'r'J ~_jg llO.rn 0,0)11$ O~ l
tiO 71.JRJ1 Q/01191 0.663 :u .nt lU.l,., 0..066.1) 0..~

65 7&-TI2 001301 O.fW ;)~ 11Ull9 G.06m 8.l202&
70 1$.1'81 OJOU1~ O.i$8 14~$) l l2J6S1 0,07U14 fl.__~
7S 93.dll 001123 D~ll 3427.1 lU.2i7 11.(0.$7:8 041ffl
so lGJ 1 OJOI3lS am 37.971 Ul.JBG am&Yl ~IH't
$S 1(11)~ ()j)~~ GA34 ~.091 JLWS ~"'lOS O..ll~

WJ U9!0 OJOJl O.Ml) t' l& l l.S-0 O,C85J8 0.~1912;
95 12&15'3 0101312 0..16J 41.119 u:S.fll9 a~ D..2l890
100
o~
]JS-SJ 01013!!6 -4!4..943 116.166 O.CPJ l4l! 0..~ I fl:6ili
lOS 149.63 0.101400 .ns .6 ilS UMQ.S 0~ 0:21&1$
IJO 16HiJ OJ(}IJ-'.I!J om ~ l 17J:03 0.09766 alii:W;
liS 1;3.U 0.()1J.i30 0.270 ~ u "J'.a O.lllt'l'ti ~1797
Ill) 185.;.84 0Jtl1 1~7 O-lSO U.Ul 113. 1Sl 4U0391 0..2frl'2
us ] 'l))_lS OJOJI * (l,UJ ~ 11R.l')l (),IOTO-l Cli.1114A
1'30 2J3.J.1 Ql)i,WH;J OJ!I-41 $S.923 1 19~ O.IIOUS 0.21715'
w ~ OJOI~ 0.198 ~/1 30 1HJI.171 O.Ulll 021fi8!
140 241..U 8.01152:! 8.184 59p764 ll9.T.!R 0.116'50 0..21643
Ha m.n Q.Oil S67 o.Sl 6.l_Jn lW-i&t 0.12288 0..~1566
l60 JJ!.t69 {l!Qil6l0 0.1}.11 67.:81:3 ~ d.l~ Cl2146J.
170 JSS.Sl 0.0 1611 0.I J,. n..JO& 120.1~1 Q,J360jl 0.'2H19
~ I)J' {itll~ IJuai ASHJ1AE ~ f~ P- l'7~. Ante~

Sari.'k-ty of~~ .aDd A11-0ditn.l~~lllllt!a hic....Aamta, 1991.

94
r
A.~ D.-L.:
i'l!!l&,.,. J.-vJI '"'"I'Jl~ 3"'...3
Ammonia., mmhyl chloride. carbon dto~ ~and other byd~ c;m 6100-e
:as ~- fblopnated hydrocar:boa came tinto common use as ldlig.mmt5,in the 19305.
Mo-.sa commoo "-ere 1he (ully~enated ch)orofl~ns, C(.1j F (tric'blomJhrommedmDe
(Ir CFC~ 11)3 iMd GC11Ft (did!l<B'OdiflllfltOmedlane or ~o:FC 12). ~ stable JIM)lccrues per-
sht in the atmf:lSphere (or hwtdreds of years. cans.fng ~ ozune dcplmio.n. Thcir pJi{Jdudion
1~ IIJ05dy mdcd. Rq}laoana:its ~ ecrtaio ~~ less dlan ruuy baJ&
~by~ whidl must; rdathfCJy l:iitk: ~depletion, and bydm~
Wibidl ooDJain .oo chloriDe iiDd. ause oo ozooe ~ Eumples are CHC~:ICF, (dicblar~
olliftoo.metbane or HCfC...l2l). CP3CH~f' (~Ll.QfOetbane or HFC-1348), ,and CHF2CPJ 1
(JXflfafl~ or HFC-125). A pre;ssurelembaliJ)' &g,nm far ~uuD~e (HFC..

I 34aJ is mown in Fig. 0..1; 1:able 9. 1 provides~ data for the amc ~ "Jfilbles
aod di.scrams fw a~ of ~-r mri~~ avf ~)' HVIQJ;ablc-.
ll..i..m.iJs placed on lbe opmltin;g flltre8WI!eS. of lhe evapormnr a:rd co~ of a remg..
er.nioo s~ a15o limit the tempmt~ diffeJW:oce T11 - l'c ~ON~ whiclJ a simple mpror-
wm~ao cycle 4iD OJ*&'~ Witb TH ~by die tan~ of lbe ~~a l(l\111}1
Umlt a placed m the~ kvell of remgerw.t~ lb:ii em be O\'ei'OOtne !by dJe operation
or r.wo or more refri.p:mtioo cycles employrng dilferent refriger.mli in ;a &tualde. A ~
cucadc is howu in Fi,. 93.
Hm-e.. tbt tWO cycle:s ~ ~Q tNt trbe hclil ~ in me lnt~IUlfi!F b:lil fbe re-
frigmmt of lhc. bi~puall.rl'e C)1Cie a serws m ,condeme lbg mngmm~ in. me lgwer.
tempenumre cycle I. The IW& rdrigmnJs are so dm5eo ~ m tim. roquiml wJIIpGJSIIIie ko,l,~
ll,;1llli.W- Cy.; IC ope ra"
---'!.. - ~C$! m.li.! - ~u ... r~
_._lliiOL~_.r.IK;> : e......
.....,.un:5,. ~VII d.Hiit-n.t.. u.-..~-rilrii llbe follcwin'I
- - ~r _......,.'-' - ~ --
~--IQS
~~Wit$ (Fig~ 93):
Tn = 86r>A r'c = 0 >f) '11, l~f) Tc =- - S0(F)

11 tdralluo~ (tfFC.. t~J ~ the: ~ mQdt 2. ~ t~te ~aDd dis-
cbar&-e piim~ for me oo~ arc iJbool 21r(pmt) and ll1(psU~. and me presmre radio
il a.bolll Sk3. If JXllPYieme is the mfrtpnnt in cyde l, lbesc ~ Brie ab(nd l(l(p5i_a) UPd
58{jpsia.), and t_hc ~w:re qli(J is about 3.-6. "fbeg mc aU mMODible 'Yill.llCL On tl:lie cdxt
h.a.od. :fot a single cy1e opefUlill-g. berween - .lOrA ami 86(0F) with HfC. ll4a as .rdrig.er
~the .i.ntake ~to Ole~ i8 about S.6p.ia}, wdl below atmosp.beric ~
MO'()~. for ,a d.~ -pRSSI!II'C of abQut l J!{psil!l) ttbc prc=s ~ ~.o ~ 20. mo big~ fi ~ate
for- a ~F compressor.
9.4 ABSORPTION AEFRIO.ERAnON
In ~-compressioo ~ d'le wk of oompretiion is uwalily ~by an eledric

molor. Buc the wuree of die el~ ener:g:y for tbe IJliOtOr , probably ~ bellt ~ (~
~ ~ ~QIJ is ngm~D:uc! gf (be 4meri~ ~ d ~ ~~& _.Air

CMiitruoniiig ~
~ASHilAL ~ f"~ OYtp. l1~ \9$9; l. 1\ Pm)1 md D. ~ ~~ ~~ ~

IJ'ffl"J. ~ ~ $fL. Sst 1-. t99'J_ res~ !btl !1W .~ 3i"e ~a "' L Haat: llftd J. s. (ia)lagbu;
R41laM
J~ Pli]::i.. Clan., \llll ; APP 63S-71}4 ~97&.

~ t.:i1: A lv."''-~
~teffl
t.'}1'5tCID.
W ;::; Ts ~ Tc IQcl
Tc
'WlJae IQcl
the hem 'lbs.oriJedl U a sw:ree of bat ~ mvWlullk t!l a rt~ ::dJo,\lle abat
of dJO: ~ ~ t 1H. theu ~ cr.m be u\JI.om~ ~ a Camor eqpne ,o~mtitlg
~ rhis tanpem.t~D"e and th~ ~ mmpature 'fs. Tbe beat .equira! I(}. fl fo:r thi
rpmdudiooof ork ) ll~l is fouod fmm Eq, (S.Sl:
t9.6)

9.4. Ab~ /Wii~
tt~!iV'nlmlfQ
------- ~-T~
_ 2_
The ~of I!211 V12 'c [ ~ &y this e<[IAtkm is or COUDe a mmimWA. ~~ ~~q
~ k ~in pncti4.
A .schematic diagram for a l)rpicd absorption re:fri,gerntnr is shown in P'Q. 9.4. 11e es~
tial dilft~E~a belWC0 a 'oqo--rorup~ and an absOipliOil refrigeratur is. in lhe different
~~ ernp~~ fQroompr.cWon. 1bc sed:ioo of me ~oo. unit to me riJbt of the dLI:Sbed
l'ille io1Fig. 9.4 is (be same as in VCipOf..C~ mfriJJ9'11IDii, bua:tbe Httioo to die left
acaJ~DPlisba eompJeSSion by what aiDOWlts to 11 btal t.qine. R~t ~ \0'-apot Ctom ~Ole
~ratot i$ abstded. i11 a ~'"ely ~~~ liq(rid Rm at lk pre.~ of t ht evapo-
mor ami at rekmiwly lOw ~ 'The bed givm off in lhe proee ~d to lhe
5UIW!rndinp at Ts. This is the kJwtr ~ture leveJ of 1M~~~ liquid sokldoo
from tbe absotbe whkb eom.iD& a rehuively high eotanrr.woo Df ~ ~ to a
pump., wbich I"Cii'tU die pre of 1tte liquid 10 ll.hat of the conde~ HeiR from the higbar
tern~ K~W"Ce . 11/i i5 transferred to, die 'COIIJPICsscd liquid sol'utioo. naWnJI. ~ ~JJ.Jpa'"'
atut;e. UJd ~tiDJik ~ from tbe solvent. pur p3S$ES from. dlc ~~((I
tile ro~ Wid sol\mt, whlcb oow oom:aim ~:~ relziely low coaamtmioo of~
rt:tums to the ab.sorbc by way of a heat a~. whk& ~to oon.sem! encqy and adj,Ult
Slfeiiii11C!Plpaat~ ICJWBJid Optiln.UJI'l val11t:s. l.ow~l'iR. S'lQIIQ is ibi: usual mun;e of fhoa1l
for~~-
The ll1lO$t ~lmlJQldy usaJ absotplion-~w S)'$lah ~ lVkb water M the
~rnm and a lithium bJDmide solution as me
.absodrent. 1bls system is O'bvioody limited
to, ~ tcmpennUR5 ~ the~~~ poma or
W8leL 11 ti'Cittcd ddail by ~ m
Wid G.reea.~ Por Lower 11Ilpeni~ ammonia am serve rdrigemnm with water lbe. soiRl'lL
An ahr.nr:nhc $)'stem~ ~1 a:s Jdirigm_nt and poJygtyoolrtber.s 8i ~m.
Cons:Wet rdrigtration at ~mtufli: lCV"eJ of--16-'C ( Tc ~ 26JJ 5 10 with a heal
SlOIIlt'e of ~.-in...w
~-.s liilf':am at nfmi\Y'Ia.rtc
--r ~1lte
r - ~ ~ ( ~ff .:313-1,t11 K" P.J. a ~.uUII,AUN!.UJS
~ ,_ e..r .........-..1:...
tc~re of . C (Ts ~ 300-.l S K1 dn:. miititmun pos i:bJe \1dttt ,o f lQn 111 Q~cf is foood
fronl 6.} (9.6):
OHI
- ~
( 373.15 ) (303.15 - 263.15) ~o.s
I
IQc l J13. [5 - 300. 1:5 263.~5
For a t aca:Wll aboorplion refri.serator~ lbe vallre would ~~e oo the Bf'der of 1.bJree times th35 ~I.,
ne meat pump.. am~ heal en:gjne.. is 3 dl=~l'ice for beadns houses and mmme.rcial buildings
~ the wintef ~cooling tl han dllling 1M mm.me:r. In ttJe 'Winrer it o:pc:mle'S so as. m absorb
hi:m rrom 1be >501'J1Cundin and rejccl br4t into the buildiDg. Rdri8crant, e\~ in c.oib
plaee<llllldagn:mnd or in the. 0\IIUi-de air; vnpor compression its foil~ by eo~on~ heat
hci.. ~ fO air or w;na. whicb n ~ w !beat lbe: tJu.ildio,g. Compre.ssion DliW lbe lo
3 pre-~ rucb b3t me ~ooden ~oo ~nli"e of lhe Rfri.gnant is hi~ rtban me~~
0 .... , ] 0
~r-........ . . . o f the
~tnre. ~~~~
.. 1-..: Ji..l: .
~Nu"""'~ "ft._ .
'ur; ope'l'l.tmg ~~" I L - -
<Xl5t Vlll ~M t~t" if\ 1b
~ UJSU___!_MtJQI!J 1: .e cost. of liPLecfne.
po'llo-et rom~tlfte ~ lithe unir basi a~~fit of ptlfOtm~'iC. fQc Vft' -:- 4, lbtt heat
~~able: to tw.n lhc b~IJuse I Q,,
n equa.J to five times lbe energy inpm ID the~ Ail)'
~OJni.c tWJ~,~ 'Of tflt beat pump as ti bemq deviee dtpmds on die cost of ~rie.ily in
oompi:i.tisun wllb mei005I. of h.lch su~b as tJU tmd IDliDltdl ~ _
TM beru pump also Rl'\'eS far air aatiliooing d:nring 1he. Ql~ The ~ of lli!frlg.1
a8JJl liS -
~titniil ~ _ _, -.1 and 11 --....l
- r..Y Fe\~~ ~
-L~ .L- olio.- '1:.-..!l.li!- . dJ .................... ti'L...,.._.t:._ -~--I~
~ II.IDI~ 15 ~~ lfvfQ ~ ~t~VJ~W~Ii.l IlL !'li-~ Jt~"'~ ~r-
groond coils or It> lbe oomde att.
ExampJe 9.2
A house has a Winter ooating requir811lel'd Gf 30 kJ s -t and .a S'Ut11Jiller cooiiDg , .
..-.t ,.., 60 1a.r 8 - ~ r.~ . ~..... . il-'""~~'"'" .s . , - ....~..."""- .......,., .,...,...
~u em~..
....,""" -
Y1 _ _ 1'!!1,.!1 _ - ~ ~ 8_ I~ pt;!ll"f,p 1'1 ~lQJiagrJP lll.l Q'lcg~' l-!ialn Il l~ UUU!Sie
ttemperature at 2Cr'C in winter and ~C itl S(lltnmer. lhls requi res drcutatfoo ~of the
rekigerant through interior elCdlanger cons at SO C in whtter and S""'C in sumrmer. u~
~001 ooi!IS prC'Nide ttta h8a.ll $OU.JQl in winter Md the heat sink f111 sumrnar. For a
year..rounc:J ground! teA"iperatute ot 15~. the heat~r cnarat:reflStie5 oflhe toils
neteS&Ita1e ~~~lgercrnt tempefa.WreS,of 1ore in wintef imdi25QC in summer. What are
me minitnuln powet raquit&ttlenm bJr wirtt8f !heating and surnmsr eooft11g?

Solullon92
'Ibe minimum povt.-er 10pir.e~ts are proYtibl by a Cutn011 hmt pump. F-or wift't-
m bra'~. lhe. boose ooilll are 1.11 the fri,gba~ IevetTn, md b ~
n:quiJaoeml is IQ a I = .30 t1 .,-t. ~tkm of f.q. (5 .1) ~:
+ 2?-J.tS) . - kJ
lOci= IQn l Tn
Tc >lin (
=.;IV 10 + 213. iS = 28."2 ~ s
A - 1
nUs i lhe heal ab.wrld in Ute gi'QUmd tCOJ'ls. B)! [f.q1 (9. I),
1
W fQal -IQcl ::::. 30 - 28.00 = l.98 tJ &-
1bus dJe power ~ement is 1.98 .kW.

,_, sUmJJ'JCf cw'f~u~ IQcl ~ 60 ld 5- L. ,~d ll't:'to be~ coili arc (11. tiE lo\\~t...
Lempenunre le\'el Tc. Combine Bqs. (9.2) and (9.3) n.nd solve 1ior W~
l'V = IQcl TH - Tc = 60 ( l5 - 5 ) = 4.::n kJ ,-l

Tc ' 5 + l7J.lS
1'ibc pc;JW'ef rcqui:fCmemll;~ is lbcm011e 4,,3 LkV .
Uf!uetiedi pses are used for a variety of purposes. For eumple. liquid propane: in ,cyfuld'.ers
~as a dolDCStic tlJct liquid O'l YI't'D is L'2U'ricrJ i r~ ruckds.. natural gas is liq~fiEd for ()ml(l
tt"~ ,and liquid iiitmgcD prm'ide& low-~ tefri,gennion. (las mixtures (e.g_ m )
are Jiqudjcd fur"~ ID[O chci:r (:QlJij)OUml' ~by ~illatJon.
Uqud':tictim reiUit$ when II ps is cvoJed W 3 ~ .in the IW&pbiiSe Ngil.)ll. 1'l'm
may be aecomplisbed in Sleli'Bral ~ :
l . By beut t:'XCiw.t~ ai rorwwn pre88ure,.

" B)t ;m exp;m_siun ~ hm -.-bkh 'iil'vrl u obtaJJJed.
J._oya.~~
Tile lim: Dldbodl ~ a heat mat. at a llmq)en~ I!~W'et lbm dllt to whieb b glia
is cuo'kd,. and is Mo$t ~ ~ to ~td a ps prior LO ib liq~on lly 1tE 6ftr
~0 Ill.e~ An ~ Nfriger.dor is requind far a 1M tempemllm: beJW 1fmt lfle 1
m
P.lmtlODdinp,.
~ thJi'ee metbods aft' illo.srmtedl in Fi!. 9.5. 1i'be. OOIJ!tutt~ proceg ( J) ap-
~ tktwQ;..pba:;c~ (and liquef~n) Jl)(&dosely ,P\'m drop ~ rc~ ror a
'11tc ihrollling ~ (3) docs DOl ~Lih in li~OD o:n!ess 1[be inilia1 smre u at tl fi'Mr
t"ipR 9.5! Coo:liQ ~ on~ 'l'S T
dQ~
enDUih lmnp&mue Wldl bigb t:DOII!b pressure ror the alllS'W1Jmtha1py ptOC to CUI. io.to the
twoo~ region. T1!ds b indlmd die situMion fotr :m ~ a~. A' . but not - A. 'lll.ileJe me
~ is dle s:ame: bOil lbe ~ l.ow'er ihm at A~ T'bc c~ cl tate [f(JfD A ~A'
. be: ltM~ by COID(5Sioo of~ to tho pre:ssan It B. and ooosmnt-p UN
ooollq ro A.'. ltefl!~~ w a TS dilpm [or ~ ~ thin M a t~DD)leli'Jltllm i'1I 3001 R) t.hc
pressure must be ,gRater 1haa. ahaut 90<atm) for 011)" Uquef~tion to Ol.iCUf wong a pamh of con-
.. - tndt~. Tl'nl~ if air is ~ 10 M ltasl 90(enn) mad.rooted bdcJ! 300(R), it is
pm:iwly lliquflled by thmtdlng. 111 efliciem ~ for cooling th~ gas i by counE~
c:h;mge wilb dW pg1ion of abe ps \\'bidl does ex Liqody in the~ PJ~:t;L
Liqueftcttoll by iscntropic eqmWoo aloog p~ (2) aeam from lower~~ (rm
g,i\'e.Q ~mp:.Jii.tm';) than by dtmtttl.Qi, Fur~ coPtJnu::rtioo of pnccss (2) Cm;m: in~
Wrtmaael), result~ in ~o.
The dmlulinJ ~ {J) ii commonly empJo.)e:d in smallswle ~ l~fildi.oo
-.ttml .i' 1'bc [ _ _,___ of Hir dl!liJ:. ri'lri. ' ~- .... -=n
r--- ,...&f,.._. __ .,. - ~ uu_ ~,~,~ ~~ ; ~ . .00.
. -iDd th1 i !...~
__.____... ~ -.:.&.
-JWJ
~ f i3Did ~ "'bt ex~e,p~ m h)-dm~n nnd

be: ~ WbMJ lo in ~ ~Wft upon t'btolllin& Ul1t it1Je Uritial tattptr.tture [ below
Qbcxn 100 K far~ Q:Dd 20 1: roc bdium. Liq~ of lbe:se ~ by ~108
~initial a'NJI:ing to~~ lower lhm obmilled by method I or 2.
1'IW Lindt liqtr.efi'lcliun ~ whidJ dcpmds ~) oo duotlling ~on. u ~wn
mFag.. 9.6. Mtt-r CO~Oi.\ ' bt ~ 1$ ~ed, 10 ambient ilt:.li'qlCnt~ h lfi1l)r. ~'1!11
furllJer cooled by Jefri~ 1lle kl\\'er' die ~rnperatnre ai me p enw-iDB 1lbe tbmtik
~"~ tbt. ~ tbe ftactioa of p rlhal ~ Fat e,gmp~ a Fdripr.mt
lhe cooler a1 -40 "F) pD'\"ii:ks a lCJ'I.\l:l tanperotnre at ~be \'ah--e lh:m if w.tta" m
IX'l01iBg mtdium.
A ~ d6*Pt Ji~oo p~ W(JU]d rq,l~ cbt difoUk vWV4' br m c::qRndn,
bm. ~ ~b a le\m into ~~~on ~ i~Cical. However. rtbe ~
pmcessj, sbowa in F.ag. 9.1. is based io pan oo lhiB idea.. GBs :n nn intennediate lmlJX'r.ltll:m
r&l c.nr--.:iC(edJ fretn tbt btat~ _~ and ~ d ~btoQgb an ~fl!I!Ddct from w:hicli it

9.6.~~ 329
3_-
exbauas as a !arUI'alrd or Miplly superttemtd ,apar~ The remain ing p is flmber cooled
and tfuro:tded tbrou,gb aJ vuh-e to prodnce Jique&-dton as in the UDde ~ The unttiquefim
ponion.. wbkb is satu__ratt'd VQK.Jr, liliEs widJ tbe npanda" ~USl and retums fm Ittycle
thrtiap lbc heat-e.xchim8-Cf ~em.
An energy balance. Sq. r.tlO). applied m that pan of lbe ~ lying to the Jigl:d Gt lhe
dashed \~ lj.Qe yields:
r~llg. + mI sJh~ - IR.j llj e! w
QUlll
Ill~ CJJP3llde:r opeomres adtabad.~til~,, Wcm as gir\'ettlly Eq. (1.13). ~

.
"~ ~ Mi2(H l l - H~)
Mmtilver. tty a mm: ~ til 1 ~ ~ ~ ...... rilg. ~ ~)' ~ :lifrer at'Visitlft by ~

tJli:Mfoo.: beaxnes.;
. .. .. .
';9n9 + f1l4 ~ ,., H" -li4 ;;;;: '11..~ <H12 -R,l
m~ m4 m4
Wu_b b dtJinitfons. t = m9/iu and .J = mnJ,h4, solution of this eqoalion for r yiclds!
.x(H,z - H3 ) + flt - Hs
t ~ f9.7)
Hg - Hu
lD ~his eqtllllion t is 1.be f:tadioo of ribe srn:am ~g IdE helJi!.~ ~ dw a lltt-
vdkd, and X ~ tbc fneU<m of this 5tmLm tJm1 is dRwn otf ~D Ole beat CXOOm~ and
~ lhrou&f\1 lhc ~r:. 1lds latiN qowily (.t) is a rt k.sip variab~ .ul triBSl be sped&d
before Bq. (9.1) am be solv.ed far l Note tbilt ~be Linde process~ wben x 0, and in =
dliR ~~nt Bq. (9.1) mluccs to~
~ - Hu
2. = -.......-..........
II, ..... u.,
~"""t---+ -
I
I
,. I[
.-.- - - - "**"..,__"""""""'.... iiiill-- ---
'
11
tI
r
l
l
I
i
113
'I
~
I 8
I
'
I
J 1.1 10
I
'
i
I

~
I
Ugul'd
Th.mi the Linde pnx is 11 limiting ~ of 1U1e Clm:tde process. ~ q'flen oo~ of me
hi~~ ~i~ ~ nt wm ~-
Eq~~ {9.1) @4J (9-1) tJP~ U:x;n uo ~ flou"1 imo t~ q~m frorn tb~ $1JnuYDJd...
ings. This &-an De'~ he ~y 1m.te.. and hem leakage may be igoifteam v.1Aeo tem~
~ \<'') l ~'ell ~'Ill ~insulated t~quipmeut.
Example 9 .3
Natural gas,~ hele to be pure rn&tnane:, it qwfied1jn a~ R)II'OOU$S. C~
pression is to 60 bat and preooofmg ts 10 300 ~The expandeJ and 1hrortte exhaust to
a pJ'fessure ol1 bal. Aecy:cte methane at this pre:ssure ~s tJw exohangef system
(point 15, Ftg. 9.1) at 295K. Assume nO heal~ into the system from U181sun'ound-
ifigs, an eq:taru:ler efficiency of 15~. an[J an aparnt.et e.dlaust oi saturated vapor.
For .a diaw..:d to the ex-paooer of .25% oi the methane entelilfllg lthe exchange~ system
=
tT 025). what fractlon t of the methane is liquefied=and wnat is me tempennure O:Ti
the higtrpressure Mream entering d!te 1hro1tle vatve?

JJI
SOildlon t .3
Diltl. for methane ~ ~'en by Peay and Gtem.1 By ~ in~~ mdie
~ble of ~es for upatlefttcd ntttbane-:
~!!!! 1.[40.0 kJ t;- (at 300 K and 60 bar)
H,s = 1,1&1.9 kJI kg-1 (til 295 K.:md [ OOrJ

By imerpobttion bw;ed 00 In p in me cahJc mpl'tlpCI1ics (or SII.Jimlled tiqwd avd
~. wt lhld for tt ~ -of I bat th~
T ,_,. :!:!! ] I LYK

"9 = 21:S.4 kJ k~- ( lllraltd liquid)
Hr1 = 796.9 tJ kg- 1 ( _Dltaled vapor)
s.2 = 9rS2l kJ k1f ' K""' 1 (~IU(BICd vapor)
The enthalpy at the draw-off paint betweeD a~.cbangen land n lis. is requiral
~u:Uoo of Bq. (9.7). Tbcl ~ cifk~ 'IJ b
f'fJf bKMo. is Hu.~ ~
~Pl' <lflbe 9pander'~ "Jbectlmlation of Hj (... Hu)~ thee~
inlet endaalpy. ~ ~ 5trai~lU'd than ~ n5UDl calcultttioo of~ ~
cmtba:lpy fmm the Mll'm:e entb:alpy. The teqiWioo deDning ~ e'flieinll:)'
can be written:
il.H. -=- 1/12 - H~ = JJ tltiH)s ='I( Hit - H~.)
Sotmio:n b Hu yicld5:
H u , !!!!! H5 + 'l'( Jl~l - Hd ( A)
~ H(l is tbc entbaJpy at J bar as lllle m!Ull of igtttropk ~ from
point .S. 1bis cmb:dpy Is reudily found GDCe tbe condilii';oos m poilU ~ are kDI:M~o.
Tbusa trial ealcubtion is iodica'tcd. 1\Wrt:in tOO liBt ~is to~ ~mpaabl~
To - .L, . . .
~ ~ 'Jitl'~ ""' vaJ
,_ S.. IIJIL:- 11'...- H
_lieS 1....., -""' ~
_:5 iUN e- .. -..- _. H
~~~ WthiclJ
1
- 11 cm1. ......._ .:....- -ilL All q;-~
VIii' J'\IWI
tilles in liqj. {A) are men kn~ llXI meir suhUirwioo ituo this eqwdioo ~
wbcdler or 1001 it is satis&d.. lf DOl.. a af:W vulu.o i5 ~ ftlr Ts. Qnd me~
oomilltiM tiiHil l3qj. ( ;I J bt !m1l56ed. This ~ leads ro' !he val~
SubstiiJmion of valUes: into Eq. (9.7t now ~Ids:

0.25{196.9 ~ l ,009.8) + :I . I-40J) - I~ -~ 8&.9
J; ~ = OJJ lO
28.5.4 - l:.l88})
Thm J1.3% of lbe methane entel'in! the ocbanpr ~ystem. m; liquef:Xtl

332
11Je ~d pobtt1 ~em ns ~emh.arpyt ~Wblcll i!. .f otmd ft(x:n~y

bal~ on me udlangc:r sysam. ~far adwlpr 1..
~~t.(Hs -It,)+ llitdRu - HN) ;;;;;;; 0
Wdh mu =114 - ~ and till)/~ '=~~ :~ lids eqnatmn my tx rerur.m~ ro gi\'t:

H . c JI'!J - I~ H ~ I ,(11)9.8 -- 1~ 14CU) 1 IoD 6
mAl I- t + ~ l ~ OJ uo + . V~-7
(Ml b:u}
~ Tr..:t fvrmd by ~lation mb ub1\ rw upelbeated mel.ban:e am 00 bm-.

For Md!ianpr B,
Wilb m1 .:....r ni.:c - ri112 d 1i114 ;;::;; niJ, - llli9 and with lbe de6.nitions of .: i1lUJ _r'.
mis equm0:r:1 upon ~ramm~nt ~c;:
I - :: 1 - 0. H30
111 '!::!!:; Hs - = x CH14 ~ flu) ~ "'009.8- _ _ O~fJ42. 1 -196.-9t
1 1 0 25
Wbeoee.
~ ilhe vaidt Of X~ l1 ~ ~ually 3PPJiO!I!Cbinl ~be~

ticc ~ iD (be sepamltJr. and teq,uirillg m e1clmnga II of infini~ area.
;c limited w 11bc higb "de by lb: cost of b ~ ystem.
T'bie Giber limit is for ~ :: o.. die Linde .syS~.CP~, rnr ~ by e.q_(9t8J.
_ :::. J..l40.0 - t 188.9 !::: ft M
1 4
- 2lS.4 .... 1,18&:9 V . IJ'..J I
In lhis.aase CXllfy S.41~ of abe emering lhe mmlde v-dlve ~as liquid.
gn&
The ~~ al me p 1,( poinl 7 ii ~ fowd from its enlhafpy. eatarbted
by the energy bll.lanr.e:
II, ;; ~ - (I - l)f H:t$ - RtoJ
Soh$1iltltiM Df bliJWn val~ tiel~

11-, !A! ~.140.0 .... 0- 0..054HU ~ I'SS.9 - 196.~) ~ 769 "l kJ q~ 1
The~~ ufthe ~ mllrln,g lhe lhlottle \t11h"e is r, ;: :;:

21)6.}6, K..

PROBLEMS
1 Wbal you pt
Measure of pesfonuunce - ~
Wbat )'OLl lp ay or
T1ul for an e_.p~, lhmnalrttlkieoc1 is 1J - IWJIIQIII: for a refrigenamr, tbe. ooef.

lici:eru of perffll"m:aDce ~ t't1;;;; IQcJJ fW I, Define a coeflicieDI ofparfonnt~~Xe ~' for a
lbea~ pump. \VmJt ils 9 fQI ~ O.rnoJ be11f IJUmp?
'..lf Tbc ~ or(be f~ in n ~ mfri_gdlllbt ~ maint~ at - l(YC_ 1'be

tir.cbtrn te:mperam~ is 20'~'-C... If beat Leaks an1oo:tlt to l25~ tJ per day. and if clee-
~ri<1t)l C05b1 $lLOli'lk\Wtr. estimate tbe )"!Uly cost of nmnmt dtr :tdti~ A$SIIfil!e:
:a~ of pcnmm-~ equal to ~~ of 1be Como~ Wlue.
,3..ns.Consider the ~up .o f a.el~- IDitiaJJy. tJK; o;nt~. ~ .at me !UJJe ~li;lf
~ ~ Tea c r,. when: TH is. me lmnsnmt) ~ tem~
W'ltb the. pa~ lor tiJne. owin~ to work iop.Jl. the C011l01s ~1Urc is mJuer;d
~ 'I"
JJI 1,'1!J_ll L(.b
liD ~~~~Ill
' .1--! -- T.C 1.-f...A.o.l
value l'l .~m; " .s..._ - US. - C
Yll!iP'.(LI'(J(r:$$ - ij
- ,~a-mfopef
r!U '~~~-~"" - -;..
nfulg ~~~ un ~hot re~r and uflnit~ cold reserrni:r 6f total beat capaaity
C' " detenDine m ~~on for lbe mi:nimmB wort required lo ~ dJe Q)D~
~ Ilium Teo to Tc.
9A, A Cam t mki~ biB tttm:O~ lii.S me woding fluid. 'I'he cyek is, lbe same
,as, that sbowo by R;g. U acep~lbe dieeticm are ~d. For Tc ;;;;;: lOt~ a~~_d
TH = JOOfeF). dletamine:
(fl) ~~~_m ~~~ J1,2,),. .a nd4.
(b 'ftJe qldtity .t"' ill ~lures J aoo 4.
(t 1be heat addftioo per lbm of fluid.
(dl The beat rejccQoB p:r Ibm of fluid.
te) The :moc.bmical pow;u per ibm[ef 8uid fur eadl or Ulc four ~
(fJ The coelicieru ~ ~1fmaDC4Z lJj fur cycl~ me
95. Whim is the more elfeem--e wr.1f ro iAaease lite c:oe.lliiele:m efpeDQI'll.laDCC of Caroot
~ 1o i~ 'l'c wilb Tu ecm51B.Jlt. ~or 1odl:c~ 1i1 with Tc constant"? FDt
~ u:a) friflg~? doe$ ti~~J of lb$e~jrs mat sense?
9.6. mcomparing lhc perfoJ1IIilallCC of a real cyde wiffl thai of a c.not ~ ODG h_as in
~le a rc bclkr ot ~npef".U:illtS to Qse roc the Camix ~ c~ a~
rCOII~ refri@eratKm cycie in bicb lbe a\'el'3ge ftoW ~~
1
tfE COO:r m
dmser and c~ ~ l"11 3nd Tc. re:;pcdi\'C!ly. ~ng; 1o TN aDd Tc.lbt
heat 'U'OD.$rd' CKCUIS with ~ I.!J SUftOtJlldi~ 3l mmpernrum T#H and T~l' - Wbica
prorides the mrre ~ ~timate. of td(Camot~: a ealadaJioo based oa 1R and
ic, orooe: ~don Tau and TDC?

9~7- A Cla;tnOt en~~ coopt~ io a~ IdiigRtnr so cm.t AD ofdie wort prodneef by
the engine is m.ed by the rretri.~ m wraction of hem from a1ir1tl ~vi.r at ()PC
IJt l!he we of lS kl ~- ~. Tbe 50UftlC of CDCq)' fmr me
Camot engi:J!Ile is a. hem resel''oir
ill 25or'C. If both deV~a; ~ beat ro lbe: !i~~ at 25: C,. ~how nwd1 bqt
d~ the c:ngi:"oe absoro liom iti br:al- reservoir?
OQIW
If die ad1ial c~ Qf perfoon:mee af me relrigemro:r is liJ 0.6rucaiid: i1fid if

-
lbc ~ e.fliciency tJf the~ 1$ rr = ft.6~. b,crw 1IWCb beott does the engine
absorb from Ms. heat-soume ~
9.8. A m~oo. system requ3res ] ..5 t"~: of pcN-er fm a tefri~on tate fJf 4 kl s- i.
(ill) Wh:u. is the coeJ5cbn of po~

(b) Hew ma batt is rejc;ctcd m&be condfmxr'f
{c-) Ji eat ~~ u-40-C. wbat ~ tbo lowest tempemume lbe system can po ibly
maimaio'J
9..9.. A wpor-~on mfripwica ')l:iile~D

opmues oo I:M C)1Clc of Fag. 9_1_ Th~ 11'.'-
ftiaenm~ !\~~(Tab!~ 9.1. Fi~ G.2). AiJr ooe of the !dlla-Mn.g <Sets oi
operating, condititn~t. ~ the dratlntion tare ot lhc ~ii~t. dte bl;tu--b'UrlSf""
rate in r~fle cood.eD!ier:. the power ~equimnmm. lbe eoelliatm1 uf peH{]UmliCC o:f me
cyd~ 3Dd dJe 1CodJici~nt of peri~ of a Camot ~00 cyde operating i)e..
tween lhe same te111perature lei els.
(.aJ E11~o t = lO(srF}' ccmdensatioo 1 = SQflP); q(cmnp~WT") ~0.79
rdrigeratioo rate = 600{Bw)(s)- 1
(b} vaponlion t -= lO(~f)~ cOlldelmlioo 1 :10a 80\f): lJ(compresso:r)- 0.'78
refii.gcrotiOD nrte ~ .!OO(Bw)(s)-1.
(c) Evapor.aaiou i = 10f'F); condama.ti.oo 1 ;- 80(-F): q(compressor) ~ 0r.J1:
~on mte e: 400(Dru){ )- 1
td) Evaporatioo l == Of'FJ; ~lion t == SO(OF); JJ(Cl01ilpl"E5sor) =0.76;
refrigmli.on rate;;; 300{8tu)(s)- .
(~) E~ r :c - lO( o. F) ~ coo~ t = 80(CF) ~ g(oGmpre:wx) ~ 0.15~
l:dri,gera1ioo Ate ::; lOO(Bt.u)b) - I.
9..10. A \ra.,or-oo~n refngera-doo ~ opeta~CS 01i the C}"Cle Qf F11,g. 9. ~. The tre--
fripnmt is l\'UWF. Giwo lkU tfie e\~lioo l - 4:;C. ~be etmdeti51ticm t - 3411C.
=
J~(OOMlIessor) tl76, and~ ...,fii~mkm ~ = 1..2.00 U ~. dde:nnine the cir.ctila
tioo rate of die rem~ lbe lbea~0'311Sfu rare lin ~ rondenserT the pow.t7 require-
matt,. lbc oodliW:m of pcd'omtance of b CJC~ and die coefficient of perf.ormanre
of a C;amx . ....., .. _ o~li
. -ation.t"Vtlt: ~-,.t1- .. r
-~ - "-l--
rrr;;;;- g ~ 1-
.. ...~.... . - .r~ ......,'D '""""" ........
Y~ ._ ~,upc::m.'~,-I!M"' cY~.
t_n. A~ whb ~~ (llih1ll: 9- l ~ Pig. 6 .2} as Jetii~ Openttes u1:1h

an eva;poridion tempel'Uure r0f - ~5f F) and a coadeos.atioo mmperamrc of SOf'F)r.
Salul"8led tiqpid rcfrigcnmt from me condeiBCI' ft!ows. through an expansioo valve iDLo
me ewpo.~ fro!m whlch it~ tl8 ~: wpm:
(D} For u cooling raw of S<Btu)(s} ...... what; is me rucuktioo mle of lbl. drig~nmt?
(h) By bow much would the cwulation m1e be redllced if tbe lhmttle \121~-e were
~laud b~ a~ mwhich abe rdri~ ~pands ~Ur?
(c) Suppose Ole cyde of (a) is modified by tm: mc1usian of a coutttm:urmn hat
e-xdlaJlF. between IIi e~ and! me tl brutile valve in ~ hkh hem .b il.:rnns~
femd to vapor rel!Uming from ibe ,e\rapom_()r.. [I( liquid 'f rom lhe coode:l:lser eru:e~S
k -~at 80(DF) and. if vapor fivm the ~IOTG:\ta5 tbe achm&er at
- IS('F) ~leaves- -7()f'F), w'lw g lbe ~tion nte of lhe re~~?
(d) For eacb or(a)~ (#J~~ md (c~ dalil'mine tho ood'ficimt of pafunnam:c Qf iHmropic
oc~fon of die 'V8J)Iilt.
9 ll.
_ .. ...-L.! :!IIi
A ~-.0DJ~IIIfiii'JJJIJ,ger:
Qailjt.~
__ ,QJI~~;!JI\ "amd
. _ .__(""'< ....a---...t
..__,;, th - ;JCQUJ}~~.,U.'!.<I~
br.al e~thang;er is msmlltd lo m:tbcoo] lbe fHquid &om !be~ "b> heill t';.t_diabge
with tbe vapor scream from dJc evapomor. 1bc miDimmn ~ cli:ffi::nmec fur
IJqt tnlllsfu i~ U)ffi. Temdloo~ is ~ tdrigmmc (Tab~ 9.1. Fig.. 0.2J.
~g m 20f)IF) amirondensing at "80(_VP). The heat J03doo [be ~.nor iis
2.,fX'O(Btu)C )- rG. If 'th~ ~~ ~fficicDcy !i 15~, wfnlt i:.~ tb~ ~1rr ~r:aumt?
how does dU;S resu_h,c:ot~~pam ilh the IJO"W requin:d by the com~ if the~
~ wfthoai dle bent ewb:mp? How do lbe ld"npam clmtlatim ~ ~
im me ltWO a;ses?
9.13~ Com.sidet dte ~JRSSioo remgeJ'atioo cyde <If Fig. 9.L with tetmiiiOIDetbane
refrisemm mbJc 9.1. nr, G.l). If die evapor.Uioo tc~ 10~ Jlww
the dfccr or~~~ ~die mE"fli(tic:m of~~ by making
~alculaOOm foramde~oo ~ of 60. 80. and lMr F).
(fl) ~~tropic ~siiJP of the '-ap.

(b) ~~ acom~.mrimcy~r7S<k.
9.14.. A heal pump is ~ t0 beat a l000$e mthe winter aiJd r.e coo1 ii! iflttile $111l.UDCr. Doring
me winrer, m:e o.uwde m ~ ns a Low-rempemure heal~ du.ring dJe ~
i~ aecs as a bigh-temperatu:re. beat sink The bem-tRtJ:JsfB JaJe duou.gh the: walls and
I'Q!Of or em s
bou~ , 6:.1 kJ .- l rwqch o-c
of kmp;ratlJI'e difrem~ bttwml ~
in&ide and 011tsic:k of abe b~ SUnlmer and winter, 1be b~apnmp momr bl mted
ut 1..5 kW. Derctmim: abe mininmm Dllfsidc ~ fix whlclll the batiSI!: am be
mainra:ined a1 ZtrC daring the Wiinl.er' and the muimom ~de tan~ fw whidl
~~can 1m~ M 2SCdurinJ ... ~.
9.'15.. Dr) ~ is SllppiJed b)' ~ rntnplleSSOf and pteeOOfiillg . ;yt_tem to dJe ti:C)(l~ of
a Una liq~ system fFjg. 9.6) ~ 110 brat and 300 K. The k'Mf"'pre5~
mediaE leaves the cooler at BJ ttmpcr:nwre ftC I.O'Ill~r dAn IDe tnnpcndurr oJ tbc m-
1
g,mill!J tdgh-~ ~ The sepwtur opemteS ar ~ bar. and tbe pmcfdd ti

saturated liquid at ums ,.res~ \Vbat is me muimu:m &aetion of tbe 'IIJedaEJ.e enter
mg Wt ~I ~hal can be tiqndied? fb--1')--; CftemiJ;.al &JsjMet1"Han4ln.:lal r(roo~
i) E5 a ou~ of dltl for methane.

336
9..16. R,~Q{1c the~a!d:mg proWm fur ~mttrml a1l00 bar-. d p:teCOOled'l:o 240 K
by 9Willll ref~;enttion
9..17. An adv~t Ws 11oud in a n:md ~t rn, a~-~ mlit dJa ~ a

mill cookT witb a 'Wa.tel beater;, Milt .~~~~al. of ~ be ~~erattd.. !ttd hot v,~
let J$ n:qnbed .tnc ~~ pu:rposes. h lmWI bam oq;W[Jp!d wilD 3 com enti:onal.
air-cooled electric. retri~ imA (til~~ water btater. 'The~' unit u
said lO plovide both du: ~~no and lbe~ ha. wruer at a~~ fur
~Y aboul UJc same as the con af liWIIIing~ l'M retqger:IkJf' in me uruai.insi.QI-
Ia1liHL 1'o ossru ~~ O(IID~ t\\~ ~on~ mrl~ Tbe ud~ unit tak._es
SOJ)OO(Btu)(br)- 1 from a milkmola-ai 30fFJ. and~ beat tbrOI.f&b a~
m ISO(OF)1ro ~!Vi.~ r~ klilpcmJJIUJI.! of~'3tu from 56,to 146 f ). TtleromentioiW unit
tlkes me ~ .a:moont of ~ frotn dlc sa~ riD. '' coola- ax :lOr' A ami discards lbem
dimugb ID air-cOOled ,eaJ!Idmse,r ;u 120f' P)~ io ,D dditfm_ t.IJt swne iliD(ID0_1! of '9-"a.ta is
~ d~y &om S6 .ro 1 1
P)_ ~ ~be trl!td electric pow~ requirewr-n~&
Cor the two, cas. ~ ,lhaJ,ft' aatl3J work in both is ~ g~ than RqUi.Nd:
by Cunot retrl.gemton operarln.g between 1be p'm rempem~~IrC:S.
, ..II. A ~gc ~ade refrigem.tioo sysmm (see Fig. 9.)) ~ bdwam Tc ;;;;; l JO k.
;uxJ T11 == 305 ll ~ ICinpenltums are 1'(: :::r 255 K .iJ.nd Tfl - 2tJO K
CoeJiident!t of pet{~ CJ ,of eacb ~Sta~ ~ 65% or die ~rorw..~ \"atUes for
:. C;unoa ~- ~ll:mlioe bJ tfor lthe Nal e~ and compare it wilh lhtn far n
CmmJt .re~ Opetatiog ~ Tc .ood l'g.
!J..U. Do a parwm~ sandy ror tht amKic ~ftl.."'liou process ttra~.l!d in Soc. 9.6 andt
&.- 9 . In p;uticutar, show llll1:nerically the ,efred .of eh;m,gmg me dniw-fJlJ :rruio ..r
on otba' ~ vmiiibl~ Ptttry'.t Clzsnicall!tig~ llandbook. (fOQtnote 7) is a
iiOQfte of <~ita b methane.
t.lO.. 1'be COIIdenKl of Il. bome Mig'ei'Mor is OOIDJDOldy li1'1derntatb the ~Iiana; dt~~
~ ~ K~Pmt ~~~ ~t wi1b ~ m. wllicb ba an a~
~ ol a~ 10F"Ft- 'b. ~ 10 reconligmwz a rcl'rigemtor so tllnt the
a)~ u or.usidtt tbe bomew v.tlere lbe average yewiry lempeulllfe is aboul sot~Ft.
D~'* the pros llrnJ oons of d:U.J propgs:d. As5:ume 3 flieezer ~empemmre of 0 .FJ.
md an aerual coelliei.em: of pell'fumu.m_ce 6()ISi llw of 111 Cam(lt t:tfrigm.tm".
!1.11,. amnoon misocmception is m:tt me coellkicnt of pcrfo.tmaJK'e of !1 re~ DJU$t

be~ tbm unity. In 'fact. dlis is r.u:d)'" dn: case'. To see wby. consider a rem refripn~LM
[or wtridt w c: 0~6cucti001 Wh3lt runtl:lrtoo ~ustlhr Siltisth:d itl o-JdCJ thtl w < I?
~that T11 is :fixed
9.%l. ~ filib in a borne ito the winttt ~-rony. me doclrlc po1.v~ rtmaimJoo. ~
~t e~er:r orlli m
~ nm. to wcuy~ itbqr'Jl move mto
the ki(Cben. where me
heat ~'ed from~ ~II,Ir may provide fDf'a ~y comforotble l),;n.g
spiOil. &we.w.u (dte engineer is remindedh die tirthtn JDs:e:s. ,b (:at to tbe utu~ ~
dB: t'olklwin! d3ti:i to ~ (be ajkJ,.,"ahhc: qiO of heat - {k\V) f~mm me kitdJeo

337
for the et]Ji~r".s ~ lo mak~ ~1\._~

&Ia: Desired .kitdwm lmlpe.rature = 290 L
Reft4.~ f~~m~e 250 It
A-.-... ~MC-kmkal powft' lnptn to r~tm;; OAO kW~
~Jf~: - Dl fiJ ;;; 65<i& Q{ Cu:noi l.i1.
9,n Ftny (SO) blot bt- 1 of liqtlid 1.ohteftr, at J .2 bar is eooied ftotg 100 b), ~C.. A 'V4pQ.f-
~on~(JO c:ydi! 1s u$ftl for die porpme~ AmiOOIIU is lhe WClltiAg Duid.
Coodensation i:n tfJe,CJC]e tis ~~Y an air~d tin1f:m beatJ ex~b ~
tht air remperatun! may be a~ osstmWly rct~mram .at 2rC Dele~Ddne:
(a ) 'nl~ Low and high ~ levels (bn:t') Ja die rdri&Ui:oo C)~-
(b) The ciJadarioo me of omJl10ftia (Dhll g~t).
Assume I (f C minimmn app:roadl tJ.ts: b beat ~e~cbanJ~ Data for IDJilJOQilia:
AH!~ _, 23.34t1 moi-
In p JAt - 45.327 -
4104 67
" - S.l46b T
T
+6!S.O~ r~
wb.\_fC' p - i in biB and r is in bhins.

Chapter 10
Vapor/Liqui Equilibrium:
Introduction
Preoedi.nJ chapters ba.\ deaJt l.aitdfwilb pt1Tt m11$m~ or with coiN3nt'ompositiOD mix
~ c.s- r. Ho\\rever. composi1ioo ~ ore me de:slred o~. nCJI only o ehemk:al
re:tttiun but of H ~ of ~ imporwn -aransfe-r opmWom. Th rompo-o
siti011 becomes a pri.nwy Y3l'iabk in the rrmainins t:bapl01 of thi: ~ Processa such as
distiiJation rption.. md UO'aOtion mini pima of diffetem ~ mro l"lffDW1:. and
when dle p~ are no1 io equilibrium. lnUL'd'er ~\11 cen tbc p alters their~
Duma.. Buch lhc c:umt of dutnp and me~ oftnm.sfer drp:nd OD tbe depa:rmre of me },ptcm
tivm eqW)ibri_om. Tbu:s. for qu:amirarivc O'c.almclll of ~ s b3Pli&r lhr cquilibriwn T. P. and
compositions mtiSl be known.
The f'DOSt commoo)y cnoot.llltJ::'Rd coeaiuin,g [n iodwtriol pr3aice are vapor and
liquid~ allboogb tiqlrl41iiquitl ~ !li4 and tiqllit.J4ol1d ~ me alw &JDn4 lu this
dulpen "-C ru c:tiwo . dJc oature ,o f equili.briu.n and men .eonsidl-r lr.\'0 1\J.Jci lhlll g1..~ cbt
JIIIQDber of iJldq:~mktll ~~bb (~;:(!~ to dctdttliM~ eqW!ibrium ta. Tkre folfo . in
Sec. 10.3 .a qualimiv d' on af podliqukl phase beha-v-iOL ln Sec. ~O.J we iotrod!!Jee
lhr r o mpJ' t formulad th:lt alJow cab:."ulatioo of lempemtwes.. ~~ md pl.ta!.r
COmpa'SI ' ror 8) lnnS in :~porlliquid equili1Kiu:m.. The first. known liS RmTJh. klw, is
ftlid only far system t low kJ ~ prcs."\ll_mj and li:n genera] only for S)'&tefih rom~
of cbemfallly similar 1es. The second llmown ~ Henry$ la91-, is \-alid for any spec~
pm~ienl m lov. coocenlmion.. but a prcsmled b.re is alio limi1ed oo ~ ~ ill ktt.l to 1tloddule
press-~ mod.ific.-ioo of RaouJI law lhalltltiO\'eS the restriction to dlemicaJJ) similar
pece . trealed in Sec. JO.S. Fmally in Sec. 10.6 c..k."11t.d.i01l~ b~ oo r;quilibrivm T.ltms
or K-~ lue JU"e co~dcr"ed. lbe tR:atmeut of ""appdliqu.id equililrium is dt'\'elopM f'u:nJxl- in
~- J2Wid 14.
10.1 THE NATURE OF EQUIUBAIUM
!E&tuilibrium ' a S~nlic cq:nditioo m 'ilich llO c~~ OCciJr i n ltle macroscopic pro~ of a.
;tan "ltb tUne.. This implies a ~ of aU potentials. dl3t ma.y l-a.\be cbansc. In eniJnen..
ing pmctilot.. ~ ~ of ~quilibriwn iB ju,~cxl when il ~ 10 JtiUJ~ of~

ClCCU~l~Cf .Fer example. in the rebo.iler (or a di1illmioo ooh.ll'lm. ~uifibrimn between vapor and
liquid phases irs COOllllOil:br .;tMIIJllled For finite vaporintioa mtes 'this is ;m ~ but
.1~
lt ~~ l d !---.l'--~ "fi .
.bnu\N~ m__gm aun (lf"(Uf mao ~_og ea_ -~JOGS-
' . L::IJI-11-'
An isol~ ~ c;umisting of liquid and '-"apttt ~ m hldli m~ rotJ.~act ~ruauy
ra.cbei a :final state 1\fw:rein no tendmcy emcs for ehaos;e to oceur vri1hin die ~ The
~~ ~ IUid~~itiU~IJ~fi..m val~W5w1Licb~~ fll'fl
lbt: 8)~1 :is in equllihrium. ~. at me mmro_srnpre ~ m nditioM are DOl static.
"l11D molecuJes CQJDprislng a [piJJg at a gi'-"CD imtant ZR oot tiE woe mola::l.l!es tlhal Laa
~py 1hc S{tl'fie p~mse_ Mokwl~ witb sufficicn~ bip '"Olocidcs ncar dwe ~eve~
surface f~ and pass mto abe o~W~ H~ tbe a~J rate of~ of mnlecules
is Ole~ in bt4 ~ and.no aet intt'pllase tranifuof mataial OCCDn..
,_sulfl8 of Composition
1b; di~ ~ i:~ ~om of ctu_pt,JS~i.QQ 11w:: ~ ~-Q.. mo~ fJm:tlOP~ and~
OO~ Mass or maJ:e. fradioo .is drirwl M tbe r:nlo of lllie ~MS.II. or IIJIIItbrr of rod~ of
a jYolfticuJar chemical species in n mixt~oe or dutioo ro lbe mtaiDJaSS or ruunber o! ~ of
JIMblre 01 soJutioq:
J.Pli
.
IRI
ilj = ~ = ~
m Vl
Molw- ~on ~ defined a!~. me mio of t:be mr4e l"nl.dion of a panitmtar chemia:ll
~ i_n a mirxture (IJf sofoti:oo to the molar VDIU~~~e of the Jllixlum Of wlutioo:
Thi quantil)' hlslmit5 of roolr:s Qf i per ooi1l vohm:~. fvr ll.(]Qjl ~ coovem~ Mtg~
i~ e~epres$ion a ratio d nw!'$, Multiplying und dividing by ttJOW Row rar~ .rj giltf;$:
.
,.._ ..... !!!
l,. r -
q
~- ri.- is molv ftow mo gf ~ i, .; md q ill.,.vfumeUic tlow rate.

The lb(llaf mass of a mi.l\u~ or &'01\llion ~ by dtfiAiWrJO. die ~lramoo--weiGhrJ
wm of the 100lar m~ of all ~ies presen1:
Me I; J~ M':1
l
10.2 THE PHASE RULE. DUHEM'S THEOREM
Tlm pbase mk for~ ')"Stems.~ widod pmaf i:n Sec. 2.1. ~ fm.m 3ppfi..
1
~. or rub= 4Jf ~ltdmL 'Jbus. the numta of miQJes. m. may be m~Dtly&xoJ m a

S)'stcm at equi]iMIIm is me dlff~ befwee~ me lOOll rtlllft~ of \>liMbles tba1 ebamctem-e
tbc imalsiw: sllb: of h sJ5tem l.l1d lba monbcr of independent equations '~hat em be wri111:n
oono:tl:ns lhc TVuriubb

1'l:le &trMSi~' 5mb: of a P v r systao c.ront.ailliJII ,V ~~ ~ and " plw;es in
~ is dutm:cmzed by die intmm~e \~ teD'l)Jer.rblre T. pres$tlft P.. P:d N - l
mole~' fOJ'cacb phase.. The nvmlm'oldmse phase-mie variables is 2+ tN - l) hr j.
The uf the pba~ iiR" DDt ~~ variab ~ they N\7e no inSQf;IJCe m1 the
Ullm~ t ale of rtbc 5.\lUe:m.
. willbet_~ dt.;tt lata m
dm ~ an ~1Jl ~brium ~oatioo
fft~ t-
--t~ ,... w.riDat ~lrivw
~ inlemhc
. _ _ 1lP~ .__.
-....!..L,l.-.. _-..--y o r...._
II.J.B: c:-.....1!.. IL4111;' _N ~--
~ fior~.u of
..---'1-. pall' _ ..
r~-.
I
--
pmsm:d. inclepmtdent: plwe~ ~U3ltlum is {H" - I)(, ), The
Idle mmiber of
cJ.iil~~ ~~~ ~ o~ fflp~...rulc ~and the number of i~LIC!w. eqaa-
tilms ~mg lhml hi rtbe number of ~..u:iahl.e$ that may be ind~dy fixed. Called the
de~ of fftedom,of 1dle system P.. rthe mlfnl)er is:
F ::::2 2 + (N ~ J)(:7tJ - (1r - I)(N)
Upon~~ this~ rb~ rP~ ~rutt~
IF :l l -1f +N I (:!~ i)
~ ,s tn~Tm.J is aJlOahej rolt,.$lmDar to ~be ~role, lm1less ccll:bmted, lt applies

to closed systems at equilibriwn foe wbh:b 1M ~j,"t ~teas ~111 ~s tbt. ~W"C stale of
the ~ U fi.IJtd!. The si 0 of sueb. D System. :is said tO fbe t:ampl~te/] tiemmbrJ~ and Q
~ DDl only hy abe 2 + (N' - l).:r inlellft ~e variabies bm: also b~ w
~ VlfhibleJ ~.,. de ' ( IDi>'te ~ of the pbasft- ~ till: ttltld
!lll*'rofv~les ~
2+ {/ll - 1 ~7 +::t =2 -i' ;r
Fu- e.diJKd Q'Stem faJ:IJMI.fFom ~ amw_uts,uf dJe ebmliall ~ies p~ ;JJ ma~riill
babnm eq&aliDn t3D be W'rillm for~~ of the 'fl.l ~ ~es. lllesc in addition to the
(n- - I )N pbase-eqllilibfium equ;dioos rep.resem a mrmber of lndepelllfeM equ:rtiemi ~ Ito:
f:r - l )N + N = tt N
For anr clOSed system fOrmed lnftlally fnHn glven masse~ ot IPI&"
crJbed chemiCal .a peclft. the equilibrium 8l8tl ll$ ~ty deter-
mined wbea py t.o Independent~ ar:e fixed.
~ ~ i~d'1l:i varil~k$ . ub.Ft
to ~fiemoo m_~ in pnend be. either iintensh'e or
a:limsn.
rc. Howe\-~ dte IIIIIDber of i/Wpmdmi bUm.~ variables i& givm by liz pbasc: rule.
Tbus w.ilm't F -= l. aJ l~ o oflbe 1l'an ,'ilfiab~ mmt be WI'Dsi\"e, md whm f" = 0~ OOd1
mube~

11.9 W.E: QUAUTATIVl5 !BEHAVIOR
~quid equilibrium (VLE~ is lhe s1ak of ~eoe~s~ m1iqtrid tmd ~ phnsw:s. lo thiSi
qua.litati\re: discosi~ ~ Jimi1 ocm..~dfml.tioo 1:0 sy,smms cmt)ll'ised of two c:hemic:aJ sped~
~ cam ,o f gRIW:rcompi.Cd.y Qulno( be r&laquatcJy ~ g&philZily.
When N =- 1 tbe pr1we rule bef.i'OJIIeS F = 4 ~ n:- Beamse lbere IDllStl be at Le:~St
one :Phase ( Jr :r 1).. lbc I'Wiili~WBD IJ'W'IIber ,o f ~phase-...we \-miabb. wbkb 1DUSI. 'be sp.xifitd to
M ~he lnteiHi\'e :Stare cf dir 5)~m i:s lhar.. ~ly. P ~ T. and oHt mu1r: (aJi mass) ~
m
An ,eqiJJiihrium statea. crf lbe .sy.smn cu l.bere(are be ~ dm:e..cli.:mmsiau1 P~T
com,pnsition ~ Jtbin Ibis space.., lbe Sla.tCi of J1(,JW of pbases t!Xltl:isting at equilibrium
( F - 4 - 2 ~ l) ddinc '~ A sc~maJic. tb.J:r:c"'llimmstunll ditp~rn UlLiSi1rating ~
aJfaces far VLE sbDwr1 in Fig. t0. L
1'l't1s 6gun= 5bow's 5dlemalically taM p , T ...compositilm ~ which a1ntain the ~equi-
librium ~ 'Jf ~ v~ ~ D~ lliquid fm- ~ l!l:ld 2 ,or~ binary q-~~
Here. sped I, i me "''i&bter"" or I'DOif1: volmDe. The wxller- surf'aee ~conlalns the Slllln'ated-
Obras pro egtoas po d1 e os d aur

342
vapor~ ; it i) lhe P-T-.. J ~ The uppr:r cont:J.irls the saturn~ liquid wn it

~ ~ P-T -.r1 tfuce... ~ ~ in~ alan lbe li~ R K. AC1 and U B II C - wbicll
rep cnt tbe \"apOf pressure-v .-T CUI'\~ for port sp-i I antl2. Momo,'O". the under and
Up.pel' ~ form lDUillkd lbe top of rcbr: ditJv.am ~"Cal C 1
and c'l. the critical poinH of~~ l IIId 2; 1bc. aitica.J poinU of the'~ mixl.urh of
tbc tWQ lie along a line on the ma:ndld edge oJ rbe urr~ bet""-em c,
Wtd C1. llrl~
critical locus i de~ b) ~~at qpo:r and liquid ~ in ~uilibtim:D Dt,cotnt
idenliem. Fmther di.srossion or ihc critical regiDo '. ~~n l:.der.
The ~-ubcool~liquid. region ms ;lbo,~ a..be upper surf: ce of Fig. UlJ ; tbe ~ted
''*~*' ~ Li Wow tbo UJ:lder mrf.aa:. 1"ibe interi<V ptce betWM"n l~ rtwo utfaoes i the
~icm ol coexktcnre of boch liquid orul 'rap.lr phu.~ I r ooe mu witb a liquid at F roxJ
red tJbe pressure at coostant ~and rom~irioo alt'Jqg vatia~ tine FG. the ~
bGbblt r \'"ap(lf op point L,. ..bicb lies on tbe upper ~dace. ~ L is a bubble-pDirrt~
;and hr ~_r t.urfuce k lhe bubblepobn ~ The of the w.por bubble in eq-tlilibriuul
'lh abc liqojd ;r~ L is rep~ by a poim un tilt: undr.r Mtrf~ dl lhe lriiiJl'Wl.Jure and
(:ftSSUIQ of L. Th~ paint indicaled by V. Li:oe LV i t liiDple of :l~ line. which
COAIIIC'CtS point! ~prc:.liCQiing ~ in rqni librium.
1M~ .b fo:nber ~ Dlong liD: FG. 1DDJ'C and more hquid vaporizes until a1
K' tbe prcx-ess CllmpJete.. '1ibus w lies Ofl the under .rurf:lfe and re~nts a Sl3lt or~
, lu~ Lhe miMure composition. B4!QIU. w l! the point wrucb me last drops of liquid
(dew) disappear. it is a ~pv;m. arul the ~ mace~ the <b~ $11I{.c~. ontiuued
recluc:tkm of~ JIR:R:ty 1.t::lds. into tiE ~ '-11pU' legion.
B of lhe complexity of .Fig. 10.1. die detail~ cha.ruc1tti!tics or~ LE JrC
u~an drpictcd by two-di~ papbs 1hat ell' lay what i.s ~ oo \"fflr'~ pia..Des that
CD1 me thJee..dime:nsional d.ia.gmm. "lbe tJrre.e prindpal pl~ e$:h lilt~ ro (JIJC of
abe coordinate ,u cs, a~~e itll~d i_n fiis. 110. l . Thus a "--emcm ptilt1t ~Jar to the r.em-
pttl"MU.-e ~~ (tUtl!inc:ll AE.DBI.A. 'fbc 'lioc on lhis planefmn a P J:tY phase diHgrdJII'
at cansmnt T. If' 'the 1~ from ~ra-.d web pliirEs are proja.'ted on P ~inglc- pamikl plane,, a
diagmm like 1-i g. 102(a) u obuirted. k shoai P -.\' 1- 1 plo r()r l.l!tr difJ~ t.cmper.dllres,
The aD1: fur T., ~ abe tioD o( PiJ,. lQ. J indicated by A 11 B LA. 1be borirorn.allines
are tio tiDes ooonecring tbe cmnpMilioos of~ in eq11llibrium. ~ ~ 1it ;wcJ
Td ~ berween lhe I.WOpurt'-$pCCICScti:ri I trmpmma~Wcntificdby C1 andC: inF1g. 10. 1.
The Olin for lhese 1\\-o a.e~ rhertJure do not oamd alllhe "'3.)" ~,.. h ~rn.
1'IR: m UIR critical poi:n ~ by the letU:r C. Each is a cmg.ern point at bieh a bor-
izooml line ~ lbc c:uf\~- Tbi ~ so bec:au:!.e ail tit' line corqx-ctmg ~ cquilibriurn w
aJe boriwn.t.JI. end the tie liDe. COillleding iJmllcnl phiD.es Uhe defirulion of a critic~ point)
IWlSJ ltk-refun: be the: lll$1 sudl Jf()e tn cut ~ dia[mim.
holizoaaal plane p~ tbmug:b Pi . lO. I petprndicular to the P uis i8 idmtilkd by

K J I H lJK. VIeWed fmm lbe wp. the li:Des on this plane repn:smt a T-.t a-)''l dia.pum. When
liD fot~r'd.\ PfC! I.Qt$ a~:e JlrO'.Fcud an u p::u'i!Jd ;plane. lbe resuUin;g <fiagrnm.a.ppea.rs as in
fig. Ul2(b). Th~, fipre is AfiaJugo~H ru Fig. 10..2{a)~ ~:tttpl dim " ~ ~ broavior
for Ibm::~ bml ~m ' 1 . (\.,aDd Pt~. 1be o~ fw P. re~nt ~~lion of fig. lOJ
i.Ddtan~l by K JIll L K . ~S!Nn: P, tit:.& betVItrro tbc critiCBI ~ulti of dJO two pure ~
at pointS rCa nd C"J.. ~Pd . ~~ thcaibl:w~r..-uresofliOJh pure~' ~efore,
x1.) 1 diugtatn appr-.d:B m. an ""is.tantlp Shnilllf P -~~ - } ' I bdla\i nr [Fig. lO.lta)l is wl~S&W.
lbe. T M

c
c
0 .~ I 0 %t1t l
(a) (b)
Fip:~T1U (a) P~-cydiapamf!fRcmm~. (b) 'T~yd~fw ~p~

- Sanmm:d liquid (lbobbte line)~- - - SatllmtM vapor (de line)
01.her pom"llle plols .ve wpm- mole fr.wtioD }.l ' :s. liquid mole l'r.iKiim .r1 for Clltbt.r che
~T aotiliom of Fig. I0.2(o) c.v lfhe constmt-P aRKli1!ian:s of M.g. lO.Ub).
The lbinl pJaue ldeobfied in Pig.. 10. ~ ~ \'Crdml .-1 perpmdicldar to tbc compositiuo
am.. '*'ie5 tbroo,gb points SL IN and Ia. When pmjecled. em :a p.mdleJ pbltt, lbe. Ones l'itom
~I pta. form a ~am suet. as shown~ M.g. 10.3. Thi~ u the P-T diqram; lines lJCl
md RCt are "~-pressure OOI'VIei fO..ihe p11re ~ jdemtfied by '~he $1liDC ~ M i:Q
Fig. 10.. J~ Each intmar loop~ du: P-T bdla\ior ~ol5aturatcd li'Vlid and of~
"''aJIOI' for a fili.f:IU1'e of:/tt4 t.~: 'lbc d'iff~nt. ~ art for ~ ~~
C'leuly" dJe P-T relation fw lunued lriqmd is diiferenllrom that for illllimted \fiJPfll' of the
&amecompodti(JD. Db i iqt~CJOR-~ ~1h Ulc bi:ba.vb (If a~~. fur wb_jd] the bQ.bble
md dew tine coincide. A1 poims 1i ODd B mFig.. 10..3 :saiW'itrellllq_-lrid and ~wpor
lines intt:~h AI ~h JilOlms a saturated liquid! of ooe co~n and ,a AIUraladl vapor of
D.DO'iber m~rim lmw the &anlt T ai);J P and ~be Ml pba._~ ~It~ meqmh"'hrium,
The lie lines, ~g IDe eaincidtDg poim.u m A mld Bore ~ulaf to the f' ..T plime,
as i:Du:Stmed by the lie Itoe L v in t'ig. l 0. ~ .
The criticaJJ poiDI of 4 bina.ry m:ixnire ocams \Ybe_re lhe I8Se or u aoo,-p in Fi1-- I Oil is
~nt to lbe l:llfdop: cun~ Put UK.Jtba way.. lhc envelope euiW is the critical toea& One
can "'eli}' 1b.i& by ~ film doscl,y ~ill ~p$ @41 1[JOtln_t; w~ hlppeqs ~{.) ciJe .P(ti.DC
of i~uo .ai dJidi a.-pmdion beloomes iD&:niteBim:d. Fi.gare: IO.J mows that the Joe.atim1
o1 lk mlk~ poiru m lbc DOSe of ~be loop ~ w.Utl com~gn. FQt o,~ ~ts (be,
erilkaJ point is the highest ~ and hlgtest pressure m wbidl wpm mid liquid p~
can e~ tm f'm a mUlnte u ~ in ~111il it~Mt. ~ ~ oMtiD wndiRons a
eoru:temmi.an proc.ess OCaiJ!S M tbe restdi of a~ tn ~

p
fip.re 11..3! PT dl~ for5e\'i.ftl f1p~ IU~ Pwtion of~ PT ~tnim u11be
cvm()Ob'(in cddeal tregDun..
-Sa~ liquid Omb~ liPc)
- - - Sa1nrmed Yiipot {dew liM:}
Coosider t& ~ ll()9J ~of .a ~e P-T loop tibown in F~J ~0.4, 1'be c-ritical
po:ml is C. 'l1:le point$ of OJUifmim ~and ~m~umum ~are ~dmtified ai M,
wul Mr. The .i.oterior dasbed aii'\"eS ~ tbe 1Dactioo of me m"':'..ldd llr.)'Sitfill thai is liq~id
ma r~base mmure of liquid and vapJL To die ldl ef dJe. critical paint C n redlrotlon in
pnmure ~a liDe m.:h s BD is ~mpanitd by voporilatioo of liquid from bubblqx>hll
lua ~ l01I.Id li:Je e:~~ However. if the original coodilioo ~Db 1to pol111 F,
fi &tam ol ~ . . .
wtnnr;
""'\!!...... ~ ~ ~uv ~.... ~ -r- ~ - Yft:' ~ .-
~~ucr-~n - - n'l'll"'ft -...1 -;:...._ of ..JL_
~~ --~~
m~ a
muimum at point G .. aller v.o113dl wpoli.DI]oo mRs, plaoe unW abe dewpoint is :fClCb.al, id
puint 8 ,. 11Us ~ c..~ ~ruth. wndmmtim~o 11 'RD be impcnmt in the
~on w deep~ nus wheJe 1IIm ~and~~ in tbr ~ud
fwmatioo may be at eooditiom represented by point F. If the pressure at me a-el!hNd ~ ~hat
of poittt G. we produc1 IJQ.m tf'o1n w."dd a ~uilibrium mixtuw o f liquid and wpor.
IJecaiJK dw= ~m'Wik ~ ~ oo~ iin the liqmd phase-. signifiemu ~oo
~ W'llhm ~ ~ ftlflDlltioo itsdt the ~S!III'e ~ends to drop as. the
gas supply (fep~ lf nut ~d, ~ ~ UJ1lbe ftmn:41oo of ' liquid plwse and
a ~ Rd!J~Ction in 100 pmdUdion .o f 1be welb. ~g is (berefore a C~U~mDm
_p:acticc;. i..~ ~ p ~itt front wfddJ lb; ~~ ~ 11~-e hccmJt:UJO"~ i5 n.muncd
to i(J}e unde:rgrouDd .resen-oir tD rnaiDain aD ~ preb1l:re.
A P..T dmgm:n f'ordle etbme'(~ )ltsJheptam::(l) &)'5t"CID is shown in Fig. 10.5. and a Y'ti
dJa~m.
e:pa~ ffif ~!IJ- ~ti~ fmthc
..---.....-- - - S~~Dr ii:V~ ap~
-- - - s..,~ ~ IDJ ~:n J01i
- &~.fjr- - . A~r ..:II!... .......
,___ Ofw....ul ~~COD\~
tim. 011e pJocs as Yl and l'( lbe mole i'raclions of lheJ more wda~Ue species i:D lite< miJmm:. Till:
Bit a ~ ~- -
- 0"' ~- r.,.,.._,_.~ _.,.. -- --- ,l'!; t.~] -
nnm
Y- V& - ---u
moimum and minirmnn ~tinrrs of die lii:ICR "'Obllile species obl:limhle by dimlla.tion
indica.............. 1he F ...~ int__.,.,;;.,_ ...,. ;~~._ mma -
VJ Y...IQ :a]Jp[Qif- ......... Y11-XI cu.n'e

.34S
~
' j I
MIJ mdl; ',i,i!lftana
~ II ~ ~ 1 ' m
~, ~ J
r' _, l. it I
, I
{j ')
1~ 11..1 rmor. S .,._,.
_i ~ J
a 8DO c. 14
/f f I
v
IJ I ~
I(
I
' ~~~~
:\:
\
. . .
,K'l15&.7 i"DDIIIIe ,.. titllll111!'
a ...... CfHI , ll ..- ~

I
-e
i 000 'I I
j
r
L
~ I ..
11 I
I
I '\ ~ iiii!O'Bl ~ 4!!llJiaM
l ~ ~J jir"
v :1'
~~ -
~ r} I I ~ ,\. ~
I
400
~
.., t"'
v ~'
I
'(
I
)
v
)
~
I /i J
'~ v~ ~ / I
/ If_)
..... v ~or ,..__
~~"""""
I
0
~ ~~ ~~ PT dl~. ~TOduo~ by ~rrn .oo. F. K. ~Yid-p AICb L

\.'01. ~ pp. 426--4..11',. 19'56.)
\vi"""" * ~ dia
. UI ~~ ... g0na
I,. e.-
-lfJf !!iJl ........
m!!t.SC 'P(Qf.lt
..t..-"1q)Oli
Y !llf:
__ _.l"....,..:d: ......... _ "'""e
i!UIU l"'llMo.!F UoQ!nil Yl .~. ttJJn~bmJ_ ~ LJ4,o~ ~
Bll1lC : "1'1.--.
ill fuel ~ tritleal Yi ~ .r~ ~ 0 or )"JJ ~ ..tt1 ~ 1. Poiru A in Fig. ~0.6 ~

poin~ llniess
n::senls 1he C0111p08ition of abe vapor and licplid ptwes .w; lhe maxiirmnn ~ a1 whidJ the
phases can~ io tluletband~tane system. ~~tion :iJ about17 moJ..% clb&me
and tilt ~ is about ~ ,263{psi:~~ 1'be eo~inl! point oo Fig. ~O..S is labeled M. A.
co~~ of~ p~~ for Ibis system has ibet1l ~by Barr-Davidl.2
The Pw T dlagmm of P~ 10.5 is lypical for mixtures &1 mmpolllr ~ sodJ as
h~. A P-T diagram for u "'trl dUferetu kind of tan. metbal:lol f~ZC~le(2), is
shtJwn in Pi_g. I0.7. TOO lllattn of lho ~ in Olis 1igum ~-"-~ hOW' difllcult it (;;}0 be to
predict phase beba\ior for s:pecies so dissimilar as~~ 'benmre.
Alchoogb ~ iu die critiml tqion Gf ~ ~in 1M pdrolamJ md
natuml.-gas in~ moot cliemic.al ~g is mxmnpll!.lrA .ut~~~~mh 1Uwer ~
g~ JO.J and l0'.g display oo.m.m:un t)'p:8 of' p ..z . .)<"" mel r--xy bdla.vior at CllDdmoos \\"'ill
MDO\'. rd ftort\ llr c:ri:tical rreglo-q_
r)!UR l0.8(a) mows dam fm mtrahydrofunmC L)fcartxm tdl'aeblor~) 3110 ~c. Here.
tJlo: p.,;rl or bubbkpojint CUJ"Ve oo a P'-x 1 ~J'1 tUgRID lies bdow lbe 8~ J' .. trel'ati-OD cfuu..
~lie of Ralult's..~ beh.a'llior, 6 de&cnbed in the rcll(w.-ing s.eaion. Wfum such JJCgllti.ve
x,

.e
~ ---~~~~~~~--~~~--+-~
~G..60
a ~~~~~~~--~~--r-~~~~
5 au :1:--t-:t--t---7----'t--1-~--:---i---;i---+-----t
0 1.0
~ .._,~ E~li~tae: J.r di~__m. ~l;;,llt:'td llJy p:mli~ F. H.. BatrDmvid. A/CtiE J...
vol z p. 426--427. 1956.)
~ from lineamy }Jea)me :saffidecdy large reJab\-,: l"0 me di1~ bctwct:ll UJ~ two
~ ~ wpor pemn~ ~ p ..,_x ClJ'n"e ahibill a minim~ .as i.ntl!mted mfig_ lQJI(b)r
forlbe chlomform(l)llmah_ dmfunm(2)sy.snm. atWC. 'thls fl.gwre-soow dmt dte p . ~ C!UJ\1e
=
aim 1m a minimum at the same point. Tim! m lb6 polrnt ,wllere ;< Y1 lbe ~and~
bkpoint ~ uc ttllllpnt lD die samB borizootal JiBe. A boiJ'i;q liquid of tbi8 rom_posidoor
pmdDOeS a 'W~ af ~uy t:1:ire ~ ~limi.. mdilie liquid ~urt:: ~ oo1 dlange m
Wl11p!ll&iliml as it evaporab5. o separation of liitieb a constmt-bolli.ng sotution ~ ~ble by
-disrillaliQQ. T'.be te>t.m ~f:r!p~ ~ u~ tv ~tw:. tbili ~c-.1
The~ for fimm(l)fearilon m&ndllori:de(2.) at J09C shawo by Fig. lO-B(c~ prm*lc an
~ (If~ ~ fvr" wbkh ~be Psm c~ &~ awve lhe linear P Xt re.btioo. The ~
mm hown in Fi Ut8(d) for elhanoftl~) nt6S exhibits po.sili~ ~ tir'om
boarity ciently larg t.o c;mse a mtUimltm m the Px1 ~lli"Ve. This ~ is maximum~
ror
pressure ~pe.. Juu as dl.t l.ilil'lirn~ azcot_rope tbe vapor and liquid phases inr
equilibrium have the Identical ecr:rmpo.~on.
Apprreelabte nepli~ depannrm from ,..x,
J li.nemhy relteet samger liquicl-.phase imew-
liXif.a}ul.a:r ~ betwtoJ llll1ike Ibm berw-~ like pam of mole.eulle5. CoDJ'Iimltly.. ap-
preciable posimle: departUres remlt for GOIDJ:iom, far wbieh liquld-~ i~ ~
~ lilt mob;pl...cs :a,n:, sttongc:r lhm ~"WD unlike. liB this latter ease lbe foJUS lbet'Weellr
3 A (Mipilulm Qf dati .r u ~ g~ i ~'veq try l Qm&1mB. ~Dam. loll" Wjky a. .som. New
~19M.

~4'1
F.lpft 11.1: ~ PT
diagmn. {lqmDfcd frm'll
~ Eng. sa.,. ,:oL a9.
JL M_ Sbaks and W.. 8_ kay,. ~
p~ ~ ofbilmy i)"
~ klrm ~.. pp. 4li...-.W4.,
(Op)1igbt ] 964....lib ~Oil
fflml ~'tel~~
Pa.~nuu.llnptiul. Thr: ~
~Lme.KI OXS
lGtL UK.)
like ma1.nfes may be~ mnng as ro prevent complete~~ wird tbe ~m then :f anm
two sepmilC liquid pba.se:s ove;r & faDg or~ dcsailal iD Sec.. 14.4.
Because ~oo ~~are canied 00_' lllDM: Deady a& ~~ ~ d1an a&
~tint ~ l XI ..)"l diapaiDI! of data 11 COIII!tallt p .art' of p~Xtiad .in~ The
four suob ~~ ~din8 to 'd:tose ~of Yi~. lO.S ace ~ for umaspflaW ~
ill Fig,. Ul9. N~ thai the dewpoim (t-y11 cunes. ~ abmre tbe btibbl~point (I'X) ~~.
~toi'IOO\'U.. the min.i:mum'"Pf1 w:e~ ofFJ,g. JO,S(lr) appean -. .a owimu.~~
(ormu:imurn-bcriling) W!Oiroperm Ftg. 10.9(b). AnanaiGBP\lic~noe~u.Uu~
Fi~ 10. (d ) and ]0.9(d). The ftX~ dlagrams. a~ oomtmi P for the same four systems ;w
5hmD in Pig.. lO..lO. The poiul at wbidJ a c;urve ~JOSSe dre diqooal line of the dia,tnun
~ m1 ~ form such a palm )'l ::: .t[ .
110.4 SIMPU: MODELS.FOR VAPORIUQUID EQUIUBFIIUM
Thl: ~ &edion d~:SCI"ibes wlimt is obsenJ~ tbtougjb ~L w~w:n lbamadymam-

ia: ii ap-plied ro vaporlfiqu:ld equilibrium. lbe goaJJ is to find by ca1al:latioD! the ~~
~ d ~of~ iD ~brium. ltKI.mtL 1betmadyoamics pnw~ the
matbem:nimJ ftamewari: for 1be sysmft'J.alic c~~ ntensiM1 ~~ ~m~
4nd ~ion of dam. M~-a.. tit is abo~ b}' '411idl '0'~~: pqdictions of vari ~
tics of~ physics nnd wuiistir-td medtanit::iS may be upplied m ~ ~ None
fJf tiW am be ccomplmxd without 11Kidt'..is for the ldavior Df sy5tmJS m~uid tqw'"'"
Ubrimn. The r.wn nmpte.~ um :llaollb' law and Ht~$ law.

160-
D 1.0
I \t
1~~------~=-=-----~
0 0..5 1.0
..r, .11
flct.n 11.1: PXJ diJipaud ar.ns1mm f: {a)~~~~~~ .at: lCPC

(b) ~~)!m:tr:ah~J at 30c; (c) ~l~ .craebloode(2) ~ JO="C;
(ilj f:IIUD(j(~ ~~) ti 6YC D.mll:d lilx:E P 1r rrlatim fm Rael.Jit's l:tW.

76
10
65~------~--------~ oo ~----~~--------~
0 1.0 0 1.0
1 51 100
u
t
- ..-
-::::
90
501
25 a.........~~~~~~---"'
0 0.5 t.O
{c)
llgU~~e 1 0,..9~ r xy ~ :rt I r~)~ (e~) kui~u~ I )tc:aJbop ~!X.

{b-) c~ttwornrm(J ~temLb)'drofLlhfi(l); ("-, 1'1.ml- I )t~btltl ~~-hloride('2); (dJ IC!IJ111101(J)f' wl~U.

350
~ l&lt:
(a)~(t~
"I"d~ #,C U41m):
~:bnMll.dcCt.
(h) cbtornfottn( ~ )f\elr'llh)'Wufuran(l):
(c)f..mm(t~ ~oride(Z.t;
(J) dJJomnt I JhOhlcDr(2)..
Rsoult'tiLaw
The til o qmjof ~ n;qulftd to~ VLE ~om. toRilUlJt"s ~.m,.A ~:
'[})c "'"Pf.k ~ ~ &rll Weal p
The liquid p1we is ideal iOluJlWn (See. 11.8).
1bc fi:rsC ~ meaDS dml Raouki's law eaD apply on.ly for kJw to IDOderme ~lUllS.
The seeund ~ llflat it~ bave ~ vali(lily only wlh0 . lt ~ lhaf ;mpri,.~
1be syDm are dlankuJ~ si mil& Just as me 1dea1 g:JS seA'e!i M il mm.tan11.0 whii'h reaf~
ps ~iar may be com;pm:d. lhe ideal liquid solutioo represen o. standard to whil:tl1reai-
SDJn(Jim bdlav5or may be ~4ed- ldeal~ti ~itlf i ellen ppm tJ by liquid
phases wbaeiD lbe mo1eall:tr species .are not too di:frmoent m&ize ,antJ are of (be same ~call
mLtllrs.. llJus,. a :mW:ure of i5oiJll:us, M~dl .u on~ttr. mmr-" :md perm xylene. DJDfc:cJm \"efY
dose1y to idea'J..-soluticm belmlior. So do mini:Ires ofadjacent memJxmc ora~~ sent$.
fh:r ~ ,..beJ.I~bc~, elfwl~l. ..wt beoKoeho:l:uem:.. OdJer enmp~
me ~~anninile and ~niUiklfiifrumclhqoe_,.
"the mat1J:matical exp~ -on which d~ 1he two listed MJJnptiotiS and Mch ~
1fole ~ qli2li~&:J;~ 10 Raoult' law is:S
~I )'J1P r::J ~li'lif& (i ~ L 2.,- . N} I 1'0.1)
":ttere ~
~ a ~mole ~ .t. is 1 vapor..~ ir.Dilk lfr..alon. u:nd Pr b t~
~ p~ ofpmc ~ i ,a tho~ of die Jo~ 1De produd YJ P oo lh: Jet~
8d of Eq. ( U). J) is bi(NIII . die ~1 p~ of qcrir;S i (S~. l 1..4).
4
FDIIiCDI M~ ~ USJ0.-1901l Fttltdl~
stb: rip!IOI.fi ~ b ~ '~ ~ ~ b} IRq. U4.h, rcduce:s tt. eq. -o.u w!GJ.
ifii,'O lt3lliiJ - tile'~

351
1k s~ lfllOdcl for VIJ! [ipwse:IU:cd 'by Eq. (I 0.1} provides ,aJ rAI.i..~c desmptioo uf
~I btb"ior ror o ttJati,.dy ~ eb of~. ~*''~. ~is usefull fOt ~iPs
VLE ca.kularions in their &impiN form. and it i1l.bo serves as a staDda:a1 of ro~ for more
c:ompla ~ A llimitalion of Rooult~s law dal it am be applied oo1y lo species of K01JWD1
wpor ~ and this n;qums the ~ to a., -~mba:itical."' lc 1t0 bt :ot a t~
~Jmv it& r:lirk1llre~
An imporuml :md useful [eat:ll]e of Rnoob' b.\\~ 11m it is wlid fur any spW~1 a1
a mole r-raaioo ~~unit),. pw.idal only dnu tw; wpGli ~ b ~n i6ct1! ~ Cbeltti~
similmty of me oo~-nrumu spcejcs is oot hn"e a ~n1..
Dewpolnt and SUIJDiepolnt CslcuJ.tlons with Raoult's Law

A.J IJ:&mgb Vl.E problen:t!i with ~ c{D]1bin:rtioM of ~ l'ft pmsible,. ~fig i.ortl'-
esl ~ oo deY.'POirtl ud bubblepomt ~111ailittio~ there are four da8Se!t
BUBLP: Cakrulrue b1i J.tlfid P,. given I-'"J) and T

DEWP: Olk:ulme: l.t:; ~. P. give~~ bl J and. T
BUBL T: Calcul:de (y; . and T. gi.~\10 [.I'~} and P
/.)B\f~ C.Wul~ l.r; } Jmd 1. giNeJJ ~}'{ l BPd p
ln ~b c::tW dg JWm: indi~ lhc qptm~ to be ~ ci:tJler I' BVBL (~ or

D.EiV (liquid) romposilioo mttl ~ P or T . Tints. one llU18.1 s.FifY ~ the liquid--phase
OJ the~~~ ~itiw t:HJd ~ P w T. d:ms 6xio,g l + (N - 'I}' or N ~
\'illl11lblcsr- ~I)" Che fitl:mbel of~ (If f:reet:k)m F ~ lb)' dJr pl:iase rule ~ (2. T)]
for "~uid equilibriUllb The rigoro113 solotioo of VLB pi!ObJe;ms is pro"idat by equalions
\\rith oowp]b; f~ity, Pd' dld.t U$C ll,n ~ bilildql(R:rtt$ and ~ ~
lteJi'arlW. ~(Sees. 14.1 ond J4.l). In me fdlowfu S:ltoni cal~aaions {1ft. made
fw eodtiom wbw'e simplifying as:~ptio~ pn:vail. The .p-nua.l pnxalUI"eS for tutioo uf
VJJ! prdbhmi tlfms ~me ~~idat~ through ~Ct.Jlari~ ol rclativt simplidty. \\b A}CU$ fin.t
on the :tpplialion of Ramrl1 ..s taw_
B~ EJ ' ~ ~ . Eq. t Ul J ) may be SU1IllruXI Omi all~ to }idd:
(10.2)
This equathm lind$ qpli1..'1rt~on in bub~inr lcll1m:ioos.. where lht ,,apow--pb t:Ompasitlon
is nnknm\11. For a bl.nar)l }'stem whb..r2 ::::2 I -- ~t 1 ,
P = P1 + (PI -1'2 lx
Wid a plot or P - . -~"1 ~ ct.I~"milllt rempet;wrre is a srrnigbt tine mnnt(t]Dg P.l:a m_tJ ~ 0 witb
P1 atxa = l. The p ..,'f ) t ~of Fag. ]r0 .8. ~tis line:aJ llelatioo..
EqoaJiop HO.J) IIU))i tho be sol\'ed fw x, and summed~ aD pdes._ With ~ .te = I,
this )'iid :
P== ~~~-
I
(10.3)
L 1d~

WI ;zq~oo ~wiled iD ~ calculalh~ wnue liqliiUJ~eomposmons we oo1 known.

351
Eumple10.1
Binary 'system acetcrillie( 11)lnitroinethan8(.2) conforms closely to Raootrs law. Vapot
Pft~UUM fOr the pure species are giwen by Ole foil~ Antoine equations:
(a} Prepare a graph showing P vs.. x1 and P vs.. '' fot a temperab.llfe Of 75t)C.
(b) Prepare a grap'h showing" w... fJ .and .t ws.. Yt for a pressure at 70 kP1L
SOlution 10.11
(a) BUBL 'I' talculalrons are nxprired. 'Tbe &am is ~be ~em f:orm of
Eq. ( JO.l1 ~[ben: D$:
( A)
P ~ 41.98 + W.2! - 41.9-1)(0.6) = 66. 12 kPa
Tbe conespo.nding \"3Jue of~ is dleu. f'ound from llq, ( 10. J):
. .rca .P~'til!j (0.6H83.2J) = O .-t~:JQ~

.trO":I!
.
~Sr ~
.7
) . .a e
p 66.72
~ IUDbs mean that at 7~C a Jiqu:idl ~ of 60 mol-~ acetQ!Utrilc and
40 mol-i- nitro.~~~etbane iB in equilibrium with a wpr rot~tainirnt: 14L83 mol-%-
ac:td~ at .11 ~ cf 66.'72 ~ The KSU!ts of alcruauoos fur 75~c a1 a
numbeJ' of wJtJeS of x 1 are tabuhned li8 foBow!i:
Pith PltP'.&L
"1 Yl .r] )1l
0.0 OMOOO 4L9& 0.6 0.1483 66.72

0.2 0.3313 SO.'Zl 0.3 0.8880 74~96
OA 0..5600 5.&41 U) 1.0000 SJ_2J
"''bcse Slliiie MSUias un sbo\m hy a- P-x~~.)"J diatmW of Pig. [0.1 l. Thb.

llipue Is a pbrui.e ~ en which tihe mui,gktli.Dt: Itihded P-.:r1 ~lillrS !SfnLe;s
of t!aBimtcd ~ dtc su~..fiquid regioo Lies abo fbi! ~ 11Je. ~un'e

3:S3
'100 r1S'C
.P:- =su-1
80
~
lfii
l.<~~~60 Fipft lO.U; P~?

!:" ~fur
~ - uile(J
~~mar 1soc .11&
4
gP'e'Q by lldt"- ~.
ll1
II
J
411..91 ~
~
~
I
J
~ I
Ytlf;Q" I~
[fl
~
21
Cl 1JO
.:r...,,
l lahehd P-y rep~ts &lilteS of s.tJiD:ml~ ''a{JOt; lb~ SUJ~.utl:lt'l--vapor re;gioo

ties bqibw this ~1.!1"\l'E- PQG n&s )!liflx tre"~~n the ~b:d-liquid and ~nntd
'WIJIGI' lints am Ht lb~ \\~ region. ~here~ liqbid and SB~llfllled \2pOI
coexis& in equilibrium. The J",..Nt mll') P-.n lioei ~at lite~ of ~he~
\II~ ~ l?rquid GUid $;lb:t:l!llttd vapor of th~t P\IH! ~r.s ~ ru. a:)le \'ftPOJ
~p~ amJPlm.~
1b ~t~ 11x wu~ uf p~ beba\flot in Ibis biru1:ty ~m we 'follOw ~
course of a eoo.mmt-~ ~on~ on_ ~be P.l~RJI &gam. A
mbcooltdllfrquid mh:iluJ'e uf 60 (!!11)~-<Jl. acdOniirilr: WJd 40 tmol-'A;. ni~
e~J in a p~ toDicylliWc:r gr.m~ a1 ?s~c. 11.5. st:Ite it rquesft\tedl by pomt G
.kn ns. l 0.11. Wlimdtuwift8 tbt pi!ton sl.ow.1y elillilugb. mhi~ mr pre_'Wlfc ~ilile
tmaintaining tbe system al equilibrium a1 7 C. Because the s~ tam is dosc4
dte ovetaiJl composition remains c-onstant dming lhe ~- and the slmS of the
systa:!u a.t a ~ fall on lhe ~ litre cl~ding from poi:m o. \Vhen 1be
~re ~~he vattue at point b, ~e S)'Sl.em is san.mned liquid oo h va;ge of
~ Amiml~ r~~ mpreu11:1e ~a bul:rbte or~
~tat b)' point II. The ~wo poi b tmd II U 1 ..- 0.6. P - 66.72 kP!a.
and'' = 11.74831 chu
~the- tate deu!fmjna:IIJ.y ~Her ~kutarions.
Point b is a bubbfqJQinL MJd lh~ I' XI line ~111> the~ ofbu.bbkpoiJJ
A the pressl.lfC ~ further Rduced. tbe DJDou.Dl of wpor ~ And 1be

aiOOWI ,o f Uqnid ~ ;itb the il:ate:s of lba tl 'D pbue:s fullUwiug paths tl c
iDd IN! .. ~ lbcdoutd 1D &om poimb lto p:iliJt c l"t:~rW lhe<ntmll
the~ ~ . y. appJOaebed, lbc1iqu.id ~
point c:
~~td by ~1 ~~, h~ ~ ~dkappe.atr.d~ wim ant:y ~ (dew)' retruilii-
ii)f. Point cis~ a~ ami the P- ~is lbB locu of tdcwpoio
ODct: lhedew tw ~only sallmltd pot at point cremains, and CutdatJ"
-A~..:- 1-..a .t~ .:l.._..._._. lil.'llilnnif .d ifir'il I d
~ ~J _ ..,l!II.Q ~o ~"-- T""'T""'"' - r"""J11
The ~rnm af w vapor at pmm c-is~~ ,_ 0.6. but tb: ~oo of the
Uqn'td ar point ~ and 1be pmmue IIDlSt eitbc'Jr be .read t'nJm the~ or caJculafcd
This is o DIIW P rl'BbJ2lion, ond by PAJ- (103)
p = -~=--~::::
11/P~

RJr ] l ~ 0..6tand I =750.~
P= . l =S9.7-l~
0.6/ 83..21 + 0.4/4L98
(b) l\'hen pressure P .is tiHd. ~ * .ne

ab:IQ with x 1L Dnd , . Pot :a
gil ~mre.llbe ~ore ~ p bcnmdtd by~ ~tm~ rfH
BDid tfl., lhe ~~~~ at which ~ pure species 'C Hit vapor ~~.ns equal
to p.;rFot the.~~ 1heic ~are~ tium b Antoine
eqDJDms:
Pot I' - 70 kP.t., rf' ~ 69..&t;;IC and 1f ~=o 89~rc. The mmp15 -wny to~
o., ...:& 1-) '11 cfiagramuto.seledwmesoh~~t,..v~.~
P11111t ard l'i_,.- for~ te~,..S evail.W.C-'"l byl!4 CA)i a-rillm:
p~p,
.1'1::! - - l
pL"iA - p2
Fm eumpk. ml C. P~~ :;; ~t. 76 ~ Pl!M :;;; ~84 kJ ondJ
m - ~84
..t"J :1 91.76 - 46.84 ;;;;; O.SJS6
By Eq. I{ 10. I ,..
_ XI '~>jtj~ (D.SJ 56)(91.16) ~l'~-rL
'11 =
p
=
10
n
=~ ..,,.
"lbe resd[l$ of tthu aod similw; c.a:J'allorlDI'I.S fer P = 10 kP,n ;m: as follow<s:

JSS
.:li ,. !r c .Itt }' ~ 'r c

OJXOJ OlOD S9-58 (t_f) OJJS6 0-67-'l 78
CU424 O.ltKJJ 86 0..7178 OJWM 14
0.3184 fL4742 32 Un:IO ] .01.))0 69.84(tf)
Fi~tll' 10.12 i5 rhe t ----1 di:ft~m, ~owi;Qg ~ ~olts. OU t:hU. pht!5 dia-
gmm. dm\lltt for a. oomtanr prew~re of 70 k.Pa, the r-;F1 arwe ~ Sl3leS of
~i(i:d va;pof., with ~~ ei s~ VQPO l)ring abtwG it. The f ..A'l ~
~t$ m~M of smumffil Iiqllrid. v.itb ~of ~d Liquid l}ring below ;1.
Tbe two-.pbase regicm llies ibelween these COi"VeS.
Wltb refeRocc to rsg. JO. Il~ rolliider ;~ oonslant-~ beating pmcess
leading fnlm a te of suhcoaiEd liquid at point 1:1 tQ a snq or s-~ va-
JXMt at poinll d _ "'be path shMVD OO the. figute is for il mfi:Wmt ow:rdl ~tifin
of 60,mol~~ acmnntrile. The tmlpmli:We of tbe liql.lid ~ i,lf; the rewll cf
bt:.uti113 fi'om. fPOiPt 1Q tfi, plint b.. w'b;rn tbt: .tiPt bnbbla of VIQ)Of ~ Thu
point b i~ a bu.bblepointt and me t .t1 curve is me locws ofbuhblepoinl!...
5
For XI = 0.~ and P = 10 kPa. t u ckii:.I'IIIioed by a BIJBL T adculalio:n.

wbieb ~Lli.re:s irern:tJon, l&fUBlion ,.10.2) !s trre wPen:
Fipw 11..12: uy
diqramftu
~~~
me (l} 10 kPu i1$
gJYm by IWluB"s law.

p
P, :::; (B)
XIII' + ..tl
~ileie (-t s P1r.u/ PlfiiM. SOOtmaiing In P1m from lD p tw &. gi\'~ by lbtt Am~.h:.c
~quations yields:
Fu:.c l
2..945.41 2_9'r264
ln - '0 .uue~ ~ + - --
r + !24.00 ~ + JOO.OO
(C)
The: JaSOll for introdbeiog a ~ tiGU as tin! oonll'O~ l'Uiable i'E is fM Jess ~fi ~
tot ti\aii afj1iiidiridnaJ '~)t ~5SUJ'C. An fuitial vaJut W II ~ f~nd for:m uWhmy
tnmmwlime ~- lt"dtitm is rbcfi M [rQ))o~
\V'uh merurrmt value of a ~e p,_wr. b) Eq. tB).
Cokulme 1 , IP tbe Anroim ~for -"PCC.i51;
' ~ . 2..m .64 - 209.00
14.2043 - lD P,...
Fmd a new Yiliue of by Eq. {Cl.
Remm 10 me initW.I step and.itemm to t'OO\WFJlC!e for a ftoaJ ,raJue of r~
Tbr ~ is t = 76~4-rc. 11bc.~m~p:rature of puiJid8 b omd ll . .F;rom the Am~oil'lie
eqWl.tilln. p~sw ~ 8:7. !1 kP~ un.tl b'y B4 (10. 0 ~ eo~tio:o at1polnt ll is;
Yl = .l't?~ = (0.6)~7911) = 0 .747.!
~~ a mixture at ooostmt p~ u.nlike vapunzmg ~pure spe~

m
lka DDti .~1 Qa}lil: ld c;onstant ~ A the~ process contlo-
ucs beyond point b., the :tem.pelilblre rises.. the amoout of vapor in.~ md ltbe
81PDUD't of liquid! d~-s.. During this ~. lhe vapor- and liqui(l..phase eom-
~ dlmge as iDdi.alredliJy ~ fie Wld IN!.. mrtU ILlie dWpoiPt is reacbt:d
point c , w~ the last dm:piets of liquid disappear. The I .n cwrve is. the locllS
af ~nU-
Tbe vapur composit:ioo ar pohu c ~ y - 0.6; ~use the ~ is aJ,50
known { P :;;; 70 kPa,)., a DEW T ~latioo is pm1ble-. Witb a Plf:Ji / P2o;a.
Eq. (l03 ) " writ~:
Pasat ~ PlY + nct)
The i~ ~ ve ft.~ before. but al'(l; based on P 11 rather tban P1 wilb
t= 1.94.54' ~ - !.24.00
14.2724 - ln. ,.]
The RSIII~ here is t 'J9.51r'C. the rempemmte of poilu!. c and c ' _ Prom tllc An-
1oioo equation. p~s'lSI::; %.53 fl9a.. and!Bq. (10.1) gives. the ccmpOOt:ion at pointe':
.nP = (O.ti)(1~)
.\; ~ = """"W ~
0411'"
~ .;u ~
p~ 96.53
~ 'lhe trmpctaliii'C tisu; fi'CID 16..42 tu 19.5 C ~ the vapori:r.dino iLep
from point b to point r-. Contimled lwrlng simply su~ the wpDT to pulDt d.

3S1
Ga:s 'HJbar Ct:U 1:(Jbar
Acetylene 13.50 fkllnm L26AOO

Air 12.950 Hydrogen 71..000
Ouboo ~de 1,670 Hydr~ Sllllfidt
1
SSG
GuborJ DllfUllide 544600 r Methwre 41.850
EtbaDe 30,600 Nitrogen 8-1.650
Ethylene 11.550 OxyFfl 44.380
Henry's Law
Applfu$tiop f Jbtoull.. ia'lil MQ sptcl i ['~tts a \ml~ for Pi~ at the ~IR cd tlp-
pliamon.. aoo lhus is not a~ for a.~es whose mncaJJ rempera.~~~m is !less man the
1elnperatUre of applliemon. lf D syslem of air in COfJba with Liquid GJ is~ eqai'"
libri1.tt11, men lbe air g sa~ ~ith Wllte~r. Tbe mole wtion of \\'lltU cvapor in tht air is,
~ fOWid from R.aouh's la~1 i!pplled 10 me waler \\ith- ~on ttw: DO air cf'mol\~
io abe liqpjd phase. Tbw.,. me liquid v..-an:r is ~ a_s ptJm aDd Raouh:" taw for the W8ta'
(~~ "'l ,._......,.~ n ~ P.~iM. At. ~o-c
~"''""'"' .... ~UJI&r.;) y:.,- ~
........ .. . . . . . -.
"'"...,~~ ~>bjf'liii_ ,......... r-.lii i'tnl-kln ..,.;,:aL<~ .....
UU\.1 -'!!-~~ ...........-..~ ~ :~ ~
P,'lifo 3.166
.lt.:i! = p = l0L33 = O.Cl)l2
w-:btte tbt- ~ ur in lkPa.. and P2 cumb fi'Qm flle .steafh Wblc$.
If Cll1e ~ co cakuJate the mole irxtlon of air dmsoh~IN in l:be wamr. men Raooll"s
law c;;40D1Ji be applkdl. ~ the mlical tmqJt.ftllUIV af' air mmudJ lbmJ ~C... Tbis 'ower
ptobleu~ ~ be soh~dl by Hcmy"s ID.v.~ applied~ f -~ to~ ~U,I}b1 lba1lll)e ~~
phase may be as~ im ideal gn.. For a speci~ ~ as a \'er:Y dllme solute. in me liquid
~. lkmry"'s law lbm ~ dle1 the partial ~ft.~ of the spccios in the wptll" ~ is
direr-.Uy proponiooal to ib. tiquid"'~ ll:llrilr f.raaion. Thu~
Vthcre '}{l if. Jimry ~;S c;DJLTtanl. Vruucs or~ rome rromapaiment. iilfidl Thbfc Ell. I W.'t valw:s
a.~ ~ for a few gases dissol\-ed in water. FM the ~rlwtef .~"itm~ nt l5~C and aJmitiplterie
~ ~~crmy l:lw Q(Jpliat co lbe ID.r (species ll ...,.;th Jt = I -0.0312 = 0.9638 yi~
Y P
II . - - .....
(0.9688)001,)J.l ....._
o--s
1-15 )("
-n. - n9Su -
11ris rr.sut J,ll&h:&r-s the a$\\lDlpD(Hl made in app1licabon 1)1 lb.oult~$ Jaw lO 1ihr, wc4mt~

Example 10..2
Assuming that rcarbona!ed Wafef ~crontains only 001(1) and H2r0(2), detenniM ihe
~of the wp and Dqukllphasesr asesfed can of'wsodar andlthe Pf&SSUre
1
aerted oo the can at ~Cf'C- He-..ys constant for CO~ in water at 10l)C is about
990bar.
SoWiion 10.2
A$ a Ql4[mr ll( (Oilm; QQC ~IJQuld .ahwryi ~ wllld~ imjgbt me J}l'a.~ mle
may provide with~ 1[D 1the solution of an eqnilihrinm pmbkm "'w!~iM
Qf tm ~~ ~ tQ "s 2"1Jib~ 2~ :S)"item ~ F .;;; 2. ~~~. ooly
me tmrpa:arnre ' g;i\to in lh: pmbklm ~. l'l:od a~ int.cMiv~ vamb~e
mU51. be specified if d-., probkm is m have a uru~ ~. 1'be liquid~
e :fJudiou of CO.a an gppropriale additiooall ~ md for a partiQulm-
~of:q me pml'dmt b;J8 a panh.'llbr snltliioJL 'Wt Ulu$trme wid. x r = 0.01 ~
~-leary's law fur species I and R.a.outrs law fm ~ 2 are writt~
'\Ynb 1i ::x 990 bar and P1o.o rm bar (rtom the SI.Ciml tuble$ a.t l<rC),
~
1' c (O~OJ )(990) + (0.99~0.0' 227) ~ 9.912 bar
Tblm by Jtaoulfslllw.Eq. (UliJ writtm for spedtS l:
= ~'2.p'J..5:1t = (0.'99)r(O.Gl221) .:~ In , 2.

001
~ p '9 .912 v.
Wh~ .n t:l 1- n J!!!!Z J - O.OOl1 ~ 0.99&8. ,imtl tile vapx p~we ~ nr.ar1y pm-e
co~.. ~e rmg:ht apcet.
10.5 VLE BY MODIFIED RAOULT'&, LAW
F4lr low- '10 ~~ ~ur.e:s a ti'JIIch more rt..ali~ ~~ for VLE~ts when the ~~JJd
major Raouli's-bw ~1ion is abimdDaed, and aaiOUDtb tll:e;n eidmanons from SGltnloo
idealil)' in lbe !liquid pba._~ Modilied Raoult's 1aw ~ wben l'i' an acm'ity t:M/fidml. is
iltsertm inm RaouJ['s law~
( 10.5)

1Bubb1qmint nod dewpoinJ ~tiOQs lil:lde wilb dris equatl_M ate only a bit mcJfe ~kl
ihafi die same ~c,f,lbt'if.ms ~Wide with Ruoult"$ ruw. A~.o'tivity ~odticlCfi are f$0Cti()(d of rt~
pernbll'e md liquid--phase ~no~ and uJJi:malely we based on e;xperimmt (~ 12 1).
for ~, ~ the JJII'J'Qsa:ry wi!IJ.'S :1111! a.ssumed kDown.(i
&ca~e l:-t ~~ ;;;: t Eq. ltl.St llla)' be mmmedl mrer 311 species to yield:
p !!:!! L X i Yr pi ( 110.6)
i>
{110.1)
hip iill '= lt6..$9l58 -

3 643 31
'" .... J>.1<1ft
"'' z
21:3~ - T~-=665
= 14-"' .s4
:53.424
I T ..... 3).,4 24 _-\1
where T Is In keMns and the vapor pressures are in kPa. Assuming tue validity of
~ (10'.5). caleUiate:
(a) P and IYt ).. forT= 318.15 K ,aJld ;;:1 == 0.25-
(d) T and {.xst. for P::! 10f1 .33,kPa and )'~ ~ O.Ml
(e) The azeotrQpic pressure~~ and ttJe,azeottopic composition. tor T; 318.15 K~

Soludo 1o.a
{a) A BUBL P ~on. For T e 3 I 8- JS ~ tbe: AnliPt ~Wii:oini yit~ld!:
Acb:Vit.y coclficimts am ~mated fr.um lhtt: ~la.ting eM~~=

A = 2.171 - (0.~00Sll}{318.15) = 1.1'07
n =ap(A~) =exp(U. l07)(01.'lS)2] = 1.864

~ =cxp(Atf) ~cxp[0-107)(0.25)l] = UY12
1M~ n pvrn by BQ. (10.6):
I' ~ (0.2S)(I.864)(44..51) (O.l5)(1m2)(6S.M); 73.50 kPaJ
By Eq. f 10..5) wriueu, JY = .tr l"i ~ ~~ P,
r
(b) A 1lEW p dlcu1atim. ilb uncba.ngcd from pan '( d)s ~ YatiJes of Pj I
.P1 .. and A are~ H~ lbe Jiqoid~ ~fi.oo is hne u:f}-
kncrwn. but is rcq~ in the cak:ulalioo of m::lhi1y coelfiaenu. An m 'tmllf're.
~- ~ _,r....,...._r. imtj
-- __ L... - . ii.~NJ~ _ ~ dlrull!.~ ___ 'l'lft'Widf!d
!U~ :ttf: rl! -.-It'$ I.
ku I"L...-tUI
r . .,.,._ __ _ V:J L - W hi.d..
IJ :W~ JW lj,;U
n -= n ::;;; 1.0. '1'be required AefS.. wilheumrd ~of n and r.... are:
Caku~ P b)' E'q. 10.1). written:
1
P:;;;:;. --~----
) "1/YI pi + )~/~P2
Cakuhte ~. by f.qt ( 10.5): 1
y,P
Xs<C-~
Y1P1
8Ya1uate k,g\>iltf -codlicic.nl8; mu:m to the 1if5t step.
{c A BlJBL T cak:ulil.tion.. AD :initial \-,due for tbe untnowo tmtpemture is foand

from me~ fm)~ cr tho JII!R species at the known (eSSU~. 1b:
Antoi.De requatio soiv~d for '1', becofllCS:
T. -'iii
i
- ll.i
Al - ;m p
- ci
Appllmtion {or P .: I 0 I 3J kPili leads to:
T1u ~ 3J7..7
T - (O.:SS) (.l:tJ .11) + (0. ~ 5) (330.08) ;;;;;: 336-51 t::

AD it~~~ of the $iql$:
For lbe. CUtRDl \l -)uc of T callcubte '11-altle$ fur A. :r, n~ aud I I E
from lhe given~~
'sJI' p]
pj
Find a new value for P1 from1Eq. (1R6) w,riuet):
A$;1( """' p
r l -
.A! I Yl +~2Yl/~
find a new wloe for T from dle Amoine equa~ioo wril.te.D for species 1:
Ba
T l::! - C1
A 1 ~ In pl503. .
ltmtnoJlto c~ on a vallte forT yields final vall~!&:

T ~ 33l,Jijl K Pt11 = 95,24 kh P1w 1;: 4ti.73 tfa
.4 :;;;; ] .03.88 Yl -.;; l.o236 i'l - 2.ll82
1k wpor-ph~ moi~ fractions lie' give-n by.

X1)'1.Jidl .-
\"1 ::::::; 1. ~ 0 . 670 and
- p
(d) A ocw T a.leul&Uoo. Beeause P c un.3J lt.Pa. lhe sa.mmtim rem~

arw: the- 5iaiJJiJe dl~ ofpart {iC)', and an initiaJ value fur the unbJmm temper.alim'e
is fotllilCJ ti ~J DlQie.fif'Qedtllfl 'il'ti~~ a"~ of~ ~
B~ 1tJo liqwd.-p compg9itio 1M bowo, dlc ..:th~i~y eoeflkieuts are

~as n
r= n =
I. Ars ifi part (t) W1 ita:uivc pr~R: iDdlcuud:
Evalwne A~ P1 , P2 , and (I a P{l P2 at lb: e~t vdot o f T lln_llll
the Antoine eqU4llioos.
Calculate .rm by Eq. { 105);
.... ;;;--
YJ P'
YJ Pa

362
Cakolllte "'ZdDC3 ,o f y, aodJ fZ fi:om the.~ equations.

Find~~ v~ftu P,~ froml!q- ~I0.1)1 ~:
P.
I
.- P (!!. + ~a)
Jil ~
Fmd a ntW nlue for T fiom dJe Antoitle tquadon wriuu ror 5pCci.cs ~:
Bt
T ~ As -ln p18J!I - c,,
Remm to th~ i.Dttbl step and iter.U.e widl. the CUil'.Jalt values ~of YL nd n Ul;l:til
dle 'PJ'it'ICim eonVGge:s on a 11Dfue of T.
1be ~ yi~ldS the timlJ ~
T =326.1DK PI s::d .... iiJt ~ Lfi...
- l"Ju.J~ ~~-Til F'l~ = 9{llr.S9 kP:J
Ar=L0624 ,. - 1..36291 )"12 1.2323
Jfl =0~ .{ l ; 0..53'98.
{f') Fir5t dC:tmniDt w~m or u an ~ ::tt dJe given ~ will
~ cakilla1iml is liofblu.ed 1)y me ttefi~ of a ~ty cai.Etd b- ~Y
lYlltlli1iry:
(10,;8)
(10,9)
1be 00:~11-:S ~~ fol -.illity oodlitJ~ $h()lllf tbal; wbcm .t~ = o.

th
f! ; I. ami Y1 ;;;:; ~A); ~bm ~ J ;;:::;:: 1. Yl ;; I mel r.t - exp(A Therd"OO! in
~limits,
p,s:a
u:nd lu).r, = Pl :Xp(A J
Values 61 P 1 ~ P1 ~ and A are given in pmt ((1) for cite tem-pernawe of l~.
The limilinJ values o(a IZ are~
(g~d.rr=O = (44.51) ttqJ('I.!07) = 2,0S2

~ 6S-M
44.5~
(wu),= = ~M~.64)ex:p(l .U)7~ = O.l:l.J
363
.8ecGIJ$e die "-aJuo limit is greater than I~ wheml.~ the l"Blue ~l ~ otlm
at one
limit i.s lt:s lban II, an ~ 'doe.& 'cxis.t. ~ aJ1a is a(Ult(Jm()ll~ flmCiioq
of x 1 mxt ~t paM mrougb tbe \'tllue of ~ .0 a some intmnediate c:omposmoo.
fottbeazcu~ual ==I. BDd Eq. (10.9) ~uo~:
r[ P: 65.64
-c.-=--~ - ~ 1.4147
1illl p 5111 + L51
- I
The diO"~ betwem the .cor:rdmfnl eqp.ations ror to,... and In Y.l [IDYlJJcs the
geoeml TelanOIC
1n ~ c: iLtl- A:~r :5 At:r1 - .tJ u-~l Xt) ~ A(~ - ..f]. ~ A(l - 2..1:.)
n
lbus the azeocropie oocurs at the '-'ahle of x1 tor wbicb 11m. eqoo.tion ~ sa.Umed
wbe.o die sdi1dtrcodficicnt nnio bas its~ 'rt'alu~ of t47-'7; i:.c... whwl:
In!!. = In 1.J141 = 0.388

n
Solution gi\!U
Eq. (10.5)~:
xr
~ 0~:115. For 1his. vaJue -ol ~. , i':a ~ ~ .657- Wuh .:tr = >f.
pu :- rfPmq; H.6.S7J(44..SI)
1b~ ~ ;:: 7.3.76 kPa .xf ... yf ;;;;;; 0.325
Dew.JI>im md bu1Jblepoin1 c:alcu1ntions me 'readi1)' ~ Wk'hh software~ web liS

M~ .00 M_apl. ir1 whidb nerali<m an intcpal IJDt. of ao cqwru()Jl.;SOhl_Q Itl1.lline.
ladle3d ~Iillm- for sd.utio:n ~EL 10~., 1J11D1$ (a) 11tr~ {d).~ ght~ tp A_pp., D.2..
CaJeuJatio fm lllliltticom:pone.m S~miS made ~imom sinqJii.fying :mmnptton5 ale
~ ~!Gd ('IQt m ~ llWJl')Gf by <i0l.DJ'Q1Cr. "The ~ are pwscot.cd in Sec. tt4.1.
110 ..6 VLE FROM K-VALUE CORREJLAnQNS
A (00~ rnea&me uf We k"n~' ofa1g:imJ. dlemiw.J ~ W partitJoo lt5df ~-

IWJ!y ~ Uquid aod ~r ~is th-e tqllrilibrlmn rmi~ ~ ~ ddtoed ~
Th~ -qn;tlltity
leo rJSU31Iy cnlltXI ~ ntplry X- ~.-YJlul!, ~ it ad(ls Pllthi~ to ~yn_q:ljc
knowledge of VLB. it does ~ a ~J~eM~~te Of'l.be 4igh'b:te-a"" ar a romrii.Dft11s~ i.e~ of
i~ lcndmc)' 10 fu\"'rl!he ~ ~ ~ Ki is~ dtat~ lllllit1, ~~ i nltibi:~ Q bi~
eo:nrentmtioo in the va.pcw pt1me; v. ben 1ft& a higher con~llniion in me liquid ptme.. andl

~ coosidc:Rd a "bca""J'.. com;~itucnl. 1\f<Ril.Wef, the use of K -\i'O.Iucs n:mkie& ft.w" C'OQ'lPUUO.tfo:mal
>mtoi~"'" ~ns ~u~ of ane ~Gf moie tramkms b't or 1-"i Jin :fmw of dte other.
RdetCDee m Eq. (10~ l) ~ 1h:W ~ K ..vaJue for R&JOlrs law los::
prJit
K t e: .:..1-
p ClOJ l j
iUld a:[elJ'ft1a: to .Eq. ( lO.S) 500 ~hal fOf' OJOC!iied Raoolf Law il ~
n P1 ~
K ,, =.;.._.;;._,
p ( Ulbll2l
Acc."'UR~ing ~o Eq. ,fUl10)_., J'1 = K;x~ . Summalion with I:, y. = I tields:

L KiXi -- I UO. U)
s
1'h1.is fm hubblcpoinl mlooltltionL -.~ lbe ..r~ are tno~ 1be problem ib 10 ti.od me :Set of
K e'fol~ lhat ~cs: Eq. ( JO. a3). Allmlad~Jy.. P.q. ~ ~0. JO) Ci!D he wrine~ ~~ = ,Ill; I K..
=
Summation wbb I:1 .xi I yiolds~
L:!!.
~ K,
= 1 10.14
1'11uB f'or dP<'()Qi:Dt ~:dCQiatiGJ~U, w~ ~ y, ~ kpmvn. dJ,i prclbb:n is to lind lbe ~or K-
vallle$ dw ~ f.q. (10.14l
tiquaticmi (10. LD mJd ( ~ U.l:!} t~_ha wiith EQ. (10 .1U) ~ ~~tana~rr for-iDS of
Raoolt ~- w.d mo4ifitd ~ou:w ~~- ~ FM ~det~ ct Raolllr$ law i~ th:at h a ...
pesses K ~-aloes ~ ofj~1 T and P. [odcpJndmt of Ule 'CIJmpc~om of tbe liquid
;md "*lllr ~- ..."bat me assumptiOCtS 'lll'bi\h lin~lie Raoolt"':$ lttw Me ll(lp'OpriMC, t.bn
4)mtJW. K -v&thie'S lU be cat~ Md etifi'rJatd li6 fl.l:Dc:llom of T and P. For mixt!J.1'eS of light
llydrocmbo 3.Ddl oth~ in1ple moleculetk in which lhe. molecu!ar force fields arc rdatir~b'
~~ correl-~1iom ,ofllri5 kiJIJdl mro"(: 111JjJroXlmak vallidit:y. fi~ tO.Jl ami I(U4,
s.h oonro~ for the K .,.~ues of H~ h~ 4B fu:oeaons ofT d P ~ p!epued
by DoP.rics.ter.7 "l'bey do 1dluw fur au .owroge ~ o ~eOPt~oo..lmt ~ e$._~ ~$ i$
R:aoult" l:rw~
E I 104
_xampe _~ .
Fo-' a mOOure of 10 mol% methane. 20 mol~% ettlet\e, and 70 mol% ~ .a1
SOCOlF).. dele:Jfmine:
{8) The dewpoint preS&Jre.
(b) Tne t:JubtJiepoint pre~re.
TheK -va1ues. are.~Yen by Fig. 10.13.
' c. L ~J~~It ~ E~- ~r. S)Drp.. $a .Yo.. ' - w 49. w..

a-n. t9Sl. "ffiq' tm\Y ~ p~bKst.!md m
moddkd furmJ ior &rm1- Sli liftl'fi (~ and tbJ ~ 0 . B..ll).)d~ OF-. CJrt. JJ~, rroL 14{4).. R1- illj...
~April, 1~7

365

I
J
ragan lO..U: K-ftlues rur S}'skms of ligbl h)~ low-tc:mp:r~~Urr ranp. t"Rcprod~ 1P.Y
~$11 fmm1C. L- ~~- C/lmL En:g. Pmgr. s...?irp, :Wr. N{l, 1. \.lll. 9. p, 41, I~3.

=
~ tO.lt g. ,~ r. sysmm of lilt by~ His~Hem~ ~ (Re~ by

~ fmm C L. ~- ~~ t::n.g. Pmgr: S:,\mp. .in No. 1. v.ol!. 11-9. p. 42. t95l.)

367
Solution 10A
(a) ~ the ~m is atJ ies cflewpoinl. only :m imi~llemtt amo:tmt of liquid is
~ Mid lbc gi\'elll lltOit fmttioas are values or Jl. For gi\~ ~
u K -values,depend on lbe choice of P and by oial we 6nd tl!le value for ahlcb
!11
Eq. {10. 14) is salimcd.hsuJts for severDJ \'3lucs of Pore gn-oo 3S flJIJCJws;
Pe]~~) I' ~ 150tpsia) P= l16(~)1
s~ )?f ~, }i/~~ K; y,,f Ki ~~ .r;/K~
t\~ O.W 20_0 0.005 ]3.1: Ot.OO& 16.0 0!006

Or%0 l z, 0.062 us M89 2.65 O.t07S
Prgp:mo (L70 IL9l 0.76[ 0.6) IJJ71 ct762 ()~919
'l:.bi/K; ~ 1.174 2: \)7/ K~ ) ~ L~
m
The rem]ts gWen the lasl two eollmlm ~ow tbat Eq. ( 110.14) i~ ~!!Xd ..-bal
P ~ 12:6(~~). ~ i$ t~ de~ilU ~~. wxllbe oompoJ.ition Clii 'llic dew is
Jiveo by [filr v-111--=s of XI= YifK~ llis1ed ln. the lMl oolum:D Gflhe table..
(fl} ~ u.~ mtem alfil~ ~Fa~ly ~it i<S at its bdlbl~ and
lilt: ,gi~ mole ~ becol'De Vldue:s of ..lj. ln dlis case we fi.Dd bJ! uiaJ llhe
value o I' for wbidt die K ~\ames satmy Eq. (10.13). Resul for~ \'Uiues
~or P an:~ rn be foDawiQ8 m.tJJe:
P z~li) p 4001:pull) p .. 38S(pm)
~ X,
i ~. Ki:I.i K~ .KiXi Kl K; :r.r
~ 0.10 s.60 O.SliO 5.25 -6.5'15 S.f9 G.549

ilbaoe G..lO a.u o.,~.,
too o.l~~ LIO O.lla
~ o:m o.n,s D.Z\5 (U1 .0:2-lA 03~ 0..131
EK1 ~i:;;;. 1:{117 EK;.r; ;:::;; Q,%3 I:Kt~l = LOOO
~oo. (10.13) is~ - ben P ~ JSS(psi~l 'Tb:is is lbe bubbleplint pres-

wre. The annposilioo of~ bubble ot~~pcr given by Yi -;;; K~.x~, , own in
l.bi: Ia rolum:fi.
An important appll-Q~tion of VI...E i.s tb:Jl&h CJllcuiaikm. 'f'be oai'DC orig'~ from ~~~ (act
that a liquid aJ a~~ co or ~diD i1B bubblcpainl ~-Oasbes"' or patiaUy
e~ when llk ~ ~ mttrrtett. ~ing a. lVil(to-pimse~y. ~ or \l~ aru1 Uqwdl
in ~ We comidu ba:e cudy the P. T &m. whicb rd'm- ~o my caladatio;n of too
quanti,t_ic:s Wid CWI)IOsiUoos of rd.: ~par llAd liqvid pba5lc5 makin8 up, a tl\'~ ~

368
in equilibrium 3t known T , P. Ulld m'WrJll eomposirim. 'DM poses p-oblem known l{) be
delaminate 011 1lx bam of Dbbems theorem. betwse two independent \~ ( r and p )
me ~for a S)'*m olbcd m'mlll compoSitioe, dmJ a Sh::m formed fmm gi\--m
~of~~aJ
~a~ rollbljni.n.s eoc ~of M~g ~dll ~pee~ \\ftlh 3fi 011~mll
~~ted by b: 5el of IOOic belicms (~). Let be tbc 1~ offi~ with
male~ u, 1. atld. kt v be lbc ~ of~ \\ith ~ ~~ (~ 1- Tht- OUdmBI-
Inbn:c.e eqWltions are:
l+W~l
~ ;;;;;; .~1.C+ Yl V (i = l.l. .._ q NJ

CombininS ~ ~ todirninam .Cliv~
(10.l5).
(10.l4)
}l ; l +l lKi - l)
8-aust I:, . == 1~ &}. (10J6) "'~ '"'~ all sp:ie8:
't""" ~ K j .
(lOJT)
-'T l + V(Kl - i) : J
~~ S14' mSlllvinJ a P~ T ..&llib (:W'Obletn is 10 iiDd rbe ~ of V which ~ this

cquafum. Note lh:tt V' ~ J is~ a trivial somtioa..
&xamp e10.5
n. QS~Sm aoetone{l}laoetm1Mfe(2)fni~Jometbane(3) at ao~c and 110 kPa has the
OW!:r8ll ~ tl : OAIS. ~ : Cl.lS. ~3 = (L20.. AHUJ'Jiing 1b8l Raoldf;~ law iS
ap,pK!pfi4te to thiS syslem delel'l'liline .l.-. V, jxJJ, and b~ J. 1he vapor p18SSW'8S oflhe
pure species at Sfr-1C are:
Solution 1OceS
ABt,.do aBUBL Peakulllfion witb ~~ ~ c {.t1 1codetermine~- B)~ Eq. ( ~o..lt.
1\ub1 = ~I p lm + ~l pliMI + .JU pjSlli

= (0~ SU9Sr1:S) + CO~l5)(91.84) + (020)(50.32) = 131.40 tPa

369
S:ond. do ~ DEW P ~n ;)ith (.z, I ! : btr I ro ftnd Pdtrv.. By Eq. ( 10.3).

J
P11t:!w = Ql _ !QII = IOI.S21LPa
Yti Pi + Y~I P, + YJIP-s
~ the .gh~ ~lies t~c~ ~and PdcW. mr ~ l!!i tr. ~he rwo..
pb:ise feBioo, and a ~b cakulmmn ,ean be liDilde.
By[Eq. {lOJ 1), Ki ~ p~ / P~ w~
Substitute know-11 ~into Eq. nOJ 7)~

(0.45)(1.7?95) (0..3.5)(0~8895) I (0.20t(O.~S7S) - l (Al
I + 0.1195V + l ~ ~ l lOSV + J - 0 .$42$)) - .
Solution rfor V by trial yidds~
V = 0.1J64 mol
, ;;; ~ - v = 0..2.636 mol
Equiitltm ( IO.lfi)' dlo\\-"!1. tlmt mm ~rm oo die left side of Eq. f i\) js m expression
for Yl 'Evall.mlioo. of~ ltemls ,gi\"eS~
a
- =0.33!9
)'?
..IJ ~ O.l&S9 .XJ ~ 0.33.31
Cbiomly, L.t YJ ... Lm .t ( :;;;; I. The procedum of this e:.u_mpk 6 valid ~dl
ol dw m~~~~be:r 0 peri~ pn'lSC(It.
F1as.h CMcolaUODi CMJ also be macle for ligkt b.,~ whh1iChe d4la of fip. ] 0.13
ODd 10.l4. The ~ hae is exactly w descrlbi=dl In EX.. I0.5. wkre Raouh'" bw applied.
nh T and P ~tk.d..lbt K -llalues.ror ltght b,)~ as giwD t.y Pip. 10.1J :mil 10.14
are kooWD. and V~ lfle. mily unhmwn bl Eq. t iO. 11).. is fOUml lb y lrbll.
Example 10..6
FoT the system desc:ri)ed in Ex. 1'0 .4. w1ta't fmction of the system is vapor .men the
pressure ~:s 200(psla) and what are me compositions 01 dle equilibrium vapot and'
Dqllidp~s,?

l70
SOlution 10.6~
The givem p~eSS~~re lies betwee-11 lbe. dewpotnt arul tiubbkpoillt ~aues ~~
tismd foT llhis 5)~m in IE.I. L~. 1be S}'Stml dlmfam coosi51S of rwo ~
With .1'-\'all:lt!S [tum lfi8. 10.13. ~ ~le ' to find lJJ trid that wllle of v
lm whih Sq. ( 10.17) is ~ the remit-s of sc,vemlll'in.ts ~ showD in m:e
~pgn__yias table. 'The ooJumD~ beaded ~ gll"C vatu~ of lhc. tenns in lfie SW'Il
of 13q~ ( J0.17),. ~each biCb tarm kin fOt1 a ~ \T&I~E.
~~g. J';/ Kt
1i rw "fj for y. far fm:
s~ ~ K, V=o.JS 'V =0-25 V = 0.273 \1 = 0.213
~
O. JO 10.0 DQJl 0.301 0.289 0.029
~ Q.10 1.76 0271 1.296 0.292 0.166
Propane 0.70 Q.S1 (}.4..~ ~t41 4 0 .419 O.:Sm
:&}1 = 0.9S'i l:Yi ::;; I.OJ.s &yf ;;; 1.((10 l:.lJ ;;; 1.000
Ihos. Bq. ( l0t17} ~ON ben V =0.273. "~be: pttase l~ 1ll"e ~~n
in die l;m two cohrmm of th~ t.lble.
PAOBIJEMS
SohdimtS to iiODle ofdle problems of lbl& ~ requile. vapor~~ a ftme1iutt of~
peoratlltt fm ~- wbidl ~IDle' 5)'5~ in VLI!. 1\ble 8.2.. A..ppendil. 8. ~ par~ter
values for ifllle Armmne reqwttion~
In ~ tal n.o..
,..... = A - tr cB c
1U~1 .i.\s.1iilming the ~ty of R...aoutt"s kw~ ao dJe folt~ eaielWrti~ for the ben-
~DIC( I )fto'~l) '~
{a) Givcn .re = O.Jl .a:nd T = UXY-'C lind .Yl alld P .

tb) Oi\'m ,~~ ~ o..JJ and T :!!:!: uxrc, lbld .111 and P.
(c) Oha xmo 0.33 lli:Dd P c 112U tPa., find }1 1 aDd T.
ld) G:M:n _,~. = Wid 1 = xw th. Jktd x~ a.oo r.
o.J~
(e) Qi\eo T = U}..'icC and P ;;;;; 120 ~ 6JJd Jtt and 11.
I'J far pan fl'). if t~ mu:aU mole hdioo fjf r~ i6 ~1 == 0.331 -bat molur
hction 01r Q.e tufoo.lpk~ syswn is ~
~g) Wby is Raotatt" t.w likeb ~ lbc lUI ~eclkm VLE model b tbiJ; ~m at lht
'tatt:d (or oomputed) condirloo ?

lo.l. ~boWt" lawaobewlid.~:ll p ..~..>diagramfwl~nttureof90!PC
and a r~~Y diagmm for a~ at 90 kJ?.8 (w <mtJ o f 1he followizr..g ~=
(at Benzene(J}lelhylben~e(l): (b~ 1-Chlorobutanet I)khlorobeozeoe(2).
lo..J. Assuming Raou_ill~5 law to apply 11 0 the sy&tml ~t-p:uk!DC( 1)/a.-bcptalk(l).

(ll) \\rut wrt ~ ,'GJ.~ {tf ..{ amJ .n 3ll::: 5saC Md I'= ~(P1~ +Plll1)"! 'Fur lheSiC
oond1tioos plot ibe fmaioo of ~y.fitaH dw: is vapor V \IS.. Olvafl composition ; I
(b) F I' - SSC and t 1 - 0'.5. pkM P. AJ. a.nd 1 ~ . 'V.
10.. Rework ~ Io..3 for one. of the following:

(6) 1 = 165aC: (b) t = 15/'C; (c) r = ~C: id) 1 = 95 C.
l tU . ~ An eqniHbrium Jiquidl\fl8POf S) item tlescJl'ibed by Rauults Ja,w cm'l.D01. e.Yri!bU

an azeotrope.
t D..6. Of rhe biliary licfllldNapm- sy tcm& follawin;g. wbidl ~be prox ifMtdy moddedl
by Raoott's,law1 For those which canno~ wby? Tabte B.l (App. B) may be useful
(a) DeozencllaiLlelle at l(.m).

(b) n-~dn-bep1mle~ 25 bar.
(cl Hydrase~ :U 200 K.
(d) booctaneiJJ-ootane at lOI:r'C.
(e) 'Water~~ at I fbar.
10..7. A single--stage li:quid1V4g)Or:se,pi1R'tion ror de benzend I)ledl)'[beoze~Ja(2~ sptem ml.lS't

produce pbasc:s of cbe following cquililRium w~tioos. fu-OJ:Je ofthes 4ct:a:-
minc lM 1' :md f' jn ~ ~L Wba1J ~ infMUMiM I&~ 00 COT.Dpnte
tbe retmve amoo.nrs of licplid and YD:pot ~a\ri.ng tbe ~or:' As:sulrlt that Raoull's
l;Jw .appli~~
{a) Z J =0-33. Yl ~ 0.70.

(b) x. -- 0.35 .. Yt -- 0 .125'.
(c-) xa - 0.35. Yt -. 0.75.
(d) ,11m = O.JS~ t !::: ().175.
lB.& Do all four parts ofPb. 10.7. zmd tu~JJpW lhlt R5PltS.. Th required ~Wid
pressures vary signifirmttly. . Dr~ pmsibk ~ impfirotions of me: various
tempen.tUre and~ lc\.rels.
IU.. A mixture cootainiag: equimola amounts of benzene( I). lotume(2~ and edl)flben
moe(l) iB Bamed to wnditroos T and .P. For one of the: eondilians folk~~ de-
~ dlli eqli'illbriwn inD~e- fiactioM [~c J afid l~ I of dlc tiquid ad \~apM' ~
fon:oal and cbc moJar &action V of the 'Va-DDf formtd.. A55umr that !Raotdt's kw ap-
plies.

372
(u) T = 110 qc~ I' = 90th~

(b) r= 110 l;" c~ , m 100 :tPa.
(c) r ~ 110 C, p ~ 110 :t.Pa..
(d) T= ~ ~o 'O c.. P .= :! 12(}1
wa.
tO.IJL Do aU f()Ur pam of Ph. 10.9~ ~ c0Cl'lp3rr. b ~ ffucnss all)' ~ tha! ~-
1-A.II.. A binary ~ 0r IUOI ~ 1::1 b ~ to ~tions T Qnd. P. f o~ af 1tw:

.U~g ~the~ l1\ifM ~ x .lmd ) 1 of die .liquid and \11)JM
pb fonned!.lbe IOOW fr..1mon 1V oflb!D \~ fwDMI. and the fractiDilll1 n:.anery
"R. 1111 &peci.~ I mb '~ ~ (d1i_ned die mio fur ~ 1 of mol in ~
apor 10 molt'S in the feed)~ A&smne ~bat Raouh Law applies.
(a) Aeetoi!C(I )/::teetonkrik(2.).. i J ;;;;; 0.75. i == 3-l01~ P ;;;; ~IS k.P"a.
{b) BC8DDC(l)Jelbyl~).lJ :; O..st~ 7: 100 P 0.7S(i!lm). =
(c) Ellwlot(l)ll,.prqpmo1(2)~ t~ = 0.25., T =- lfiG P = O.SO{atm)
{d) l ~ l)fcblombenzatea}. .t 1 c 1()..50. T Cl .I ll a c. P c 1.75 -b:l.r.
tU1 Uwnidily, mtuing m 1be quurity ar moi&nrre in ~ mr. f5 ~, gi\*ert

by eqllaiions dm'Wed from Ole idal-p31 Jaw md Raou.ltt bw f(Uf fil:O.
(D) The IJbsc"* lumJi4ity Ia dc.fioed a5 dJe ~ of W-Illa ~ io 3 unit mm.i af
dry a.ir. Sbo\\~ ibal iit Jive~~ b)'!
where _W ~s 1 mobr rrms5 and PJbO ~ die panial ~u:re of dJe u a

\r~ i..t,. A q o ~ YH1oP
(b) "'I'bc sal.llt'rltitNJ humidll)~ h: ~ b delincd as Ilk \'1due ofl ~'hen m is in equiliooUilll
with a laJF br,dy 1o f pne water. SbrM1abai it Is gf\'cn by:
I. .AI P. W
lf!"W _ .....HtO H;rO
- .w. p ... p~
wllere P1:;b is the w:par pres.sure &f water am the ambie.m ~re.
(c) 1be ~r'C.mlfiiJ~ lwnddilj" ~ a$ me ~ o{ h 1.0 iH ~lilf;ltiOO ~111:, e-1
~ .as a percentitlge. On the odls bamL the ndm/1~ 1,- ltJJry is ddioed lhe
mtio or tho pa.Jtia1 p~_re or \1.~ "~ mair mit$. ~ p;-~~ ~
u a~" What is ltbe reLnioo between lbese two qwmUJ.ies'?
10-.13. A ~ 1binary ~utioo amm~ mo tly species 2 ~ Xl ;/; 1) ' in equj...

h"brium witb ,~ phase ~" both ~Ies 1 l1ltd 2. 1be Pf<t$$urt of lim
tl\'0-plw.e sy.em i!! I ~ dle tempemtnre is 25ec Determine from the folkw.~ing
~good CSJinm1 of Xrl and fl
n~-= 2no lr4

Stt,ire and j1J!S!ir}~ d mpdoos..

)10..14. Air, o.~n 1lltl1T ~ ~ c~ dioxide. is ~osiYe ao.d ooruoxie. Wby iJS til ootlbe
gas of choice rm
rooking soda water and (ebeap) cba:mpagn_ df~,,eseco Table 10.1
1DiDJ ~~ uscful ,f imr
J~O..lS+ Hd~ ~~~.liS brealhinglilt'dia ford~ -adi~a-L Why'! T:abk 10. 1

may provide useful dma
10.16. A .b inary S)'Uem of~ l and l ooosim of vapgr and liquid. pfm !t equih"brium m
at tempmtlln T. Tile m-rtmlJ 1mole fl1!(._1iolJ of spcci- I m tbe sy~ .: 1 : : 0.65~
A1 ~PlpeiQlbte T.
In Yl = 0.6i..r~ lll Y1 = 0,61xf-

p l'SIA = 32.%7 kPa plti'ld ;;;;; 73. ]4 kP3..
~the wUdity of b). {105);o
(a) 0\-n wban range of~ can tlris system a1~ two~ 3t p~r1 T and
(b) Nx Ill lkJuid-'~ mole friiaioD Xt ;;;; 0.1~, what ls the pJeSS!.IM I' and 'M lta1IDOW
fracdon )) of tbe S)'$tCm is vapor"?
(c) Show wh~ or POt d1c system~ un uem~
wn = 0.9Sxi hln =0.95~.

p.~ c 79.80 kP1I p...511 =:I 4(l5(}1tpa_

l\s.'Rlmi08 lfte 'ddir,. of eq. (10.5),
(a) Make u BIJBL P c:ablalioo forT ;;; 343.15 K. Jl) ; O.O.S~
(b) MAktaDEW P ~~ukihon ror
T =343.1SK. .' = O~OS.
(c-) Wb.u is die ~pr '-eaupctb.n,n EiDdl press~~te at T 143. ~5 K? =
tO. IlL liquid mi.l.rure of cydobex:mone( L)lpbenol(2) ror wbidl XI _. 0 .6 is in equ:ilibriwn
"tl.ilb i' vapor a:t I 44C. [[)c(mninc 1he cquib"'hrinm ~ P wkl vapoc oomposiamn
) ''I from lbe foD~g. iM~lllon:
lln n ~ A4 == Axf.
hi n
ru 144 , P,Sill = 15.20 and P1DI. = 31. .66 w..
'l"1le system mnns an ,~ at:l44~C lor wbich tf .... rf' -. 0.29!1.
l~l9r A binary system. of~~ 1 md 2 ronsi...qs of~ and rtiqu:KI pbas~ m~ilibriiDD,
at~ r. t'-"11hicb
11n n == t&ri mn = L&rj.
p. - 1.24 bar p~ = 0.89 bar.
.
374
~me wlidiey of F.q~ ( liJSa,
(~) For what mop of V".llu~ of thE m-~mll mole fraction z t caR this two-pba.se s,~em
ctiu. \\i tb a liquid 8\tlle ftactioq .rt = 0~<151
(b) Wbal is dae ~ P Wid \11tp.lf illi03c IOOI.DD wilhm dli~tt r.m~T ,.J
(r ) W1m are me pressure and eompositioo. ot me ~ at tem.pu3tllt'e T1
lO~. For 1bc acdlJne( 1)/Jildlmool(l') S)"5tem, a "~ mix1mc for ~11ich n ... o..n mad : n -
0.75 i ~ t o ttmlpbnttuJc T 1 tho tw~ ~{ID aDd ftovn. mt:o a ~om
cibamhet n.a ptaiSme of I bQ.r'" If lhc Cillti_posidon of lbe Jiquid prodUcf i to be .r1 =
0.175. \\ibal ~ ilhe reqpfred v-.due of T, 8M what b me wh1e. of J i ~ For liquid ~
of tlU ~mJ to a lood QPlOXima.tiOQ;
m~ = n.Mxi ba n :: O.M.rf
10.2L The I\) IIewing i:s a rule or thumb! For a binary .sy.stem in Vl.E at Jo.w presmge. tbe equj-
lfbrlum '"'iiptlr1l~ mole f"r'acdali Y o~ tO an equi molar liquid Jlli.u~ is
aw~Y
Yt = p~ + J1'.,"11A
-
W~~ P,
i ~ ptlte'-~tS vnpur ~ ~C[e.tU"t)1. U.is f:l1\lati'Oll ~ V4!.lid ~~ .bontt"s
Law~- Pmve dw it~ also \---aHd for VL described by Eq.. ( LO~. wilb:
llo.:D. A JPff!ICeS t1mm contains filb~ species I and bet~\'f species 2.. A !lelalivel}' ~ liqWd
~o:t-am rom.oi:Din - mostly 2 is desimd, t'lltained by a sf:n:g_IMuJe Jiq_uidfvnpo:r se~
tioo. Speciftcatiom on me. ~equlliorrum ~tioo :1re: .rtJ ;;; 0~002 and J~ ~ 0 .950..
Use d.am ~ bdow lO derermine TOO and P(b:al for lbt separator. Ass:ume dt_at
Eq. <10..5) - ~plies.: the ealculared P &houJd v:ill~ this assumption. Data:
ru 1h(: llq\dd pba'le. In ,. = 0.'9l zi ln n = 0.93zf
Bt
lnP1 A~fb~- A., - T/K
1\ 1 = ~0.08, llm ~ 4572Jt, A1 -= ll J .l) . B2 .e:::. 6,.254J0
10..:3! It fY. mu "Diu VLB.r ;tl ~t me"' lk K -vat~ m~"' bel lftllet 1..0 and at
l~l one OllilA be- bs man 1.0. otTer proof of 1.b.is o~"illion.
] 1).24
_ _ . ... I" - . ' --
Cl,;w,L . calc:uhf~:.r,.i'M!: -1.-..... L..... U -- -
I_,~ ______ yy~ QI1C 5Imp'~ lUI 1\Jtmuy
~-rilio~ ,.k..._., ~ d'!" dil!!rill! - .:U - oi~nl
,~_..,.~ UIWJI ~QL' ~~~~ ,e---ntl 01~"'-,.....,.._..--
~. Mca.u&e tilt ~fil'ml ~~{)M ror I bir~ ate indeperldeot of [be o\'a'ai]
aJIIDpmQOIL Show '"' f biruuy system mVL.
I - K1 K \(1 - l(tJ
xm:c Yl ~ ~~"""""""'~
Kt .... K2 K t - Kl
Vc li(K I - Kl) - U- K 2)
( Kt - l)(l - K ;2)

17!5
1035. A..~x the "'lltiditY of~ De Pri~ cfuvb. ~ rbt.: tc:Mowinl VI..E ca1oJla.ti0118
ror the ~(1)1dhylene(2~~lhlmc(.l) sysrem:
(a) BUBL fJ, giv-en .r1 ~ 0.10.ll:! ~ O..SO..Iillld t ~ - W (9F).
(b) D-EW Ptt. gj""ttl )'11 ~ 0.$011 J'l ~ 0.2:5, and rr!::: - 60rF).
(c) BYBl. T.gl~Cn .lt] = 0.12. ;(:z t::: 0.40. and P = 250(psia).
(d) DEW T,. given }l = 0.43. }"2. = 0.36, mxl P ;;;: 2SO(psia)t.
lo.l6t ~&the validity of the De Pric'si.tf charts..~ tlit foDowing VI...E rolc:ut:mms
for me eUmne( l )1~{1)fisobu:raile(JYJSOpentane(4} s~tem:
(a) B'UBL P. gi~en .r1 :c: 0.. tO.zcz c 0.20. X') = 0.30. and t = 6l.r'C.
(b) DE'V P" gi\'m J~ c 0.48, 12 = 0'.!5..~ ._ O. lS~ and t ::;;; 60"C.
{(") BUBL T. .tm = 0..14. X'! = 0.13, Xl ; 0. 2S~ and P ~ IS bar.
(d) DEW T~ ~ -~ = n
0.42,. ''2 ; o.JO,. := o. ~ s. aDd P ~ ~s bflt.
10..17. The strerun from il ~ \\tdl l 0 0\Uture cmttnininl!, s~-. methane. J(}.JooJJ-'.IfJ
ahane. 2o.iJ1W1..1' prop~nc, aPd 20-rool-'% rz..,~ Tbi:J ~ 1:5 :fed into n ~
~bdeme.r ~ at a pressure of lSO(ps:ia~ wtlere its te,mperamre i:i brought lo
80rflM Deemline abe mo'ar fradioo of ltle gas lbal: eo:ndem and abe oompositiom
of llhe liquid and vapo!f pk"es leaving lhe ~-
10.2&. An cqubnd:;ar mixture of n-bo.aoe wuln~nne at preswre P' i:s brought ;o a.IJ:mpei'AO
ature &f 9 C~ where it exms. as a vapor:Mqu.id mi.xtue in equilibrium. If the ~
:fim:tion of rr..hex:me ill the liquid phase is 0.15.. what is ~ P (in barf, what ~ the
IPDbu' fllldien 'Pii be ~ ~ iii lkpiid, and 'INhat is lbe ~om_pMilloo of the ~
plmse?
10.19.. A i'l'li1tlme-15-moi-'J. ~~~nlii.De. 45-mo1-~ n-be.ane. andi )O.JM1-4k ~ is

!brought to a coodition of 28t A and Ualm). What mol f~oo of rg ) :tm1 u
Jiqmd, amid wbdt ~ 'the ph$ c:um_po:sidflt!S'1
10..30. A mixmre oontmru~g l5-mo1% etbmle, 3:Srlll01y~ propane:. and ~oJ..!% n~nG
is bmught to a condilioo of 41YC a1 prt~re P, If rwe molar ffootioo of liquid in ~be
s,rswm i5 0.40. wba~ i5, p~ P On baf) ::md wllat me the com~ o1 tbr 'tiqldd
and ~r pb;a;,_r.es?
10.31.. A mi:u.ure ~stiR& of 1 -mo:l--~ ~ 5--mol--% p_ropme., #mol-4 Jt-butane. and

.
so.~ % ialbutuc ~ broggba ~ 3J ewldition of ~P) ;11 prt;s$~ P. U' lbt IDID-
lar fraction of 1hc ystmn ~bat is \'apot ~ 0-1 whM I! pressure :P ~ rum wbat are lbe
compos.itioas oftbe vo;por and liquid jp~mses?
UU1. A mi.u ure ~of moo-~ melbane. H)moi-~ edr.me. .30-mol-% prr.1PIIIO.
and 30-.rno:i-% ~ is brought n> a. eonditioo of - 15-oc' m pn:'$50Ir P ~ ~
exi$t$ ~ a vaporniquid mixmre i.n equilibrium. If fbe 100le fmclioo of die ll:)elhane in
't
1be \'apor ~is 0..80. whm is ~s..~ I' fm bar}?

li.ll. ~ top tny of a distillla_tioo calumn and d:Jo ~ are ld a ~ of lO(psiaJt.
1lJri'J liqQid oo b top tn.y ~- ~ ~of ~e ~ n~e. ~
vapm flnm lbe top tmy~ - ---ODltd ro- lie in roqui!l~ woo me litfw~ goes 10 ~ roo-
dlmsa" wfae 50r mol-(} of ilbe wpl!l is COilldmwd. ~ tbe lelrl,pem~ 011 te top
nay? What m .n =~ llld~ or die~ lesring t~ co~Kknser~
10-\l. ....aoeme is 51eplmted from. :m eqoimolar O"'elhanetn-botane gas llli:x'nlm by oompres-

5Wn of lhc ga lQ .-ess:we p at 4Q'>C, If..t&i of 1110 ftcd OD 8J malt b ' i ~
what is~ p (in bar)rand wlmt - lht. composilio.os of H1e resuldn~ \1tJM)t $1ld
JiqDid pbasa1
J0-15. Tile NJST Cbmistry ~bBool f0pert5 mticaDy ~ fbJY" ~-o_nts ({JC" Kp
~ diem- ms io ~r aa iSVC~ ll-leoJYs oonsmnts fro:m lids 80UJ'Ce-. rdmo'ted bete
J.J t .. appear io die VI..E eq_llalion writte:n for the iolute in the fonn:
whne .,\4~ is the liquid-phase molality of sol~ 5pecies i. mp~ moJ JJl~ ot..
~
{,a) ~a.n ~br.clic m~on connecting t. w'ifl1o Hem}~& ~~nt itt Eq,. ( 10.4).
Assume tMt ~ k ..,smnD.no
(b) The N1ST Oh.emi.my ~bBoot ~des a value of0.034 mol kg-~ bnr- ~ for l:1
of~ in H~ at zs~c.. What is~ 1mplied wa!Ur: of Hi m
bar? Com~ this.
\\ilb d.: \i'DlK ~n iD 'rub!e IO~l r \tPbid11~ fom a dilferem ~-
lU6. (D) A fmt.Ctmtshriq c(Jvi:moltr ~ of~( J) iiQit1 ~~mtrile(2) is dlrooldl

lll p~ P and M~ T. For what pressure .range (litll'l) will two pba.~
(liquid aDa VilpOC) ~ r~ rot T ~ w~ ~~~tDt dl~tt ~ts taw app1i~
fb) A feed con~ equiloolar ~of ~lime(]) and ~wmim:le(2} isdu'tJltl~
to~ P and~ T. Forwbattem~uue m:nge ro
wm two~
(liquld aru1 vapcr) be ronned fOF P = 0--S(atm)~ ~that Raool&~s ~a,,,l applies.
1U7.. birJaJY lniull.Mofbmr.bllf(J ) axl tohlent'(l) is ill Mil to 75 'kPaand 009 C. .Amlysis
of me e:tliuent fiquid and "W~pX" 5treams &om tlbe separator yields: .1(1 = 0. 116C);I and
y~-;;;;;; 0.2919.
An op:mtor lmUib tmtt l:be product ~__m 11ft ~'olf-spec;~ and you !Ire ~ ~~~
~the probkmL
(a) Verify ibaJ; the emtq SU'eWDs are OOil m blrtacy equilibrium.
(h) 'ftril)' that ao1ai ~ ~n~o lbe- ~could be me case.
lOA Ten (10) bno~ ~u-1 of eool doe .1 111 UXFC is fwtbu adGd to :!SeC. ~ iM
amtanlal !(ftt[Q). What ~ etat<:ofhe&~~ fur 1lbe ~? lmlitl.l ~po$ition
&f lk :ill am ~ .J01 ~ Cl.IB87 ., .~ t::1 0.12M. -'~ :;::; 0 .0'175 ,~ JlbO ;;;;- 0. JS50.

171
1!039. A 1Qb1 hydrocarbon ~ ~:eotaining S mol-t1 prop:wc. SS mol~~ ~~ and

10 m.ol--* ~pen~~De i.s stura1 as a liquid Wider its ~ pn:SSUrt liJ a l'd~nt.tt:d
tm~ Available ~ernlion keeps Ole oootelltS of me tm:tk at 40\l). Alt!boogb tl1e
tank eanWns ample vapw space, it is essentially fuJI of liquid on a t'lf()/,cu basii.. WbaJ
is lho 5tonlg ~?
lOAD. Teo (10) tmoJ &r- ~ of b)-~ sWJidc gas is.~ with the. st ~~nc amQVIIt
orpure.-)'Fn ina~BianiL ~ enter ~-~Cand Hil'JID). Prodlit.::ts
le:iwe as rwo me-runs. in ~brium ar 7<PC and l(atm): a phase of plll'e liquid l\"3fee'.
andla~w,por mam~~H~OandS~.
(Q} What is. tibc composition {quilc ftaltli~ of dm ptod.uM ,,... $tl'ml1
(b) \'Vh$l are ~ t3IC!i (ltmul bt- 1} Gf rhe tlWi ~t ~~'!
IOAL P!hy:s.iolo:gical smdies slxPw lbe DRltnll com!ou l~li (NCL) vf IIKJ~ m
tQI ~
~ _ _ h-!..l:t..
I Q Q" ""'"-lUte ...r .iil:x""''
Hiftl!.uy"' _ ~ O.tQJio
~ .... H20, pel'
--- ,....,of
--Q< II.&!I:J st't.
I.......
(a) Wll3 i& ~ vapor-pb.~ mole fractioa of 1120 m me NCL?

(b) What is the partial pressure of tt,O mthe NCL'! Here, 3Dd in pm1 (c)~ mire P =-
1.01325 txar..
(e} Wha~ is tlu:dl;wp;rinu~~ ~f) -dlc: NCL"J
JUl. An irubtrial debwn.idifier ~.SO kmul hr- 1ol01Cli51 air witb a dewpoiu.1 vf2fFC.
CQDdiriaoQI Dir b-wifi~J dJC dchumidi:fier IItts A dcwpuhu ~mpcrurure of lWC. At
'Wba: n.te (k&.llr_ ,) is liquid W2J:er reDlO\'ed mtdti.s steady-flew process"! Assume p is
~am at 1(~)-

Solufon Thermodynamics:
Theory
Ow ptupuse ill this chapleT to lay lhc l.becn:tical [wndQtioo for applirnti~ of lirnnody-
Dallll~:s 10 gas mi:u:urea. arull.iqHid ~om.. In the lrmie8L petr()lcwn. clOd ~caJ
ioduslries malticampme11t gases and liqu.ilb a.nmanl. under~ cornpo ftion cb~ broo~1
uboai by mi in& aBd ~ pt~~ tbe mmncr o( spea from ClDe pltase to WlOl.b,
aDd c aJ ~anion. 1'bus ~ 'bt:tnne 'ran
:tbtl ks. aJool with tempemute
and p~~ tiJe Vlriables c.oo:sidered in de1ail in Cbapt. 6.
\\~first dcvclop a.{imtlattJaml ~rl) r.lmibn mC~te can~'h"C tba:n Eqy{6.l0J
in lbal i pr extrnd lO' opco Jl)hues \D k composit:ion. Cotl\1 im~ Mre prompt$
defta:l1io_n o[ 1b8 chf!micid _potm/141, a fund;jUJ]mbl] BOW proprli1), which ~itJlcs tre3UD.ent of
plw and cbemlcaJercadicJoequihDria. This promp inrmdoction of 011 entire clas!, or~
d.)'l propeni~. lnown ~ ptiflif/l ~rtiu. defined m~allbf so as to suggest rntet>o
preutio.n as ~ of indi"idual ~im 65 they e:d! in $01ution They am oomposjtio
or
dcpc=ndlent. aud distinct &om at IJlOiar propc,rdes pure species.
Ptopmy J'e:la:l.ibos for mimln:s of ideal p.~ prmjde rthe bas~ fur treatmem ef real
,...~ m . .Important heR ~ abe. ddiniuoo of _e1 anodler u.se-ruJ property, lhr fogacrty.
It m ro ~ ct.mniod potentiaL it fl::nds itKJf to lmltbcmatical fOI.'ID1Jlatiun of borb p~
aml~~problans.
AQD(.he( usdul d~~ or
dution ~ known as a~u prtJ~rtiu. ~ iruroduccd
in conj rn with an i<bfiution of sol.l4ioo ibeb3vior culled lhe idl.al ~olurioiL I role is
h that of the ideal ps in lba1 it saves as a ref~ io ~ ~ for real-solution ~
ior. 01 panicuftar- intm:SZ i.~ thee- Gi energy. a property which~ the: activity
ooe:ffi mtrodocr.d ftom a _pr--~ poifil of view in tbt precofi~~~: ch~
11.11 FUNDAMENTAL PROPERII 'I RELATION
Equation (6.6) retaces Lbe I.Xal <iihM ~y of any closM ~t.eni ro ill ~m.f vtlri~~
kroptlillute and ~
tl(nG) .- (nVjdP - (nS)dT t6:6)
378 Obras proteg das por dire1tos de autc

379
where n ~ me UJtal. ll1lfiibef of ~ cf ~ $)1~m. A~ appropriate upplitman i& to a single-

phase 1luid in a closed S.)'Stt\Dl wbertin oo cbemicd ~lioO$ oowr. For sue.b a !iystem tbe
composiuoo is~ com&nn~ and d'!~
C:hnG)] =- nV
[ o.P T.-
lbe ~t 11 ind'idtteJ dlat tlr ~of moles of (J/1 ~mitt\ ~icll ate bfld ~
1Por tbe mow1eoeml c::ase of a single-~ lfl"'!n system,. mate:riaJ rDal) !pUS into ;md out
of tbe s~ .afld rtC beeam a flmclioo <Of fhc ~ of mo1a of dw cbemicd ~
~lt ~1y iJ il-stiU ~ :futu;tRMI tJf T Mdl 'P ~ and w~ todllooidilx t~ fam~~l l'$'tion:
nG c g(P. T~ n i Pll .. . n, .. -.)
wbe're: ~u is ~he number of moles of species i. 1'!he lou! difrem~~ of nG is tbm:
d(lr<l) = [- acna)]
aP 1',11
dt' + [a~4G )]
I ar P.a
dT + E ["u~G)]
i an, "".n,
tilll
~ uamm:uioo is O'Ve1' nil species ~ ruld m~pt n 1 irutf!!::EM ibat aU mole lllltillber8
scept 11m itb we bdd eoDit&l'll. The c;leril.~ iD lbe final tam is given ies. awn ~ and
name. ThliS.. by. ddtmdon the dzemi4YJ/ pq~nztial of ~es ; in the mixrurc i ~
p; E [a~,; l..T.OJ (ILl)
With lbb ddio:iritm and Mth the Jim. two pmial deriwrlves rep~! hy (nV) and -(rrS'Jt f t
pmceding ~oatioo beemnes:
J(nu) :=I (n V)d P - (nS}dT 'E p.1 rtlnJ . (l 1..2)
EquM:ioo ( 11.2) lsi the fnlldaxntllnd pniprll)' rei~I)Q for ~ ltluld 5')'stan5 Qf
variable ma:ss and oompositioiL It b lhe foWklatioo qpoo wbic:b me ll'llr.-mre of SC))mioo thi:f..
modynami is WilL :For ~ spceial <:ase uf ooo mtile of solution. n - l and IJ, : 1:
(1L3)
Implicit i:n lbTs eqmamn i dlte fnnaio:nal ~l~p ef lbe molar Gibb!. energy ro its caNmic-ld
"~~c:: T~ P , und (:f,i)~
G = G(T. P .rJ. ,-f!. __. ~,~. -->

Bqtwioo (6.10) for a OODS1fti11"'1o.'"tlmposition s.olulioo is a special CiiSe of F.q. (~ Ll). Al
though me moJe nullllbers n~ of Eq. ( 11.2) a:re inclepmdem variabl~ tbe mole fraaian& -'i trn
L
F.q. '(a 1J) are ~~ ~ _ Xi ;: J_Tim p:ru:ludes oortlin mathcma~ opentions wbicb
depend upon ind~ of lbe. variables. Ne\~~ Eq;.. (1 [ .3) ~ ifnply:
0 1.4)

'Other mlulico ~ oome from deDni:tions; e._g... the embalpy., ~ H. :::!. G T TS. nus,
by Eq! (l I .5),
8
H;;;;;;, G - 1' ( f.!).
IT l'..s
WA n the GibbS fJJTBrgy is &xpruse-11 as a lunetton of Its ,cananJcaJ
variables, il J{tays 11\e fo!1e Of a ,generating tunctkJn. provlalng the
means for catou1aUon of an other lhermodrnarnlc propeme. by $kn-
plt maihematial ~t{diftwrepfiatJon and etementary a~Jebn~),
and rmpiR:iO, represettts eomplefe property information.
11~ THE CHEMICAL P~L AND PltASE ~QUIUBRIA
For a t:~Mnl syam consiWitg of ttvro phaws in eq-uilihripm.. ~b mdiritt...J ~ is qptQilO

tilt ~ erul Jb&.~ lniiiSiu bd.Wn plla5lc~ 1m1 OCCUJ.:. :Equation (II :2) npplies s~y m
~ph:i~
~ ~ et and IJ idm1ify l:bf: phase& The ~on h~ is. Um1 t'qmllbnrmm

Imp _ --~1'-IIJ.J.UJ.Y 0 r t _ ...
- - 'l'jm u-.u...........:., ~ 'lu.... "he
D . . _ _ ... .,:.......
Y.11!\ci'D~\I- 'UJ!i CIJ!!!M'!!!"
i!M!!Q' 1 """~
~
"'J ...
The cbanse in dlt. I DW 0~ ~ of~ two-~ &)"51~ is lhc sum Qf ~ ~
tioos. 00. udl tOOil~ ~ is~ by 3D eqna1ioa of me fonn,
11.&f;: (nMt" + {11./ltVJ
c~<, G) = (n vwp - (nswr + :E ~~-r ~r + I: 1..rdtif

II
BcciJQSC d ~phase 5)-stcm is elmcd. Eq. (6.6) is alsu wlitl Comparlioo o! dte two equa..
licm ~ lfm at equUibrinm:
The d_tmp:s ddJ and dnr I~eSUlt from .IDmS tmosfer bd.'ween the ~ m38S C~tioo
~(ll!e -~
aml
Qgaat__ities,dtlf Sill! indc~ ud ubDnoy. abm.ion tlhe only way tbe left side ofme second
eiPI'ioft 1Ciln ill,~ be~ fm~ ~ ~bt.~ ~~ to~~~ Hmot; m

JSI.
~N is lllt 1td~ of~ ~m 1... Ute sy~, s~"'tt ~li~ of this t'C$illt
10 ~of phase~ permits tbs ~2liltlun m muJtlpli: ~~~ fm tt phmie :
UL6)
A ii:m.ihlr bvt IJlOK ~~1:' daiVDtioo fw'f,\ (as we ~.,. up~ dlat f'O equilibrium
T and P mU$1 be til~ Sl\1:DC i:n all pbases.
lhua, multiple pba- at the ume T and I' . . in equilibrium hen
the chemiCal polemlal of HCh apet;let It the UlfJt in all pMtet..
The application of Eq. 1( 11.6) iD bt~ dlapten to specifK pb~ pmbleiM n:-
quim use of ~~LJ ofwJulion beh_avior, which provide ApRSSions for G and IJ;t as funttiaos
of~ ~ and OO~Oit. The simpJle&1 m.f these-, dle. i....p.'i mUrtllfe aml[
lflc ideal solution. arc tmlled in Sees. 11 .~ 3Dd ll.8.
11.3 PARTIAL PROPERTIES
The ddinition of me cbemical potendal! hy Eq. ( 11 .1) as die mole-number derivath<t of nG

SUSF-SU lhat Olb lknvarl..l:t ,o f thi~ kind sbookt JBiO'e -..scl\d. il1 wlutiou ~~~.($.
Th~ we ddit~e partid molar pmpeny M1ot species J" in solution as:
me.
b is a 11tBpl)ltl~ frmt:lim,. ie._, a tttMmN of ~se of ttxal ~peft)1 n M to ~ oddnJOD at
<CORS1ml1. T and P of a diffenmlial mnwnl of species i w a .finite ilmOU.Dl of ~lution.
The ~e ~)$ M ,:mfl 1Ui 1U!iJ ~Jilts:S I-nion ~iC$ on Q uni1--mlm ~as
wen as oo a mole bilsis. 13quaoon (1 1.1) reCiios me same form.. v;idJ n~ the number or mol~.
n:plaom by ~ Tq)~ting 1IJII5.S. and yielding partial spijic pwpn ties .-ather tbm partial!
mullli' propMic$. TCil acconullOd= tither. one may spt4k &imply of partial proptnies.
Interest bae oente1i"S oo solLIIioo.~ tbelli molar (or ordl~) ~are. ~ore~
~ by the plain ~ A-f. Partial :PfVPMes ue dmotod by an ~~crhlr, "'il& a subsaipt
~ idcmlfy IlK: ~; ~ ~1nbvl i5 time"ftJR. M1. Io :ldditioo"" ,ropc;Ities of tbo indi~
s~~ m ~Y ~ irn tllc ~ sr~ m r!e T mul P of the wlmiM are ide:ll.tiicd fly only 1
mlm.rlpt. Hfill r:h= ~ymbol is Mi~ rn ~~ di ~- ~ or ~es U!icd m~~bfi~
lhemJudyrumili:s ae distinguisbed by tbe folltowlmg ~
Solutioo pmpat.ies 1.' 1~ for 9Mnple~ V 1< U. H S .. (}
RmW pmpenil ii= forQampte~ V;, 0;. ii,, si't .Gr
~~pmpaties Aff... far~: v,.ui.H,.$t.6,
Com_parl~ uf Eq. (J l .l ) wilb Bq.. ( ll.7) wriUeo fur the Gibbs maw ~ dmt the
cbemkal poteMia1 and l!be prrWiJ mot ilf ~Gibh! ~ are h,lcmical~ Le....
-
/Ji - G1 ('11.8}

J 2
Example11 .1
The partia~ mdaf VOlume is,defined as~
~ =[il(JJ V)] ( A)
l 8lJI t.r -1
'~t l)hysicaJ interpretation can be given to' ds ~e quaDon?
Solution 11"11
Ala ope:o ~ ~~ an cqnimolar mil~urc of aleoho! and water occupi~
a 10131 v.ob.l:me ,y at .room ~ 1 and m~ ~wr~ P _ Add w
~ sOOnion a drop of pure ~ter. al"'' aT Md P. ronWnil~g A n moles. and
mix it tlb~y into ilie solution, ~ing wftk~11ime for hr!at e~.ch:mge 10
~me ~of tltc ~to the unlhrl rettri:pt!F.dlrre. OAC Dri!ftr ~~ llitiir
:die YOlume of soluti0o ~ by amou:m eq1Uiao lbe \'lll1ume of the \\\ ter
added. ilL. by V: An v~ \\fbcn! v; ts Um moJ!nr mlwne of pore water at '1' and P ,
H" thi wen: tb:ve., 1t1m mgi lvlD[I]II; dlrmp wo~ld be;
A (aV ;;;; \l lln 111,
Ho\\"C'"ef experiment~ lhatdle ,ar:lD:aJ \"':tnme dmnge SOUJe\\1m1 ~less. f!vw

'bknll)'. the eJ/ec~ nnHat rofinnc or \\o"akt" m dte finnl] solutif)lo is ~ man me
mobr \ l~~~M of pure " ' ter At 1be same r ud P. \Ve ma)l therefore write;
(Bl
wbtrt W ~ ~ effedl\ic molar l'DlliltiC o M'Mtf Ui dir Hoal.s_~uli(ln.. l.:s
01
e.1:pHimental valut:' i& ~'Ore ~'~ by:
(C)
In lhe ~ ~bed & drop of w-~tu r orlx.ed willh 8 t:Jstanti3J arooun.t

or stdtttioa, abe ~t ~ 3 small bur m~k d~ mC()tlipositiao. of me
.s.olutiOB... Par the rellecti\-e roolar \'OLWDe of (be 'Wilter to be oon.s.idetred a !PfOpeny
of the arigintd ~ !lf ution~ d1e process 111ust ~ Ul.ken W .te Li.mit of an
Urliru'teslmal drop. Wbeoce. All -.. 0. god Eq. ( C beQomes:
v. = Alnl' ) = d (nV)
liro
~~ An dTi
~ T~ P, and JJa (lfle ntbet Qf mo~fif aloobol.) llte t~ drii equation
j more n~ly Mitten:
v = [a(nV)]
- a.n~ .P;r .tt.J
~D ~itb Bq. (A) shows llw in Ibis limit 'V ~ p:utiaJ moW \1ol~
UOJC f., of abe W3let iD We equjmoln,t $0lwio~ te., tk 1'U1e Gf dlu~ uf l&e rota)

sutrnioo wim ~t.... .111 ooostant ~~ ,, and n~ fur a s:~ic ~co~n..
l"OlU~
Wfirlen f [be additioG ot d~ .~ ofWJ~ ~tbc: soluti~ Eq}, ( 8)," dt~:
dOrV) .- P. dn (D)
Wbm V. is(~ dJe motu: IPf01JCI1)I' of water as it '~ in :ro!ution" lk te-

~ vo.lwne cba;cgo d(R V) is mmtl'y tis molar JIIIOpe:dy nndtipliod t.y b number
Qf :~ d.n 10 of WBt.W .-cldtd.
If diJ omles of wat .is. a_ckfed to a \"0~ ofp~~rn faler. thEm \\<"e bm-e evt!r!J
~- Ul ~~the vw:aluux change of me ~*m to ~
cl(rrV) c v~ dn {E)
wbm ~ i tbt molar volllml'! of pure Y~'ate:r 1!1 f and .P. ~of l!qL (D )
aM (.) mdiales th:d Vflt' = Vi&' When lbe ~D~ i! pure Wii.te'f.
Eq-"ons
""'.'' _ n911!1~ui9 o'-
a--*'~ - fiPI -,__, ~...,.., ~-- a~.
_ iiJf """"' ,_., IQU "'""""' r~-
'--
'IRR!I'
The dctinhioo of :a 1J1dial molar l'f'Oj)a"ty. q. ( J J.~ provides. the means for ~k.-vbdioo of
pal"b1 ~ ffool soliiJiml..:propen-y duu.. Impli61 in dlis dcfinitioo d anodtet,. ecp1aU~
impornmt.. equatimlbat allOW'S tine evme., te . calcuJ.alioo of so.lu.tioo propmties from mawt-
edge of llbe pmiaJ ~es. The derivalion of dJ\s equation staru with tbe observalitallibal
lite :tcN:aJ ~ properties. of a 1\om.ogeoeous pbase are fundims .ofT. P ~ and d!le
pwnbo.fs of~ of die: indivKlu.J ~es ~ ~ ~ pb~ 1 ~for pxupal)' M:
The tOOII differemial ofnM is:
dOMJ = [Ci(nM)]
- ap _T,fr,
dP + [a(,.M}]
- &T _P.A
JT-+ L [i(tt&l)]
;,n;J P,T.AJ
dnl
~ subscript ~ indicatu Ibm all mole nwnbets are beld eomtaml. awl .subscript 1111 J dial aD
illiJ!Ille i1iWt1bers 6dpt Bi are bel~ ~am. Bcoaibi!e me first r.ro pittial dcn"r\'1ini~ Gql We
right ue eYaluated ali amstmt n and became the pa:rtml ~~ of lbe ilas1 tmn1is gjveo by
Eq. ( L1.1). dD.5 ~q ~ the siQUlla fl.lml~
cn.9)
where :snbsaipt .J: dmol~ d~on at OODSI3Ill romposidcm. !Beal~ ,ni == x,, l,
dn4 ; ; x, dn + 11 ~
d{nM) = n tiM+ ltl dn
~ fiDICOOnalily does ~~ot 1n11te a.1m 4JI ~t.~ l:aro ~ aRab'ln. ~am me~~
r.J!lb (or G.

[ d.M - (~)
BP T .A
dP -1(~)
,aT IPJ!
dT- E Mid~]~~+ [At ~ E ~i4ili] dn:;;; 0
i I
In applation~ one b free to choose a S}~em f1f mty Me~ ~ ~nlt:d lly n~, .~l1Jid 1.o
dJ~ ati)' 1lilliatiOD fA l ~ ~ by dn. 11ms II and dn 4l.le i.odependau nod
~- 1'h: Cllty ~ l hn tb;: Wl 5I& of 11W equaduo eao ~ in poe.~ be zero fur
tddt GBm iiD bmch~ to be zero. Tbm'efore
t 11.10)
( U .ll)
nM = I: lli M i
}
Equdon fl.~-tO) is in fat:tjus:e a~~ of!4. UIJ)~, ob~Mnoo by ~ngn ... 1.

whidt also maw ftJ = Xl f4uaticms U 1.11) and (I l .l :f~ 011 l.l:e ada! b;md me IK'W ttd '\'itidJ.
Jt_j)~Nrf) as !JIIMtublUt, rdatif1115, by a1klw ealeublion ot" mixture pi'OJJedies hm pania.l
pmpcrties. playing a mfe opposite to bl1 .or &t t ~ 1..71. - b.icb pnwi:dcs for (he Gilleu.l.ution of
,mial ~ hm ~ propalies.
One fUJtbtr important tqtt iOD roUows ~diredly frmn ~- (1 ~. U)) md ( 11. J I). Wldl
iHq.. (1 t.l ~)a~~~ for t, i .ditf~U.IiM yields a.~ ~an few d 1;1:
tiM== ~ ~d i1 + E &1.u,
~
Co~ of dds ~ i\ith Eq. (ll. IO'J. anot~ae;r poem~ eqwrtioo ior dM. yii~ lbe
GIJJbdlklhem Zt!qr_m1imr.
(1J.t3)
Obras protegidas par dtreitos de autc

This 6if~ nnm t.e&tlisW for all ebmges in p, T . ..t me Mr caused by ~ofsaare
ma homogeneous phase.. For lhe imporumt ~ '-~ of c~ 1
~t T aud P, it
silnpti;ks tG:
:E xrdM1 ;;;;;Q (con5t T. P) (1J. l4)

l
CentmJ to applml solution thennodyiW:raics~ the ~ipNferty ~ impks thai a sotu-

ti.on
. - - ~a ~WI'b_ ol- ~" .I.C lht::
fllRJpC'Illy --~Its pBII5 DS ""'J(___._.._...,
_ ..sum I.H. ~no.r~ .... wz~ ~~"
II'--
-~
or
Mt ot tbe oonsnmem $pedes.. This b ~be implication Eq. ( 11-I IJ a.Pd is a JHUPCr inttfpfeta-
tion tp:nwi&d one ILllldmrands ttruu the defining equation f<H" .M,.. q. ( f I.7). wan appo:rtionmg
~~a
VWQ.II,I. wblch
._ -~...!I
aruu"UIQ.F -.;n.s
1_0 - ' L ~~
C~.J r liS ~OJ we; MQU~Jll ~Jty.
- L ~ ..L- ....,..L..!~ -
1'he ~of a soJotion are iD fuet i-nfim:rtely ~ and owing w 11101eco1ar

illlerBClioos Qllnul ba.'-c p:rivatc propcnJcs of their own. Ncvatbelcs&. panid .Pf'OPC'nKs..
ddirned b)' Eq. ~ 1. n~ ttave all me ~~rerudcs of~ o~ me illdMduaJ ~ they
uist iD mtution. Thus fc. pnetical rp~ lbey may be .twi~ as property ~ t9 the
:iodivfddill ~~
~rlid ~
lib solution prop:rtles.. are functions of compcmioo. I:n limlt as t._,
a dution ~ pme in splcles i, lbotb M and ~~~ approedl the ~speclt:i ptopedy M,.
Matb~Mna~imlly.
lim M;;;; Um MJ~ Mt
~~ ~ .14 ....... 1
For a~ rhill app~ its intlni~Ltnlon limit. 1~ liE value as i1s molr. fta.Cii(ID
~bes mm, we eo ll'UlK no genaul ~- ValDa ooiDB Rom aperimenl or from
mlldek (J'f sohitioo ~ Bei.."B~ it is an ~ qLUUJtbt~ Vir do g)\~ i:t a ymboi~ g,pd
by definition write:

6m !f;
q-0
-
= .... l)C
.~11
'the es._~tial cqua.tiuM of lhi& se~L"tion aR summarized as follorws:
nm~ M.
; &3
[a(nM)]
8~r~; ' T Jlf.J
U L7)
wmm yiiZ:lds ~ propmies from mmt pmpertfes.

(I LUJ
wtn~b yitlds twd ~m rNJD partial pmputics,.
GlbllslllDb= l: ,(f dMi = (!!!)

aP T..s
dP+ (~M)
&r P...c
dT (I t il)
whfd1 ihows dlat tbe p;utial ~ of species mating ru-p a sOtUtian :are nt~t ~pendent of
ODe~
:$~ ~fulijag ~. ~
iNJriAitlv ~
"* diff:rmt ~ , _ (ilf 1t1Jc allitiQg po.pmy. ill=~ n liR

186
Partial' p~ Ill,.,., Solu:lloM

Alo ~ fer i }Wtial ...Ujatf fuodioo of compoWcm (;aiJ always be &Je-ri~ from
an eqnatkto for lk SGJution ~Y by di~ app1~ of P4 (11.7). For binary systems.
~.. al~ proeedum IDlY be 1DDJe auNnitmL Wrinm for~ binary ro1uti~ me
sumiJIJibilify lt1uion, Bq. ( 11 .II~ benomti:
M = .rlMt ..... %1M2 {A)t
dM = .,I'JrdM +Mh] +.a:z4M"2 + tbdx2 (B)

When M is mawo as a fUIIdion or XI at Q1Df4a:nl i and p ~ me appropriate. form of me
~DuhGm~islq. UJ.l4)-. ~~ :
-
XtdMa +.tzdMJ. oO- (C)
_lkek~ JJJ +~l = 1,. it ~ lfllt U] ;;. ~ . ElinliDaling dX2 mD'-VT -of4.x~ in lEq.. (B)'
and c:ombilrmg 1M~ wbb &J. (C)tgt'ti:
--
M ,_. .~v, -
- - M;d
.q(Mt - M :I:
- ~
X1J(.M, - -'12)
-
+ Mz
In ,COOlJ:rination wilh Eq. (D) lbae ~
- dM
Aft ~ M ..&.. ...., ,;;;__
.- .-. iii ... (l l _lS) (11.16)
U'XJ
1bns b 1~ ~~tile p:trtiaJ ~ iW ~y CDI~ed di~ ftom ~ ~

dOD h the sohmoa property as a, fu:actioo of eompos;ilion at oonstaol T a.od P. 'Th:e ~
~ ~tiom fiK m..atk~-,o~ ~ . iRWdJ more ('{QJ]Pfa,w a:rc Mi'~n m
~by Yan Nes! 1Uid Abbou.~
lqua-tikm (Cl tbe Cii~Wmm ~ 1m)' be wOtlm in deri\raive funDs:
~H. C. V:m - ' M.Ahbm. ~~~~, " 4~~ ... -- . \\""lt~ltl

.~ ~ w-46--st. ~Hill. New Yod:. 1982..

387
Th~ ptoQ Qf ~~. and M2 n. Xt ~i lwrizontail as QCb species .approaches purity.

Finall). gi~~ un ~ fOT Ma (,~:~ ), m~on of JBq. C) or Bq. (F) yidd8 an
e:qJRS5ioo for .1ii:!(l; I) dml satisfies the.~ equliwL Thh mem~ Lb21 ~oos
eamwt be ~ed ubilfari1y fur both Mt(.r 1) and M2~'x J).
Example 1'1.2
Describe a graphioal iftt8'fJetatfotl,of Eqa (11 ~ 15) aPd (11.18).
1
Solution 11 ..2
Flglll'C 11 _1(a) Siltows it ~ve plot c;rt M ~"- :c1 for lbinNY
iji$ttm~. 1"')c)
tmJgent :nine shown atend& a~ the li~ inter:sedi~g the e~es (ll XJ '!!!!!!: I and
.r-'t ;;;;; 0) 11 poims labeled I~ Wld .#;,. As is evident from lbe figure.. two eqWvalem
~xprcs.sit~PS eao be writt~ f<w lh 'ilope of thls tmgan tine:
' M
M
Jl;
J,
112
1 0
dAI ~~I - /2 tl rl.

- ;md - ~ ' - 12
h. ~ ~~
the fi~ ~I!Jlltion is solwd fw b ; it combiE5 with die second tu live f 1:
l 'l = M - x1!_! nnd 11 = J1 + (1 - xtJdM

~~~. d.t~

COill)JQiisoos of these ~DJS with EqSw (II. L6)r.and 4~I. I~ ~, dt3.t
I~ :: Air aod lz = M2
Th~ the mngcnl ~pis gtVt; di_ruUy ~ ~s of the lWO pania1 ~P'"
edies.. 1bese ~ of course !Mit t i ~ point m ilmtmeY lfii.J\'CS along
the CUI"Ve. and the limiting values :are ind.icded by the 001lS1i~Uelicms ~D in
Jig. 11_1(b). p~ Ole ~ IH:oc dtawb d .liJ ...; 0 (pyrn ~ItS 2), MJ = Ml.
and ac lhe opposite ~~ M11 co:: Mf'.
Sim:ihr OOJDIIlellts apply m me tangent
drawn at xa = J (fJme species W). In mis ease M, -. M1 ~ M1; J,fr . ,:::!2
llxample11.3
'l11e need arises In a Jaboratory for 2,000 ari' ot an Mtlfreeze sobJiion oonsfsting
013Q..moa-%o mf,Jtflanol in waltuL What \'dUtne$ oil pure methanot .and of pure water
at 250C must be mbced ro t'Jrm d1e 2, .0 00 cmj .of ardifreeze.. also a.1 25C? Partial
malar \!Oiumes tor rnelhartol aJild water :n a :30-mo1% methaool soludon arid lheit
pmrspeele'S nm1at volumes, :bOth at 25"C, are~
Melhanof(1) ~ ii:1 - 38.632cm3 mo~- v1 . 40.727~Cml mo~-
Water(2)~ vl - 17.785 rcml mct 1 v~;;; 18J)68 em) iifl()l-~
Solution 11 ...3
Equal;ioo (ti.J 0 is writtm for the molar ,.,'Of:ome of the binar}' antifreeze wlulli~~
and known w.Ioe:s ue sllbslhwed for the om1e fracl:ioo.s aQd partial vo.f~:
V = zt V1 +.x2 Y2 = (0..3)(38.632.) + (0.1)(J7.l65) == 24-025 em' mot-
So;;~ ~ MJuittd w.tal 'd:"umt of t~tion is VI ; 2,000 em~ . d:Je telal
lWilber of moles required is:
V'" 2.(0)
n = V == 2.4.-o:zs =83.246 roo!
Of bis-, ~ g mrelhaDol and "11'.i I! ~arer;
"J =(Cl7)(83.246) == ss.m mot

1be wlwne of eadJ pure. speaes is Vl ~ ~ t 1
,-:. thus,
v: = (24.974)(40.12.7l = l,Of1 Vl ; {S&..li2)U8.06i};;;;; l,OS3cm 1
vh
Val'c:el of v
Vl~ amd fonhe binary 'sollll:iDO ~QI'ft,l1 l )lwattl(2) ill ZSO'C are pl~
iD Pig. 11.2 a5 flmcUODS of' X . . 1be J:ine dfawD tmllgellf! lO 1lae V VS.Xt t."Uf\'e at N l c- 0 .]
ilhmftll~ dJe. ~~ ~rc. by "ill.~ \i&1~ of VJ and ii1 may b ~ed- N~ th;rt
in amfo.nnaru::e widl dte OibbsiDohem eqmu:imt lbe ~ t4 ~ ~ines fur V1 and V2 we
C'\~ofQ.PIK)Si~ .... and tb.t V1 ~~ ~ (d V1/d'J. ~ ; 0) a1 x,l = 1 and the
fllll'Ve ror Y2 ~ lb:orizooml a1 -'l = o or 12 c l . 1be ~O:tVeS ror Vt Md V:z in f'ig. ~ rf.l
appear to be bo.rimntal at l1h ends; .niB ~. a pocnlifmty of the system eomidered.

JI..J. Rlltf..d ~ )891
40
vr -
35
i
130 Ft 1l,l; Molar
YOI UIIII:I h
}15 lllellwJol(t~)
l,SOC ud I (a1DJ).
umeacd \'&lues
rrclao m lEx. ~ l .l.
20
1.0
Example 11 ..~4
The en1hatw Of a binary liqUid system oJ &pedes 1 and 2 at tf~d f and r ~ repre-
semed by rJte ~
H ~ 400.:r] + 60Ck:!-+ J:}XZ(*hJ + 2fh:!l

where H iS il1J mOl- L_ Demrmin& e.pressiens tor iia and ih as functions of t 1
numer1ca1 values for the pure-species enDlalpies H1 and Jll , ana nttmetical values for
the partial enthalpies a~ infinite dilution ilyo and iiJ .
SorurtiGr111 ..4
Repbce ~ br l - x~ in the glveo ~o fQr II ru'ld simpUfy:
11- W..- Gxa - ~ A)
-ddllrJ =-180 - ro.rf
II1 = 600,- l8<l.l1 - 2or. - JSO.t.! - (j()qXl

Rsplacc xz_ ~r I - -'I md mnplify:
;;J t= 428 - 60!rf +40xf (8 )
~e cap equaUy well ~ wd.b ~he gl\~ eq~tion for fl. B~ dH ldx1 is
mcal~~~l:is notaoon!ftaL Ako.q c;;; ~ -.ra; therefore dx1{d.r 1 :!- - L
Difi'~ of the pwm
DC}Uilino fw H ~ )ie~
dH
- c400 - 600 +.1 t~l40 - 10) +(40.ra +~(-za + x1 )
d.r1
R.q>-*iilg -i'3 by .~ - ~~ ~~~ tbc ~W! pmriously o~
A m:IIDlarieal \"aloe mr H 1 msWts. by substirutiotJ or ~~ ~ J m ei~ Bq,. (A) ts
(B). Both CQuatit~~.D )iddJ ll1 = 400 J mal-~. Simibriy,. HJ is lwnd from eit.bef
Bq.. (A ) M'(C')wbm Al = 0. li'hensuJH l:h ~ 601J morr- The infi:nite-dlJotion
~ nr nr and are fmmdfmm Bqs.. (Bl aM (C) \Yiro Zl e 0 in 'Eq. (8 ) and
XI ~::~: 1 i.DJ F4 (~The ~IS are:; Hf =
420 Will~ = 640 J moJ~I
~ Silo: lbatrttx partidpropm1ies as ~rm bJ Eqs. (8 ) rmd ~C~ comb~ by
~.......___.ty to gil~ :Eq. (A.)..Mdiccaarcm alheq~ofb.G:ibbs~Duhem
eqnarinn.
IIIUJimts 8/nGng Palflal Prope111es

We $bow DOW bow~ pNJ~" ~ rela.rd ro oue ~Uih~ BY f'q_. H tiO. IJJ. =Gj. aDd
Eq. (U .2) may be 'lli'ritteo:
d(~G) = (nY )dP - (nS)iJT + EGidrJi {(1.17)
~of !be aitaioo ofaDCtDess. f4 (6.11!1). yldds llh-= Maxwell retmiCUl,
(:~t- -G;t. (6.16)
where s~ ti Indicates CO'Ih1.mcy of an R j. and, tlletefotc or ~tioc.. snd mb$triptn j

rod~ that allll'IOle ~ ~the ;th me fleld eOilSimt. In \'lew of Bq. f 1m. 7). me last
lWO elftlillJ.tm.s ru1e ~ mnpliJ ~iitd:
39l
( a<i~
-
) = i,.-;
I
ap ' r,..~~
(1l.S8t (ll.l9)
'lhe5e a,par___Wns allow adcubltJoo of the: e:ft'ects of p :md r 00 tlx partial Gibbs. t.tfWlJY \OJ"
dvernioal ~- They ore the pariiAII-propedy ~of R(p.. ( I L4) and ( l L5).
Every eqwd_lon lMt 1p nwfde& a flnMI' reldon emo-. lbetniOdynlltmlo
1pr0perti1180fa ~~~tolutiOn M~ IM~
an equation connecting lbe c:orreaponding perlfal prapertlila of each
spede:s In the sokdlork
An1eumpJe is ba&ed om.lbe eqnillioo tbru ddioes ,emJWpy; H- U + PV. For n motes.
P [3{nV)]
aiJt fi .T. J
By Eq. (11.1) 1hi!8 become ~

- = Ut- + P'Vi
l:l;
~
v.ilicb . the ~"JD'Open}' 1D:Wo1 wBq. (2., II).

rn accmt~uu~l)n solution. G~ is a~ of P 11:\d T. mtdl ~~
By Eqs. (ll.. L8) and C U . !9')~ JG, ,.., iuJP- Sr dT

Thi:S Dtty be~~ wilb F.q. (6JO), 'l'hesr ~~pks il1ihdli!Ule me pamleJism tbn emn
between 'ecJ1l3.12ioos {or a rommnt-eomposirloo.sohaliioo and lhe com.spoDding eqg;rtioas for Cbe
~ ~~ties: of 1h~ ~ in ai~lalitm. 'ft~ (."a_n dJm:tbrc write simp])~ b:y arudogy mJJDy
e~~dt~~~al~
11 .. 4 11HE IDEAL-GAS MIXTURE MODEL
~piw :its !limited ability to ~~1:1e

~ ~ kluwim",. the ~ ~~ modd
prov~ a ~al badis ll(lOO which to bui.hl the &tnlmlre of $0ldlfon rhetmodynamics- D
is a weful propt'It) model beea!ISO it:
ApprOximates reality io [Iitie Y~eU-dt".ftned limit o_f zero~~
rs ftOllfyrleaOy simple.
AJ che m~Jar ~ ~-e~ an ideal .~ a coDectioo of panicles 'Vith no i~"Uliir {(JI'Ce8
Lnd neg)~!* pmick \'OJu:me i(tmp;m:.d with rib. mob ~). Howe. abe. parddes
~h~ ~~e ~. UmJd ditJR'll~ m
m.oJcatJ - UUCilVRJ giwe riso IQ diffcrt:~ m
idiW-~ bm capar4D (~. -t I).
The rnolm- \WUDl~ gf ,; m ~d~ ~ i!s v ;; RTI p [Eq. (3.14)ls:qrudl.ess or the Wltnn:
<Jf Hie ps. 111m. WI :idtal e~ wbtih. pllfi!! Of ~ ~ the same ~fiii(Jiar ,.t.m.t:n~ altbe
san1e T and P. 1be pulia1 mdJlar \'OiuJrne of ~ies I in an iinn-ps llllinuJe is fmmd from
n
eq. (i l- ~lied tb lh~ vvl.otue~ ~pt i.g ~ au: ifkiJ ..P' 5tale;
v~t o; [i(rrV
an;
.t)]
T.II'..-J
; ; ; {a(JIRT/Pl]
3tt, 1'. P'.li t
; RT
p
(an)
Ian~ "'I =
RT
p
tr
v. =:1 v iJ. t:::"
..1
v .g ~ -
RT (U.lO}
r I /)'
We ddlt~ me ptflfi~ p~ of s.pedes I in all ideal-p minute as lhe rPresam: ~

species i would e"J;a't i1 it olooe ocaqried 'IDe IIJintar volwoe! of die mixture. llws.l
(i = I. 2, .. _. N)
v,~ }";; is the wok hclioa pf ~ i. The p;gtid JJIWSW~ '*"iwily 5DUI 't o tOO wtd
~-
~ the ideaJ..a~ mi.ltme nmdeJ ~ mol~ of zero \"Oiume that do oot
~~ rdle ~yOamjc ~ (..- ~ OJl(J[ur \l'Olumt} of dm co~ ~ks
.are~ of one~ and exb ~ ~ iU own set of private~ 1"hi& b
the ba_. Cor the fnlJn.wing ~DJeJ!Jt d Gibb.:vs 1~
A partial molar pn;JpBrty (uU thanr'fUiume} Oil a co.natttu.nt apeoln
In en ldealopa miXtUre Ia eq~t to U. COJN$1)0ndlftl' molpro,.ny
Gf tt. apectea as pure Ideal' go at a. mlxbn .....ndure but at
prtsswe eqg~t to b rp artill ~ tn the rnlxtu,..
Thi is etpmssed madlematlied:y for g~t pra.JitiaJl Pfopetl)' ~~ ~ v i i( b)' 1fle cqwnioo:
~--,..g i
Mj ( T. P ):: M 1 T .. p, ) ~U.2J)
'1'bc enthalpy of an tdcal ps indl!pDden1 of~; tbcfdgm
il~~( T, P) ... H'/rr. p;);;;; H?(T, I')
([ 1.22}

w~ li/ - rbe pore-$~ ~ ar lbe l1lbmtlt T ~ P~ An atmlogoiH equation applle8
(fit vt +Uld 16lbetptu~ Out.are ,im/qpt!~t afp~Z:#Jitr.
lbe eDlimp}' or aD ideol gas daes depend on~ ud by Eq. (6.241~
dtfl
l
=- RJID P (const T )
~ from .Pt 1.0 p gives:

...i - ...J p p
:;/(T.. P t- i:)/ fT. Pi) ~ - R I~ - !::!' - R In - :~. R lilJ"~
Pi JtP
~~(T. Jjt) :=1 ~(Ti P)- R my1

Substhnting tbis result in1.0 &l- ( ll..21,) written ftx- the mnropy )idth=
S/tT. .P) = 5~1 (T, P)l - Rln Jr
w~ i.' is the .ptrR~ val'IIG a~ IN rm,{'l!M T and P-

Fm- k Gibbs energy c:f an ideal~ tl.'iixtUR:~ G1tJ = H1 & ,.. T s-s; [be pataUell mlariOQ
for- pan.in1 pmpenies ~s-~
- u'i - T ..II + RT In
;.~, -
~i i) i . _'!il
,.-
01 p~1 :a or ;: ~~ + RTID JJ (J 1..2-&.)
Diflerentiatinn or tbi~ equadoo in ~-or.d 'Wllb Eq,s.. ( l 1.18) and ( 11. J9) conlinm llb resul l!l
e.qlft'S!ed b Eq ( 11.20) m:l (] ~ .23).
'lbc ~ilitr ~dati~ Eq;. (1 i .In. witlt Bq$. n t 22)T( I t23). apd (11.24) ykl1:b:
( lL25)
S1' = E >u~-'- R E Yi hi YJ
~ I
(11-26)
Gf.r c: E r.O:a~ + Rr I: -~ :tn. yi ( 11.27)

f J
EqumiOM Bfilii~\OUS U) '&(. ( 1125) may bt wril1lm f'tlr I)JQ(b c~Hand V 1' . 'Die fofft1:tf appt.~m
as Eq. (4.6), but the laUu ~ to an ickrdity beeanse of Eq. ( 11.20).
When liq. f 1] ..lSl writam.
HJI - L YI H~ - 0

D dL~ tm dit kft i$ d1e ~y dJsqe ~with a process in ~hleb ~pnrue
Cll1li:IUIJIS of the pore~ al T and P are mixed 10 form ooe UJO.ie of mi:uurc it tbe same 1
ami P. tu ideal~ ttm ~ ~ qfliiUJJJ8 ~ [1..3) -~ 2-
Wbrmf4. {U.2:6)is~ :
S'~- ,LJ,
~ J lie : R ~
LJ 11 In_!_ U'l
i 1 -"t>
'*'
~ 1~ 8id'e tbc rntrrlpJ mtu1t~ cf ~~& for ml case- ~u.w I f.' "i > t this qwn_ticy
is ilways ~ m apeemenll with the serond. raw.
1be lllixing ~ is inbe.R'!ltly ii'R
~tea'b~ and ftll idblt ~ miDDJ; at ~vanr T and P i,. oof ii!Ccompanied b)" heat ~er
[F.q. ( ll.25)].
An abmmlivc ~for die cbcmia1 potcDtial ~~~ FeSlltb v..-hen
is replaced by au ~ siYinB bs T ~ P ~~ "'iim comes fmm Eq.. (6.10)
~~ Eq. (11.:24) o:
wrine.n fir an ideal @H.!
-iii - RT
dru{ ;;;; 'Vjt tJp:;; p-dl' .... RT dIn P (Mihl T )
llmegration Bi~ c;!g -~ f ;(D + BT In P ( 11.28)

where r (T)J the .i.nmgmdon ronsmrtt nt Cin~ T~ u a ~dent fundioo .o f rem-
~ on1y.6 Equalioo (l 1~ is now wrillea:
I,.: u. ~
IS f', (J') + RT lm(y, P ) I 0 1.29)
~~ tnt 1Wg~1 (;_ ~ lo,8tUilhm n 'lhe ;pgttDJ ~_R!., Application .o ( tlbe summabitity
rebtioa., &q. (I 1.11).. prodDQe~ m ~oo fGr tire Gibbs~ at an idea.J~ps mixhlle;
(Jla =: I: i r~ (T) +RT E )ll lnol P) ( 11.10}1
'
~ C!ll~~ muukilb~iD rtbcir s;rmplidty. ~IJ~Qvicka fuU d~ 00" ldeal~tlebav:I:or.
rw-
Became T .. P. and [}d me lhe canooJ~] \1lriublcs rheGibbs ~.. all t~tbcr eqations fw
b icka~gu IDOdel can be gmcratecJ from tbem.
11.5 FUGACITY AND FUGACITY COEFPlCIENT: PURE SPECIES
As ~idem frum F.q_ (I] -61 ~ dnlitul ~ ~; ~ lbB f~l criterion fm

phase equ:i1ibria 'lb~ is uue m weU ror
~-ma.Gtioo ~ (bria. ltowr\'a~ it e:~tlu"bits
A~ a~tty k ~ .-Jtt.:Eq. ( 11.28) ~,.. - ~~inm 1o JODow m P u~~~DJn.

whmti fu P DD~ h: dim ~ Ttlk E:i..ffialtl) b. umre ~ ~ fl2l. ~~equ~ a.c ~ eDCfJJt il ~:s
~ iJRIII ~ ~ ~ bciblf ~ - ~ ilftl.J ~lift Gibb! ~
- _ ~lO.rG.tim ~ _ mn otprml.ft mdr IQ'I!II'.KIJI oidlt ~ TMUdJ ~ijlrud h
Cb:al.~Of~ .- ~=i~

195
~th which clisco:l.ml~ iU osr. 1k Gtn_ ~ ~ ~JJi ~o is.definedm reb.tian

to tbe ~ em:rgy and entrop). B~ nbst)mtt. values o f intemaJ. energy are IJI.JltnowD.
1bB wnc i5 true fOT ~J.i . MOP:O,w. Eq~ ( 11.29) show tbal f'!g
approad;a oq,h-e i_nlinity
wbm ei~ P (Ji Yi ftP~ zero. 'iflds iR ttue not jnsr ftv an ~ gas bln (or Mf p.
Although these e~i.es do not preelDde abe use of chabieal pobmliab. the app&alioo
of equilibriwo crilaia o, fa_cilitned by ~ of b /fiQf:il}'.' u fPI~ry dllll ~ llle 1
p1a(.-e of JJj but v.tlidl f)ocg not e.tbibil im I desimble cbarac1eris1b.

11m origin of lf5 fupcity ~pt ~ JD Eq. (m t .28). Wjlkl6ft.\,. fot plfe ~liD
tbc ilb.'f-jas~. For a r;ca.1 ftoid, "'-e wrim an mWOf.lXHiteqmuJOO that~ Jj. d~efogaciry
of pure species i ~
Gi - ri (T ) + RT lnji Ol.3)
This. oew ~It}' fi~ wilb unit& ofpRSSotr, ~f.-rs Pia fBq. ( II.28J. ~~Y1 if&{.. 01..21)
t a &peCia1 taSe of Bq. ( I L3 [ ). lbeo~
f/ ; p 01.12)
imdcbe (Qp,cit)' of IX!-P: ~ i ~~ idal ~itS ~SS!Iri)y tqiial to )U ~om. ~DtJ.
c.
of Eq. l1.2B) rmm r
f.q. (I] .31 ), lbolh wlittem for b same and pI gi~ .
G1 - G~ == .RT ttl flp
B:y tilt ~finJtificl ofBq. (6A I.), G~ - c;;s is abe Ma.iduol Glbb.t metD.. G~ : thus,
[or - RT [orJ I UJ .33).
wMt8 the di~~ nWo Ji 1P ~ !Men ,drflllfd ~as~ ,mc.ther lii6W property. d~e /Wgacil)1
t~.. gh-eo by symbol ~i :
=.. = ~ 1
lbese eqoatio.ns app1y to pure spEcies i in any ~ .d any cooditio:a- Htw~t. ~ a ~
cU.34)
case they ~ l1e wlid for ideaJ psa, f'OJ" v.'bldl,Gf = 0. 1/li ! : ~~and f..q. ( LI~ is mcove:.-
from E;q. ( ll.J I).. l\toreorer~ we may write. Eq. 111..33) Cor P' = 0. 100 wmbiDc it vntb
f.q. (6J45)~
As expiDJai in C'O.DIIeClJDu wim Eq. (6.41). dliC value of J i~ in:mlaterial, and is set equ.alro
2.'ei'a ~,.
7 q -t)~ Gillm~-u.JLmlis ( lD~I!HO). Ammlu~c~~~mbo~

oped f.b!: qltl of~~ t'f'QI) mdJ itl.e ~ loi).'tatii.IO,
Obras protegrdas por di1eitos de autc

396
1bc- idm:ditiiMioa II) In~ wdb G~ I RT by E<a~ (1 .33) pcflllin; its CY'"Wu:Jtifln by lbe
imqri!ll of F4 (6.49):
,p diJ
ln c
lo (Z -1)-
p
( LI35)
itllb~ ~u. (and therefore f!upcl.- 1 for ~ ~a~ twtduatw by this equation
f"toro P'' T da~ ocfrom a ""'J~&~tequm.tion ofS\ate.
Fu- exmnp]e. "iM=D lhe ~ fac:tor is~ by Eq. rl.38).
B~j p
Zt _. 1 WI RT
8ccamc the sceond. ririat coe:ffieient .8(~ i fundion of tem,~ mil)! for u pure ~
&obsulwi :ium E.q. ( ll 35) gka
(ama T)
eJ 1.36)
Evalumon of fugaeil)' ~\eint lbmuJb cubic equatioos -or litate (e.g.. lhc \~ del' 'Waab;.
IEtcdll.ichJKWD.Il& SoovcJR.cdljdlfkwoog.. and PenlfRoblnson equ;rlons fo1Jtm,... ~11)' from
oombit&l.rioo of&p. ( I LJl) nod (6.fifib):
l tn~ - Z; -l-Jn .Z~ - , 1) -qi l~ ' u 1..37)
where A ~by Eq. (lSOJ; q; , by Eq. \3.5~ ~ anJ t,, by Eq. (6~65b)~ an \111'ittel'l fot pore
&Jl"~ i (t\lc lbe vaa der vmws aapal!mL Is ~ A/Z~ 1- App1icalioo of F..q. cll .31) at a given
T Wld. P ~ flOOr solurimrJ. of on equaoon Qf bl:e fur Zi by iq. (3.5~) for a ~ ptm5e
~ Eq. (3.56) b a liquid pb:tse:.
'VIIpoi'/I.Jqllld &qulllbrl um to.r ~ure Species

Eqlmti~ ( l J.3 1). wbidl ~ 1M t\apcity or pute ...p~ i ' lila)' be V..nllm for~ i ~
a~ntrattd YapOr ttnd as a Siltl!rntrd Uq-llid m tl: same mmperatme:
(J l..Jib}

397
This cqualioo .~plies to lbe change- of scn:e from YfUJ':ltied liquid 'lo ~ vapor. bolh at
~ T and u lhe. vapor~~ et_ Ac~toEq. 1(6.69'~ q -G~ = 0; t~~:
(l !.39)
hele /, bwliC128
. 1 me
value for eitba' Wutared l:iquld ar B!allll!'amd ~ ~ pbase.s
WJf ~mcd liquid md atunted vapor &K- i:n ~ibriu.m~ Eq. (I~ .J.9) them~ ~ i
1\:mcbmeuul priru:jpie:
For pure PICM coexiattng liquia ~vapor tQIIBJD..
rium when they have the same~ ....-sure, and fupclty. 1
,_....,.in
An illt~ formulation is based oo tile> ~g fupeity OQdficim~
(l~.40)
WMnce. ~f ~tit e. ~~ (U.41)

This~- ~mg ~~y of 'fugactty c:od'ficicrttsr i ,ali tqually ~d cntmQD of VI;.
~ eq.wiThnu:m,ror pure specie&.
F--vgsclfy of a Puffl' Uquld

llJei upclty of pure species t as a~ liquid may cal~ from,me prodUct of etiiiy
evaluated r-~:
(A ) h!) ~Cl
A_tl t----~
,.__ ......... __ .a
- ... - the - ~ U~~
~UJM;U!;M4~ =--
-# ,db.;;.~.._
Mit de~ pnxt~ a malhemmicall id.'entitJ~

~t"
~wn . . '
~ .~ ==:.lari"'-
!!_II;!~~ ~ ......
w ~'f~ ~~!l '!JI!- iJI
RJitio ~cA,, ~ tbc vapor~ fugaci1y codticlen' of p~ Vlpllf l at ill. ~uid s:atg..
nulQd p-essu:re. dt:si.gua.1td 4-rBi}J. 11 . gjYen by Eq. (ll.lS), wriUCL
:to ~4 = L; cz; ~ n
pqt
4
: (eoost T) u 1.42)
In ~~ with Eq. ('I L39) ratio (fJ) ~ wrll:y. Ratio (C) Mllcds dE elfed of pa5UK on dle
fng-utily mpue liquid i. The lb nil (Of im c;~ti(m i!. &:t- (6-10), ~~ 1~1 T lO
tn..e S'Oid~ty r,. based tllll ~ Larla faOl ~1~ 11 10- . . ~ i!BJtl ~~ tor~ ~fagim--... ~
ft:Jp.ily hti ~ ~ 10 nv.m ~ :f}' ~ tM ~~ ~.d. (bt ~ lWO w-
-ih'lhcr .-c ill equili

398
Anoc:tw:re:q:tlfe.ssioo.for rdtit ~ re!iQ115 "bm Eci- Ul.31) is writtm for both Gr and G i ~
wharaction eben yieldS:
G:: - GI
I
= fi
RT In !J~
1IK1 tmJ ~QIIS for 0; - (J1 ~ se1 eqiW~
~
ln It -.............
~- RT If
1,. V/ dP
J!(P) .... , .....!._ ,(~" v.' dP

Jlf~1 ) up RT }p l
Ut4l)
8ec:anse v{ .. the liquid-phase mom YO!InrQe~ Is ~ \-ety \\leak fu~ioOJ af .P at~~ weU
l>elow J;,.. M ~~ ~iml is o(kn obtlitltd wb.p V/ ~ eoo5taD1 a1 tbe n
~ or~ liquid. fn lhis case.
( 11.44)
The~is known as a~ fa::mr. Dlt.ii1 ~for applicarioo of am ~(I~
Values of Zf f calculatioo of fl,sa by Eq. ~ ~ 1.42). "Jbosc may come fmm an equmoo
of~~~ from ex'pet'ilrient. or from a~ crelaiion.
The liq~ mobr vdumc 11{ IJSUally me wluc fer s:.tturated liquid.
1
- A~for'Pt. .
(11.4S)
Ja ~ follcwing ~e data fmm the~ lab1cs fUiiiD 1he bam for calculation of tire
ftatlleity and f~ ~~u of '!Jodi \upot Ufid liqnidl WMcrr as ~ .fun(.'tion or pt-t's.:W.m_

Example 111.5
f,or litO at a t~m or 3QOOC and a pressures up to 10J)OO kPa ~(100 bar)
carcwate values of J. and q,. from data ~n the &team tables and plofl them vs .P.
Solution 11.5
Bqu.ation {11.31) is wri.nm m.wi~ 6~ for a smt- at ~ P; ~ fot a
lowpressure refereJ!Jce swe.. denored " ' 1 both fm tempe~ f:
G, t:!l f"t(T ) -:- RT ln}J wld a:~ r"l (T)+ RT lo f:
Subtrlicti<U~ d!Jminms. r,(n. and yidds:
J, 1 '
In f!;;; Itt (0~ -- o:'l
By fkftoilion Ga === ffi - TS; ~ G; = lli ..... T Sf; ~t.Vaion ji\~

fn _h D ~ [Hi ~ y i ~ (Sj ~ s; )]- (AJ
r, R T
1bc 16'\r'CSI pres~tn for "'1JidJ dati at J.OI:rC .are given io ~ sceam tab:tes ~
l ~ s.tam at ~ oooditions is I"CJ prneti~ ~ tm ~ ~tot wbicll
fi 1:2: p m ] lkP-a. Data for this. !t'3re provide. me foJLmvil'lg ~ ~
n, :; ; 3,016-i J , ...1 s; ; 1O.J4SO J 1 - 1 K..
Eq0300n (A) ll'laY oow be appfied to mtreS of superbealed S(e.am at for :ore
\wious \~ues of P from J klPa to die saturmon [piCWII'e .o f 8.591.7 tPa. Fer
exampclc. ~ P = 4,COO kPiJ ~ l()WC~
II; ~ ~0 J Ll- ~ Si =6.3642 J ~- ~ x:-
YaJu~ of H md S ll:lalit be multipfied b. the IIJOlu~ mwat08.01S) to Pld
mem oo a IIJ()Jm' him~ fix' !lubstiwtruli mw Eq. (A}:
In 4f ,:7 HUJI5 [2362-0 - 3:076.8 -

8.3~4 573. 15
(~3642 ~ 10.3450)] . 1911
WberJce. h i/.-- J.6J 1.0

~ ::o (J.6lJ.Ol<r) c (3.611.0)( 1 th} Q J,611.UkP.l
Thw the r0igity ~delll m. 4.001 kPa. ~ :
fl, 'C f.! :::::~ ~ . 61 LO :::::! 0.9t'P..8

p 4.000
Similar C1ll:nlmions ;at Olhw ~ le_ad to die w.loes ploded in fig,. l l..J 11
~ l.lP tD diG ~ioo ~ Pi"* .:: 8J92..1 t'Pa, AJ, this~
q,,:w. :: 0.7843 and /,w : 6,738.9 ~

alAPfHit II. Solutioo ThemtodyDalfli : 1'lletBy
llpn U.J: Fup:ity

f UJp~~Cil'I
ooefflcm of f.1ram .at
c.
/' X 10~';
Aaording to Eqs. { 11..39} and ( ~ J..41 ), the :saruratian ..,-aJues are u:nchanged by
mlllfens.atlon. Allboogb ib:- plots ~ lherefore c:onti:nUQU$, lbey dD ~ discggJi-
nuities in slope. Values off; mel for liquid ~at hi.gbu ~are foond
by a~:ioatioo or Eq. (11M}. wilb. vf
CQU&I tu lhe molar \nlumc of ~
liquid v-111er 300 C:
v: = (L403)(18.01S) = 2S.2S m.3 moJ - 1
AI 10.{)00 kPa, ftw~k. Eql ( 11.44) ~
- . . - (2S.2ti)(l 0 000 - li~ 1) - 139 8 I..D...

/; - (Q7843-"8592.7)Clp (S.3I 4 J(S7J.I5~ - 6~ ...ns
1k fotl~J(tty cnd'ficic:ul vf liqWd wan:r dJc5e eooditiP i41l:
~ ==== fi/ P ~ 6.789.8/10.000 ~ 0.6790

1
Sod) caL ulaiJi.o(lj allow cumplelio:n of Fig. ~ ~ .l~ where l.br solid lines ~ bow
Jj ~ vary ~lb~

The~ for /i tarts at the eri~ and deviu=s ~)y from die d:aSbed
f!
liJJc; for 111 i~ PiS (/ ; ;;; P ) as tbe ~rises. At 5& ttbae is a discontinuity
in dope. and l!:te L'U:tVC-lben t bc$ ''~ skJW!y wilh i~n.s p-t'!SSWf.. indical-
ing that~ fugacity of liquid ~terM :'iWC ~a w.~ rwxrum of~ Tills.
btba\iQf i ~c of liqlilid&m tempcratur~ wat below tbe ailkal temper..
atme. 1'ilie fo~ty rJcCfu.::ic-.ot , ~ steadily flozn 11;.$. l~~ va.h1e
of unity as abe ])RSSIDe rises. Its rapid decrease m 11m liquid region is a ~
qtleDC of the .mn'-ctmsttmcy (If '~ fog_BI;ity i~'lf.
11 ~6 FUGACITY AND FUGACITY COEFFIOIENT:

SPECIES IN SOLUTION
'The .:kfiiLidQD ~f 'tbf; fu~ily of a ~es iD so11J.lim is parallel to the ddirnition of die pu:e
species fu~. Fol- .sptdes i in a mixtaK ofreal pscs min a so1ntiQp qf Jiqujd$. ~be! oqnali<Jn
a_n;a1ogous to Eq. ( l ~ .29)~ tbe ~g.l& ~on. tis.:
( LL.46)
whe-n= is~ fugacity of ;pedes I msolution.. rep~ ~be p:mial presmre )i;P. 1bis
j.
delinitioo of fi cloe5 :oot make it a putial molar property~ and it is rtDe:refore itrelllilied by a
cirotlmfldt rlltlter 1 tr.'m by au 0\tr:.rhalr.
A ~ applicaliun of diis definition indk~ itt potcntW ulilit)'. Squa_lioo ( t] .6) is the
~ rcrlrMOD fOT~~ri~ ~$e aJJ ~ tin eq~u:m :GJeat ~ ~
tWI~ an t\llemat:h'e mxl eqoaiiy genernl crtterioo foH\lw-s i.Jnmedimely froorl: Eq~ ( ~ 1.46)~
! -
G =i;
jj h
= ":; JJ
]I
1 (i ; ~~ 2 .... . Nl (] l.41 J
Thus, ~ phlllles ia l the &aiM ., l llld pare in equilibrium vmen

thefugacity ot each oonatltuenl speeie11 the same lln all phases.
This ai.kWm of equilibrium iF; lhe ~ mlWII[y np:pJ~ by cl&-mioa[ re ngll'lrtn in the sollllionr
of p'basc--equilibrtum problems.
For the~ case of multi~ vaporlliquid eqWIThrium. Eq. ( ll.41} becomes:
(fa L~ ..... NJ
Equation (1 1.39) remits as a special ca0e when tim relaf.ioo i:i 3fJplied to the \~
equllibritnn ofpun spair:s i .
~ &mntiDR of a Jaidm!J ~ Is gil.'erJ in ~. 6.1!
~6.41)

Where /.1 ls UJe JOOW (Of IL1Dlt~S) ..-atoo of a d.mnodyoomic property .m d .J1 f. U the value
hal ~ Pf(IIJCll1 would ~-e rot an idclilJ ;u.s of the same c-omposititl!l at abe: $WJ1e T and P. The
defining eqooOOn for a~ rtt:rii!JilJI pm~lf}' .M.f follows 6om llh:is equation.. Multiplied by
n mol or mixlllfe,lt bcooo1es:
(11.49)
Bceause msidutd proputie.~ ~ deplll1l~ rom ideaJ...ps vain~ lMJ:r ~ JqgicaJ u.~ is
gns-phasc ~but in fact rhey ulso find nse M liquid-phase~-
Written for lbe usidna1 ,Gibbs e;oergy. Eq. ( I J.49) lbeco.mcs:
IGf = (;, - c:zI (l LSO)
an. equ4tion wbidb defines the lHHfilll' nrrid~ Gibln ~rv-

Subm!ding f4 (L 1.29) from f.q. {1 1.46).. both written for lbe 15811le f iUid P.. yields:
!Ul- ~~~ = ItT ll!l l ';P

l.
A_
0 ]..51)
~ ft
,::: - _ (11.52)
,P
1k di~4Sioo1~ mo ~~ li ~1100. lbe~il}, ~ofsrp:ecin i itt ~ AJthOU&h

mos1 commonly applied lOg~ the fugacity coeffid_eor may abo be used for liquids, and iD
lh.ml ~lOOt~ fractW Yi i.s rqP]~ lit} ~i l.lecau5o f.Q.. !(~ ~.29) fur .m i~ p a ~Uti
case of the Bq. (11 ..:16), there
1~'-
i ....,... Tr p ('11.$3)

The~ lltlsidUtJI~ IIBhlthm
Tbe fumbmemal ~ reJafiM ,given b)' Eq. ( ll2J t$ pm imo an alltmah'"ve ronm lt.roogb
1be malhemabeall idemity (ab~ us.ed in s~ 6,1):
tJG) I 1tG
f.t ( RT 9 HJ(It61 ,.... ;rr:dT
b lhi& equatioo J(n G) 15 cfim1DMC1 bl)' Eq. ( ll.2J mdl G ~ lq)la!lat by i'~ dcfifiillmt. .fl - T S.
1l:w: ~ aftu dgdxaic reducflOO. ~:-
(11..54)
(U.5S)
~ (11..55) is the /~JJi!ff141 ~'dwl~rty rdtBion. lb dah'ltlon from Eq.. (JJ 1.2)
~k ltre: d~riWllimi in. Ch:tp.. 61hm ~ rum l3q. (6..10) ID Eq. (6-..42)- Indeed, ~ t6~ 10) and
(6.42) ilre specia.ll ,~ of ~ ( l I.l) BQd t ll.5S}, \'.td!id :fur l fQOl of:. ~Jt--eompo5ili(li[IJ
ft'uicl. An alternati\-~ form of Eq. (1 J..5:5) follo by i.nltodll~ of IH fug.ac!JY ,~mt as
~'~ tiJy Eq. ,(I 1.51 ):
(11.56)
EquatiQD ~~ poernll as ~~ ( II.SSJ and (] 1.56 are useful for pndi&al awJicatioo
Old) i_n reitridedl fottM. Dh!Uion G1 Bq~ (II.SS) IUld (11-S61:, first. by d 'P wiih ~ttiorn~ ro
cw:JStan.t T and om..-position. and seo:Jod, by dT aDd ms1rictkm to~ cmswu: P and cmnpositim1
lt'mh m~

(I LS8)
~ ~ns-.. msia~Dl$ at eqs. (6.43)1andi(6A4)whcmn 1tbe restriclioo oflhe deriw

'bws m ~ compofitioo is d\\fft ~ They Wd to 13q (6.46}, (6~48). and (6.49)
.fur dJe tal~lalioD of rmdual JP!Ope:rtits tom ._~ data. Mmeo~ l!q'" ( 11.57) is lbe
b3;sis ror me dimct daivaakm of Eq.. ( ll.3Sl.. ~yield$ :~ty codfici~ Cmm 'w"'Oiwnd
ric data lt . tb.roogh ihe residwd f.*VptJilia that dM ~Jid of a.pemnentnl inf~mll emen
~Dro, me~~ .pp3Dtiwl wthc1111DdJD~.
1m udditinn,. from 54- (ll-'6)t
( l1.59)
bample11.6
Devetop a ganend equation to calcu1ata ln~ values frDrn compressibJdyfaaor data.
SOIUiioft 11...6
Ftx A mol oi amsl1ml-mmpositirm mixture~ Bq.. (6..49) ~~
nG
~
1
IZ
1~ (n Z ~ A -
dP
RT o P
m~ wit.h &l (11.59) r:bi cqwttion may be differe~ witb Jielipect ItO ltj
COIISlam T. P. md nJ to yield.:
1111 ~:!!!!!: ( :r Z -11)]

[OC dP
Jo &IIi P. f.N J I
lkause tf(nZ)j &nr ;;;; i~ and lltt/ &1, - :1. this reduces ro:
IDJ. "'ftz. -I)~ ( I J.60)
wbeJJre inlegndioo lJ 81COfl!iiBN tem~ and CQ:mpmilfoQ. 1"bU )Wl,tic)~ ~ d)t

~ ~ Qf lBq. (~~iS). It alkJ,e the Cllco'~un of~ wlucs from
1' \' T dalft.

11.6. Fugacity and Fugacity Coefficient: Species in Solution 405
Fugac ity Coefficients from the Virial Equation of State

Values of; for species i in solution are readily found from equation s of state. The simplest
form of the vi rial equation provides a useful example. Written for a gas mixture it is exactly
the same as for a pure species:
BP (3.38)
Z=l+-
RT
The mixtu re second virial coefficie nt 8 is a function of temperat ure and composi tion. Ills exact
composition depende nce is given by statistica l mechanics, and this makes the viria l equation
preemine nt among equation s of s tate where it is applicable, i.e., to gases at low to moderate
pressures. The equation giving this composi tion depende nce is:
B = b b YOjBiJ ( 11.61)
j
where y represents mole fractions in a gas mixture. The ind ices i and j identify species,
and both run over all species present in the mixture. The virial coefficie nt Bij characte rizes
a bimolecu lar interactio n between molecule i and molecule j, and therefore BiJ = 8 ji . The
summati ons account for all pos ible bimolecu lar interactions.
For a binary mixture i = 1, 2 and j = 1, 2; the expansion of Eq. ( I 1.61) then gives:
B = Yl Yl 811 + Yl }2 8 12 + Y2Y I 821 + Y2.\'2 8 22

or B = Yf 8ll + 2Y 1Y2 B12 + y~ 822 ( I 1.62)
Two types of virial coefficients have appeared: 8 11 and Bn, for which the successi ve sub-
scripts are the same, and 8 12, ror which the two subscripts are different. The fi rst type is a
pure-spe cies virial coefficient; the second is a mixture property, known as a cross coefficient.
Both are function s of temperat ure onl y. Expressi ons such as Eqs. ( 11 .61) and ( 11.62) relate
mixture coefficients to pure-spe cies and cross coefficients. They are called mixing rules.
Equation ( 11.62) allows derivatio n of expressi ons for In 1 and ln 2 for a binary gas
mixture that obeys Eq. (3.38). Written for n mol of gas mixture, it becomes:
nBP
nZ=n +--
RT
Differen tiation with respect ton 1 gives:
;:; [a(nZ)J
z, = . = 1+P-
[8(nB)J
an I P. T.ll?_ RT di1J T./11
Substitu tion for Z1 in Eq. (11.60) yield :
In 1 = _l_ { P [ 8(nB) ] dP = ~ [ 8(nB)]

RT lo an) T./1?_ RT d/1) T./12
where the integration is elementary, because B is not a f unction of pressure. A ll that remains
is evaluation of the derivative.
406 CHAPTER 11. Solution Thermodynamics: Theory
Equation (1 1.62) for the second virial coefficient may be written:
B = Yl (1- Y2)B 11 + 2Y1Y2B12 + Y20- Y1) B22

= Yl Bll - Y1Y2 B11 + 2y1y2B12 + Y2 B22- Yl Y2 B22
or
Multiplying by n and substituting Yi = ni In gives,
By differentiation:
~ p 2
Therefore, ln</>1 = RT ( B11 + y2 8 12) (11.63a)
~ p 2
Similarly, ln 2 = RT (B22 + y 1012) (1 1.63b)
Equations (11.63) are readily extended for application to multicomponent gas mixtures; the
general equation is : 10 ,
(11.64)
where the dummy indices i and j run over all species, and
with on = 0, Okk = 0, etc., and
Example 11 .7
Determine the fugacity coefficients as given by Eqs. (1 1.63) for nitrogen and methane
in a N2 (1)/CH4 (2) mixture at 200 K and 30 bar if the mixture contains 40 mol-% N2 .
Experimental virial-coefficient data are as follows:
B 11 = -35.2 B22 = -105.0 B12 = -59.8 cm3 mol- 1
IOH. C. Van Ness and M. M. Abbott, Classical Thermodynamics of Nonelectrolyre Solutions: With Applicarions to
Phase Equilibria, pp. 135- 140, McGraw-Hill, New York, 1982.
SOlution 11.7
By dt'linilioo., ~n ~ 2Bat- Du -= Bn . ~~
~h! =2(-59.8) + 3S.2 + 105.0 ~ 20.6 m:fi mfJ'l- 1

Substitution of ~lk.ul 'Wlles iJlJ IEqs. ( 1 .6-ll yiclcls~
.. 30' . -
lo1 = (8l. l4'> (lOO) [ - 35.2 +(0~6~(20.6)] -~ -OJ).SOJ
ln~l = (8.3.~:(200) [-lOS. + (0.4),1(20.6)] == ...OJ S
~ ~:(t95LL md ~=OJOU
No[e lbru: l.be s.ecood 'firtal CMfftcieru of lbe milrure asp~ by Eq. (11.61}
ifl 8 ~ - 72.14 an' mol-1 IDd thiit s-obstitutim in Eq. (3.38)1yields a ~
~ity f~ z = 0.870.
11.7 rGENEAAUZED CORRELAnONS FOR THE

FUGACITY COEFFiaENT
The senr.mJi~ lllelhock de\<daptd mSec. 3J6 f.or lhr ~iliiJ fimtnr Z and mStc.. 6.7
for lhe ~ embalp)' 1Uid enuupy of pure pses are applied belre lo the fugacity ,coefficimt.
~ (llr3S)'li put iDJn ~ud foon by ~fl!1iou o(lhe rel~
( U .M)
0t66)
Pr dP.
lo
<z0-u~
P,

408 CHAPTER 11. Solution Thermodynamics: Theo1y
The integrals in these equations may be evaluated numerically or graphically for various values
ofT,. and P,. from the data for z 0 and Z 1 given in Tables E.l through E.4 (App. E). A nother
method, and the one adopted by Lee and Kesler to extend their correlation to fugacity coeffi-
cients, is based on an equati9n of state.
Equation ( 11.66) may also be written,
( 11.67)
and we have the option of providing correlations for 4> 0 and 1 rather than for their logarithms.
This is the choice made here, and Tables E.l3 through E.16 present values for these quan-
tities as derived from the Lee/Kesler correlation as functions of Tr and P,. , thus providing a
0
three-parameter generalized correlation for fugacity coefficients. Tables E. l 3 and E.15 for 4>
can be used alone as a two-parameter correlati on which does not incorporate the refinement
introduced by the acentric factor.
Example 11.8
Estimate from Eq. (11 .67) a value for the fugacity of 1-butene vapor at 200C and
70 bar.
Solution 11.8
'
These are the same conditions given in Example 6.9:
T,. = 1.127 P,. = 1.73 1 w = 0.191
By interpolation in Tables E.15 and E. I6 at these conditions,
4> 0 = 0.627 and 4> 1 = 1.096
Eq uation ( J 1.67) then gives:
4> = (0.627)( 1.096) 0 191 = 0.638

and f = P = (0 .638)(70) = 44.7 bar
A useful generalized correlation for In 4> results when the simplest form of the virial
equation is valid. Equations (3.61) and (3.63) combine to give:
Z- 1 = P,. (B 0 + wB 1)
~
Substitution in Eq. ( 11.65) and integration yield:

409'
or (U.68)
This equation. used mooojuncrloo wiiJh IEqs.. (J.M) and (}.(!6), provides reliable \:l[ues of '
for any flOOPOltU" Ql' slighdy polar gas wbc:D applied m eonditiom wllere Z is. appro~:eJy
linear in~~. FiJQJe 3.1-t ~n SU\~ as a guide to its wtabt'1ity,
~ hmctioo.s.. HRB{TI\PR.OMEGA) :md SRB{IrR,PR,O.MEGA},. for emll:ltioo
of HRt RTc ~ S"IR by~ gmcmdii:ed virw~cw~nt ~orre1miOD \\.~~bed m
Sec. 6.1. Sirmilarty. ~'e im~ here a f~QD ~ PHfB{TA.P~OMEGA~ f eval~
u:ttion of~:
1P = PH19(TA,PR.OMEGA)
[I combine:s 4 t 11.68.. wim ~ 0 J65) arul 1(3.66t as lodiealdm dJC ~tdi\ ~
~ ~'Q mJ\pp. I)_ for eumpie. fb: \~ Gf ~fur J..butDe \!tip(lr at tbe oonditions Gf
Eum~ 6.9, Step (b} ~:
PHrB(0.650"0.0316.0.191) = 0.956
ne ~ ~Oii ju 1 daaibed . for pure~ only. The remainder of~ seaian

shDw:s bow rtlte \l'irial ~M mll)' be~ tr> all~ eakulntion ol fupeb.y ~
~ for .&pedes In ps mix~
The geamj, ~ foe Glk.DJ.atioo of [In .. . rrom seconfl.viriaJ..~ciau dam u
.g iwn by Eq. 0 1.64). 'Value!~ii of tbe p~cs ViiriaJ coefficia& Bu. BJ ete... a:.re fOund
Imm dlt gmrrdlized oont-latlllll ~ed by ~ (3.62). (3.63). (1.65). 8!1d (3.66)~ 1'he
cross Coefliciem. Btt. ~ Bf i , m~ ttre foe~ &oro .an ext~t of tilt ~ eC1~oo. Foc Lbi&
~ F.q. {3.6J)1i:s rewrineo in the more general fMD:m
{ll.69a)
where BiJ lljjP~j ~H.69b)

R7dJ
md 8 and B [ UJ"t the ~me fll.k()Qt km of Tr as Ji,-en by Eq"- (3.65) and (3.66). Th~Z combinL,n.g
llllles proposed by Prrulmiu: et .t i. for ea.Ladadoo of fDIJ Tr:;;. ll11d P.a1 we:
(1 LJ'3)
IIJ. M_ .f"'tlii!Sib{l_fR_ ~ ~Tb,. m:d 1i. Q _ ~ Azn~ Mdf!Dl/tu ~of Fh{i:d l'fm.l'Jf Eqmtfb.
,g 11.1~ pp. 1)2' A1 161.. t~. En~ ~ Nt 1986.

4U)
u i.74 )
In ~ (J 1..71 ~~. kiJ i& m empirical~ parame ~specific wan i-J moleailm pait.
'Wbtrm t =: j ~~ fJOr e~f s niDar ~ JiJ ~ 0. ~~" it ma smO pwith-e
onm'brlr ~alu3ted frou1 rni.n_ilnal P 'V T dam ,or in die ~~ of darili set tquel to Wl). Wbm
i = j .. aft equations redlu:e. to die appropriate '~ ftr a pure specl~ WbeD I j ~ l~
eq~ dfinc iii 5d of rinlactio ~fal havinR oo ~ 5lgnificanee. RedliiCed
~~ is, gil~ for eacb I} pair by T,;J i i T/ TdJ- For a mixnireFwa.IOS of llJj from
Eq. (11..69b) substituted mm tiq. (1 t .6~} yie1d the mixlm'e seamd virial coe1ftcim~ B. and
' bsrltll!cd iD1o lEq. (1 1.64) ~ (J 1~63) rur "'
a biDIJ,yl they .ridd Yllha of ln fli ~
~ pftllliif}l' virtlle. or~ gali:l"~ ~lalioll fBr ~ ylria] '"~m~w ~ntal
!be~ ~licity; ~ ~IP1ll~ bi.Jt mo~ oompfcx. CIJIICbd.ivm ~~ iD itbo lituatw'e. 12
Example 1 1.9 1
Eslfmate ~1 and ~ by Eq,s. 1{11.i)1for ,an equlmolar m.-.um of methyt erhyt ~

lrln8(1)J!*IIn8(2) at !W-.C and 2S kP& Set all~, :: o_
SGIUtlan 111.9
~ requiml ~mew;. foUuwtL
ij TnJfK Pr!i.JI'Ur
H SlS..S 4~.S 1.61. 0249 0.323

22 S9Ml 4LJ 3Ui 0.264 0.262
ll 563~0 --11 _3, 29l. 0.156 0 .29]
w~ value: mu.: Last mw bave "'beeo caltlllar;ed by Btf ([ ~ .10) ~ (I l .74)_

1'lle ~of TrlJ ID~ wilh fiJ ~ 8 1 and Bjj ~ fw each ij pair by
E!qs. 0-65l~ (3 .66) and {I1-69 are as follow -
fj TrtJ afi B~ Bulcml mol.... 1

u OliOJ .....o.8td -1..300
22
~2
0.546
0514
- IJOOi --2.04S
om0.9'4] -1.631.
........
- 1JI7.
- l !iU.
_
l:'lc_ 1\0nv'91" AI{:~ 1.. wl zn pp. :!61-TT.t. 1914~ 1lllt. ~I. iPP- ~7-82'9. 19?'5. flll_ ~ pp. I I ~ 1 liiS.
1971.: C. ~ Nh. lit ~ ~s 1~- pp. 1-D-61. 197'9: J. G. llhy~1 Iliad J. P. O'Coaned.
llJd. nj. OVJn. ~.DA ~ ,.._ 14. pp ~~6w 1915>0'. W. MrCaooad !It 1~ ~Ibid. _ '\_<l.lll2:3~ pp. n.9-
Sll., ISIIW~.I. A"" ~ 'l!ld ~ fl. ~.'JCitB./.. 'd. .. W -Ill , 19S9.

411
CPIC\IIa.tins &n ~rdi:IJ810 iU~ rd di J1itiw gh"C$:

&u c: 2Bt~ - B 11 - Bn !:: (2)( -1,6ll ) + l );lll + ~~860 =lS an~ mo~-1
E.qumons ~ ~ 1.63) theo yield:
p " 2S a:
ln.9J == BT (Bu + >1&~z) = 4
(SJ.I HJ2JJS) [~ I .38'7 +(0.S) <1SU = ~0~012~
.. p ., 25 ....,..}
IJ'l~ ~ RT
(fh2 + ))8u) :;; (8.r314Hl23'.S>~~ t!60 + (O.~r{1Sn = ~CUl112
a a
~ ~l :=l 0.987 aodl ~ ~ 0.983

~ treml'ti are-rep:resemarlve of wlues o'bmiruxt for vap:Jr phases at. typical corr
ditioits .of low~rc \~ Ql)lili.briUJB..
11.8 liHE IDEAL~LunON MODEL
The ~mica! potrmial M sim:. by me ldml-c mWrJ:m modtL

#f,:J =r{;~ - a~~(T. P ) + RT ~o Jf~ (11.24)
oootai.M a final ram liw gives it ~ :Wnples~ possible cotttpoSilim depen~ indeed. one
tMt oouk!l reasouabl}~ servo for ~ gMiGS a:odl liquids.. Howr:~-a. 1he- pu.rc--t~pe~e5> btbavior
implied by the lerm <f,8 CT. P ) . ~ ~ fur ide.ai gases., A nablral ~on of
o:
!Eq. ( l1 .2~), thad'c:R ~ 1 (T, P') by Gj ( T, P), the Gibbs tneqy of~ i in its ~e~~l
physit:t~J SiaM of~ iiqrrid. rCII' evt"D solid. Thu.s,. We drfiar; an itlml solution M ~fur wbi.eb.J
wbare. supersaipl id dieoDtes an Mlealsotution property. Mole fractico is b:re ~ by

:1i lo rdl~ tlw ~ that appti~tion b. mos~ oftm 10 liq~Dch.. lfuw~ 1 Q;JID_~~m:e of this
definirioor is lbaa an i:deal-p atixro~ l$ a spa:lal. <a~ namely,. an idl:a1 ~'Olufum of Edle;d pses,
for 'W'bid:u:., iD 2q, ( U .75) is lq)J.eed by ~.
AU other thamod~ properties for. .n idcd ol~ follow fium Eq. ( ll .15). 'J.bc
partia1 vdlmne resubs from cfi:fram'WIIion wirll respect to p:ssnre at eOilSUIIt tempemrme' md
m
fXllupu:sJ."lkm aaxJid with Eq. ~I J.18)!
y.id
t
~ (!S::)
aP
r~
= (!!.) .,
&P .
By Bq. ( II ,4,, (9G / oP)r c ~: wbe111.1e.
Iv~ I = Vr
412 CHAPTER 11. Solution The1modynwnics: Theo1y
Similarly, as a result of Eq. ( 11. 19),
By Eq. ( 11.5), I s;d = S; - R In x; I (1 1.77)
Because fi}" = G}d +..T S~d, substitutions by Eqs. ( 11.75) and (11.77) yield:
or (11.78)
The summability relation, Eq. (1 1.11 ), applied to the special case of an ideal solution, is
written:
Appl ication to Eqs. ( 11.75) through ( J 1.78) yields:
I
cid = ~ x;G; + RT ~X; lnx; ( 11.79) Sid= ~ x;S;- R ~ X; ln x; ( 11.80)
J
( 11.81 ) I Hid= 'L, x;H; ( 11.82)
If in Example 11.3 the solution formed by mixing methanol( I) and water(2) were a -
sumed ideal, the final volume would be given by Eq. (1 1.81), and the V-vs.-x1 relation would
be a straight line connecting the pure-species volumes, V2 at x 1 = 0 with V1 at x 1 = 1. For the
specifi c calculation at x1 = 0.3, use of V1 and V2 in place of partial volumes yields:
V{ = 983 V2 = 1,017 cm
3
Both values are about 3.4% low.
The Lewis/Randall Rule

The composition dependence of the fugacity of a species in an ideal solution is particular~_
simple. Recall Eqs. ( 11.46) and (1 1.31 ):
)L; =r; (T) + RT ln .fj "

( 11.46) I G; = r ;(T) + RT ]n /; (11.31)
413
For tbt s~~d ~of an ~ soluon.

~~., =s~<~ ;::: G r 1- R'l rncf,411fi l
C,ompllris~m w~tb !Eq. 0 I .15) gh.rcs:
(] LSJ)
This eqw'IW:n, b'iQ\IIlQ ~ rhc: ~i'f/Rurrd411 r#/~4 upptit;~! 10 eaeb ~~ man ~ttal sobnion
at all ccmditioru of~.. preswre. 1iDd compootiml. II st.ruws. dw ~ fupclty of each
s:pec1es in .an ideal~ solution ils p.nlportianal 10 its mole {mr:tian; 1he pmportioo:llity ecmst=rnt is
W~ fugacity ofpll~ SJX!cics i in Jtlhe: same Pb)'sic.aJ state iS tbe solubon aDd at cbe same T and P.
!DLvi!dol!l o:f ~~des nffq, (U.S:l}'by P~; ut~.d $Pbstiwti(ln(lf ~!l't fc.ll" f/d /Xi 'P [Eq1(1 t .Sl)J
and of f{J~ for /riP [i.Eq. (I ~.34)] gives an a.ltenmtive toMb
Thus~ fu8-aciry co.emdent of s-pecies i i.n.ao, ideal solution ~~ tqcud i.O the ifog-.wiry c~n.t
of puw ~peoies J in the s:a.me. phytiical .state as. the roluoon and .a abe same T and P. Because
Ruult's l::lw is bwd em die assumpllion mid'aihsolutinn ~ far tbc ligoid ~ 'rhe
same s.~[etns trhat obe) Ral)lJJ:t'&Jaw far.m mtlgi.d solmi-QM. Reoon that p~ comprht::d ~f 1iq~
w~ w~Jos,c; molccu'l~ ~ Qf mm~ar me and which~ of imi1ar ehe~ 03lU:II'e appro~
ijdeW wlu1.io:rua. ~ui"CS of ~~Denj cl~ly Cf..lllfCJDIJ to 1dle'se condtirio~ Mbturcs of IK{jPCc:nt
me~ ot bomwogow series are also 'examples.
11..9 EXCESS PRO~EATIES
The mid\1$3 Gi\lb$ 'One.ti&Y and.~ :fa;l:.leiY coo "'mot ~~R~- discll)' ~dated w ~~mtl
PVT data by Eq5. (6.49), (1L35). and. (11.00). WheT suCh._~ be aquatdy ~
J:at~ by oqullliom of state. tibmnodynamic-pmpen.y infot:11Wi<m Is advantageoosily pn~ded
rtly :rei2dwl ~ Indeed if w nvcnimt rrc.Mmm:i of all 1ft~ 'by lllia0$ Qf ~ggofi:S
of sg,~ -wr~ p)S5ttld~ me lhsniwd)'i!Wiiie--pro~ RllliiOOJ B&Gady !(Rseumd. woofd.~
How~ver. 1Jqul4 solucJo.ns ,are ofle'll mare e3.~y de-alt wilb 'tlu'oogb properties 1lhat me.aw~
~eir depm_ma. 1101 :from ideal-p ~vi. but ftom ldeai<sotmion iwhavloc nms lbe lmlh-
m~ f'Ofmtl___lism ,n f ut:ea iPfo.~~ ii M31os.vuli ro uwt of tm m;ld"al p~.
1f M represents 'lhe moW' ('o r u-lllt-mass) \'lllu.e ,Gf any enen$h'e ~ody-namk ~)'
(e.g., v? U. H. S. G. etc.). then ;m excess prope-rty M" is deilDe4 u abe di1iere:nce bet\\.-=o
~e oorwd :~ii1Y value o f 11 SO:Iuliuo iDd the. villlle: il would ~ 11:$ an ideal ~lnti<m: a:. tbe
same ~per;Hm"e. p.ressme, arul cornp.osmoo. Tht:ts.
Obras protegidas por direitos de autor

u:e =u - g l4
GE c HE - TsJ!
wMcb fo1lw ffom Eq. (11.~ ~ ~ '(6.3}. t~Je deiillition. at G.
'Ole demruion of M1t j~ anal~ to~ dtOnilinn of a residual ~Y :as giveo by
16q. (6..41). :Indeed. uce.s -propmies bae a simple mlmioo to resido.a:ll propenit&. ftru:md by
w~s: .Bqj, '( 6.4 J) trrom Sq. ( ltl.SSF,
M. - JIR = -'(MJ~ - Mt~ )

As alrtldy Mtcd. m idoal"Cps 1 llimn i1i an msOJl .w.lutian ot i~ ~ses. Equan:oos (1 :~ .79)
!hmug.b (1 1.82) 1hemfOR bec'ame exp~tiilm.\ for M"' whe-e Mt l~t re~-ed by .,wfB. Equa,.
oou (U .81) ta.w:Jla Eq. (U.25), IEq. 01 ;80) ~ Eq. (11.26). tu.d !Bq. (U .19) ba.'ltrmes
l!q>(J 1.:27). Tbe t[Wiil se1S ofeq~DM. for M 1d 4}rul Mi.~, the~ pP'kle ~ g~n.md million
fW"ilbl:~
~~ - M11 ~ 'E x,M~ - lJ .X! M: ~ :E XJ J:t,''
~ I .f
vlhmin :fbr. ~ terms with logarithms ~l'l canc~:ood this kads ~let, ro:
~~e = M'R - 1: ~ M," (1 J1.81)

Note dJat ex~ pfi"Opttics htwe no- ml!aning fur pme spcei~;S. w~ esiduill properties exlsm
fnrpore species .as wdl as, for~
1&e pmialepropa.lt)' relatio-n an:alo;oos ID Bq;. (ll.49} .is:
(] L&8)
\\~ Mf is a parttal GeeS'S propertY. Tbe 111'1damellW ~~-,pMpetl)' relatio.n is de:ri\etl

i~ ~4111..0 ~ w.q ~die fvnd.Mli:11Uil ~~~Y ndai.Wo mu.! kad 'to 3milbgo111s
!n::8ults:. A)1Wi't!n Ul.S4),. written for lht pecla1 atSe o fu ~ solu.doo. is subtracted f'mm
Eq. {U .54) ltsetr, yieldirrg;
This is rhD fu:tula.tttcmr.aJ a.:us.pJ'iJfkJ'l)' relmlo.n. arud&gOIH 1o fAt- (I~ .j5).. llll~ furul~l
~ J.du~~l' r:ttition.
'nt ~ ~ogy that e:cw betw~u ~ies M. EeSidu.al propmies Mil. ~ :and scess
~ M 11 is i_ru:lkmd by Thbte 11. L AJ~ of tih:e alimul lbar i!ppf'.illi are ba..~c ~y
iidltim . alfbnup mily 6q~ {11.4) 8Dd ( J ~.5) iba1r'l:: bmi sbown ~tly bGf<JR..

-
._
~
"fiillle ll..ll: SronmarJ" ol ~f me Gibbs liDfJIY del RPJUnt 'Proptftles ~

~ mlldation tv ,c; :If 11 in Relation to G" M lDI Relali.:on rto G
l!
I
v ~ (Bv/8P')r ..1: ,, l tJ.>~H vR!!:!! c~aJa Pl-,._:r v = caat:/8P )T..m
S c -(i G/IJT)f'. (U.S), S1 -HJG R/8T),.,.. st--.. -raG/3Th~..ll
H~ ~G+TS H1 = G + TS/f. H E= Gc +TS'
0 = G- T(aGJtiT)r-...: ~ G - T(aG11JaT~r. ~ ,c B - r~taaJttr>,.,.

o- - ., c -
oi
(/) :g - Rl"~ [a(G/R'f~] ~ - RT: [4'(G / RT)]
2
.. ~Rf:! [ii(G /RT~] _
"0
~
aT p_. ar ,.~. ar ,..,.
0
~
a:
m
(/) Cr = (iJHtaTh"-3 ~c: = ((U/~(iJT)pJ c: . ,. CIJJI'/Df) ,._.
v0 ~ , ;;;; -71{8~G.t j.'IJT1 )P.x
, .!!!!! - T~a~o (a'f~) f'"" c:; - Tt~& 1,GIRf8'T 1 )t!..s
a.
,
I
(I) - - - --
--
0
(/)
0.
(I)
-""'
"""'
m
--
c
0
416
Examp1&11.1101
(a) If C~ ~s a constant, in.-penden' elf T~ find ~p~esslons ~r G1;. s~~ and n as

tunc:tiona cf T.
(b) From tbe equadON ctewloped 11111 Part (B). find vAlues for c.e.,. st:~ and n 6 tor an
eqyirnolar solutllon of bl~ene(1' )I n-lllt:exane(2) at 32'3..1 S K, glvera tne foJIOwfng1e.~~;cess
properly vatues for an eq-Liimolar solution 81 298.1 S ,J<!
Solutlon111.11o
fl
=- -
T
GE)
(-anr ,L~
- u ~n 1 + lJ
when! b ~s 11 eoosmnt of int~ra&ic:m. A sec:ond intr!Jillli()f) ~'"''el:

+t;T +,.
r;J:!!!!! -~(T ln1T - T) (,4)1
where c i~ u.thllhc-r iru.:pi(t't mMAru. With st - caa 8 /8 T),fl. (TubL'!:l 111 . u.

sZ (j 'In T - b, tB ),
!Ba:~ H~o c;E + rsfi .~CoiJlbj,n~oo of Eq,,. VU and (8) yid<b:
H, 41 +.. (C)I
~b) Lem c}'o

1C0Mtlrn11~
I Hu" I Md a: I'VJ."i"C II' llia i 'WetllVill Ue?il At 7u ~ 29ft I' 1:(, Dum ~c~ L~
11\l ltncf'tf~ro (I (~~ w -1.86,,
By Eq. (A)~
By Eq. (C)~ - UJ.Oin'l
II f.' 826.4 J mal- 1
Ob1 as protegidas por dir eitos de aut or

4JI7
The ,E xCQS Gl,_,. Enrgy snd the Ar:tlvlty CoeltlciMt

Tho e.J:~~ rQib~ CJ!tttl)' i uf~~lar mn:l~C. Bqwnlon (11.46) 11111)' be wriLtCD!
r{ ;1 f1 ('r) + .RT In .ft
~n (L-"CCfd whb Bq. (I ILSJ) roran ideal $Oiution. t~ booo~ :
G~ 11 ~ r~ r(T) + Rl ln '.ti}l
By ditlC'l'enoe. G~
- G~.
- J RT In - "
Nt/1
The ~flt s~ of chi11. ~equllflon h ~be panillll exec~ Gibbll,encl'({y l;f; ~he Ji.m.e11 ionll,Sx rucio
,,,'( .A ~tppemng on tbe nsht j lhe iJ('rl't'fty ("fMjfN'icm of Jlp!etb i tn mlullion. ~)'mtilol J'i!
Thus. b'y ,deftnltkm.
(U.90)
0 L91)
Thts.e equ:u:loo~ UUibli&'h u lhc:11:1UKI)'nrtmtc ~oUlldallion ror the nctivil)' cocfftcicnm. which u.p-
pe;trtd tn S. 10..5 as u (-uetm" 'ntroduud t11to Rooulm"&lnw to ccounl for U.qulde;(.!lnase rKNJ
1
kklalhic . CQmpllris;vo whb Eq. ( I 1.S I) ~bow 'tlmt Eq. t ll.91 ~ rehtCCi y~ 'lO C;f e~~lr f -
Eq, u1.51' 'l'ttDfC~ , lO a:. For JlH ideal ~Oillei(lli'l, lif c o. ~l'ld lharel'orc ,., - l
A Jurther rre1n.tkm uf irm~~'it ~UWU Cmm dJ~ COOibinatlcm of lq. ( ~ 1.'9 t l whb Eq. (I 1.88)
wriuen IQr rhc ~1\ Glbb!\ en~r,Yy:
RT ll'll',...t a G, - O~J
Eliminutinn' of the fin11l term by Eq. ( 1 ~ .7S) and ~(!'l\llltnl gives:
G~ t~ G1 RT Jo Y.l~l (11.02.)
One could ~or fiJCt LLq rth.l.i eqwUiiion w. m uJtcma.tliiYe definition ~of the ucriv.i~y ewffecien~
The concep:~\!.1\l de'-''tlopmem leollinJ (0 Sq. (II .92J ii cvldaH in lhe folIJowins Net of
cql.mtlUPtli
~~L!' a:' + R:T In 11 ( I tlA)
~\C.~d- Ga + RTIIU1 (I 't 7S)
f.l.l ._ G1 + RT lnY~Xl ,( If .92)
n.t fint off~ ~UIIIio:ns n:vcuT.li ~~ si;ni ftew!IW ur d'te id~aJ..gas miJUIIJ\'l mtMlc11,The ~e:ond
equmoo. for be lde:tl.:\03U1hm model . plieSCn'CS abc lmn giving com~itioo depmticnce,
but mclu<kl!" a p~~pcciP lmn of phy~C'ul rwJjty_ '~'be drud ~on~ mto"~ iDCilliion ~(Ir
Q C~itionpcnde'n ociviJ1 ooeflicient ha~ 4he copllblli~ m ~~l fwly the acwilll
behavior of sm~ILi.cms.

,_
4_18_ _ _ _ _ _ _ __ __ _ctl.4FniR J 1. Solution Thcnnodyn:.~mic<: ~'W)'
ExceBB-Property ,R'ellltlon
An ahcmadve fonn of Bq. (I.1.89)1follo~ b) ~nlmducdonl ot' tlrle (lc=_CiVh)l coom ieot lbroue;h
l?.q. (H .Ql):
0 1.93)
The mcrulhy of the~ equation preclude cbeir direc~ 1(X'aclicul :tpplW:alion. Ritthu, tm~
i., nmJe of rei\Uicwd fomu, which are written, b)' in peccion:
(11.96)
E4:(uatiom (U .93) dtrou,ah (11.96)' on nmlo~~S of Eq . 0 tl6) tl\rouJh U LS9)1:fur rcsidLWl

prupclllios. WlJ~JNta!l d1e Amc:ltmwnal w, idmJ.Ii'Pft'>~ n:lmitm ckriive.. Its uM:fulnt:S.' from
ic' dl reet rei 1on ~o experimentlll P V T dam and t uations of ~L\le,. the fundame11to1 c,'I ,-eiJ
prapetty I'Gblian ~ u;cfuJ bccma!Oe v, H r:, and r. 1111 e.xpetimcnudly !I ible. Activily
~odlic:iclm woe fwnd from vapor/liquid equihbrium dAr11.. IUld V b' o.nd Jl '" vutue1.1 come fmm
mlxin experi_nw:rtl topec ~ io the (ollowlng eha~
Sq.wnion (1 1.96) <kmon.r.II'Qie th:t.t In y, l11 rt pmiitJ property with t"e'\pl (n G"-1RT. rc
i the~ of Eq. UI .S9}, wbldu~ th ramo relntion ()fin~ to G11/ RT. The partiol-
prpeny ana~-1 ofEqrw, (I I .94) md U 1.9$) lin::
( ~)
8P 7 .-
'11tese equation Ilow c.alcu~iun of lhc c:fll ot' pre W'C und II.:IDJ)CMfUrt (1ft the ucti'\'ily
~ocf6cient.
lbt .ftliiOwif\ (oom of the !i\Dllmubili~y 11\d Gib~u_b-em equmtioru rt. uh ft0111 ~ fu-t
IJJ l In n il a p ni 1 prt'lpCny whn n:. pecc 10 GJ.j RT:
~~ -~x~lnnl
~con t T. P) (ll. HXh
n.ese equa~>ion fl11d ampm1mt n:ppUC"a4Joos: in ph ~-eqoili hrhtm ahelmod),nrun ic~ .

f.quarLon nn:d 0 1.95) allow dinx"l c:u1cu1utlon of the effect. or prec~~11e mul
~ 1 1.94) 1
lem~rtliW"e on lhc Cli.CC""-Ii Gtbb energy. "For erknmp1e. nn ~;quhnolur mixl,ln!' or benl ..COO md
Obras pro id s por direttos d autor

4ID9
(;)dobeun~ 112SOC and llbir has liD UWS5 '\'tdmne of about 0.65 em~ moJ- 1 md an '~cess
~tochaJpy of a'boul! goo ~ moi- 1 Thus .u~ Ebcse 'ooodiliuos~
a(GE{ RT)] O.ci.Si .., , _, o- -:s~J..-,.- 1

u . c ..... 6- K 1 llNU
[ iP . 'l'...t (83.l4)(2~ . .l5)
.
a(G / RT)] ~800 1 OS 0-3 K"" 1
[ 01T p ,x. - {8.314)(298. L5)~ - - X l,
The .mosm! U'ikl1ng observal1oo. about I IIese res.nlts .is Uta~ urakes .a pt"~re c.haqe o( Dum! lh11n
40 b.1li to haw rut m oo 1tDc ~c~ss Gibbs C11Uf!Y <Cqlfrirw.lttnt tJJ thai of~ ~ obm~-e
of ~ K SimilarcaJculati.ons blLscd I.'Jn Eq~. (t ~!17) mid (11.93) produce similar ~~ufm. This is
~he reason lhat :fer liquids ru: low ptesillre.ilrhe effe.c:t of p.ressure on rbe. e~cess Otfbb ,ene.J'@Y
:md on the aculllily coefficicm&s is USiu.ali:Y neglected
Jt.m ~ U.c: f\lQ(bmm@l pru~rty n;:l!(icln ofll!q: (! 1.54) provides complete pr~rr)l' in-
fonnanom from a canoo:ical e quatm of smte expressing G1RT as D funaioo of T, P. md
composiliioo_. so the .Nndla~ ~idawkwojla'ty rebltiO& Eq. (11.SS) or (tl.56), pv-vides
cumpltcre ntrii.f.uel--pmpt:rty infonnaJJw.ta: frum 31 PVT eqnudo.n of :slate~ from 'PVT daca. uli"
from gememl'mxi P YT coneldioos. Mov,-eva. fur co:mplm: pro~;zy infomumoo. one nddi
in addition m P Vr data lhe ideaJ..gM...stttte beat: cap.acide~ of die spQcies llml comprise the
sy.sllml. mcomphne ~. ~~-fun~ e'..WUS""f"Qpt:'ny ~l:ati~ EQ, ( 11.89 or (I J .93}. 1
)
prtW'~ c~te &'\l:'l!.t,)..,.~. tinf(iD'ffi.aiiou? ,gJ~~r~ i1D ~u:.~tiou :fut G&l RT as a fl.fiil::riou
of its canooica1 wrillb1~ T ., P. and! eomposilioo. Howe\rer, tms fwmlilil.tion ~hi l~
o~m:plete ~Y infonwtkm dmn ~die ~-profl'C'rt)' fonru.b&n, ~"U~ H ~,113 ~
.rwtbing about lhe: prope.m~ of dte p1are co.n.'fill.luenm d:emi~ speci~
Pm!Jiuritie-.s or liqui4-miJ~ ~havior arc dral'l13ticaUy revealed j n 1be ~c~ 1~pcniei.

1'bose of p.ftmacy interest ilflt G~ . R .. and sE. The ex.c~ Oibbs ~ romt:B rfrOOll ex
pe.rni:mtDt chooo,gb redocdon .ofvaporJJiquid equilibrium d - ~HE is&~ by miJ:,.
i"'g ~mep~S (Oap. 1Z). "Jbe ~(:;9$ cn~py ~~ p(ll :tneii'SU:red ~ly., bt!:t.r. ~jl fOtriiid :fimm
Bq. ( ~ 1.86}. 'f.\1DII~
&CGSS pl!'Of)Grtifi llW oft.;m strong rnncdoo..s ,of 'tetnfi!GJJltUN..ibut at oonnaJ t~res; 1Ue root
~1 ~.,d hlf ~ure. 'l"fwir composffiun ~~ i.~ ~in Fig. I ~.4 for
S~ix binary liquid mixtiJRS n ~~C and approxinm_ely all~[c JJess.l.Uie.. Por .oo.mis!ency
wilh E:.q. (I m. .ll6), t b; prodh~ f $'f: is. ~bown. mlhrr man $ 8 i~. Ahboilgh the: ~1111~tm t;Xhibfl
a ~dlh~er.sity ofbemviar. ibey 'have eomBlO.n f~:
l . All~ ~ properde.s beco:m:e .zem as e.'lber species appro.racbes purit).
2. .Ar~Jb GE ~. }r 1 its ap-proximately pa:r-abmie rn dtn.pe. oolb HE and T s exhib1L
mdividuaJ..imc CQ!llposioo ~~~-
3. W.benune._u:css propen:y ME ha!i ill ~lnglesign (.IISdnes G'E to dID c:ases). dieexl:rcme.
w:h!.e of ME (nuWmmn Of:' m.inimum) often occurs JKtal!' tJ.e: ,Gqmmola.r. compo.smo:m.

_ _. _ _ _ _ _ __ _ _ _ _ _OJ_
4 20 .~
- 11 Solution 'Tbf1TDOdynlH11~ : Theory
.. ...
1.., I
I -ooo
"'I
00 1500
- ....
...
0
.,1 '
l., 0 l..,
- 500 _,000
0 1 0 1 0 l
' I K.
t )
'
(d {11
IF--~ 11.4: ce\~ PR,,pcztlc~ ;J ~~c lor tllx lbJIUIJ)' Uqu d tcmw: (tJ) ~;.h~roform~ 1.1/.'ll~pr.:mc ll ~
(~~) ~QI~e( II Wm~thaool~lt. (c) .K1:!1011eU)k.tlJororC'Iwnfll: (otl} tiJ,unol IIVl'fltepmn:nc(2):
(;r) t(bt1.001(,1)lcl}lCmlff!lmCl); (fl dlr.r~r( I )lw'.Jtrn'2 ~.
If' r~ I i a ton equrilCt of lbe dc'llnidon of U~"<' propc:ny, Sq. ( ~ S.8Sl; ali nny ,'1: 1
ppro eheil unl)'. btllb M irul M J p~h M1, tho OOrFe p<)rWin (lrupc'rty o( pure ~e!> J,
1
f 1un:\ 2 and 3 urc &t~R"f'QU:tatiom lmai un ~ation. And odmim CXC~J'IIi n (~t. e.g" rbe
behAvior of H~ for lhe ethAnollwtuer bystem).
A dt:rwlod d v:u ion of~propcny bell vior i &ivcn io . 16.6.
PROBLEMS
U.J. Whtt~ ~ t~ ch Di,C: in mtropr when 0.1 m' ofCOJDI'Id 0.3 m 4 of N.1. et~.;h 1 l b:Ir
and 2~~- c blend 1t0 fnrrn,et gns mlnure a1 tho lUJI(' cundltlon.'l? A!IScume idleru gnse..'l.
11.1 A m.scl. di"ldtd into two pam by a partilloo. eoncrun 4 mo11af nlrrog~:n gus~ iS c
und 30 'ftwtr on unr cit: 11nd 2-S rnol of lfiOIII am 130 C nd lCJ boar on mhe m~. n
tho panhi(lln L remov d Md lhe sa "' ml:\ tldi~tbatil.lllly ~nd Nmplctc!:y, what ~8 tbo
Obra prot idas por direitos d utor

Problems 42 1
change in entropy? Assume ni trogen to be an ideal gas with Cv = (5/2) R and argon
to be a11 ideal gas with Cv = (3/2)R.
11.3. A stream of nitrogen flowing at the rate of 2 kg s- 1 and a stream of hydrogen flowing
at the rate of 0.5 kg s- 1 mix adi abatically in a steady-flow process. If the gases are
assumed ideal , what is the rate of entropy increase as a result of the process?
11.4. What is the ideal work for the separation of an equi mol ar mixture of methane and
ethane at 175C and 3 bar in a steady-flow process into product sueams of the pure
gases at 35C and I bar if Tu = 300 K?
11.5. What is the work required for the separation of air (2 1-mol-% oxygen and 79-mol-
% nitrogen) at 25 C and l bar in a steady-flow process into product streams of pure
oxygen and nitrogen, also at 25C and 1 bar, if the thermodynamic efficiency of the
process is 5% and if Tu = 300 K?
,..
11.6. What is the partial molar temperature? What is the partial molar pressure? Express
results in relation to the T and P of the mixture.
11.7. Show that:
(a) The "partial molar mass" of a species in solution is equal to its molar mass.
(b) A partial specific property of a species in solution is obtained by division of the
partial molar property by the molar mass of the specjes.
11.8. If the molar densi ty of a binary mixture is given by the empirical expression:
2
p = ao +a1 x1 +a2x 1
find the corresponding expressions for V1 and V2.

11.9. For a ternary solution at constant T and P, the composition dependence of molar
property M is given by:
'
where M1 , M2, and M3 are the values of M for pure species I, 2, a~d 3,_and C is_ a
parameter independent of composition. Determine expressions for M 1, M2, and M3
by application of Eq. (I 1.7). As a partial check on your results, verify that they satisfy
the summability relation, Eq. ( 11.11 ). For this correlating equation, what are theM; at
infinite dil ution?
11.10. A pure-component pressure p; for species i in a gas mixture may be defined as the
pressure that species i would exert if it alone occupied the mixture volume. Thus,
y;Zi RT
Pi =
v
wbtm ,_ is mhe mmeflnltlbl nf~f!$ i mlhe ps mi~. Zr is ~raluatcd :at PI and
T .md V is. abe molar volume o.trlllrLe- ps 1ntOOnre. Note lhat l'i M defined~ :b~ i~ ~
a pmtNll ~urt Ji P. dCCJJl for in .idCa11 JU. Dalton's "ku.\r'~ of :uld1mre ~
mnes llbat die lDt.a1 pres!!Uftl exerted by ill ps ~~ure Ls rqoal tn' lhe 511lJl. of tile p~
HD]ICMnt p:ressures oi iii oon~limenu,peeies: P :::: ~ p; . Show-mat Daltlms 4nw..
implies tbat Z ;:::;. 'E ~ .Y ZJ, ..~ Z1 ~ the wm~t)' fadar of pure spedes l
eva.1.D.ued at ti he m.b:lure ~~but ""~ pu~~n.t prCtiSLTR.
ILU. If fur binary ;sclotioo ooe ~tu:ti with m ~oo fur M (ur MR. or ME} ~$ u
111
fuoaitm of ~t and ,Qp;ptles Sq$. ( II. ~S) ~d ( I ~ .16 ) t'O Dod M1 ;md. M~ '(or M~ ud
M,'R tlf j[ a:n~~
u'"l!;P) liltd "" _... _ . "..""'llli" J"
.- .&"ffi:'ribin r:.~ .......,
l'!'ri'lrii!~~"
...,................s ~;., ~.. c~J ~1} --~ ~~-:~~
" -- 1nt.l.iU
2. 1 '"'l(:P ""~ ~Y ~ 11. 't
expr;es.sicm farM is re~md. On the olherffmnd. if one .!Wll1! wilh 9pre_Wofl$ fur
Mt and M1. ccmhi~ ibem in ~"Old' wltll,e.q. (I tl U. ~ tha~ appli-e~ Eqs. (U . l$)
mel ( 1I . ~6)~ the inbia:JJ eiJlm-~OOs for Mr aid MJ iJR; ~~er'..tied :if and o.nly u liM
~ ~~.Wns for~ qu:mtities :meet a ~citie ecmditio'.n. Wbm:is 1be -oondltloo'J
llA W"llb td'~Jlmcc: to Bx.. U A.

(a) Awly Eq. f1 W .'1) t0 !q. (A) w ,.-mzy fe4s. r( B) md (C).
(b) Show lh~tt Bq.s. (B) ud. (C) C():mbino 1n :u:eoro witb Eq1, (] i .1 L} to tegeoetate
Rq..(.A)"
(c) Sho-RR 1hat Eq~ (B) arut (C) $tis:fy &}. ( ~ I . tJ), dn: Qlbb!siDuhcm equu:rion.
~d) Soow mat mcoosmm T 100 P.
(dHt/d.t~)A\.= 1'.!!!!! (d~fdxi hc:c:(), '=! 0

(e) P'kA \'Uwll of
points H1., Hz~
H."
Hr
,g HJ. Cldc~:a'tcd b-y Eq (A)~ r( B). Lm.d (C).
~ .md 14.~. ;ilild sbow iheir alue.~.
\r"S.. ~f]. LabeJ
D.Jl~ The, ifil;)1ftf YOW:me (.c,m3 MO!- a) d 11 billiaty llqwdl mi~Wt'C D.l T and P is gi~11 by.
Y ;:;; ~lOJJ~ + ~ + USxm +i.r;,)RtXl
(d) Find expm~oos tor the: p:urti:ll mnbr volumes ot species ~ and l at T and P .
(b) Show ~ wrum tbcsc ~B :e combined im .accord with F.q. ( [ 1.11) the
givm.cq~nn far V t ~~cl
(c) Show illbat lb~ ~~ Hatisfy Eq. ( ~~ t ~1 4)', the C'~sJD.ubem ~:~tioth
(d'J Shew fham(d V1{dx.J ).~:p=t -: ( d V;i/d..Tt)x1::::(J ~ 0.
(c) PL~ vruues of V., l'l andl Vl ~a1u1ed by the given equ~ for V and by lhc
~UoDB dGvoJ~ in (a) VS. Xt . IJ..abel ,oir:Jls V1, l'2. V[. md
lbeir w!Lues.
and show vr.
ll. W. For a 1p!III:ieolar bimu:y liquid soturi.o.o at constmt T 11.1\d P. 1he m:~r ~enthn'tpies o.r
mho.tll'M ;llrt ~epmentod by iibc ~Wilton:
H ._. XI (aa + li-1~11) + .Kl(Dl + bcl.Xi)

wihue. the a,and =me+ b;.r1. Show w~lm mis its
m_igbt be dlt!!l iJ;
b~
fll.
Oomlmts. Be~ 't~ ~Wltic.I!l 'hll& lbe fdttm, O-f Eqr ('I l. J 0. it
IDU).
Obras protegidas par dir eitos de autor

ll.lS. AoalogOllS to ~ coovenmiomd paJ1ffil p~ll'llf MF, one ~em definl! u c.~.JIUWnlT.Y
partial fPI'OIJCllY M1~
Dem.on...tralC ~h:u mt M~ ~QJli$fy Cl Kl.lntmublltty ~1:lti<ln.. M es :E ).~ ii,.

-.
,I 1,.16. From the foU~LI'IJ co~ibtlityftic1tlf ~111 rof CQ: ., J~ C ~lillie p1<MN ,o f Ute
~UJKily Md frugJKily c:or:fificte:nt ,p( CO: vt.. P fw ~~ up to SOO' bu. Carqp,~W
resuh1i with lft O!.t foulld from mhe genenli~d conel:atJon trcpre~tsued roy Eq. t ' 1.68).
,pfbtJt z I
Plbul z
JiO 0.98-5 100 0.869
lO 0.970 200 0.165
40 OJJ42 I
300 1
0.762
60 0.9U 400 0.824
80 0.885
. - fOO 0.9]0
I l A.,. F'nr so~ 41t 600 K nd 300 INll', ,LfetemllUC good e dmme-1 of lbe (up::ity .and or
Gtt(RT .
ll.JI,. Estinwe w fusacity of isobut)'ltne ""u ~&'~:

(a) AI 280~C &&.Dd 20 lbut: (b) Al m C wid B>O bw<.
11..19.. Es.ti l11iAte the. fupcil)' ,elf oM of tbe following:

(a) Cyclopen:hllle at l l(PC nnd :21.S b:u. At I JI0C the por p.reuuM ofc)lel~
tJi S.1671bW.
(b) l-BU-(C'I]e.lll2t~JlCMd34bar. A1 I20 ClhcYdJtt,r~ urcm lbutmai 15.SJim:
U.2D. Jollify uhe following, eq~,W.titlru;:
aIn ~ ) if.R
( ap
T,:r
=RT
1: Xl d lo~; ~ 0 (con T. P)
'
ll.lJ. From data in lbe steam cutes. dc:termin~ II good cMimlte ror fir" leu Hq,oid wmer at
uo ~e W1dl a:so bar. whelre /'fJj is tbe fugndty ~of samruted ~ icvrid mlSOC.
Obras prot gidas por direitos de aut or

424
l !L12. Pot one afrt:~ 1fo11Dwi1Hg.. ~mine lbe mtii) of eihe f~ity in l bc flrrulll uuc 10 1tm.at ln
the i nU ~ 'ltllt for Meam \.111dc:'Soint lbc: isot_l"iaifiQQ clmng.e or tate~
ta) PJQI11t 9~000 kf',;~_ ood ~ C lo JOO kPa..
{b) Prrom1 I.OtlOtp~~) QDd 8:00(-.)f) lO jCI(p~ '
1l .ll. EsrimaJe the fug~il1 CJf ontt d the t'ullowiog ltquicb. at it.~ rtmmnJ ..bftHtn -..pmal ~~~~
1
perature amd 200 lbnr:

(a) n-Pen ULne; Cb~ I ~bucylellc~ (t.") I D!llteoe.
IU.l4. A.M~1.11ning lm~ Eq. ( I US8) iA v:illd lOr llbe v:.por 1pll a'i!O nd mac 'he mo1&r volumt or
otamrme!J littuad l!i Jlt\c:n lby ,Eq. t(1.1l}. !Fftl'tli'C plo~ of J' v!t. p nnd of 4J Y~ . P for nne
of tbe rouowiQg~
t~J CWoro-fmm !J~ ~C fw ~bt p~!ii.~.m m.ngc Jirom 0 o 40 b:u. Ait 200 C tb; vopur
f.!R!!k'\Ufe of mlmut'nw b! ll.l, bw'. 1
(b) Jsobutooe nt .ro~ c fOJ 1he Jfm.JIDM 1rM~ f-rom o~ m 10 bu. A~ 40" C the \!tlfH)r
pr~UN crt" obtd11ne I ' S.28 b:!r.
u~. for ~he ..ysttfn ethylene{ I)lpropylenef2) u . o ga... eMlnm"' i . /2. 4>~ Wid ~ Ill t
150 C. ~11 e 30 b{lr. and .~ 1 !!!!!:' 01.35:
(a) 'niMf;h upplic t)on of E<p. ~ ~ 1.6at
{b) A~~-uming th lhe mixwrt i51111 icieoJ elution~
l!l.l6. RnJionolize the rolf.lt;wi'M 8 ex_prutcio:n, wlid Ill t~ufticle-nl)iy 'low ~1!U:Felt, ror ~!ltimtUiD(t
t~c fUI~_uc:ity ~ot:~ie-n\~ Jtn f/J -:;a: Z - I.
11..rl. For th~

.. sy~~otcm mclhan~:--t l )lfll'\;ut~' lJipror;mc( ) ~ 11 gus, 1C~ imu.to i L.l~, f,, ~~. ir,z
und ~-; 111 r I00 lc. P - lS Ibm', ) ' I 0.21. and yz 0.4~ :
ttj)11uuuah upplh:llicn of Eq. ( l i.Ml.
(b) f\jj~\lllling th tlhe m'~ ~ ~ ~ ~ idMI nhnion.
11.28. The a:u:as Qi.I'Jbs enorM)' of li 'binary Hquid nli!xture oa 'I' and P s ~lYim tty:
a'-JRT (- 2.6vt - I.Bx:~'JtxiJ~.
(") f'rnd '~ 1lilfWion~ for lo Y und In Y2 1 T and P.

(b) Shuw 'cbal wbl:n lb!!!it! upre~oru are t."o::ibiMdl mllCCQI'd willi f..q. ( I 1.99) m~
gi\'tP equation for G1f I RT i regovcNd.
(t.) Show 1t]rw.1 ttt~ tUp~~oo ~r;,fy EQ:. ( ll . ~ ()(D), d-Ie (iib~~m ~ootio111.
ht Show llw (d In 'Y~/dJ:1 ~. 1 1 '( dIn ,.,/dxd~ 1 -o a 0.
co) tl<K u 1' / RT.Iot:rt. and ln ~us calculated by the ~vn equiltiOll f(l" Gli / R'I' and
try' the CtJUBiios ~Ju;ped in ~c) vs~ .r1 . l..:LbeJ:point~ In y1~ Wld In ri ond ~
their h1a.
Ob1 as protegidas por dir eitos de aut or

Problems 425
11.29. Show that y; = ; / ;.
11.30. Given below are values of c EJJ mol- 1, H 11 mol - 1 , and C~/J mol- K- 1 for some
1
equimolar binary liquid mixtures at 298. 15 K. Estimate values of c E' HE , and sE at

328.15 K fo r one of the equimolar mixtures by two procedures: (I) Use all the data;
(II) Assume C~ = 0. Compare and discuss your result<; for the two procedures.
(a) Acetone/chloroform: GE = -622, H E= -1,920, C~ = 4.2.

(b) Acetone/n-hexane: c = 1,095, H E = J,595, C~ = 3.3.
(c) Benzene/isooctane: GE = 407, H E= 984, C% = - 2.7.
(d) Chloroform/ethanol: G E = 632, H E= - 208, C~ = 23.0.
(e) Ethano1/n-heptane: c = 1,445, H E= 605, C~ = 11.0.
(j) Ethanol/water: c = 734, H E= - 416, C~ = 11.0.
(g) Ethyl acetate/n-heptane: G = 759. H E = I ,465, C~ = -8.0.
11.31. The excess Gibbs energy of a particular ternary liquid mixture is represented by the
empirical expression, with parameters A 12. A 13 , and A 23 funclion s ofT and P only:
c 1RT =A 12x 1x2 + A 13x1x3 + A 23x2x3

'
(a) Determine the implied expressions for In Yl, In Y2, and ln Y3
(b) Verify that your results for part (a) satisfy the summability relation, Eq. ( 11 .99).
(c) For species 1 determine expressions (or values) for ln y 1 for the limiting cases:
x 1 = 0, x 1 = 1, x2 = 0, and x3 = 0. What do these limiting cases represent?
Table 11.2: Excess Volumes for 1,3-Dioxane(1)/lsooctane(2) at 298.15 K

R. Francesconi et al., bu. DATA Se1:, Ser. A , vol. 25, no. 3, p. 229, 1997.
XJ V E/10- 3 cm 3 mol-l XI V/10- 3 cm3 mol-l
0.02715 87.5 0.69984 276.4

0.09329 265.6 0.72792 252.9
0.17490 417.4 0.775 14 190.7
0.32760 534.5 0.79243 178.1
0.40244 531.7 0.82954 138.4
0.56689 421.1 0.86835 98.4
0.63128 347.1 0.93287 37.6
0.66233 32 1.7 0.98233 10.0
11.32. The data in Table 11 .2 are experimental values of V E fo r binary liquid mixtures of
l ,3-dioxolane( 1) and isooctane(2) at 298. 15 K and 1(atm).
(a) Determine from the data nu merical values of parameters a, b, and c in the corre-
lating equation:
(b) ][)crcfminc fJor'nltht! l:'c utu of pan (u) dm m:Wmum 'IIUlul! of V t. . AI wbt\1 -..alu.e
of x 1 ~ thi octur'J'
~.c) Detemmine &nm the tresult~~ o f p;m 1{t1) e~p ions f~rr Pm
' nnd V'J8 P~p.a.M [j, plot
of~~ quutili~ \'$. "' 11 ~md di 1.1 itt :f.c:ru~re
ll.Jl. m- :m oquimolat a.POf m~ of ~U) Wllll n"lJ;;CntMe(2'~ L'll ?Sole~ 2 bnr.

z. ,HR.IlJ'ld Sl. Seeoodl \lirlld oocfft.criC'Itt ~~. em~ moJ-~:
c-s~imate.
,t ~C Bu Bn 8~2:
SOt -331 - 910 --$S8
15 -~76 - 809 -466
~~oo - 235 -684 - J99
Eq,uado11 (3.31), (6.!-!), {6.!6), ond{l 1.6:l) are putinelll.
11.34. U~ the daD Of fb.l J1.JJ to deletmiiW.'I ~I IIJid ~ furu::tion,~ of cumpusJtion for b tllJI]')'
~por :mtuu~U of prt1plil~(.l Jand n-pe.nume(l:) tl7,1iC' ftJ1d 2 b;!t. Plom .~l)e rt ults O'JJ a
hqJe 1JUph. Dllcv. tlhe fi191lllm of lhi1 plot.
U.35. For birwy p rm1~:nrte dtse1bed by Eq (3.38) nod ( ~ t62). prow that:
'nlble 11.3: 111 v.. ' J.J..DI~l)ll)bDctbJI Carboaatet2-t at l u.as K 1
R. Fmnc~ ec 11 1m. DATA Sn, Srr. A. val~. oo. 3. p.m . .1001'7.
Xt 1J I!IJ mnl1"' 1 XI H'I?.IJ mol- ~
0!04,26 - 23.3 0..3~6) - Z04.1

0J()811 - 45.7 0.61S6 -WI.7
0. ~1 1 77 - 66.5 IC}J)81:0 -H4.1
O.~S.It -86.6 .0.7621 -~4 1.0
0.2107 - 1 1~8.2 ~~)'.8181 -] 16.8
0.2614 - 144.6 'O.s.!iSO - 85.6
0.3472 - 176.6 0.9276 - 43.S
o.415s 1 - 19,.7 0.91624 ~2l~'
ILJ6. Tho d:uA In TLtbbc 1l.3 CU"e expuioten~l Wlllue.>~ of If i fur blruuy liqut<l mhccurd f)r
J~l-dichloroed:ume( I) umd dimethyl calboo:ue(l) Ill, 313.15 K and I(JJim),

427
(a) De~ fmm ~~be datil~ :tllllDefiml ~.atoes rtif pat"'t.l.mel:er& a, b, am1l e in. lbe OOI're-
l'ating eqwrtion:
HF.. ;;;: _'f~.f;'!(a +b.f. + C;1?)
(b) ~ (rom me reslililts of pan (u}rilibe mirunwm vtittre of 112 . At wham value
of X I does dJis oca.l!f?'
(e) DetelmJne from t he rewlls of part (a) a~o~s fo:r iil aad ii115 Prepare a plm
ef ~~quanti~ '~ ift, ;md ~~it& fewu_~.
11.37. Mm use .o f .Eq~. (3.,38). (3.65)., (3.66). (6.54), (6.55). (6.56). (6Jl9). (~90)~ (] t62),
nnd (1 .1.69H11.74). ro csti mate V, H rl, 51t .udl ,Gft for one mthe. fbllowiqg bin=uy
wpor fiii.x\11.1~
(o) A~J~1.~b~i~ne(2) wilh mol~ fm~;:tions 1 1 ::;;; 0.2i ;~,_n d ~ ;;;;; 0.12 at
t .e M~c and P ~ 170 kPa.
{b) AaaonitrikO Ydietbyl et~r(2) witb ~ &acuiom y~ ;::;;; 0.:37 aJid 11 = 0. 63 at
I : SW'IC nfid P : 120 kPa.
(c) Mdhyl c,hJ:orlde{J )Jeah:i] cblorr:i'd'd2) wiillbr~ ftllt'liOJIU.i .n !!!!! 0.4S CQ:1d 12 ~ 0.:55
at t = lS<tC cmd P = .100 kPcL
c~ Ni&roJen(l )lommonht{2) wUh mole fraatons 11 ~ &.83 o:nd )11 ~ 0.17 a! t ~
20~ and P c .ltJO .tP:..
~1!) S\Jl;fur dioxide(l)lelhy!en~2) with mdlt fraclloos Y1 ~ 0.32 and~ ~ 0.68 ut
t = ~C and P c: 420 kP.L
Note: Set IGJ ~ 0 in Eq. 0 L7l).
11.38~ CalculaJ:c 1(1 and f

by fle Redlicb/Kwoo1 equ;ntion Qf ~~~ fw on~ o-1:' the foll~1u~:;.
::md compare re~LL1t:s wi~ vlues wk:eo wm a Mlftab.fe ,geoeru~Ued Qll'feloooo:
(a) A~lene aj m
K andt ~5 bar.
(b) A:r;ton 1U 100 K und WO bar.
{c) Bcmc.oo Ill S7S K.and 4t) bar.
(Jlf Carboo &oode w 350 K and '3s liNn'.
(.e ) Bhyle:..ne o.t 300 'K Mil :51!) b:ir.
(/) n--H~e r.tt S2:5 K. Md 110 b;.v;.
(g) Metibane Ull25 K and. 25 lw.
(ll) N1tf01en at 20 :K: rutd 1S bat.
llL'W. Calculale ~ andl f by the SoaveJRedU~hfKwoo& eqnllliO"n of stnre for~ sub3..~

mid coodhiUi gi11-c,n by om,e c'Jf ~he p:gl.li ,Qf fb. Jl .33. n_nd cmnparo rc.~!ts. "'ilb vallucs
i.a'keo from a st:Li tatJI'e general~.ed rOI.lf'1'daiion.
llAO~o Calculate' and f by die IP"-eng/Rooinsoo oqueioo. of sccwe fo.r trbe oktanc:e and am
djti.OIU ,tVM by one OJ tbo pam of Pb. I 1 .3~. and cum.parc re~W:ts wich val11e5 lake_n
frum a.Miimble gerrml'illedl ~orFelucirrn.
Obras prote.gidas pot direitos de autor

4211:
llAL Lab4rnt<KY A. ,~ lbc foiiGY~U., lC!iuhi fu ,cq~or wliiJt of QE for liquid mh

tum. of bem:eM(J ) wilh l he:lunol(l):
,e !!!!! ro6oJ :rno11 '-t r 3m3 K

t\Te b ~S\llll fiP.Xn1th~ (WO htboraJOfie lbclrm~ynami:cmly CotOOlttemt wilb \'IOC WI
other? ilxp!JkimL.
UA2. ~ follUWill8 a:p~e8.,t<m. lut.ve hem ~for the p~ninl malar pi'Opc:rt~~ of o
panicular tlllty lnOOure:
11.4-l~ 1\l.io '(2.) ~rru.d kr- 1 of liquid IJ--oetrme (~c:la I) are ~c:ontLnuOU~Iy rnti~ wil[h four<( 4)
kmo~ hr 1 of Hquid tt~n.oo (Npccict~- 2). The mi.d q P'OI-~ liN!CUB Jtt ~--oDllt nl T
ond P ~ :m tclwla power requi~n1 arre nqJHJiblt,
~a) Ux un cna'gy ltmh\ntc m~nnine b nue of hm lnmltfer.
tb) URl 1m~ IMdWI~t 10,delamin~ the mm of emropy pentliol) (W K- '1 )..
Slmlc mdJ just\fy d 1 mnptium.
llL44. Filly (SO) mo~ 1- 11 cftnritbcd w (SO mul~ N1~ 50 nw!~ Ozl,are produced by coo-
tinuot&Sl)- cambirring ctlr (7!J mo11. N~.. l 'l mu:t..'% O,z) with1 i lrt.anl ,Lff pure oxy en.
AD~ arc :11: the conldmlc eondillions 1 2.S C and P ~ l.l(1um), ~ rurc na
movin pnru.
(CJ) Detmn1ne he ri"ABl~, of oir mod,o~yp (moJ s- 1).
(I,.) wam, i~ ahc :rnte of tat ~rcr f(Jf lhc piUOCII~1
lc) WIW is We 'ftiTC of~ ~ioo Jo (W K- 1l?
State 1111 umpdom.
S..g~/JNW: ~t the overu.U ~-"" {Jji a combt.rut~on Gf demix1t1J 1nld mixill.l !iWp..
111..4$. A ~~UPie t~siom1 for ltle oti ~>'fiilfiC'Iri~ai biOOI')' ~~rem i M 1; Axr1 x~. Jltw
c:vu. ~cuundus odMr maphiad ,~on ' am be pmpolied which ex hl'bit symmeuy.
How miUible wou1dllhe two ftdln\!aina ~t;~;~inm. 'he ftw rc~ oppUauion?
(a) M 11 A~r.rf: (lJ) Ml! l!:ll A ~tlll(tx.'fd
St~:rllolt~ Look ntlhe impJied pmtin1 pmperti9 ilf nntl .Mf.

Problems 429
11.46. For a m ulticomponent mixture containing any number of species, prove that
-
Mi = M + (a
- M) - L (aM)
Xk -
Bxi T.P k dXk T.P
where the su mmation is over a// species. Show that for a binary mixture this resul t
reduces to Eqs. ( 11.15) and ( 11.16).
11.47. The following empirical two-parameter expression has been proposed for correlation
of excess properties of symmetrical] iquid mixtures:
M = A X t X2 ( l + - -I -- )
Xt + B x2 x2 + Bx 1
Here, quantities A and 8 are parameters that depend at most on T.
(a) Determine fro m the given equation the implied expressions for Mf and iVtf.
(b) Show that the results of part (a) satisfy all necessary constrain ts for partial excess
properties. ...
(c) Determine from the results of part (a) expressions fo r (M{) 00 and (M,f)00
11.48. Commonly, if ME fo r a binary system has a single sign, then the partial properties
f
M and M.f have the same sign as M E over the entire compositio n range. There are
occasions, however, where the i(E may change sign even thoug h M E has a single
sign. In fac t, it is the shape of the M E vs. x 1 curve that determines whether the MF
f
change sign. Show that a sufficient condition for M and !Vtf to have single signs is
thalthe curvature of i\1 E vs. x 1 have a single sign over the entire composition range.
11.49. An engi neer clai ms that the volume expansi ty o r an ideal solution is given by
{jid = L X; {3;
i
Is this claim valid? If so, show why. If not, find a correct expressio n for fJid .
11.50. Gi ven below are data for G and H E (both in J mol - 1) for equimo lar mixtures or the
same organic liquid. . Use all of the data to estimate value . of GE, H , and T SE fo r
the equimolar mixture at 25C.
At T = l0C: G = 544.0, HE= 932.1

At T = 30C: G = 5 13.2, H E= 893.4
At T = 50C: G = 494.2, H E = 845 .9
Suggestion: Assume C~ constant and use material developed in Example 11.1 0.
Se~llution Thermodyna1
m ics:
Applicatilon-s
AllJ of the ~td ~ODS md ~ definitions of' ~lotion lbel'tllodynamics Wle

given in lhe pmcedi:og ~r. ln dri!i ~~ 'We eumlnc wb~t ~ !be l'C!HiDod from ex;perl-
ment. am~~ fimt me meuurell1el1B of wpm11iquid equitiMium (VLJB) da~a. from "W~tdoh
acdrviiydlicimt tQOmlacioos, are derili-cdLSewod. '" 1rea1 mixing cxperimentll. ~bien p~
v~ da'Q.for propcJ~ty ~ges uf ~mg. !IQ ~llfU;. ~ appfi'C'"..Itions or
dil~ mbalpy
~ ~or DJixina.,
~tho be;~l o f mimtg. .; ue pmemed tn .de:mJ in Sec. 12.4.
12.1 LIQUI~HASE PROPERTlES PROM VLE DATA
F~re 12.1 shows a vessel in whiclJ a vapor miX~Wtc wtd u Uquid wludon r.:~ irn va-
~uid requifibrimn. Th~ tempcmnure 1' and pressure P are uniform tibrot~:gbom. the Yl::~-sd.,
and Clln. be mea~ witbr.ap,pm~ insttumtnts. V.1J)Of' and tiqrllid srunples rna)' be wiitft..
drawn for Q'M~~~~. and ihtJ provides ~pedmeiU:id wlues for .iiDOl thleicm; mtbt:: \o~ tYi I
and mole fndfuos in rtbcliquid (xi).
FUflllclly
F~r . pedes ,i in (]](: vapor m.l:tliit"C; B4- (I ~.52) is written:
/l- YJ~rp
1'bc criterion of 'L"'Ippriliquid itiJbrlum. as gben by 1?4 (a 1.48:). ts tbru if ~ it. U~furet
J~= ~p
Alldwl!sgh wJues for ,1lpCII-pba._~ fugacity coeticieot ~7 are easily ctllewil.Wd, CSee&. l1.6
~ 1] .1). VLJ3. ~urre~nts aJie .,.~ o~n .~ !U pressgreslow ~ogp (P ~ 1 b:u) tkmt
tbe vapor phase may 1be Ml!llllliet1 m l~ gM. 'In rMs ~ .f ~ L, ~l'ld rtbe two ~ing
a.quatimt_q ~d~ xv.
430 Obras protegidas par dir eitos de autor

43 ~
1bw. die fugacity of <~~pecie' J (~n borh tllu: liq111id Clfid '~ pi\Mes)1I eq-u:t.lltto tie ~.wti
prcssun of speei I in die wpgr phl8c. Ill,_ w lue 'nc.r'I!A.~ fmm r.em I .infinite dU~Iim
(xJ = >"F . 0) tu ~ w fm pUl'i! specie~ i. This is Ulusarmd lb)' the ~ of Tab~ 12. 1 for
lh~ mem.byJ etb)'l~ lketoOO( ')/tolue.ne(2) ~y:~ ~t soc. I The R..m lhre" N lumn.'i u~c u ~r o(
CilC!pmmr:nlul P-.c 1 .~ 1 dilm ,illld Colu mm. 4 afld S how:
and
PJtPu A' I ,. j. YIP A nP n

li2.:\0(Pl11 1 OJCOlO @.OOOU 01.0001 ~I Z.JOO EJDl
lS.S1 o~os.9s 0.2716 4.112 U.298 11.304 L.009
Ul.6l 0. 1~W @.4S6~ 8.496 ~1 0. 1 ~4 ~1 . 18S :~ .Ol6
21.63 0.319'~ 0.~934 12.835 8.79'5 ~I .U4 ~ .O..'iD
l4.0J 0.4l32 0'. 68U 16.363 1.691 L071 11.018
25~.92. fi.511'9 0.7'440 t9.284 6~~636 li.D44 11. 1~
27.96 0.6096 0.8050 21.50R 5.542 11.023 ].135
l<Ul 0.713S 0.8639 26.021 4J1)Q9 ~I .Oit O U63
31.7.5 0.7934 0~.9048 2S.727 :ul2J 11.003 :11.1 ~9
34. ]~ 0;9102 ()'.9.5:90 31.7~ l o~400' ~~Mt97 1.268
36.CrP,,.) ~oooo ~.0000 36.000 OJOIJQI UMI
'rlae rupeieic..~ are pt~ in V-a, 11.2 u solid line~. The itlmlghl dashed lina ft!Pl'ac!nt
Eq, (11[.~). tbe L.mvi~4311 !'~ wh'ich: t''~" t[ he ..,am~ilitm dt~e $(me c."ud
tituent fupeities iro an ideal mt'ulioo~
it1 ;;;;; ;fJ~ ( 11 .13)

0 0
FlaM~ 1U: 1\!pG'It e5o ((l!r rnc~l'lyl ethyl ,f 1i pn 11.3: ComJ!Oilicn, depend occ ~i
lllcMmrJ(I)/Iolurll(tl>4lf so(", 1bc ~ lllquld,.~~ ~U.uchle::~ Cor spIH 4 i111 I!J binUJ)
~inc~ ~m ltu: lewis/IWI~U role. MJJudoo.
AldJouJb d'uived (rom a pwrtlcuw W!'~ uf data~ Fla. 12<'1 ULu m~ th~ ~ntmlu cure of
lbc / mIDklfi J1. 'II: ,1: 11 JCIMion~hl~ for a bi.~ liquid $Oiutill)n 4IQOJISII:\I\t f . Tlic ~ell(W ubriun\
pmmn: P varies with compos.hlotL but illlnflu~m:e on de Uquidpiwe vllloo11 of fe and /J
~ ntlli lble. nw ~ ptotac co _cwn 1 gffd fl ~wid lOOk lbe :,.arne.~ hJdic;1U:d in Ale. 12.3
ror ~cs w' (i ~ . l) in ,1 lbintuy sdtul'im ac eoo&Uiflt T cwd Ji'.
'lllbe lower d;a 1led line in Fig. 1.:,,

reprciem.tlng. 1he J..ew,iJIRQll.d~l rule:. i!t. chMtetcri~~<Lic 4-)r
ldedo:d ~on lbduwror. It pro\lides ~e 5lmplat po ible ,flll10dcJ (or me composition depcJ!I,..
1
diUKIC of ~. rc~q:ntilij! 11 ~ m wrueh wuAJ ie~Vll'Of fllflY be compwrcd. Ind-eed. 1M
w:tivity coeffickmt ID~de:nned by~ 0 J.90~) fonnnlizc~ thl compgrlr..on:
'1l.ilm5 lhl: IICUVtly coe1lficietll of~ pec:ie.Q in ~oLwi.M ill.be r:ni()l o:f i~ ;wtuall rupciry to rUle
value ,~v.en by die Lew~~ nle &U ~e IWJ.Jt\ T, p . and co~l~iOl1t, for the cmruauoll

433
(If aperinltnnd vaJUr;S.. both ii nnd j~rl are clfrmjJnated in &var of mearumb1e qmmlities:-2
y;P YJ P'
n =- - (i;;;;; L.. l ... . .. N) {12.H
x~ fl :IJ P"sat
'nli~ is a rt!t1.'1llemenl ,ofEq_ ( lO.:nmodified RMmU' 11~1N. and 15 ~~11telut~ pt1~
allkrwj ng easy ~aku:l>atio.n. of a.ctiv.ity coeftic:lenL>J. from experimeDtl1 row-pres~UR) 'VL.E dum.
Values tfum dli6 ~WriO[ll qppt.w in l'he ~ lW1.J a>l\lm~ ofTa.blc 12. m .
1
m
The sclid lline8 boelh, Fags. 12.2 iWd U~. re:pr.eseMing experilmnml: valLreS of h~
!become um,pnt m ~he Lewis/Randallr-mr:e lillnes at x, ; ;
t flris is .a coo~uc:ooe of the
G~Qb~ Oq~;.QU:~oo. a.-;; [S. sh~ ~att::>r. fn ~e ~her limh. ;(l -.. 0. fi bcQume~ ~ero~ Tbu$,.
ft
b: riiJio / Xi ig ttlde(enn:ittale tlL lhi.J Wnii. andJ i!pp1icalkm of ~" lffipilal '! n.aie )"ifJds:
p ..
l.wfl _.
'"'--o .Y;
fi = (dfi)
-
.d x;
'1.1.
Ei5 ' 1"1 { 1.2_2)
.xi =O
.&a_iJUIItm ( Ell) l;li;dint;:.ilJi,~ruy"'s LY.J1Hlpn11tt flS :tlie Htn,ting sl(!l~ of th~ ji~vs.-.x1 arnt~ ~
x, r::~ 0. AI :bown lb) Fig. 12.3. this is me slOpe-of iii l.inedmwn mogen1.m[lil.e run-e au x; 0. =
"[be ~oo ofthis. Wtgentlicc ~esses. He~try"'s law.
I~ 12,3)
AppliQbl4 in tt:w l[m_it u X~ _,. o. ~~ is aJI 0 of a,wJOXimate ~ ror smd V'.Jiua w -Xi .
~l!'lry"8 law M given by 64 (l<Ol4~ :FoUow.s .Emmedim.ety ftum dO& e.quad.oo when fi !!!! } } P..
:lee, WMll J. b:B ils i.d'e:d-gas va1Me.
Henry's law is rolmd to lbe ~"isfRancbll mJe lbroug'h the Gib'bs~Dubem equ11rhm.
WtidA8 Eq. (ll .14) ror" ibWMY sdu.tion ~d !'placiAg M1by Gf ~ t41 &i~~
~t d'pr + .11 rl1A-2 === 0 (lll5t f. P)
DitfORoli~ttio-n of&~. (J l46) at comumt 1' GDC!J P )ldB: d /JJ = R'f dIn~; wbencv.,
x 1t:l Jn /1 + ":! cUn /z = 0 1
{OOIISI T , P)
Upon divisioo by d.tl this bemme.~
(c:ommT. P) (12.4)
~ is a speeia!l form of t-k O:ibbsiDuh.eal!i. eqmtion

~ol.ld <
t wm rprod~
,IJ
Jtn/1 m.h
=X"'....d dx'2 ()11
d'h/d.Jt ~ dh/dx,.
d..:n filxa - h !"'r2
ltJik a jj]fiie if1t<inili.'o tfeimlllal (St. f.;_ !l )~ h ts &Jii"en by :H4 (ll.S'2,. (n, wmcll Ca..'ll:.
~P
r; = A{P"t

434
lim d l1la'x = lim d hldxz

.-: .... L .A:/~::~ ~'0 /z./.x2
BCEaUse j. ~ 1 'K'ileft ._'fll ~ t .nis ma.y tic rewritten:
~
/J.
(dlt)
dx1
!!!!! tJ/2/~d~2)'K<ef!.
lftn (h/XIJJ'
..i''= 1 Jl'l ....,.0.
AccQTding 'o Bq. (] 2..2). the numt:rutw and ~IJJiiJ.imitor wlho rigkt side of lhi5 eq_u11tio:n are
equal. unt,i t~rrrare:
( 12..5)
Th1s etp~Miti is lbe exa~l U;f~E ion l])f lhe .Lewl~':IDIIal~ mae as. applied I& :reaJJ solmio:ns..
lt also imp6es 'Ch:it Bq. ( I ~ ~83) pR}vi.dcs app~tdy ceorm:t w_lw-s of /;. wooo ~i ::lP$ l :
.iJ
f; ~ f [ :: ;q fi ..
tteJJ_ry"s law appJI.. to p~CW as lt approacMt Infinite ditutiott 111'1
a binary aaturloft, end lltle GlbbaiDuhem ~ lnauNa validity ol
tbe Ltwii/Randali rule for lhe D4her apedea .., tt .~.hn pt~~rlty.
F~ U.A: Compositioo ~'*ooc ol

~ .f~t)' o! 1leJ1QIIti illl ftl&'Q b.iswy tLqu:id
I~~U:.s<PC.
j

43S
The fupacy hown, b)' Fig. l2.l &s ror a q.;edts wid\ iPDsitive dewhniOll'S from ide1,11it)'
in lbc: senW! of lbe LewiJIRmld11ll ntle. egativt devicfltions 1m'! ~~~ t-(!lmmon. but Pre ~~
obKned; lbe j;.w.....r, WJ'\'(: lb~u Iie,~; bti01N (ftc IU\\!i~outltdl Unc. Jir1 f;g. ~ 2.4 lbc fU(l'ltJt)'
or llQCI01)C ~ ~OWIIr a " funclic:m of oompmidon fm two differmt 'bJniU')' ti-q,uid soluti-on~ Dl
S0'1C. Wihen lhe -cood :i~ieK b lbeLlwnol. ~ ~hlblt.~ :po~itivc dtVr~don!i from i<klllh:y.
Wh:cn the ~ond spwk$ i 101blorofotllL lhc d\!ilmion am n~pti'~ . 1ih~ futteily ~lf pure
acetone: j~ hi a~h!oW"'C lbe ~me. reprofegorrt~ ldenti.ly of the ~~c: ~ Howcv-u,
Heory'li eonMilllt~. np~o~d by ~0~ or tb~ lWO 4o~ttd JlQC~ !U'e very difil'~ll' fru the l'WO
e~ .
Exeeu Gibbs Enettw

~n Tllble ll'.l the tim lbree Qol umn~ mpecn the p.,,1,-,:y, dlltn ,o f Tobie ~2 . ~ far ~he yste;m
meth~il ehyJ lkeloM11)lloluent(2). 'The,c dnta poinbt ore ..oo !.how11'1i circl~ m Pis. i 2.Staj.
Va.IUCI+ of I n,Yt :md ~n t':! we ~ ll'lted lt1 cQium~ 4 and S. and ore huwn b~ the u.pttn ~ mdl
lrianclc.'i ,q(Ftl;. 12.S(b,. 'J'ky r.lJ!C.CW1biocd fof billmy ystem in~ wilh Eq, (l l .~n
"2.6)
nac Wll.lC;!I of G'/ Rr so c:ub:ulw:ed liT&! then divided b)' x~x~ tu provitk \!lll.ue~ of 'G~/i"l!l"!Rr ~
lb..e tW0 l~ of numbers liD: 11 aed ~~n~ .ootu mn.' 6 and 7 ofTablt 12.1. ~~ appe:u u !ltlJi:dcin:l"
on ,Fig. l2,,(b).
PikPi ~\'I Yt In,y~ lnn G~/ RT G8 /.r~Xl RT

l1.30(Pt'1) .. ~UKX)O O.OOOC 01
.000 o.ooo
IS.SI 0 .089~ tO.l?l (; 0.:166 U.<M>9 rO.OOl O.J.'SO
L8.61 CU98 1 1(),4S65 0.172 Ot.OlS O.OS4 0.342
21.63 ft3 ~93 0..5934 0.108 0.049 o.oe;s, 0.)12-
Z4.'01 01.4232. '0.6315 0.'069 o.ms ro.m 0.291
25.91 O.' SU9 10,7440 OJ04J 0.100 0J}11 0.28J
21.% 4UJotl96 0.80~0 OJOlJ 0. 127 0 .063 0.267
30. 12 0.7135 0.8639 0.1018 O. tsl 10.05! 0.248
31 ,7~ 0.19)4 1().9048 0.00)
1
0.11) 0'.038
1
0..234
34.115 0.9101 '0 .9.590 - 0.'000 U.23'1 o~.o~ 9 0.:!27
36;09( PI\ilm) 1.0000 11.0000 0.1000 0 .()00
ilbct"ourthmnodynami~: ~rjcm . In YJ , lu ~. c;&l R"l. and GF./x1 ,.:Jtr,arepmpcrli

of lb~ Uqu~d pb~. r~~ 12.S(b) ~~ how ~ir expemmcn1Jd ,f81~ fliY "Ni1Jil compo. iJJoo
for ca particular bifl:&f)' y~m at DJ ~peclfied tempem1u.rrt~ This li~ is c~temtic of sylitems
far wllich:
~ ~ J ancJ, In Yi ~ o v ::= t ~,
0.2 0.4 O.t U l.O
..... 11
(a)
~ 115; 1bc lmlhyt ethylb1011.e{l~ne(2)sy.stematS(J11C. (a) PX:J.l daraanddloif~tiot'i.

(b)~ pro~ aod lbeir~rKh
lbi $lreh ~S d~ liquid phase ~OWS JNUfJi~ tmrlatft1ll'S firom bolill'sahlW ~behavior'. 'Thls ms
seen ak0o .in f'1s- 12.5(~1 where ~b~ P-x1 tbm (l(Imw aU Ye 11~ Ulc da&hed straight line,.
whi:cb JC~ Raoulf5law.
B~ m
tEm oc'tiviry e_oeflicicn~ ()fa s,ecies sotutkm becooteS uniey as tbe species
~pum. eacbln ~ (r;;;;;; l.2) rends1DZeJC:HIS.q -+ L Thls.isoevideftr in Plg_ ~2.S{I.t). At
me ~ thnQ, w.~ ,l!l -+ 0 -~ ~ .; ~ mtmitdy dilut-e.ID yr appJ'!OO.Olles a finite
limit.~ fu rr.
lln rtlhe Limit as,( t --. D. me dit'netiloolefiS e;wen Oi.bb~ energy Gl5/ .RT
as g~ by !.q. (I 2..6} ~es:::
1'bo :same r~II is ctnained or .r1 --+ 0 (.tl -+ (). 'The vatu.e o f fil:/ R T (and G ll) ts.tbecrefore
~ adliCllh A" I e 0 .iindl.it1 ~ L
1lw quantity G8}KlX!RT 'bGcc;mw ~ bolb m x 1 c I md JJJ: i o m beat~
1GB {is :zero mbo4h lilllit$, u .WI, the product JrtX2. Tbu.s. fur %11 ~ 0, ~'HOpiGii7s IIUle yie1ds:
tim GE = li:m G / .f:lT = tim .d (GII{ RT) ( A)
A&-o XIJI.'lilf -J""'11 .l'IL ~ 0 .Jx.a
Diffimmtiation of Eq_. (12.6)whh JeSPOC' m XI pro:viides 111lile cktiwtive of~ f\irutl me4Dbe:r~
d(G/RT) d In -
~--:---
iJx1
IC ..t' d. In --
rl
U X(
}1 + ln Y:l1 + Xl Yl - In n
(l,:(]
(B)
1be minDS sign ~tding the~ !last term oom~ from dx:,;j dx1 =: - t a consequence of lbe
437
eq~. xs + ..t1 ~ I. 1'be Oi,l)bNDuf1c;:m eql:l.lition. q. I 1.1 00). written for: n brn.a:ry ")'stem,
illl divided by d.ra to alw~
(C.'Orull T ~ P)
Subslit.nioo ruo Eq. .B) r11.1cts it to:

)It
In -
n
Appl~ ~o the compt)Jiliuo l imlt nt .1 1 O. 1hj11 equ lion yield&:
~1t m lllG";I RT)

I' ...
111n1 u11-
Yl In .....
)''I
"I n .dx1 JAI~ -o n
Simihn1y.
1bu tiiJ limiti ng \'gl~ of G 11/.'fm;t~RT life equ:d IO rth.t ;ntinittdtomion ~~mi., ot'lo Yt ~lid
In YZ, 1tds ~lilh ls illu.~mml in Pig. 12.5(b).
The.~ rc~ults depend on Eq, Ul.7'~ which i"' \'lljd fDr <nlf44nt T and P. AlEhoua;h mt
dam of 1abl~ ll.-l llJC fn1r consc.:~m T . but ' ' :rillble P. nqU,Pble ewr i , intl'Od~l lhnlutb
Eq. 0 2J), ~ liquk\1-pbasc m.-ti...,il)'' axfliclmtl' arc 'lief)' nr.arl)' independent or p (O'r
sy~ lit low 10 modeltlte ~~~wes.
!qLmtLM (12.1 >bas (IB1her krllucnec {)D the llAtl.lfC o.r F;i,g.. n..5(b). Rcw:rittco I
d rn Ytl ~'l d 1111 ~

~.....-. w - -~---
d.r~ .:1 ~ d Ztt
it requi~"" the Jopc of Wle In Yl CW'\'" ~u be e\...:rywhtre of ~in: ~.111 \u me, .dope of 1tbc;
In Yl cuM. Funl~. wtlen x2 ..... o tand x1 -.. m). me IQpe of mhe ~ n~ n con.re ig nro.
SimLl.Mt). wbf.n .1'1 ...,... O. lhe lope of mbc mYz ~curv-e i~ zero~. "hms.. u ch
=
l(.nnlnare:." dJ ~t!Jio with t.eru .!~I<Jpt at ~ ~ I,
(~ I , 2) curve In , ...
,_,. Plllducllon
Of thee~[& O'f pomlll'J tth~wn il\ Fig. U.5{b). ll\(1~ fot o E;x~ nRT ~1 lOS(ly C(ldfCII"m lO ~
:im;pk Dllcbe.llliRtical n:llltiorh Thu mlsht lioo rpcovide"S a ~I:C u.wlmimlfJioo to lhb
s:e of :poim~. llnd malht;marlcaJ ,expreuion is aiven1ac:. dJWi linear rrdatlon ~ lhe CC}uat~un:
aB
;;;; A 1LX + A r2A'l
XlXl RT
where Al~ ud Atl m consmnm rn 2my pmienlv ~iatli.on. Attema'l'ely.
06
RT ( AllA'I + Am.:.ll).K'a.lfl
438 CHAPTER 12. Solution Thennodynamics: Applications
Expressions for In Yt and ln Y2 are derived from Eq. (12.9b) by application ofEq. (11.96).
Because this requires differentiation of nG/ RT with respect to a mole number, Eq. (12.9b) is
multiplied by: n and all mole fractions are converted to mole numbers. Thus on the right side
Xt is replaced by n,j(rq + n2), and x2, by n2/(rq + n2). Because n = n1 + n2, this gives:
Differentiating with respect

.J>
ton 1 in accord with Eq. (11.96) yields:
Reconversion of the ni to .Xi (ni = nxi) gives:
Further reduction, noting that x2 = I - x1, leads to:
(12. 1Oa)
Similarly, multiplication of Eq. (12.9b) by n. and differentiation with respect to n2 yields:
(12.10b)
'
These are the Margules 3 equations, and they represent a commonly used empirical model of
solution behavior. For the limiting conditions of infinite dilution, thyy become:
~
and In y~ = A21 (x2 = 0)

For the methyl ethyl ketone/toluene system considered here, the curves of Fig. 12.5(b) for
GEl RT, In y,, and In Y2.represent Eqs. (l2.9b) and (12.10) with:
A12 = 0.372 and
These are values of the intercepts at x,

= 0 and x1 = 1 of the straight line drawn to represent
)
the GEjx 1x 2 RT data points.

A set of VLE data has here been reduced to a simple mathematical equation for the
dimensionless excess Qibbs energy:
3Max Margules ( 1856-1920), Austrian meteorologist and physicist.

nus eqila~Jioo C'01lcise1y tOJ1'e ij)e inJormamiolil of tlb-: dattt set. lnde~d. llh~ Mw:guJ~ eq,ualions
ror ln Yl P8d In )I) .allOW' CO:Mtrutm<m o:f D OOJR14Uon of lite ofig~ P .t~ ~ )'1 data set. !qwttiof\
{12.1) is re:~mmged nnd written for ~~~es I nntll 2 of 1 bin:uy syt~mm :11..'1:
1
and
12.1n
'Values r-17 Yl nnd )"2 t'mm1Eq. . U2.10~ ~lth lla::t llnd A21 w dcn~rmincd (C'lfiM mabyl
tblbyJ t~:runc(l)ltolumct'2) ~} rem un: c:ombi n~ whb lbc t:J{perhncnllll vulue." of l't 1 md /12
10 enloolaCc P iiD(il >' by Bqs. 0 l .U Uind ( 1,2Jil )'ll.1 v:uiOtt'i val~ of.W
l Thc~oJ aroJbowin
b)' the solid lhu:s. of Pig. I'!,S(a), wbicb ~vnt dle cftlcul~ed :P-.ta and I"YI relation~. 1'bc.)l
clo;atly PfOVIde an adequi!lae curre1aaloo oflhe CAperr,LJnental dam poi~
1hblt 12.3: VLJ. Data (or' Chlorofdrm('ljll~DioxiDICl)' atJO'C
p~ Xrl )'I 111 ~1 In Y.t G{j/ RT Gn/ Xi1XlR1'
t !'.79V'~dl) o.oooo 0.0000 0.0001 0.000

17.SJ 0.0932 0.1194 -o.7n o.ocw -0~064 -0,.7~8
11.15 0.1 248 ttll83 ~0 .694 -0~000 - 01,.086 ~0.190
19.30 0.17.57 OJJOl - 0.648 - 0.007 -o~. t20 - 0.82.5
19.89 0.2000, 0..1691 -0 .6~36 ....0.:001 - 01.133 ....o.m
2~ .37 0.2626 Cl>.4628 - 0.611 - 0.014 - ()1.17) - 0.112
'14.9.5 0.3615 0>.6184 - 0.486 - 0J0!7 - 0.212 -o.ng.
19.82 0,47SC) 0.7.SS2 - OJSO -0. ~1'27 -o~.2~8 - 0.992
34.80 (J.~S!SS O.Kl78 - 0.279 1
-O..l18 - 0..2.52 - UH9
42.10 0.67JK 0.9137 -0 , 1~92 - 0.3!5 - 0.2AS -l.liJ
601
.38 o.mn 0.9:860 -o.o~ -0.8.14 - 0.,201 -1.1l4
65.39 0,.9'398 0.994S - 0.001 - 0,912 - 0.06! - 11,074
69.36( P,IN'I) J! .OOOO~ 1 ~0000 0,000 0.0001
A~ set of /.!'.tiY t dltll. fGJChlomform(l)li,c4-dioun~(!) II~ $0~;1 iJ &itven in f.l.

ble 12..3, along wilh '~t~,"l~~ of[pcninent chermodyno.mic: funcriaos. ftpn:M, t2.6(a) o.nd 12~6)
dispiCL)' poinas aJI of the ~experimental values. This ~)'sem show$ ntllUi'.V' cfeviBtiona from
R.uoul ~llrw beJwr.~ier~ tH!~ Y1 Wid~ .IUC lw Or.lm runily. v. lues ofln;-'\ 1 I'D )"l, GE/ RT,
;md G 6/Kii.XczRT llJl: MJDilv~. Mo_rea~~r .,,r Pa:x;. ,cb~ points in fia. ~.6(~) um He below tl!le'

1U
-tu
,. ooiO
0.8
30
....o.o
20
_,.0
U)
1.2
0 <0.:2 Ot" O.'f 0.8 1.0

''
11) (f,~
f'1l;uJit w~ n10 d iluroroml( I)J~AdlcJ.flt~~~d 2) 11-)')JC:m ut SO C', <al P~' duAt~ cmd lhl:ir ~CJIJ'ft;.&n . lb~
liqul(j.,pf'IMC pN~~Cniet &md 1htiJ ctlfl:niM.
dashed Hne IY~Iltlng IRIIO'Ulf law behtv~ar. ~\pjn tlbe dat points ror -0 8/XIiXlRT m l't'-U
OnCibly wcll eutelutcd by Eq. ( 12.91)~ Wld d'l~ Mu,b~IA cqwuiullilo ~Eqli. ~ ~:tl0)1 a;uin nppt)',
there with IJiilltuneu~n :
.A12 a - 0.72 Au a - 1.17
'Valua of G/RT, lny~ . In)"!. P. and Yl atcr.ll'ntedl by &p, Ul.9b). {12.10). ~1l. U,. nnd
(12.12) pfOVide Jfhe ~'"W"'t''O hoV~~'R for~ qwmddett in Fl,p. 12.6(u) ~nd 1!2.6(b). Again. the
apcrlmtntal P ".lt,\'t dlil ue ~rely c:orrelmte&
Although the ~co~ion& proV~ldcd hf lbc: t.ktrttolcs eq:wnion f:or 1lbc 1wo sctt of VLE
d3u ~u::d ba1: woe sati ,r~rury. ~hey U1T nor !per!C"ec. 'nlt 'wo
IlK' ibk ~~ ,tn:~ fi ~t~
lhlll ttM MrlrJ.ulei cqu:nlon ,arc n01 precisely snLted ao m~ d:u 11et: second. eh:M ma p,..!f. ,...rv 1
d11t11 lhcms.dves ue- iiY: lemadW'Uy ln1e-l'f!WI' \!Cht thai dJe)' do not conform to ~h_e rrequtrcmen~
of l1w (iib~ ~tui~n.
We have presumed in applyios: the Mft!iiul'ell,eqmmoru mm the dc'\li:I.UOM of lhe e-xper-
ifu~nl41 polnb fotr G I "J1.Kl RT from the srrru_ghl Uotbl dta.wn to represent d'ttm re:-.IJJt tmn1
mndom cmr iD 1lbe 4bui.. J~ ~~~ -~rruij_hA lilles deptrtWLid<c e,K,OCII!nt ~m l!iQQl'l of (fW I:Jiu
11 trcw d\0 poifWI.. ~Only t~ ~ Q( Adi""mm Dre 1ht:~ signifie11nt ckou1miom, ~oo r~
have' been di~d, bcc~JUSC the eJIQf OOLm4J Widell tru~dly ~ lhe edJJ~!t. II di~~gcrum an: ae
tppr0 cbctl In 1 ibe Umits .11 - 0> cmd :r,, -.. L G txmx~ llT ~ irulcrer.mil'J:ue: e-x~

12. 1. Liquid-Phase Properties from VLE Dala 44 1
perimentally this means that the values are subject to unlimited error and are not measu rable.
However, the possibili ty exists that the correlation would be improved were the G Ejx 1x2RT
points represented by an appropri ate curve. Finding the correlation that best represents the data
is a trial procedure.
Thermodynamic Consistency
The Gibbs/Duhe m equation imposes a constraint on activity coefficients that may not be sat-
isfied by a set of experimental values derived from P-x, -y 1 data. The experbnenta l values
of In Yl and In Y2 combine by Eg. (12.6) to give values of G / RT. This addition process is
independent of the Gibbs/Duhe m equation. On the other hand, the Gibbs/Duhe m equation is
implicit in Eq. ( 1J .96), and activity coefficients deri ved fro m this equation necessarily obey the
Gibbs/Duhe m equation. These derived activity coefficients cannot possibly be consistent wi th
the experimenta l values unless the experimental values also satisify the Gibbs/Duhe m eq ua-
tion. Nor can a P-x 1-Y l correlation calculated by Eqs. (12. 11) and ( 12. 12) be consistent with
experimenta i values. If the experimental data are inconsistent with the Gibbs/Duhe m equation,
they are necessarily incorrect as the result of systematic error in the data. Because correlating
equations for G / RT impose consistency on derived activity coefficients, no such correlation
exists that can precisely reproduce P-xJ-Yl data thal are inconsistent.
Our purpose now is to develop a simple test for the consistency with respect to the
Gibbs/Duhem equation of a P -xt-YI data set. Equation ( 12.6) is written with experimenta l
values, calculated by (Eq. 12. 1), and denoted by an asterisk:
G E )*
( RT = x 1 ln rt + x2 ln ri
Differentiati on g ives:
d(CE/ RT)* d In y*1

- -- - - = x
dxt
+ In y* + x 2 d ln y*2 - In v 2
"'
J dx1 I dx1 '
or
This equation is subtracted from Eq. (12.8), written fo r derived property va lues, i.e., those
given by a correlation, such as the Margules equations:
d (G Ej RT) d(GE/ RT )* Yl Yt ( d ln Yt d ln Yi )
- - -- - = In - - In - - XJ +x2--=-
dx1 dx1 Y2 dxt Y2 dxt
The differences between like terms are residuals, which may be represented by a 8 notation.
The preceding equation then becomes:
do(G E/ RT) Yt
- - - - - = OlO - - ( XJ d ln d ln
+X? - -=-
Yt Y{ )
dXt Y2 dx 1 - dx 1
442 CHAPTER 12. Solution Thermodynamics: Applications
If a data set is reduced so as to make the residuals in GEl RT scatter about zero, then the
derivative d 8(GE/ RT) jdx 1 is effectively zero, reducing the preceding equation to:
y1 dIn yj d In Yi
Dln - =XI + X2---=- (12. 13)
Y2 dx1 dx1
The right sJde of this equation is exactly the quantity that Eq. (12. 7),
the Gibbs/Duhem equation, requires to be zero for consistent data.
The residual on the left therefore provides a direct measure of devia-
tion from the Gibbs/Duhem equation. The extent to which a data set
departs from consistency is measured by the degree to which these
residuals fail to scatter about zero. 5
Table 12.4: VLE Data for Diethyl Ketone(l)/n-He xane(2) at 65C
P/kPa Xi Yl In yj ln y{ ( c
X)X2RT
)*
90.15(P sat) 0.000 0.000 0.000
2
91.78 0.063 0.049 0.901 0.033 1.48 1
88.01 0.248 0.131 0.472 0. 121 1.114
81.67 0.372 0.182 0.321 0.166 0.955
78.89 0.443 0.215 0.278 0.210 0.972
76.82 0.508 ~
0.248 0.257 0.264 1.043
73.39 0.561 0.268 0. 190 0.306 0.977
66.45 0.640 0.3 t6 " 0.123 0.337 0.869
62.95 0.702 0.368 0.129 0.393 0.993
57.70 0.763 0.412 0.072 0.462 0.909
50.16 0.834 0.490 0.016 0.536 0.740 ..,
45.70 0.874 0.570 0.027 0.548 0.844
29.00(P sat) LOOO 1.000 0.000
1
Example 12.1
VLE data for diethyl ketone(1 )/n-hexane(2) at 65C as reported by Maripuri and Rat-
cliff,6 are given in the first three columns of Table 12.4. Reduce this set of data.
5 This test and other aspects of VLE

data reduction are treatedby H. C. Van Ness, J. Chem. Thermodyn., vol. 27,
pp. 113-134, 1995: Pure & Appl. Ghent., vol. 67, pp. 859-872, 1995. See also, P. T. Eubank, B. G. Lamonte, and J. F.
Javier Alvarado, J. Chem. Eng. Data, vol. 45, pp. 1040-1048,2000.
6 v. C. Maripuri and G. A. Ratcliff,
J. Appl. Chem. Biorechnol., vol. 22, pp. 899-903, 1972.
12. 1. Liquid-Phase Properties from VLE Data 443
1.4

90
1.2
80
1.0
70
0.8
C'O
0..
60
E:
0.6
50
0.4
40
,.,
0.2
30
0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
x1, Y1 " x,
(a) (IJ)
Figure 12.7: The diethyl ketone( I )/n-hexane(2) system at 65 C. (a) P x y data and their con-elations.
(b) Liquid-phase properties and their correlation.
Solution 12.1
The last three columns of Table 12.4 present the experimental values, In 1n Yt, Y2,
and (G E/XJ x2RT) * , calculated from the data by Eqs. ( 12.1 ) and (J 2.6). All values
are shown as points on Figs. 12.7(a) and 12.7(b). The object here is to find an
equation for G El RT that provides a suitable correlation of the data. Although the
data points of Fig. 12.7(b) for (GEfx t x2RT)* show scatter, they are adequate to
define a straight line, drawn here by eye and represented by the equation:
cE
- -- = 0.70.~-q + 1.35X2
X1X2RT
This is Eq. (12.9a) with A21 = 0.70 and A1 2 = 1.35. Values of In Yt and ln Y2 at
the given values of x 1 , derived from this equation, are calculated by Eqs. (12.10),
and derived values of P and YI at the same values of Xt come from Eqs. (12.11)
and (12.12). These results are plotted as the solid lines of Figs. 12.7(a) and
12.7(b). They clearly do not represent a good correlation of the data.
The difficulty is that the data are not consistent with the Gibbs/Duhem equa-
tion. That is, the sets of experimental values, ln and In Yt Yi,
shown in Table 12.4
are not in accord with Eq. (12.7). However, the values of In Yt and In Y2 derived
0
u r-
0
an
.. /~
Ftpq 12.8>Cmtlii*!'IC)' le1lt <'"~
dfila fot dlclb)ll
~

0
~I
- .,
..I ~
k.c:lDJ~e~. J)llf.bcJ:~&ndl'J ~ M iAC

- O.l ~
!' ()
,n
") oo
.Q
0
- 0.2 t- 0
I
0
0> 0.1 , ,0
.,
/rr:tm "''~ t.'OI't'riulion llf.':CC.~'ty obey tbi~ cquacion~ tbc expenm~ alld ~rtvedl
values ~beman! c.annm pos~hly ORe. ANI !(he re!IDilill rCOMLm:t:'tOn .emnoG IPf'D"'
I
v,idr a. p~i repre ~of lhe romph:te~ litt u! P.ttJ 1 duttl.

A.NJ31auion of 1thc 1w for ccm.'\tlttmc:y rc~ntcdl ~ Eq ( tl. J)) ~
Clli~JutllliOil of lhe ~~eMd u11ls d( G1tRTI ~ lln(yt/"t'l. ). \'alues of which are pltcdl
1
w. XI 'to AJ. 12.8.. tbe ~- idulll d(Glf/ l1')1dislil\ibute ~'h~m ~v abou1 am.'
lt.li ILK reqelrcd by lhi! ~~~, but the midWtt~ I In( Yl/Yz). ~'hi h 'i iMW the .C.XItilll to
wb~ll'l: I he d~t ! il~ 1[0 ~~ti ry Q\:: OI~ll/Dobem ~~u lion. clturly rllo ln/lt. A\'Cfllge
.IIMluto ftluc of ~1Vr te:Jidui~ Jc ~ than t(),C}3 indic;~.r_e d':IJ~ of .a ln.igiD deg;ee or
COll'lSI"CnC)!; ~- absolut~ vuJ'ua of~ lh1111 O.:lO L11C prObably ~aa:~pmblc,
The dam set ,con idered h.tre 'how an1ll\'tl'lll'e rab.ro.lwe vi~lon of obout 0. 'IS,
and must itl\trcfure co:nmi o ignifkant eA'Or. AEtboug:b1one Cannat l/le cc.rt~in '!!\'~"'
u.e mm Hl till~ Vlli~.!Wi oJ Yll ~ umully 1QIIOS\ U'jpcet.
The rudhod JW!t dese~rfbed procha1 crel~lh:m thai ~ o:lllnm:e 1\rily d'Ytr-
gent tmm t~e ~mcn~il volues. An llllernn,b~ b 1tu pruces! josl d~ P-x:1 dtl ~
lhb i pM5lbltJ I~ tile PA"1)'r t'l:lta ~l includ mot~e infOfDilllionJth:m W'!'&
mary. The ~cbl:re requi~ Ill OOiiJP'Uitr,l but in prmclple i~ ~~n~ple e:noush. AI-
wm; nJ d'm1 ~be MnJ:Ju1 equ1nlon ~~ l~Jr~Proprime ro ltb:e ~~~~ one mtl'C1y rarcbc~
for valu~JI or the [pi.U'IIInet~l$, AJl mdl A:l Uml yield I~WJre.S b,)' J!.:q. ~ ~2. lll )t m;n
m M C"I'O$JC possible to ~ me.oJtmrtd VlllDel. Tilt r'Mihod b ap,pljieublc ft.,
IJ!ftllHt oJriJb~ tmreltlUDJ equlliOD WllC!d~ nd i !mfi'JII lL! 8fHktF.l' fl'tl!thad.*
1 ~
1\Jmpl _ (K~Y~ tp);OtJI I'IV!\1 liJ. I nd I ~lirlll l(tr G '/R1' v.o~ll,l'I(J 11~ ~bll btl 1m~~ b)' a rcJI~\1011
~tt'iun,! tbat dtff'nniJ'II!f. IIIIo ~ l'll ~ll Ul'ldl AU 11'1m ml1t m~ ltlC Ufll d( ~uro< o:I ~IJ!e rt;t.id!Qlw l(t;#.t iU),
J. A.. 'IJ.Ir,._~,. ,w,,~ J. 'Clltm.. '~ 6.1flPo lOl-l tO.. 19'l.

0\,6 -<0..2
0.4 -GA
-:O,.G
~
- o..e
, 0
.r~
1
A'1
"'"'
.(p) (~)) M
Fipft U..9; Logn.rl1hlll$ 0( tbc .lk'liliity ccdlki~Bl'S at Sf.PC filii' sfut biiiU)l li:qui:d S)'SI:e:ms:
(a) C'hlot\lf~rnUV~t~ep~);, (b) ~tOIIC( l)lm~l.:l5(Z); ((') ~~I 'ca-tl~oml(l):
(J) rtliCIIIU'I(J )ln4tepmoc(2) (e) mbnnol( li)fddorofm(1)~ ( /} ccb11oof( l)t\\~h=:-{2) .
A m:z = l .l.Sl
Use ofthese pw-ameters.in .Bq ( l2.9a~ (12.10~ (ll.ll)>. and (1~ t2') pr-oduces 1lbe
~vhs destribcd ~ ~d1.1 bed Hnes ofFies. ll.7(a) ruld 12.7(b). Thee(llll!1ttlion
camoot be p;eeise. bot rt deB1y pmWrl'es a lbenm overall repre.sentalion o f tho
~~~till P..x~''1 dm.
Fig.ure ~2.9tJIIO\vs plo~ ~of In ;n ~ on Qpaimaml ~1$ tbr siJ biJWy S)l.$-
1te&n. a lS<FC, mustmcing lhe variety of behavior lhil is obser".~ Note in every c ue lhat as
Xf -+ .. Jn n ~ 0 witll!J 1DO ~ Usually (but DQ1t airway ) tbcJ infurl.tc-dilulioo l!diflty-eoef~
fidem is .-n exueme \'Mile. Comparison of ~ SJ11J)b$ wilb ~ ,of Fig.. 11.4 indi~ lha1
1 be Ln n geoer.&y kn~ tbe same~ as ae. That is. posiiD'e (JK imptl.es.aaiv,i:ty ~coefficianu
.~am- tbnnt nnity andl negaJive G!t implies .actf.vify oodfici.mts 1m ~ban nnlty~ '11:1~-a.~t G\i'et
mo5t of de composidon ranp.

446 CHAPTER 12. Solutio n Thermo dynami cs: Applica tions
12.2 MODELS FOR THE EXCESS GIBBS ENERGY

moder-
In general c Ej RT is a fun ction ofT , P, and compos ition, but for liquids at low to
of activity
ate press ures it is a very weak function of P. Therefo re the pressure depend ence
coefficients is usually neglected. Thus, for data at constant T:
(consl T)
The Margul es equatio n, Eq. ( 12.9), is an example of this functionality.

A number of other equations are in commo n use for correlation of activi ty coeffici ents.
n is
For binary systems (species 1 and 2) the function most often represe nted by an equatio
G/xtx2RT , which may be expressed as a power series in Xt:
(const T)
nt
Becaus e x2 = 1 - x 1, mole fraction x 1 serves as the single independent variable. 9An equivale
power series with certain advantages is known as the Redlich/Kister expansi on:
(12.14)
In application, different truncations of th is series are appropriate, and in each case specific
express ions for In y 1 and ln Y2 are generated from Eq. (1 1.96).
When A = B = C = = 0, GE/ RT-= 0 , ln Yt = 0, ln Y2 = 0, Yt = Y2 = 1, and the
solution is ideal. r ;ol\.
J-.1\. r ' ./ \
If B = C = = 0, then: Yv, _.{}_ - ~L' "'X~~
GE
- - -= A
XJ X2 RT
Y2 are:
where A is a constan t for a given temperature. Corresp onding equatio ns for In Yt and In
v~ :jy
1
,-:1 ,. ,, I
In y , = Axi ( 12.15a) linn= Axl (l~.l5b) 1
activity
The symmetrical nature of these relations is evident. Infin ite-dilution values of the
00
coefficients are ln y~ = In y2 = A.
If C = = 0, then:
c
=A + B(x t - x2) = A + B (2xt - 1)
XtX2 R T
A 12. the
Jn Lhi s ,c ase G 1~/x1x2RT is linear in x 1. If we define A + B = A21 and A - B =
Margul es equatio n is obtained:
9 0. Redlich, A. T. Kister, and C. E. Turnquist, Chen1. Eng. Progr. Symp. Ser. No.2, vol. 48, pp. 49-61 , 1952.
at.
----- IDr An.cm + A 11-'l
X aA'!.,.
(l2.9a)
Aovthcr wcH~ktkiWn cqkl.J.llltn t'tll\lll' 'Wibco ihc ~~o'l!lr1.'JC;d exp~ion .~ ~ RTI G E

c=:tpre~~ o~~o ~ ~ri A~~r fiJnctiOn<tf "' ~
.rr. X2 t I , , ~ ,
OJj iiT 1:3 .ot (.ll~ .t~) + B (.q -lfl ) J!!! (A + B }.q +(A - B 1-''
Wfb~ Ill.~ IP~DlCtl!~ :xrc rcfi!til!led by ttle e.quatlorut, A' .L ~~~ = 1 /A~~ ttJJdl A'- B' =. UAI:
on et.fUh'Dimt fr'"u h. ~ined~
x ~" .~ ~ '~1 ,.,"''1zill + A'l pX:t-

li ~-;-+-;-- I I
c; I RT A21 A 14 AuA 21
or
,G;; AI:A2,
Xl<JzllT - A~-z.t~ + A% 1 '2
100 ~~~Qriv~~,., ~~>ellicieuJ..; implri~ ~y lhit~ ..:llfW11iou arc~
~ U. lln) lnr.!
_. , ( 1
n:zt + . _,, klm"'l)-z
I ( fl. J111b)
nttfl
11u:tW arc lknnwn ll'\ the vt~n l.nnr 1 ~,~ C-<J,LmriUWI. When XI = O.myt'"' A ~ 2 ~ wJtm .t1 G.
~n r.r c: Az1,
The RledfJc:hiKb1.er e,..;p ~ion,, 1M M IIQl;UJ6 eqw.dbu:m IUII(l U'IIC V"illl Lwr ~rnllliQD. will:
aU ;li~ CU.'C~ tliJf a ~cruJ tlre".u.tmell. ~J DO md.onal rfw":doru k~.~ em t}W&lion fnr
,c;t/.'IIIAzRT Jiwn b~ ruAJios ,u f twJlyn~midK. H The)' rrmnid~ gJe:U ftcJUbilil)' in llite lbli._a
.._,r V datitlor binru-y )'~t~ms. HQw~r. ahcy lhQ/11'C' iir.lfir tbmlrli:caJ fouodiiliu-o. ~n d ~he~~
'ft1re rail mv udmi1 a rntional hll,.i.Jt for 1;':\h~n.\lnn tto mmli;o~po,nm 5)"5lml, . M<novu, ~
do 004 Ll!'la'lflii'DniiC. UJI &e:'Cplic il 'cmpcr-.t1Wfil dc:~ndet~ rnr dM: pim111ll~~lr~, mhous.11 ~ hil'l CIJO be
U,P,plied oo 11n ctd lwc ll;JAbc.
Locai.Composltlon Models
Theoroticlll dc~ 11opmrntJI,j i111 the mol~u~;Jt ~11cnnodymJ.!tli4~ of l!QuidM 1110huioo l'Cb:J\iior tn: of
ttcn lwi'tl!d cJil elK t.~~pt oi iocal CtHJIJ)Vstlitl'n. WHhln ,a Uquid solution, I~ I oom~iddn.~,
dl~Temnt from 1(hQ PVemU fDM'(~I..i~ t"'llm~icio.nj ~wn~ lor:account f\ll' U'il: hort--runF
IOj~]a"lft"' 'w~ L.df(~ ~~~l!O.I)iutc:h p~UII~telw;mnl.
II K C.: 'l,'lm ~ oe llOIJJ ttt ~t Atlxtti. rt.."tu'-rJti'J.t ~1rtiftlMmt ' ( 1\\rnrtn.I~rr S,Jbltmlfl' ~~,ohr ,tpp/'f"NiiriiD tr>
~ ~,,J1.brf,t. Sa'. ~.1 Ftok;(lfWFr~J!Jidl, D1 Yi.... ~ ~~~l.
Obras pt otegidas par dit eitos de aut or

\
448 CHAPTER 12. Solution Thennodynamics: Applications
order and nonrandom molecular orientations that result from diff~rences in molecular size and
intermolecular forces. The concept was introd uced by G. M. Wilson in 1964 with the pub-
lication of a model of solution behavior since known as the Wilson eq uation. 12 The success
of this equation in the correlation of VLE data prompted the developme nt of alternati ve local-
composition models, most notably the NRTL (Non-R andom-Two-Liquid) equation of Renon
and Prausnitzn: and the UNIQUAC (UNiversal QUAsi-Chemical) equation of Abrams and
Prausnitz. 14 Afurther significant development, based on the UNIQUAC equation, is the UNI-
FAC method, 15 in which activity coefficients are calculated from contributions of the various
groups making up the molecules of a solution.
The .Y9lson y quation, ~es and van Laar equations, contains just two pa-
rameters for a binary system ( L\ 12 and L\ 2 1), and is written:
( 12.18)
(l2. 19a)
= L\ 12 L\21 )
ln Y2 - ln(X2 + Xti\ 21) - XJ ( - ---- (12. 19b)
. XI + X2 .L\ 12 X2 + XJ L\2 1
For infinite dilution, these equations become:
,...--
and ln y,;x> .- - In L\ 2 1 + I - A 12
~ -
Note that L\ 12 and L\21 must always be positive numbers.

The NRTL equation, containing three parameters for a binary system, is:
..
C 21r21 G 12 T1 2
----+ . (12.20)
+ X2 G 21 X2 +XI Gt 2
X(
( 12.2 la)
2
1ny2 = x 2, [ r 12 ( G12 ) G2tr2 1 ]
+ -(x_1_+-
.x-2C_2_ (12.2lb)
x2 +x tCJ 2 1 )~2
Here, G1 2 = exp(-ar12) G2 1 = exp(-ar21)
I
12 G. M. Wilson, J. Am.
Cltem. Soc., vol. 86, pp. 127-130, 1964.
I3H. Rcnon and J. M. Prausnitz, A!ChE J., vol. 14, p. 135- 144, 1968.
14 0. S. Abrams and J. M. Prausnitz, A!ChE J., vol. 21, p. 116- I28, 1975.
15 UNIQUAC
Functional-group Activity Coefficients; proposed by Aa. Fredenslund, R . L. Jones, and J. M. Praus-
ni tz, A/ChE J., vol. 21, p. 1086-1099, 1975; given detailed treatment in the monograph: Aa. Fredenslund , J. Gmehling.
and P. Rasmussen, Vapor-Liquid Equilibrium using UNIFAC, Elsevier, Amsterdam. 1977.
b~l
and ~"I"=-
- R'l
w~ b L'2. mid bam tPartmttm; 'Jllfto iD u pa:ml~-U![m p.alii! O f ~cit&. are 1ndepea.denl of'
f I
composOion and tempe~ The .mfullte-ditudon values of lbe ~rity ~ocnicien._, ~ ~

by mbe eqllldioru;:
Tbe UNIQUAC eqlmion and.ihe UNl:FAC method .are mode.l~ of ~tcr complu_ity and
are Ue&ted in App. H.
The loeaJ..compo:siril.ln IIKJdel$ ba"-e li:mitedl Ot1ibllit)' in ate tiJ.tirlg of dml. bw; they
are uueqw:ne Jior :most engmeerm.g
~~ - I'
puposes.
. 'U . . .........
IY10fie.OV, . licit,1!.r .;,......,_l]zab.] - ......
u-:r are mp !A!II7 p~~---~- ,1,0,......
maltiewnponml So)'j tc'Jm wic:bou' me
mlrodY~tioo of UI,V ~~~~" beyond I~ tequin:d i.O
de.llfribe the com&riwem Mll;a:ey s.yt;tems. Fer e.~ ~e Wilson equatioa furmulticornpoot:ru
~~is=
In Yi e I - tWtlt t(E
I
XJAtj ) ~ I: ' .rtAw
.t l; Xj hJ:.j
U\2.23)
i
~ AiJ ;: J for i ;::: j ~ tt(!. AD ind:i= refer m lbe same spe.aes, and summ.aii.mts are over
(l/1 ~pccte&. !for eadi i j pmr were ore tWQ pMHDeters. beGilu.se AtJ .j;. h Jf. For a Wcrmuy ~m
~b.etlm:e ij pairs are assaciated with b p~~m Au. A:n ~ Au. A:n ~ and ATh An.
the tanperatu_D dG(ndi!DCG of the pmtrneltt$ i5 giV'tn by:
(i '# j )
where Vj and V, me abe mo.lar vol\IIDeS at te~ T of pue liquid i IHld #. arlll DiJ
:a COIUU.JJt ~l o( Clil~positi~n ,IUJd fempmtttWC. Thu~S lhe Wilson equmoo~ like ail
Q1her ~'OOal-t:am~tioo i:fiOdelg M8 buil't inm it 4.1'11 appmtmme ~ depe~ Cur
tbcl ~er.s- Momo\'Qr. :J.ll i~r~ me found! fi'oml diU& rem ~ (in OOHII'ilxt w mlllliA.
component) 8YfitmL4!. 'This mates ~erer ~cion fur the: locaJ..ann~oii m~ a
mst. of Jllllr~..a.gea_bJc !PfUpnnifm. .
1U PROPERTY CHANGESOF MOONG
'Et}'Wllloos ( ll. 79) 1L1llrongb ( I ] .S2) are expressio11s. for tbe propatj'CS of ith!a1 ~alwlom- ~h
m~ tz comhin~ with. the ddnins equatian fm an ~~ propen)l.. Bq. ( 1 1.85)~ :m yie1d:

G
5
.::! G- lJ 1
"'' Gr -Iff E .t,In 1

S~ ~ S - ~ ~ S; + B lJ 1 In 1
,, c. v - E' ~ .1}
'
n~ H - E- ,f.rH-
~
~ fum t"WO ll:nn" on tbt. d81JI ~4e Q.r cm;h eqw~rioo "PIUS i.l diff'cn:na= rur\lmg B f.mm,
t - E~ Sl ~~~. These qwmliliCfl ~ pmp~rtydm!1ge.v ofmlxi'QJ.symbo~ AM. 8y dafinilinn,
[AM EM- ~ .,.w, I

wh~ M j'i a mohlr HJI' umt'lmiSS) ~tullon ~ nnd MJ is 12. Dltar i~Of mil-IDDSS) pi.R-
.sped~ pmpen:y. n111!lit d3e ~ T tmd p I ,li)W Eqs. (I~} through ( 12.2:8) elm be wmen:
0 =- 40- RT :E J 1n .'\'J ( 12.30) sE-AS+ R L x1 Ln'.t' Ul..ll)

, ~
VE = A'V O' ~2) Il l:= I!. II ~ 1 23l~
wht:!rn Au. AS.Il,V .aDd 611 are. tho Oibbts energyc~ cd mUin:gT ~c entrqpy ch:u1ge
uf 'mixmg,. Lbc valtrrOC cllWJse pf mi:UQ.8. md 11M endmlpy eho~~~ge of mi~iog. For an ldal
s.aludoo, ~ !!~~ propeny [s RJO, mKii far l!titSo pe:cial oa.~e.lbe$tl rquntian:'> ~co~
AGi:a = RT I: -"i m.10, Ul..34.' t:.SS11 - - R. }: "J In x. ~ l1.3SJ

I
.6 ,,J.J = 0 ( 12.36~ I!:.H 14 -. 0 UZ.J7)
1bcse cquadnau rue nlti:rMILve fcrrm of"&js. (U.79t lhrt.lUfil (I Ut2). A!tt wnut:o ~ diey
appl)' tu ~-gcu ~"tinFC!i as "1eJ.t ;~n to ~.dml ~cibmPJ~S.
~1Uit:foo ( 12.29} I!DIIf be Wrlth,n for M ideill SQ'Iution:
AMtJ ~ J;Jilf - I: XI Mj
I
Suboucling rbis cqWLtioo from fi.t. ' 12..29) pe~:

AM -AM 1 d~ M - M'd
1n rornbinfltrjo_m whb Eq. ~ ll.M th:is become :

Mil = AM - AM'd ( !2,38)
Obras proleg1das par d1re1tos de autor

453
EQ,wliom (l2.l0) W:ough l2J3> sbow that Cltnll propmi~ lmd iPfQP\Y dim~ of
1
(
mblng CJfe trt-<ldily (;ulcut:atcd one from the other. Allhou[lh hi~c:nll) propm)l crnmg~s o(
~nixing were inL ~ fLnJI. ~c ~ of tht!ir di:red' reluoo to cxperimen~ actsS proper-
ties til. lOON trc:.adH)' ~nto me t~t~ti~J frniD.cWOtk of j(l4)1udon lth~odyrmm~e B~-w tlf
~heir di~c me umbility, 6 f and A II uriC the pmpmy cb~ of m~~iJtS or nwjor ~ntct~:~tt.
MONovu~ they m ldentkal wilh lhe~cue J)OodJn~ exec:ss propcnies.
iPatltldon
flu"' 1'110: .~bnww dill.iruln ol

experimclltll mim f!roc ,
'"~ t ,f tj' 11-*- - P

r, P
An uopet~htlCDtW mli\.irn; 1~ for ~ biMry i}'S~n ~~ lq)feSCfllcd ~~tU~,tlgdly h'l

Fms,. ~ 2.lt. 'Tht e~o pu~ ~s, both ru r
ai'l.d P. Am iniclan~ ~m~ b)t ~ pan_ttia:tl.
wilbdni'W'DI of which allo~ Fl'll :dng. AI mtdna oceun.,,e:qmns:ioo or ~ticn the ly~m or
ir. ttcto~icd by 11)011CJr11CI~' or. ~he pi!w11 S9 jhru lhc prcsmro i con cmt. fn liddil ion. hem
is odded o:ll' c.xnucd tonrninwn 1.'1 com1wn lc:mpuotu:rc. When mixins: i.s c~mpl~te, the wla!
"'OlurM ~.-'hange of ~ )littcm 1( n~wt1d by pbton d3 .;1ncemem d) i :
AV1 - (,~~ + n~)V - 111 V1, - ltQ~~~
Bocllu$C lhe proces..~ occurs ru consUUtr pro6 u:rn~ tht toct1 '1nc.u: crnnsfcli Q tq, cqoall.o lhc lotai
cmh11lpy ,eftmngc of the 'Y!Ilem:
Q ~n - '('"~ .,. " l )H - nt1H1 - t~~H"J
AV'
AV V - x 1v, -x;z V: = - - -
nt + 112.
AN II - :(ttH~ - :r~H:: -- Q
"' + "2
fhus chc volumt chwJ~ o/"Jixlns AV tmd the tntlullpy duJJJt> oj mmusA H ara found f'mm
~he me~urcd Qwmtllies o vt rumd ,Q, !at~~ or~~ usoe~tinn w-~th Q .o.n ij nruqlly elllled
~'ltl ~or ofmi'<IJ11.

Flpz'e U..U: B,;eess wh;ilptcs ~
~e[bal~Dliwaucr.
figure 12.11 ho~ ~:rimmlal bea11 Qf mixi_oJ I:J. It (or ~ mcbalpies HE) for
lh.-t eibaru.t~retr ~ .16 il ifWlt1ion ~uf composilin fur' st.Vf'!li:ll ~dlure& bem.weeo 30
,lll_d 1m~c. This fig,urc :iJhi~, mudiJ of the variety of 'bdmrJor di"ou:nd. mr IJ e. - 0.11 md
v8 ~ ~ v dara illr 'blruley liquid srlefl'l~ S:'ttc.fl diila me fitso,ufrei'll RF~~d by c.'litUMl.CfiS
simihr 1:o lbose 1usedl for GE dam. in particular iby the Redlichlf!is,ter expansion.
Example~ 112.2
lhe e);:tess ernhfpy' (hmll: c:d moongJ fo1 a liqwd macwm of species 1 and 2 a1 fDEpenies ,a.fe :J~IilUd Q;y a~oo of lEq&. 0 LLS) and ( HJ6) wiitb
M e: H E. 'Oms.

45)
( B)
Elimhrnimli o~ ~ ill fllvll}r u~ .ll l in lhe given ~LY.rll.o:m for He mtd d:ifferemi."llioo
.o f ilw resnlt yields:
[ H" c1lb:.- 2o..r (C) I ~ ~:zo-W, CD! I

Su'bsLitudon o Eqs. (C ) ~d (D) i ntl) boll b. ~- t(.r\) and (8) ~ ItO:
These equanom cl;)of:airt, I1'Jl;icb tbc $JIIM iJafotm.utioo t~:.'~ tlto~ of Ex- I i .4+
l vflf)r<: I~ 1:4L~m ~ o:f the C:irl.'~D far H i$ lie$'1l!l ro
dle ex(l~lltl 8fveb here
fur 11 E. '"IY<rdore.
II o;;; 400vl + 600x:t + It'
Cleatlyt 1-i! .1:2 400 J mdl- 1 ll.Dd H: ~::~ 6001 J OJW-l ~ The ~ tpmpmia of
IBx. 1 ~.4 race rcl:amd to Rf nnd fi] by the cquatioo.s;
fl1:;;:: flf + Ht1 = ifl; + H1 == ft~E + 400

- .~t 1o E -
~ ~ c ~ +~~ ~+~ c ~ + ~
These~ eq~;~:atioos follow 1
t'Fom ~i:natioo of&J!;. (J J.1S) :and ( l E.$S).
~ '$'0] D mos ( vulumc cb:.mp of ~m WnS) ror cfl.e mechanol(l )lwmet(2) system .at
~C can be e.akul:.ted :rrom tbc "~1wne~ric ,t btu Q'fFilS. l1.2. B:y IOq. ( l l..88
!Bqwtioo1( l t. lrl) may be written ror the oe~ volume of a biJilfifY .rstem:
E ~,_ &f
v = .X.t v, + ..r:'Vl
l~ults ure tihowo in R:g.. 12. ~ 2. VaLliJe;S on cbe ~gure Cur 1t 1 ~ 0.3 cume tr'rom EA. 11.3. ll!U&.
V{ ;;;:a.J'lUBl - 40.7%7 ~ -1.095 cw? mo1r- 1
~;l f1 .765 - ] 8.008 c - O.lUJ e!M1:t motr

pnd \fl! = (0.3)(-ZJO'/!i) + (O.'H(-0.3031) ~ -01.841 ~em~ mqr 1
Obras prote.gidas pot direitos de autor
454 CHAPTER 12. Solution Tbeimodynamics: Applications
-3.0
...
- 2.5
...
I
0 -2.0
(')
E
Figure 12.12: Excess E
~
volumes: methanol(l)/wate r(2) '3. -1.5
at 25C.
- 1.0
- 0.841
- 0.5
- 0.303
The tangent line drawn at x,

= 0.3 illustrates the determination of partial excess volumes by
the method of tangent intercepts. Whereas the values of V in Fig. 11.2 range from 18.068 to
40.727 cm3 mol- 1, the values of vE = 6 V go from zero at both x,= 0 and x 1 = 1 to a value
of about -1 cm3 mol- l ala mole fraction of about 0.5. The curves showing filE and vf are
nearly symmetrical for the methanol/water system, but this is by no means so for all systems.
Figure 12.13 illustrates the composition dependence of ~G, 6H, and T 6S for six
binary ligu1d systems at 50C and approximately l(atm). The related quantities GE, HE, and
T sE are shown for the same systems in Fig. 11.4. As with excess properties, property changes
of mixing exhibit diverse behavior, but again all systems have common features:
I. Each 6M is zero for a pure species.
2. The Gibbs energy change of mixing 6 G is always negative.
3. The entropy change of mixing 6S is positive.
Feature 1 follows from Eq. (12.29). Feature 2 is a consequence of the requirement that the
Gibbs energy be a minimum for equilib1ium states at specified T and P (Sec. 14.3). Featme 3
reflects the fact that negative entropy changes of mixing are unusual; it is not a consequence of
the second law of thermodynamics, which merely forbids negative entropy changes of mixing
for systems isolated from their surroundings. For constant T and P , ~S is observed to be
negative for certain special classes of mixtures, none of which is represented in Fig. 12.13. A
discussion of the molecular basis of mixture properties is given in Sees. 16.6 and 16.7.
4.5S
'R)QO
- 1000 - ~
I.., I
~
0
I
- 11100
- 2GCIO
1 0
(11
'V,
0
-'' ' ~
1
ta~) Cb) (,It')I
0 , 0 1 0
t11UJ"ll113: ~"Y ~11'\C~ of mb.i"' m $0 C f Ill:~: lbtrmry liqu d.~<~ :

Gel) f:ltJ!olfQromttl )In htl1J4~ane(2\; (b) ~Wt:tU~tC( LV1nclfmool(2)~ t r ) ~ooc( LVcltJNOCMn(2)1.
~d)~~ nol( I ~nhCJ1M;o(l)~ ~(r) e~b oot{l )l~hkmJtrn(l)~ if) G\lwl~( I)!w:ttcl(l),
Exarmple 1.2.3
IProp&rty ~changea ot m1Jilng and toss PfOPSrtle& are related. Show how Figs. 11.4
andi112.1S are generated from COflrelated data for 6H(x) and G8 t,.l').
SOlution 12..3
Whh tHI(~) and G8 (.1') &liVen', Eqs. (J2.J3) nd 1[ U..tJ.6) ~ide:
Th~ oUow compl~tkm ~or Fig. t 1.4. ~~ obru'!ges or ~ins A ,G wu1 t.S
follow fmm c;h rrnd st by mpp1~atlon of&J . ~( ll.30), andr (l!.JO:
4G G 6 + RT L: x~ ln .t~ ~s - s - R I: Jt' !'l'l,o/Yj

~

4S6
12.4 HEAT EFFECTS OF MIXING PROCESSES

Th~ bwt of m.i:J;m,g. ~4ofiue4 in ~ with Eq, H:l-19).. ;
AH ~H - E lif ~
Jl giws (be -mtball)r ~Change \\Dm pure s.-p,ed:es are miad at oon!r.mnt T ~ P ro fooD one.
.DIO!D 1(ar a unit mass) of .wb.Jtio:n. Data .are mos.: ctliiiiDOD]y .amLab1e for binary sysw:ms, fof
\\1h'ieb iq. ( 12-.39) solved for H' ~~
H = X1 H~ +.lHz + All l2-40)
'il1lk o:p:1ir)D pmvidH fur m ~~aUoo ~or me ~es c0f lbibary maw~ f;mm endmipy
d:f.m fnr poe species i and 2 m'lii hm dte beats of nti.'d~a.g. 'l""refimtnltlit ls ~ re.~~ w
bi:Daty ~
&.am f<lr .h&t$.C>fmlfKir1ll~ we us-u.al!ly a:vailablc b u liCrf UOLh~ r.~umbcr of ~~rn~es.
ft' ~ ~ ~es of tho [l'llin.'l ~ptties and o1f 'the mixlwre D~~e ~ bem of~ ure
weu~Bcl tor Qther ~tures by a mefhOO a.nalf.liO-u~ ro ~~ eal~u.larioo or ii(:(IDdcm;JI ~
ofmiiC1in m~ mnper~ :tlmm tbe ~'aloe u 2 C.
HealS of ~~ms are simill.at i:n1many "~ to bGats of rncri<Jn. w 1w1 a ebemie3J
~n_ ~ 1 cbe energy ,of rr.he pmcmcts is ~mu. fiiDID lbe MefiY of lbe tta~ ~t
It:~ !i&ITie T and P bealme of the ohemical re:m:angement of tile conmment a_lmn8. Wht:l'l! a
.m mure r fmm_ed,a imRar eo~ chang oomr.s ~i~tlws bd'1-wn 'the lORe fields
oflite and onlib ~ula are diffet~eD~. 1bse e~trgy <"mop ure ;&rcmerall)' mucll malla
than ~ ~~~ with ~eht-mictl~ bond&; dms hca1s of m~ ::ue ~oemlly lllUCb mullet
rkn1 .heat at m-.il..Ct1mL
"-t ot Solution
~solids W' ,gases ate it.sd"~ in tiquids., tbo h~\ deet "s.called a he.m of soJtWn. and ~
based tOl'll .the d~o Qf J mol t1/ salute. U' sp=clo ~ u ~~ sclut~ ~ ~~ ~ the liW~s of
.mluco per mole of waJi(Jil., ~~ All iB the lwat ~per mole .o f !I!Om-uon. A H 1.ra is lhe
!heal e-~ per llllille ofst)JUie. 'Ji'bu:,
.-.....
~ JJ..l l [s <be hc:n of satu1ioo. em. rbe ~of a moJe of solltte.
So'bllion~are mm~ni~tl,y~ed by plf1.vienlwe1mllKe equatiommalo,Roos
Ito d'lemiea.J:..readi.oo egwdklos,. When 1 llllol ol!UC~} is mixed 'Wltb '12 mol \'ff HzO~ I.JiJc
~ r rro~edby;
UCI(.s.J + 128.!0 fl--+ Li01(l2Mz0 )
The ~gruWi:oo UCf0'2HzO~ llef~nLS a w t11CJioo o1i J mdl Of n.JC.Ldlsscl~ io 12 mol ar
HzO. '1bc heat of sO'Imim fur &his pmc:~ a1 zecmd ~ bilr I.B AH 10;1 - 33.614 Jr. 1bs
mean libtt lbt:e~~ of I~ mol o-f~_jCI in 12 ~ of K:20 is 33,6[4 I ~c.~ than cbs combiocd
enthalpjes of ~ moJ of pur-e IU~} and 12 mol of pure U10(1}. .Bquafton :for physical clltmee.&
sudh ~ lhm are r vadil)f oomhtned !iWth ~uations fm ohemiadr~renctitms. Thl:! i iUus1nlmfl in
~ followtog ~'-n:lfllci whfeb i 11C(tl'plta~ lba d're.l\sofution piO!Ce.Ss Jl!c'\it de~liibcd..

12.4. Heal Effects of Mixing Processes 457
Example 12.4
Calculate the heat of formation of LiCI in 12 mol of H2 0 at 25C.
Solution 12.4
The process implied by the problem statement results in the formation from its
constituent elements of 1 mol of LiCl in solution in 12 mol of H20. The equation
representing this process is obtained as follows:
Li + 1Ch-+ LiCl(s) t::..H298 = -408,610 J
LiCl(s) + 12H20 (l)--+ LiC1(12H20) t::..H29s = -33,614 J
Li + 1 Ch + 12H20(l)--+ LiC1(12H20 ) t::..H298 = -442,224 J

The first reaction describes a chemical change resulting in the formation of LiCl(s)
from its elements, and the enthalpy change accompanying this reaction is the
standard heat of formation of LiCl(s) at 25C. The second reaction represents
the physical change resulting in the dissolution of I mol of LiCl(s) in 12 mol of
H20 (/), and the enthalpy change ts a heat of solution. The overa11 enthalpy change,
-442,224 J, is the heat of formation of LiCl in 12 mol of H2 0. This figure does
not include the heat of form ation of the H20.
Often heats of solution are not reported directly but must be determined from heats of
formation by the reverse of the calculation just illustrated. Typical are data for the heats of
formation of I mol of LiCl: 16
LiCI(s) -408,6101
LiCJH20 (s) -7 12,580 1
LiCl-2H20 (s) - I,012,650 J
LiC1-3H20(s) - 1,3 11 ,300 J
LiCl in 3 mol H20 -429,366 J
LiCI in 5 mol H20 - 436,805 J
LiCl in 8 mol H2 0 - 440,529 J
LiCl in 10 mol H20 - 441,579 1
LiCl in 12 mol H20 - 442,224]
LiCl in 15 mol H20 - 442,835 J
Heats of solution are readily calculated from these data. The reaction representing Lhe
dissolution of l mol of LiCI(s) in 5 mol of H20 (l) is obtained as fellows:
Li + ~Ch + 5H20(1)-+ LiC1(5H20) t::..H~98 = -436,805 J
LiCI(s)--+ Li + 1 CJ2 t::..H2_98 =408,6 101
.,......_;
LiCl(s) + SH20(l)-+ LiCI(5H20) t::..H 298 = -28,195 J
16 "The NBS Tables of Chemical Thermodynamic Properties; J. Phys. Chem. Ref Data, vol. II , suppl. 2, pp. 2-29 1
and 2-292, 1982.
Thb ..~uliJ,iuo r,;:w ~ c~mcd w1 for~ q~~miy .,, K.:tO OX wbich dat~ nn~. ifl'\>cn.
The rcwh~ are then eon'V"4!ni~~mll)' ~eou:d grapbim1 tr by 11 plot of AftM d.e lk!Dl or solution
n,
pet mole or ~lute, \~~. tt ntole; of WI'Yetl( IP'U molt of WiUl!Z. 1be COmpwt]tion ~lil)l~
i "''1./IJ I i." rt.lat4 14' A 1!
I
za-
l +n
~
I.Ut !::!! -
AH
AI
AH(I + -n) or AH~
!+n
-
Fig-ure :ll. l4 bow~ ptoo or A f} -
!!. i; fur LiCI(s) ILKI HCI(j )1dtQOlwdl in W.lltttr ot zs,('C. IDma
in this rorm arc ru~dily applied to the soh.nioo ofpn~~~ic:4Jirpmb1em.
IBcellt~. water nf hychticm in ~ri:ds t 1113 mpl part of u cbemiealt:OfllpOLtDd, the }Jeat
of formJith:m of .1) bydrut.!J ~t1 incl~ the bca of rt'o11nti:Llloo of 1be ~~or tlydm.d-oo. The
di"~Ut~~m ~f l PlU~ {I( Li(~. lJf~Of"') iD 8 rnnJ CJtt' HlO ~\l~ l1 ~nl~utt..m ettftlninillj I 1001
UCII in I0 nltlJ ~of t-i;zCX ~pn~ted r~ Ll ( JOHtZ O). The ~qumkm~ wbk:b ~lilm to gi~ lhL\
pt"UC~t;afe:
U ~Cll: + tOU,O(l~ ..., UCIUOH:~'O) lll-1~. - 44 i.S79J

UC121ti0(~) _... li + ~ Ciz .r 2H; + 0: 1). H:w. tO ll-.6SO I
2H~ + 02 _, lH~.~~ 1:'111~ (2)( -~85.&10') I
~ -~----------------------------------
t::Hm - 589 J
Example 12.5
A sJngte.effec:t evaporator o,peralng al&tmosptterie preaute CO()C811flfates a 15% (by
welgntJ UCI aoJutfoo to 4l0%, Tnt feed enfe'8, me evapo:ra:t"Ot a1 the r ata of 2 kg1s 1
at ~~~c. Tilile norma~ boiling point ,of a 40%. uo~ aolutm Is about 132 eNand! Its
specific heal 1IS elt1ma1ed 41 2.72 kJi ikg- 1 0 iC- 1 What iS lhe he8llf8ntftr rate IIIII the
evapcr.ator?
S01utton 12.1
The l kR of ~ ~ ~ LICI w lulion tntuing rlltt ~~porntor ~eGCh ~ec~nd, eon'lliM~t n
O.JO ~ IUCIIlnd ~ .71) kJl H10. Am tcriA1 h lmce lilt~ that L2~ kg of W:O
ir. I:VIlp\mli~41 11nd ~ O.?S k& ofr 40<11 l...ia wlu\ion L11 ptoo~l.l Th~ ~'t.lltt 1,..
ra:pt'C:Ioentcd "Y ,FiJ. ~l. IS.
The enqy b.allm.ee fotr lhi:J flow prooc. 'iil ~H' = Q, where All~ !s tnc latlll
~nt!wlp)'nf ~he produce :Stn:wmc minuli 1he t<lt4~ enthulpy ef the- ~'eed ~ n. 'lfhu~
Ob1 as protegidas por direitos de aut or

!..,
:I",
-,,TT
!~I
' r\C\\g) + ~
uwlmlliiilll ~~~~~~~~~~~illlllfial
~
siiiiOOIIIIIII~~~ .I I'IIH~IIIIIIIHIIIIIII 'II I I I I HI hl~
~ ~
1'-..
- JO
~('t)
(")
r;;;
~11111111-W+rl illllll:lllllmlill lillll!lllt~~~~~~ll l l iI mi!IIIII~HIIHilttlillilUtUlltatlllllitilllilllll 0
'""1-,
~
><'
-Q) ::;
~ ~lllllll il ,~ , lm~m~.:~~~-~L
Crq
l+t-t:t+mOO!tiifiiliiBEtillmHM ~~~~~~~~~~~~~~~~~
:J
-
0
0
C/)
E
-
50
~
dn
~
(l)
....Q) II Ill I IIII
:1111 11'
Cll
...,a.
~
1~,
- 40 ~~
,:V.:tU-U-1111 iI! IIII IWlml : ~~mwurLl

ttm.
,
IIII 11-
2 3 4 6 8 10 20 .30 40 60 80 102 200 300 400 600 800 103
ii, moles of H20 per mole of solute
Figure 12.14: Heats of solution at 25 C. (Based on data from "The NBS Tables of Chemical Thermodynamic Properties," J. Phys. Chem. Ref Data,
vol. 11, suppl. 2, 1982.) ~
U\
\0
460 CHAPTER 12. Solution Thermodynamics: Appli cations
1.25 kg superheated
t---~ steam at 132C and
1 atm
Feed at 25C ----+-~
2 kg 15% LiCI ,.
L-._
- - -- -:- ____;----:. ,. . 0.75 kg 40% LiCI
at 132C
1
Q
Figure 12.15: Process of Example 12.5.
the problem reduces to finding ~ H r from available data. Because enthalpy is a

state fu nction, the calculational path for !:l.Hr is immaterial and is selected for
convenience and without reference to the actual path followed in the evaporator.
The data available are heats of solution of LiCl in H20 at 25C (Fig. 12. 14), and
the calculational path, shown in Fig. 12.16, aJlows their direct use.
The enthalpy changes for the individual steps shown in Fig. 12.16 must add to
give the total enthalpy change: .
!:l.H' = 6.H~ + ~Hh + 6.H: + 6.H~

The individual enthalpy changes are determined as follows.
6. H~: This step involves the separation of 2 kg of a 15% LiCl solution into its
pure constituents at 25C. For th is "unmixtng" process the heat effect is the same
as for the correspond ing mixing process, but is of opposite sign. For 2 kg of 15%
LiCI solution, the moles of material entering are:
(0. 3)(l,OOO) 7 077 I L'CJ

1 (1. 7 0)(l,OOO) = 94.366 mol H2 0
42.39 = mo 18.0l5
Thus the solution contains 13.33 mol of H20 per mole of LiCl. From Fig. 12. 14
n
the heat of solution per mole of LiCl for = 13.33 is -33,8001. For the "unmix-
ing" of 2 kg of solution,
~H~ = (+33,800)(7.077) = 239,250 J

b.Ht: T his step results in the mixing of 0.45 kg of water with 0.30 kg of LiCI(s)
to form a 40% solution at 25C. This solution comprises:
0.30 kg ---7 7.077 mol LiCI and 0.45 kg -7 24.979 mol H20
Thus the final solution contains 3.53 mol of H20 per mo le of LiCI. From Fig. 12.1 4
the heat of solution per mole of LiCI at this value ofn is -23,260 J. Therefore,
~Ht = (-23,260)(7.077) = - 164,6301

12.4. Heat Effects of Mixing Processes 461
2 kg feed at 25C
containing 0.30 kg
LiCI and 1.70 kg H2 0
-~~~~~~!::~:.~----r-----------------------------------
into pure species tlH~
---~-~~~5:~- _____ 1_
0.30 kg
LiCI at
25C
0.45 kg H2 0 at 25C
-~~xi:: :~~-4~-kg ~~- --~- flll'
water with 0.30 kg of flfl

LiCI to form--a-4-0o/c_o
solution at 25C ____ l~
0.75 kg 40% LiCI at 25C
Heatin~ :I 0-;5-k:-o~--
LiCI solution from
T
flH:.
Heatin~ :I ,-:5-k: -o~ --
water from 25 to
T
uH:,
25::t~~~------l--------"-------~~~-t~~~~-----l ___ _
0.75 kg of 40% LiCI 1.25 kg of superheated
solution at 132C steam at 132C and 1 atm
Figure 12.16: Calculational path for process of Example 12.5.
~H~: For this step 0.75 kg of 40% LiCI solution is heated from 25 to 132C.
Because D.Hj. = mCp D.T ,
D.H: = (0.75)(2.72)(132- 25) = 218.28 kJ --7 218,280 J
D.H~: In this step liquid water is vaporized and heated to 132C. The enthalpy
change is obtained from the steam tables: ...
D.}J~ = (1.25)(2,740.3- l04.8) = 3,294.4 k1 --7 3,294,4001
Adding the individual enthalpy changes gives:
D.H = D.H~+ !).Ht + !).H: + D.H~

= 239,250- 164,630 + 218,280 + 3,294,400 = 3,587,300 1
The required heat-transfer rate is therefore 3,587.3 kJ s- 1.

462
1-W ~
1\
120 ~
1 "\ '' ~., I
100 ~
\ \ l 1\ ~.
\
\ \
\ \ \ I\ ' ~
~ \ ~ 'l
\ '
\ \ \ \ 1\ ~ I
1\ i\ ~ '\
~
~,
\ \ \ \ 1\ r\ \
\. ~. \ t\ '
'\' \ I
I.
\ \ \ \ \ \ \' ~ 1/J
\ ~ \ ~ ~. \ "'
'~ 1'\ r\' \'1\ ,"'\
i\
~\ ' \ \ r\
' \' '
i\\ ~"'\
~ \' \ \ I'
i\'
\
\
/h
I!J
I'
1\.
\ \ 1'\ \ 1\.. 1/J I.J

\~ [\ ~ \ I\ \_ ' 1\.''\ "~~ \..
~
'-:~ VI vr
)
:\' ' ~' ,.. 'J VJJfj
'~ \ ' \ '\1"\ ~l ...
\ \ J
.L 'I V!J
'' 1\, :
~
-eo \ i\ \
I~
~ '~ x~ ~ ._ L 'L if!Jil
~"'- "~
~h I(~,
... ..,. ./
~ \ .~ 1' - ' -
.... ..., / /JJ "h
- 121!
"' ~
" ~
~
~ ,
II..
~
' -- -
....... -; lf/ / #j
./ . (~
~J'
_ ,~
~
....._ ' ......
~ ...... ,&
c;.;'
Cl 10 :20 :3D .0 50
" &0 70 :00 90 'ilOQr
Wt. %UzSOc
t'lpl"e Jl.J 7'~ H .t di~1tl1 for ~~2S0~(1}11~0(2j. (Red.su:v. l fi!oUt d~ dn~ ofW, D. IROISS,
Clttnr.. 6-f$. Prqg" \'Ot. 48. pp. 3 ~4 :md 315, 19:S2. lBy IJliCiiDll~ioo.)

Enthalpy/Concentration Diagrams
The enthalpy/concentration (H x) diagram is a useful way to represent enthalpy data for bjnary
oJutions. It plots enthalpy as a function of composition (mole fraction or mass fraction of one
pecies) with temperature as parameter. The pressure is a constant and is usually l(atm). Figure
12.17 shows a partial diagram for the H2S04/H20 system, where enthalpy values here are for
a unit mass of solution. Equation (12.40) is therefore directly appl icable:
(12.40)
Values of H for the solution depend not only on heats of mixing, but also on enthalpies H 1
and H2 of the pure species. Once these are known for a given T and P, H is fixed for al1
solutions at the same T and P, because !:1H has a unique and measurable value for each
compositi0n. Absolute enthalpies are unknown, and arbitrary zero points are chosen for the
enthalpies of the pure species. T hus, the basis of an enthalpy/concentration diagram is H 1 = 0
fo r some specified state of species 1 and H2 = 0 for some specified state of species 2. The
same temperature need not be selected for these states for both species.
In the case of the H2S04(1)/H20(2) diagram s hown in Fig. 12.17, H2 = 0 for pure liquid
H20 at the triple point [ ~32(F)], and H 1 = 0 for pure liquid H2S0 4 at 25C L77(F)]. In this
case the 32(F) isotherm terminates at H = 0 at the pure-H20 edge of the diagram, and the
77(F) isotherm te1m inates at H = 0 at the pure-H2S04 edge of the diagram. The advantage
of taking H = 0 for pure liquid water at its triple point is that this is the base of the steam
tables. Enthalpy values from the steam tables can then be used in conjunction with values
taken from the enthalpy/concentration diagram. Were some other base used for the diagram,
one would have to apply a correction to the steam-table values to put them on the same basis
as the diagram.
H,
>-
a.
:1
.c
.....
c
Q)
R,
0
;;:
0
Q)
a.
(/)
.._
0
.....
Figure 12.18: Graphical
:1
0
H2 constructions on an H x diagram.
E Jj2
:X:
0 1
t x 1, mole or mass fraction of

species 1 in solution
t
Pure 2 Pure 1
464 CHAPTER I 2. Solution Thermodynamics: Applications
For an ideal solution, isotherms on an e nthalpy/concentration diag ram are straight lines
connecting the enthalpy of pure species 2 at x 1 = 0 with the enthalpy of pure species 1 at
x1 = l, as mu strated for a sing le isotherm in Fig. 12.18 by the dashed line. The solid c urve
represents an isother m for a real solution. Also shown is a tangent line from which partial
e nthalpies may be determined in accord with Eqs. ( 1L15) and ( 11.1 6). Equations (11.82) and
( 12.40) combine to g i'!e 6 H = H - Hid; 6 H is therefore the vertical distance betwee n the
curve and the dashed line of Fig. 12. 18. Here, the actua l isotherm lies below the ideal-solutio n
isotherm, and 6H is everywher-uegative. This means that heat is evolved whenever the pure
species at the given temperature are mixed to form a solution at the same temperature. Such a
system is exothermic. The H2S0 4/H20 sys tem is an example. An endothermic system is one
for which the heats of solution are positive; in thi s case heat is absorbed to keep the temperature
constant. An example is the methanol/benzene system.
One useful feature of an enthalpy/concentration diagram is that all solutions formed
by adiabatic mixing of two other solutions are represented by poi nts lying on a straight line
con necting the points that represent the ini tial solu tions. This is shown as follows.
Let the superscripts a and b denote two initi al binary solutions, cons isting of nc' and nb
moles respectively. Let s upe rscript c deno te the fi nal solution obtained by si mple mixing of
solutions a and b in an adiabatic process, e ither batch mixing at constant P or steady-flow
mi.xi ng with no shaft work or change in pote nti al or kinetic energy. ln e ither case, 6 H' =
Q = 0, and the total energy balance is:
In add ition, we may write a material balance for species l:
These two equations may be rearranged as:
Di vision of the first equation by the second gives:

He - Ha H e - Hb
(A)
X' c - Xa - ,..< - .xb
" I I -~I I
Our purpose now is to show that the three points c, a, and b represented by ( He, x~'),
( H a, x]'), and ( H I>, xf) lie along a straight line on a n H x diagram. T he equation for a straight
line in these coordinates is:
H = 111X1 + k (B )
If this line passes throug h points a and b,
Ht' = 1nx~ + k
1
and
Eac h of these equations may be su btracted from the general equation, Eq. ( 8 ):
I !J
500 '
I
"""' :k
~
~
I I I I I I I I I J.~~ I ~
450 I I I I
trJ
~
(')
I I I I I I I I :b-~~~~ I (7.
400 I I I 0
-.,
~
-.
c:
350 -
~
:::s
Crq
-
.Q
:s
---- ----
---- ----
---- - ~
0(/)
300 --- ---
--- - : : - 350 - - ----- ----
---- ----
---- ----
---- --
0(')
(b
---- ---- -
V)
.0-
----- ---- :;,
- -- - -
:::::::
:s 250
..........
--- -- ------ ---- -- (b
V)
-
aJ
~
;;.
a.
-
..c: 200
(0
c:
Q)
:x::
150
lOOFJ . I ; I I ~ T'""" I I I
150
I
so[ 0
1'1J:"
0.1 0.2
ll ~
0.3 0.4 0.5 0.6 0.7
x, mass fraction NaOH
Figure 12.19: Hx diagram for NaOH/H20. (Reprodu ced by permission. W. L. McCabe. Trans. AJC!z.
, vol. 31 , pp. 129- l64, 1935~ R. H. Wil son and ~
0\
W. L. McCabe. Ind. Eng. Chem .. vol. 34, pp. 558- 566, 1942.) VI
Dividing the first of these by the second yields:
H - H(' XJ- xf H - Ha
or
H- Hb - Xt - xr Xt -xf
Any point witb the coordinates (H , x 1) which satisfies the last equation lies on the straight line
that contains points a and b. Equation (A) shows that (H e, xf) is such a point.
The use of enthalp-y/concentratjon diagrams is illustrated in the following examples for
the NaOHIH20 system; an H x diagram is shown in Fig. 12.19.
Example 12.6
A single-effect evaporator concentrates 1O,OOO(lbm)(hr)- 1 of a 1OOfo (by weight) aque-
ous solution of NaOH to 50/o. The feed enters at 70(F). The evaporator operates
at an absolute pressure of 3(in Hg), and under these conditions the boiling point of a
50% solution of NaOH js 190(F). What is the heat-transfer rate in the evaporator?
Solution 12.6
On the basis of I O,OOO(lbm) of 10% NaOH fed to the evaporator, a material bal-
ance shows that the product stream consists of 8,000(lbm) of superheated steam at
3(in Hg) and 190(F), and 2,000(lbm) of 50% NaOH at l90(F), as indicated in
Fig. 12.20. The energy balance for this flow process is 1:::. H 1 = Q _
'
8000(1b111 ) of superheated
steam at 3(inHg) and 190(F)
Feed at 70(F}
1O,OOO(Ib, } of ---+-~
10% NaOH 2000(1b111) of 50% NaOH
~--~
at 190(F)
t
Q
Figure 12.20: Schematic diagram for process of Example 12.6.
In this case !:::.H 1 is easily detetmined from enthalpy values taken from the H x
diagram of Fig. 12.19 and from the steam tables:
1
H for superheated steam at 3(in Hg) and J 90(0 F) = l , l46(Btu)(lb 111 ) -
H for 10% NaOH solution at 70(F) =34(Bru)(lbm)- 1
H for 50% NaOH solution at l90(F) =215(Btu)(lb111) - 1

Thus, Q = D. H 1 = (8,000)(1, 146) + (2,000)(215)- (10,000)(34)

= 9,260,000(Btu)(hr)- 1
A comparison of this example with Example 12.5 shows the simplification intro-
duced by use of an enthalpy/concentration diagram.
Example 12.7
A 10/o aqueous NaOH solution at 70( F) is mixed with a 70/o aqueous NaOH solution
at 200( F) to form a solution containing 40o/o NaOH.
,.
(a) If the mixing is done adiabatically, what is the final temperature of the solution?
(b) If the final temperature is brought to 70( F) , how much heat must be removed
during the process? ,
Solution 12.7
(a) A straight line drawn on Fig. 12.19 connecting the points representing the two
initial solutions must contain the point representing the final solution. The partic-
ular solution represented by a point on this line at a concentration of 40% NaOH
has an enthalpy of 192(Btu)(lb111 ) - 1. Moreover, the isotherm for 220(F) passes
through this point. Thus the final temperature, obtained graphically, is 220(F).
(b) The total process cannot be represented by a single straight line on Fig. 12.19.
However, any convenient path may be selected for calculating D. H of the pro-
cess. The energy balance then gives Q = D. H. Thus the process may be con-
sidered as occurrin g in two steps: adiabatic mixing, followed by simple cooling
of the resulting solution to the final temperature. The first s~ep is considered in
part (a). It results in a solution at 220(F) with an enthalpy of 192(Btu)(lb111 ) - 1
When this solution is cooled to 70(F), the resulting enthalpy from Fig. 12.19 is
70(Btu)(lbrn)- 1 Therefore,
Q = D.H = 70- 192 = -122(Btu)(lbm)- 1 ....,
and 122(Btu) is evolved for each pound mass of solution formed.
Example 12.8
Determine the enthalpy of solid NaOH at 68( F) on the basis used for the NaOH/H20
enthalpy/concentration diagram of Fig. 12.19.
468 CHAPTER 12. Solution Thermody namics: Applications
Solution 12.8
The isotherms on an H x diagram for a system such as NaOH/H2 0 terminate at
po ints~ where the limit of solubility of the solid in water is reached. Thus the
isotherms in Fig. J2.19 do not extend to a mass fraction representing pure NaOH.
How, then. is the basis of the diagram with respect to NaOH selected? In the case
of the water the basis is HH 2o = 0 for liquid water at 32(F), consistent with
the base of the steam tables. For NaOH the basis is HNaOH = 0 for NaOH jn an
infinitely dilute solution at 68(F).
This means that the partial specific enthalpy of NaOH at infinite dilution (i.e.,
at XNaOH --+ 0) is arbi trarily sec equal to zero at 68(F). The graphical interpre-
tation is that the diagram is constructed in , uch a way that a tangent drawn to the
68( F) isotherm at XNaOH = 0 intersects the XNaOH = I ordinate (not shown) at
an enthalpy of zero. The selection of Ro;
0H
as zero at 68(F) automatically fixes
the values of the enthalpy of NaOH in all other states.
In particular, the enthalpy of solid NaOH at 68(F) can be calculated fo r the
basis selected. If I (lb 111 ) of solid NaOH at 68(F) is dissolved in an infinite amount
of water at 68(F). and if the temperature is held constant by extraction of the heat
of solution, the result is an infinitely dilute solution at 68(F). Because the water
is pure in both the initial and final states, its enthalpy does not change. The heat
of solution at 68(0 F) is:
,__, <Xl - 00
6. H NaOH = H NaOH - H NaOH
However, H~OH = 0 at 68(F). Therefore,

,...._. 00
!:l H NaOH = - HNaOH
The enthalpy of sol id NaOH at 68( F), HNaOH, is therefore equal to the neg-
ative of the heat of solulion of NaOH in an infinite amoun t of water at 68(F). A
literature value 17 for this heat of solution at 25C is (basis, 1 mol of NaOH):
.-._. 00
D. H 'aOH =- 10,637(ca l)
If the difference in temperature between 25C [77(F)l and 68(F) is neglected,

the enthalpy of solid NaOH at 68(F) is:
,__, 00 -(-10,637 )(1.8) - 1
H NaOH = -6. H NaOH = 4
0.00 = 478.7(Btu)CJbm)
This figure represents the enthalpy of solid NaOH at 68(F) on the same basis as
was selected for the NaOH/H2 0 enthalpy/concentration diagram of Fig. 12. 19.
17 M. W. Chas\!. Jr.. ct al.. "JANAF Thermochemical Tables:' 3d cd .. ./. Pllys. Cllem. Ref Dala. vol. 14. suppl. I.
p. 1243. 1985.
Problems 469
Example 12.9
Solid NaOH at 70(F) is mixed with H2 0 at 70( F) to produce a solution containing
;!5/o NaOH at 70( F). How much heat must be transferred per pound mass of solution
zormed?
Solution 12.9
On the basis of I (1bm) of 45% NaOH solution. 0.45(Jbm) of sol id NaOH must be
dissolved in 0.55(1bm) of H20. The energy balance is t:.H = Q. The enthalpy
of H20 at 70(F) may be taken from the steam tables, or it may be read from
1
Fig. 12. I 9 at x 1 = 0. In either case, HH.,o = 38(Btu)(lbm)- The enthalpy of
45% NaOH
,. at 70(F) is read from Fig. 1 2~1 9 asH = 93(Btu)(lbm)- 1. We assume
that Lhe enthalpy of solid NaOH at 70( F) is essentially the same as the val ue
1
calculated jn lhe precedi ng example for 68(F): HNaOK = 478.7(Btu)O bm)-
Therefore, the heat evolved fo r each pound mass of sol ution formed is:
Q = t:.H = (1)(93)- (0.55)(38)- (0.45)(478.7) = - 143 (Btu)
PROBLEMS
12.1. The following is a set of YLE data for the system methanol( I )/water(2) at 333.1 5 K
(extracted from K. Kuri hara et al.. J. Chem. Eng. Data. vol. 40, pp. 679-684, 1995):
P/kPa XJ )' J P /kPa Xt Yt
19.953 0.0000 0.0000 60.614 0.5282 0.8085

39.223 0.1686 0.5714 63 .998 0.6044 0.8383
42.984 0.2 167 0.6268 67.924 0.6804 0.8733
48.852 0. 3039 0.6943 70.229 0.7255 0.8922
52.784 0.368 1 0.7345 72.832 .
0.7776 0.914 1
56.652 0.4461 0.7742 84.562 1.0000 1.0000
(a) Basing calculations on Eq. ( J 2. 1), find parameter values for the Margules eq uation
that provide the best fit of G 1RT to the data, and prepare a Pxy diagram that
compares the ex perimental points with curves determined from the correlation .
(b) Repeat (a) for the van Laar equation.
(c) Repeat (a) for the Wilson eq uation.
(d) Using Barker's method. find parameter values for the MarguJes equation that pro-
vide the best fit of the P-x t data. Prepare a diagram showing the residua ls oP and
O_)'J plotted VS. X J.
(e) Repeat (d) for the van Laar equation.

(j) Repeat (d) for the Wilson equation.
12.2. lfEq. (12.1) is valid for isothermal VLE in a binary system, show that:
dP) > _ p sat

( dx, xi=O- 2
12.3. The following is ~a set of VLE data for the system acetone(] )/methanol(2) at 55C
(extracted from D. C. Freshwater and K. A. Pike, J. Chem. Eng. Data, vol. 12, pp. 179-
183, 1967):
Plk.Pa X) YJ PlkPa X) YJ
68.728 0.0000 0.0000 97.646 0.5052 0.5844

72.278 0.0287 0.0647 98.462 0.5432 0.6174
75.279 0.0570 0.1295 99.811 0.6332 0.6772
77.524 0.0858 0.1848 99.950 0.6605 0.6926
78.951 0.1046 0.2190 100.278 0.6945 0.7124
82.528 0.1452 0.2694 100.467 0.7327 0.7383
86.762 0.2173 0.3633 100.999 0.7752 0.7729
90.088 0.2787 0.4184 101.059 0.7922 0.7876
93.206 0.3579 0.4779 99.877 0.9080 0.8959
95.017 0.4050 0.5135 99.799 0.9448 0.9336
96.365 0.4480 0.5512 96.885 I .0000 1.0000
(a) Basing calculations on Eq. ( 12.. J ), find parameter values for the Margules equatioc
that provide the best fit of cE I RT to the data, and prepare a P-x -y diagram thx
compares the experimental points with cur ves determined fTom the correlation.
(b) Repeat (a) for the van Laar equation.
(c) Repeat (a) for the Wilson equation. ....
(d) Using Barker's method, fi.nd parameter values for the Margules equation that p~
o
vide the best fit of the P-x 1 data. Prepare a diagram showing the residuals P 21":-<..:.
8yt plotted vs. XJ.
(e) Repeat (d) for the van Laar equation.
if) Repeat (d) for the Wi lson equation.
12.4. The excess Gibbs energy for binary systems consisting of liquids not too dissimilc -
chemical nature is represented to a reasonable approximation by the equation:
c1RT = Ax1x2
where A is a function of temperature only. For such systems, it is often obserYed
the ratio of the vapor pressures of the pure species is nearly constant over a con . ...._
able temperature range. Let this ratio be r, and determine lhe range of value
expressed as a function of r, for which no azeotrope can exist. Assume the vapor p
to be an ideal gas.
Problems 471
12.5. For the ethanol( 1)/chloroform(2) system at 50C, the activity coefficients show interior
extrema with respect to composition [see Fig. 12.9(e)].
(a) Prove that the van Laar equation cannot represent such behavior.
(b) The two-parameter Mrugules equation can represent this behavior, but only for
particular ranges of the ratio I
A21 A 12 What are they?
12.6. VLE data for methyl tert-buty1 ether( I )/dichloromethane(2) at 308. 15 K (extracted
from F. A. Mato, C. Berro, and A. Peneloux, J. Chern. Eng. Data, vo1. 36, pp. 259-
262, 1991) are as follows:
P/kPa Xi Yt P/kPa Xt Yt
85.265 0.0000 0.0000 59.651 0.5036 0.3686
83.402 0.0330 0.014 1 56.833 0.5749 0.4564
82.202 0.0579 0.0253 53.689 0.6736 0.5882
80.481 0.0924 0.04 16 51.620 0.7676 0.7176
76.7 19 0. 1665 0.0804 50.455 0.8476 0.8238
72.422 0.2482 0.13 14 49.926 0.9093 0.9002
68.005 0.3322 0.1~75 49.720 0.9529 0.9502
65.096 0.3880 0.2457 49.624 1.0000 1.0000
The data are well correlated by the three-parameter Margules equation [an extension
of Eq. (12.9)]:
cE
RT = (A2tXI + At 2X2 - CxtX2)XtX2
Implied by this equation are the expressions:
In Yl = xi[A12 + 2(A2t - A12- C)x1 + 3Cxf]

In Y2 = xf[A21 + 2(At2- A 21 - C)x2 + 3CxiJ
(a) Basing calculations on Eq. (12.1 ), find the values of parameters A 12. A21, and C
that provide the best fit of G I RT to the data.
(b) Prepare a plot of In Yl, In Y2, and c
IX IX2 RT vs. XJ showing both the correlation
and experimental values.
(c) Prepare a P-x-y diagram [see Fig. 12.7(a)] th~compares the experimental data
with the correlation determined in (a).
(d) Prepare a consistency-test diagram like Fig. 12.8.
(e) Using Barker's method, find the values of parameters A 12 , A21, and C that provide
the best fit of the P-xt data. Prepare a diagram showing the residuals 8 P and oy,
plotted vs. x 1.
12.7. Equations analogous to Eqs. (11.15) and (11. 16) apply for excess properties. Because
In y; is a partial property with respect to c
I RT , these analogous equations can be
written for In Yt and In Y2 in a binary system.
472 CHAPTER 12. Solution Thermodynamics: A pplications
(a) Write these eq uations, and apply them to Eq. (I 2. 16) to show -that Eqs. ( 12.17) are
indeed obtained.
(b) The alternative procedure is to apply Eq. ( J 1.96). Proceeding in the manner that
led to Eqs. ( 12.1 0), show that Eqs. ( 12.1 7) are again reproduced.
12.8. The following is a set of activity-coefficient data for a binary liquid system as deter-
mined froin VLE data:
~
Xi Yl Y2 XI Yl Y2
0.0523 1.202 1.002 0.5637 1.120 1.102

0.1299 J .307 1.004 0.6469 1.076 1.170
0.2233 1.295 1.006 0.7832 1.032 1.298
0.2764 1.228 1.024 0.8576 1.016 1.393
0.3482 1.234 1.022 0.9388 1.001 1.600
0.4187 1. 180 1.049 0.9813 1.003 1.404
0.5001 J. 129 1.092
Inspection of these experimental values suggests that they are noisy, but the question
is whether they are consistent, and therefore possibly on average correct.
(a) Find experimental values for c I RT and plot them along with the experimental
values of In Yl and In Y2 on a single graph.
(b) Develop a valid correlation fo r the composition dependence of a I RT and show
lines on the graph of part (a) that represent this correlation for all three of the
qu antities plotted there.
(c) Apply theconsistency test described in Ex. 12.1 to these data, and draw a conclu-
sion with respect to this test.
12.9. Following are YLE data for the system aceton itrile( I )/benzene(2) at 45C J extracted
from I. Brown and F. Smith, Ausfral. J. Chem. , vol. 8, p. 62, 1955):
PlkPa ..q Yl P/kPa .XJ Yl
29.8 19 0.0000 0.0000 36.978 0.5458 0.5098

3L957 0.0455 0.1056 36.778 0.5946 0.5375
33.553 0.0940 0.1818 35.792 0.7206 0.6157
35.285 0.1829 0.2783 34.372 0.8145 0.6913
36.457 0.2909 0.3607 32.331 0.8972 0.7869
36.996 0.3980 0.4274 30.038 0.9573 0.8916
37.068 0.5069 0.4885 27.778 J .0000 1.0000
The data are well correlated by the three-parameler Margu les equation (see Pb. L2.6).
(a) Basing calculations on Eq. (12.1), find the values of parameters A12 , A21 , and C
that provide the best fit of c I RT to the data.
Problems 473
(b) Prepare a plot of In Yt, In y2, and c!x 1xz RT vs. x 1 showing both the correlation
and experimental values.
(c) Prepare a P -x-y diagram lsee Fig. 12.7(a)J that compares the ex perimenta l data
with the correlation determined jn (a).
(d) Prepare a consistency-test diagram like Fig. 12.8.
(e) Using Barker's method. find the values of parameters A 12, A 2 1, and C that provide
the best fit of the P-x1 data. Prepare a diagram showing the residuals 8 P and 8y 1
plotted vs. x 1.
12.10. A n unusual type of low-pressure VLE behav ior is that of double azeotmpy, in which
the dew and bubble curves are S-shapecl, thu s yielding at different compositions both
a minimum-pressure and a maximum-pressure azeotrope. Assuming that Eq. ( 12. J I)
applies, determine under what c irc umstances double azeotropy is like ly to occur.
12.11. Rationalize the following rule of thumb, appropriate for an equimolar binary liquid
mixture:
c 1
- ( equimolar) ~ - ln (y 100 y~)
RT 8 -
Problems 12. 12 through 12 .23 require P'1a1meter values for the Wilson or NRTL equation
for liquid-phase activity coeffidents. Tc?ble 12.5 gives P'lrameter values for both eqw1tjons.
Antoine equations for vapor pressure are given in Table 8.2. Appendix B.
12.12. For one of the binary systems listed in the preceding table, based on Eq. ( 10.5) and the
Wilson equation prepare a P-.x-y diagram fort = 60C.
12.13. For one of the binary systems listed in the preceding table, based on Eq. ( I0.5) and the
Wilson equation prepare a t-x-y diagram for P = I0 l.33 kPa.
12.14. Fo r one of the binary systems listed in the preceding table, based on Eq. ( l 0.5) and the
NRTL equation prepare a P-x-y diagram for r = 60C.
12.15. Fo r one of the binary systems listed in the preceding table, based on Eq. ( I0.5) and the
NRTL equation prepare a t-x-y diagram for P = '1"0 t. 33 kPa.
12.16. For one of the binary systems listed in the preceding table, based on Eq. ( l0.5) and the
Wilson equation make the following calculations:
...
(a) BUBL P: t = 60C, x 1 = 0.3.
(b ) DEW P: I=60 C, Yt = 0.3.
(c) P T -flash: I = 60 C, P =~( ?bubble+ Pdcw), Zl = 0.3.
(d) ff an azeotrope exists a t t = 60C , find p az a nd x['z = y;:c.
12.17. Work the preceding problem for the NRTL equation.

Table 12.5: Parameter Values for the Wilson and NRTL Equations.
Parameters a1 2, a21, b12. and b21 have units of cal mol- 1, and Vt and V2 have units of
cm3 mol- 1. Values are those recommended by Gmehling et al. Vapor-Liquid Equilibrium
Data Collection,. Chemistry Data Series, vol. I, parts Ia, 1b, 2c and 2e, DECHEMA, Frank-
furt/Main, 198 1-1988.
,
v, Wilson eq uation NRTL equation
System v2 a12 a21 bt2 b2t a
Acetone(l) 74.05 29 I.27 1,448.0 1 631.05 J' 197 .41 0.5343
Water(2) 18.07
Methanol(l) 40.73 107.38 469.55 -253.88 845.21 0.2994
Water(2) 18.07
1-Propanol(l) 75.14 775.48 1,351.90 500.40 I ,636.57 0.5081
Water(2) 18.07
Water(1) 18.07 I ,696.98 -219.39 7 15.96 548.90 0.2920
1,4-Dioxane(2) 85.71
Methanol( 1) 40.73 504.31 196.75 343.70 3 14.59 0.2981
Acetonitri le(2) 66.30
Acetone( I) 74.05 -161.88 583.11 184.70 222.64 0.3084
Methanol(2) 40.73
Methyl acetate(l) 79.84 -31.19 813.18 381.46 346.54 0.2965
Methanol(2) 40.73 '
Methanol( I) 40.73 1,734.42 183.04 730.09 1,175.41 0.4743
Benzene(2) 89.41
Ethanol( 1) 58.68 1,556.45 210.52 7 13.57 1,147.86 0.5292
..,
Toluene(2) 106.85
.. 12.18. For one of the binary

systems listed in the preceding table, based on Eq. (1 0.5) and the
Wilson equation make the following calculations:
(a) BUBL T: P = I 01.33 kPa, x 1 = 0.3.

(b) DEW T: P = 10 1.33 kPa, Yt = 0.3.
(c) P , T -flash: P = 101.33 kPa, T = ~(Tbubble + Tdcw), Zt = 0.3.
(d) If an azeotrope exists at P = 10 J .33 kPa, find yaz and xfz = yf7..
12.20. For the acetone( 1)/methano1(2)/water(3) system, based on Eq. (1 0.5) and the Wilson
equation make the following calculations:
(a) BUBL P: 1 = 65C, Xt = 0.3, x2 = 0.4.

Problems 475
(b) DEW P: t = 65C, Yl = 0.3, Y2 = 0.4.

(c) P , T -flash: t = 65C, P = ~(?bubble+ Pdew), Zl = 0.3, Z2 = 0.4.
12.22. For the acetone(l)/methanol(2)/water(3) system, based on Eq. (10.5) and the Wilson
equation make the following calculations:
(a) BUBL T: P = lOI .33 kPa, x, = 0.3, xz = 0.4.

(b) DEW T: P =
101.33 kPa, Yl = 0.3, Y2 = 0.4.
(c) P, T -flash: P = I 01.33 kPa, T = ~ (Tbubble + Tdew), z 1 = 0.3, Z2 = 0.2.
12.24. The following expressions have been reported for the activity coefficientc;; of species 1
and 2 in a binary liquid mixture at given T and P:
In Yl = xi(0.273 + 0.096xt)
...
In Y2 = Xf(0.273- 0.096x2)
(a) Determine the implied expression for c
I RT.
(b) Generate expressions for ln Yl and In J12 from the result of (a).
(c) Compare the results of (b) with the reported expressions for In YI and In Y2 Dis-
cuss any discrepancy. Can the reported expressions possibly be correct?
12.25. Possible correlating equations for In y 1 in a binary liquid system are given follow-
ing. For one of these cases determine, by integration of the Gibbs/Duhem equation
[Eq. (1 1.1 00)1 the conesponding equation for Jn Y2 What is the corresponding equa-
tion forcE I RT? Note that by its defini tion, Yi = 1 for X; = I.
(a) In Yl = Axi; (b) ln YI = xi(A + Bx2); (c) ln YI = xi(A + Bx2 + Cxi).

12.26. At 25C and atmospheric. pressure the volume change of mixing of binary liquid mix-
tures of species I and 2 is given by the equation:
D. V = XtX2(45x, + 25x2)
3 1
where D. V is in cm 3 mol- 1 . At these conditions, V 1 -:; 110 and V2 = 90 cm mol- .
Determine the part1al molar volumes v,
and V2 in a mixture containing 40 mol-% of
species 1 at the given conditions.
1
12.27. The volume change of mixing (cm3 mol- ) for the system ethanol( 1)/methyl butyl
ether(2) at 25C is given by the equation:
Given that V 1 = 58.63 and V2 = 118.46 cm 3 mol- 1, what volume of mixture is

fo rmed when 750 cm3 of pure species 1 is mixed with 1,500 cm 3 of species 2 at 25C?
What would be the volume if an ideal solution were formed?
12.28. If LiCI2H2 0 (s) and H20(/) are mixed isothermally at 25C to form a solution con-
taining J0 mol of water for each mole of LiCI , what is the heat effect per mole of
solut ion?
12.29. If a liquid solution of HCl in water, containing I mol of HCI and 4.5 mol of H20 ,
absorbs an additional] mol of HCI(g) at the constant temperature of25C, what is the
heat effect? ~
~
12.30. What is the heat effect when 20 kg of LiCI(s) is added to 125 kg of an aqueous sol ution
containing 10-wt-% LiCl in an isothermal process at 25C?
12.31. An LiCI/H20 solu tion at 25C is made by adiabatically mixing cool water at l0C
with a 20-mol-% LiCl/H20 solution at 25C. W hat is the compositi on of the solution
formed?
12.32. A 20-mol-% LiCI/H20 solution at 25C is made by mixing a 25-mol-% LiCI/H20

solu tion at 25C with chilled water at 5C. What is the heat effect in joules per mole
of final solution?
12.33. A 20-mol-% LiCI/H20 solu tion is made by six different mixing processes:
(a) Mix LiCl(s) wit h H20(/).

(b) Mix H20(I)with a 25-mol-% LiCI/H20 solution.
(c) Mix LiCIH20(s) with H20(!).
(d) Mix LiCI(s) with a I 0-mol-% LiCI/H20 solution.
(e) Mix a 25-mol-% LiCI/H20 solution w1th a 10-mol-% LiCl/H20 solution.
(f) Mix LiCI H20(s) with a I 0-mol-% LiCIIH20 solu tion.
Mixing in all cases is isothermal. at 25C. For each part determine the heat effect in
J mol- 1of final solu tion.
12.34. A mass of 12 kg s- 1 of Cu(N03)26H20 along with 15 kg s- 1 of water, both at 25C,

are fed to a tank where mixing takes place. The resulting solution passes through a
heat exchanger which adjusts its temperature to 25C. What is the rate of heat transfer
in the exchanger?
For Cu(N03h. ~HJ298 = - 302.9 kJ.

For Cu(N03h6H20 , ~ HJ29x = -2,1 10.8 kJ.
The heat of solu tion of I mol of Cu(N03h in water at 25C is -47.84 kJ, inde-
pendent of i1 for values of interest here.
12.35. A liquid solution of LiCI in water at 25C contains I mol of LiCl and 7 mol of water.
If I mol of LiC13H20(s) is dissolved isothermally in this solution. what is the heat
effect?
Problems 477
12.36. It is requ ired to produce an aqueous LiCI solution by mixing LiCJ-2H20 (s) with wa-
ter. The mixing occurs bolh adiabatically and without change in temperature at 25 C.
Determi ne the mo le fraction of LiCI in the final so lution.
12.37. Data from the Bureau of Standards (J. Phys. Chem. Ref Data, vol. I I, suppl. 2, 1982)
include the following heats of fo rmation for 1 mol of CaCI2 in wate r at 25C:
CaCb in I0 mol H20 -862.74 kJ

CaCiz in 15 mol HzO -867.85 kJ
CaCh in 20 mol H20 -870.06 kJ
CaC)z in 25 mol H20 -87 1.07 kJ
CaCh in 50 mo l H20 -872.91 kJ
CaC)z in 100 mo l H20 -873.82 kJ
CaCI2 in 300 mo l H20 -874.79 kJ
CaCI2 in 500 mol H20 -875. 13 kJ
CaCI2 in l ,000 mol HzO -875.54 kJ
_..._,.
From these data prepare a plot of 6 H , the heat of solution at 25 C of CaC!z in water,
vs. ii. the mole ratio of water to CaCh .
12.38. A liquid solution contains 1 mol of CaCI2 and 25 mol of water. Using data from
Pb. 12.37, determine the heat effect when an addi tional I mol of CaCI2 is dissolved
isothermally in this sol ution.
12.39. Solid CaCl2 6H20 and liquid water at 25 C are mixed adiabatically in a con tinuous
process to form a brine of 15-wt-% CaCh. Usi ng data fro m Pb. 12.37, determ ine the
temperature of the brine solution fo rmed. The specific heat of a 15-wt-% aqueous
CaCI2 solu tion at 25C is 3.28 kJ kg- 1
1
oc-
-..;
12.40. Conside r a plot of 6 H , the heat of solution based on 1 mol of solute (species 1),
vs. ii , the moles of solvent per mole of solute, at constant T and P . Figure 12. 14
a linear rather
is an example of such a plot, except that the plot considered here has_..._,.
than logarithmic scale along the abscissa. Let a tangent drawn to the 6 H vs. 11 c urve
intercept the ordinate at point / .
(a) Prove that the slope of the tangen t at a particular point is equal to the partial excess
enthalpy of the solvent in a solution with the com position represented by ii; i.e.,
prove that: ,_._,
d6 H _ H-r:
- ?
dii -
(b) Prove that the intercept I equals the pattial excess enthalpy o f the solute in the
same solution; i.e., prove that:
12.41. Suppose that /:). H for a particular solute( 1)/solvent(2) system is represented by the
equation:
(A)
,--
Relate the behavior of a plot~ /:). H vs. ,-i to the features of this equation. Specifically,
rewrite Eq. (A) in the form /:).fl (n), and then show that:
,......_. ...
(a) lim /:).H = 0.
;;~o
---
(b) lim 6H = A12
n.~oo
/
____.
(c) Jim d/:).H fdn
,~o
= A2 1
12.42. If the heat of mixing at temperature to is /:).Ho and if the heat of mixing of the same
solution at temperature tis /:).fl, show that the two heats of mixing are related by:
6H =/:).flo+ (' /:).Cp dt

lto
where 6C p is the heat-capacity change of mixing, defined by Eq. (12.29).
12.43. What is the heat effect.when 150(lbm) of H2S0 4 is mixed with 350(lbm) of an aqueous
solution containing 25-wt-% H2S04 in an isothermal process at 100(F)?
12.44. For a 50-wt-% aqueous solution of H2S04 at 140(F), what is the excess enthalpy H E
in (Btu)(lbm)- 1?
12.45. A mass of 4000bm) of 35-wt-~ aqueous NaOH solution at 130(F) is mixed wi th

175(lbm) of 10-wt-% solution at 200(F).
(a) What is the heat effect if the final temperature is 80(F)?
(b) If the mixi ng is adiabatic, what is the final temperature?
12.46. A single-effect evaporator concentrates a 20-wt-% aqueous solution of H2S04 to 70CC.

The feed rate is 25(lbm)(s)- 1, and the feed temperature is 80 (F). The evaporator is
maintained at an absolu te pressure of 1.5(psia), at which pressure the boiling point o:
70-% H2S04 is 217(F). What is the heat-transfer rate in the evaporator?
12.47. What temperature results when sufficient NaOH(s) at 68(F) is dissolved adiabaticat:
in a 10-wt-% aqueous NaOH solution, originally at 80(F), to bring the concentratic~
up to 35%?
12.48. What is the heat effect when sufficient S03(l) at 25C is reacted with H2 0 at 25cc ~
give a 50-wt-% H2S0 4 solution at 60C?
12.49. A mass of 140(1bm) of I 5-wt-% solution of H2S04 in water at 160(F) is mixed _

atmosphelic pressure with 230Clbm) of 80-wt-% H2S0 4 at 100(F). During the Jh'L'-
cess heat in the amount of 20,000(Btu) is transferred from the system. Determine ...2
temperature of the product solution.
?roblems 479
U .50. An insulated tank, open to the atmosphere, contains 1,500(lbm) of 40-wt-% sulfuric
acid at 60(F). It is heated to 180(F) by injection of live saturated steam at 1(atm),
which fully condenses in the process. How much steam is required, and what is the
final concentration of HzS04 in the tank?
12.51. Saturated steam at 40(psia) is throttled to 1(atm) and mixed adiabatically with (and
condensed by) 45-wt-% sulfuric acid at 80(0 F) in a flow process that raises the tem-
perature of the acid to l60(F). How much steam is required for each pound mass of
entering acid, and what is the concentration of the hot acid?
12.52. A batch of 40-wt-% NaOH solution in water at atmospheric pressure and 80(F) is
heated in an insulated tank by injection of live steam drawn through a valve from a
line containing saturated steam at 35(psia). The process is stopped when the NaOH
solution reaches a concentration of 38 wt-%. At what temperature does this occur?
12.53. For a 35-wt-% aqueous solution of H2S04 at 100(F), what is the heat of mixing f). H
in (Btu)(lbm)- 1?
12.54. If pure liquid H2S04 at 80(F) is added adiabatically to pure 1iquid water at 80(F) to
form a 40-wt-% solu tion, what is the final temperature of the solution?
12.55. A liquid solution containing 2(lb mol) H2S04 and 15(lb mol) H20 at 100(F) absorbs
l(lb mol) of S03(g), also at 100(0 F), fo rming a more concentrated sulfuric acid solu-
tion. If the process occurs isothermally, determine the heat transferred.
12.56. Determine the heat of mixing f).H of sulfuric acid in water and the partial specific
enthalpies of H2S04 and H20 for a solution containing 65-wt-% H2S04 at 77(F).
12.57. It is proposed to cool a stream of75-wt-% sulfuric acid solution at 140(F) by diluting
it with chilled water at 40(F). Determine the amount of water that must be added to
l(lbm) of 75-% acid before cooling below 140(0 F) actually occurs.
12.58. The following liquids, all at atmospheric pressure and 120(F), are mixed: 25(lbm) of
,.
pure water, 400bm) of pure sulfuric acid, and 75(lbm) of 25-wt-% sulfwic acid.
(a) How much heat is liberated if mixing is isothermal at l20(F) ?

(b) The mixing process is carried out in two steps: First, the pure sulfuric acid and
the 25-wt-% solution are mixed, and the total heat of part (a) is extracted; second,
the pure water is added adiabatically. What is the temperature of the intermediate
solution formed in the first step?
12.59. A large quantity of very dilute aqueous NaOH solution is neutralized by addition of
the stoichiometric amount of a 10-mol-% aqueous HCI solution. Estimate the heat
effect per mole of NaOH neutralized if the tank is maintained at25C and l(atm) and
the neutralization reaction goes to completion. Data:
480 CHAPTER 12. Solution Thermody namics: Applications
For NaCL lim i:iJ = 3.88 kJ mol- 1

li -700
For NaOH, Jim ;;:H = -44.50 kJ mol- 1

li-HX>
12.60. A large quantity of very dilute aqueous HCI solution is neutralized by addition or
the stoichiometric amount of a I 0-mol -% aqueous NaOH solution. Estimate the heat
effect per mole of HCI neutralized if the tank is maintained at 25 C and I (atm) and the
neutralization reaction goes to completion.
For NaCJ, Jim i:iJ = 3 .88 kJ mol - 1

li -700
12.61. (a ) Making use ofEqs. (11.15) and ( 11.16), written for excess properties, show for a
binary system that:
-
M ., (
1 =x? M+x1--
_
dA1.)
dx1
and - E
M2 dM)
= Xj., ( j\.1{- X2--
dxl
ME
where M =-
x l x2
(b) Plot on a single graph the va lues of H E/x1x2, Hf. a nd iiF determined from the
following heat-of-mixing data for the H2S04(1)/H20 (2) system at 25 C:
1
XI -b.H/~] kg- l XI -b.H/kJ kg-
0.10 73.27 0.70 320.98

0.20 144.2 1 0.80 279.58
0.30 208.64 0.85 237.25
0.40 262.83 0.90 178.87
0.50 302 84 0.95 100.71
0.60 323.31
x1 = mass f raction H2S04

Explain with reference to these plots why sulfuric acid is diluted by adding acid I
water rather than water to acid.
12.62. A 90-wt-% aqueous H2S04 solution at 25C is added over a period of 6 hour ro
tank containing 4,000 kg of pure water a lso at 25C. The final concentration of ac ....
in the tank is 50-wt-%. The contents of the tank are cooled continuously to maintain_
constant temperature of 25 C. Because the cooling system is designed for a con ta:-:
rate of heat transfer, this requires the addition of acid at a variable rate. Determi~~
the instantaneous 90-%-acid rate as a func tion of time, and plot this rate (kg s- 1 ) ...
time. The data of the preceding problem may be fi t to a cubic equation ex pre i,..;
H Ejx 1x2 as a function of x 1, and the equ ations of the preceding problem then pro,:-.-
expressions for iff and ilf.
Problems 481
12.63. Develop Eq. (12.35) for D.Sid by appropriate application of Eqs. (5.41) and (5.42) to
a m1xmg process.
12.64. Twenty thousand (20,000)(lb111 )(hr)- 1 of an 80 weigh t-% H2S04 solu tion in water at
120(F) is continuousl y diluted with c hilled water at 40( F) to yie ld a stream contain-
ing 50 weight-% H2S04 at 140(F).
1
(a) What is the mass flowrate of chilled water in Obm)(hr)- ?
1
(b) What is the rate of heat transfer in (Btu)(hr)- for the mixing process? fs heat
added or re moved?
(c) If the mixing occurred adiabaticall y, what would be the temperature of the product
stream? Assume here the same inlet conditions and the same product composition
as for part (b).
12.65. A storage tank contains a heavy organic liquid. Chemical analysis shows the liquid to
contain 600 ppm (molar basis) of water. It is proposed to reduce the water concentra-
tion to 50 ppm by boiling the contents of the tank at constant atmospheric pressure.
Because the water is lighter than the organic, the vapor will be rich in water; contin-
uous removal of the vapor serves to reduce the water conten t of the sys tem. Estimate
the percentage loss of organic (molar basis) in the boil-off process. Comment on the
reasonablen ess of the proposal.
Suggestion: Desig nate the system water( I )/organic(2) and do unsteady-sta te molar
balances fo r water and for water + organic. State all assumptions .
Data: Tn 2 =normal boiling point of organic= 130C.
YF = 5.8 for water in the liquid phase at l30C.
12.66. Binary VLE data are common ly measured at con tant T or at constant P. Isothermal
data are much preferred for determinatio n of a correlation for c
for the liquid phase.
Why?
12.67. Consider the fo11owing model forcE I RT:
cE ( )1 /k.
- -- = x1A~ 1 +x2 A12
XtX2RT
This equation in fact represents a family of two-panrme ter expressions for G E I RT ;
specification of k leaves A 12 and A 2 1 as the free parameters.
(a) Find general expressions for ln YI and In Y2, for a ny k.

(b) Show that ln yr = A 12 and In y~ = A21, for any k.
(c) Specialize the model to the cases where k equals -oo, - 1, 0, + 1, and +oo. Two
of the cases should generate fami liar results. What are they?
12.68. A breathalyzer measures volume-% ethanol in gases exhaled from the lungs. Calibra-
tion relates it to volume-% ethanol in the bloodstream. Use VLE concepts to delelop an
approximate relation between the two quantities. Numerous assumptions are required;
state and justify them where possible.
12.69. The table on p. 474 gives values of parameters for the Wilson equation for the ace-
tone( 1)/methanol(2) system. Estimate values of In YF and In Y2 at 50C. Compare
with the values suggested by Fig. 12.9(b). Repeat the exercise with the NRTL equa-
tion.
12.70. For a binary system d~rive the expression for HE implied by the Wilson equation for
oE 1RT. Show that the implied excess heat capacity C$ is necessarily positive. Recall
that the Wilson paratfieters depend on T , in accord with Eq. (J 2.24).
12.71. A single P-xt-YI data point is available for a binary system at 25C. Estimate from
the data:
(a) The total pressure and vapor-phase composition at 25C for an equimolar liquid
mixture.
(b) Whether azeotropy is likely at 25C.
Data: At 25C, P1sat = 183.4 and P2sat = 96.7 kPa

For Xt = 0.253, Yl = 0.456 and P = 139. 1 kPa
12.72. A si ngle P-x 1 data point is available for a binary system at 35C. Estimate from the
data:
(a) The corresponding value of YJ.

(b) The total pressure at 35C for an equimolar liquid mixture.
(c) Whether azeotropy is likely at 35C.
Data: At 35C, P 1sat = 120.2 and P.2sat =73.9 k.Pa

For Xt = 0.389, P = 108.6 kPa
Chapter 13
Chemical-Reaction Equilibria
The transformation of raw materials into products of greater vaJue by means of chemical re-
action is a major industry, and a vast array of commercial products is obtained by chemical
synthesis. Sulfuric acid, ammonia, edlylerre, prof!yleae, phosphoric acid, chlof)ne, niU)c aciD,
urea, benzene, methanol, ethanol, and ethylene glycol are examples of chemicals produced in
the United States in bj)lions of kilogra\}1S each year. These in turn are used in the large-scale
manufacture of fibers, paints, detergents, plastics, rubber, paper, fertilizers. insecticides, etc.
Clearly, the chemical engineer must be familiar with chemical-reactor design and operation.
Both the rate and the equilibrium conversion of a chemical reaction depend on the tem-
perature, pressure, and composition of reactants. Often, a reasonable reaction rate is achieved
only with a suitable catalyst. For example, the rate of oxidation of sulfur dioxide to sulfur
trioxide, carried out with a vanadium pentoxide catalyst, becomes appreciable at about 300C
and increases at higher temperatures. On the basis of rate alone, one would operate the reactor
at. the highest practical temperature. However, the equilibrium conversion to sulfur trioxide
falls as temperature rises, decreasing from about 90% at 520C to 50% at about 680C. These
values represent maximum possible conversions regardless of catalyst or reacti on rate. The
evident conclusion is that both equilibrium and rate must be considered in the exploitation of
chemical reactions for commercial purposes. Although reaction rates rue not susceptible to
thermodynamic treatment, equilibrium conversions are. Therefore, the purpose of this chapter
is to determine the effect of temperature, pressure, and initial composition on the equilibrium
conversions of chemical reactions.
Many industrial reactions are not carried to equilibrium; reactor design is then based pri-
mari ly on reaction rate. However, the choice of operating conditions may still be influenced by
equilibrium considerations. Moreover, the equilibrium ~0nversion of a reaction provides a goal
by which to measure improvements in a process. Similarly, it may determine whether or not
an experimental investigation of a new process is worthwhi le. Fot'"example, .if thermodynamic
analysis indicates that a yield of only 20% is possible at equilibrium and if a 50% yield is
necessary for the process to be economically attractive, there is no purpose to an experimental
study. On the other hand, if the equilibrium yie.ld is 80%, an experimental program to deter-
mine the reaction rate for various conditions of operation (catalyst, temperature, pressure, etc.)
may be warranted.
Reaction stoichiometry is treated in Sec. 13.1, and reaction equilibrium, in Sec. 13.2. The
equilibrium constant is introduced in Sec. 13.3, and its temperature dependence and evaluation
483
484 CHA PTER 13. Chemical-Reaction Equilibria
are considered in Sec . 13.4 and 13.5. The connection between the equilibrium constant and
composition is developed in Sec. 13.6. The calculation of equilibrium conversions for single
reactions is taken up in Sec. J3.7. In Sec. 13.8, the phase rule is reconsidered; muJti reaction
equilibrium is treated in Sec. 13.9; 1 finally. in Sec. 13.10 the fuel cell is given an introductory
treatment.
..;
13.1 THE REACTION COORDINATE
The general chemical reaction as written in Sec. 4.6 is:
( J 3.1 )
where Ivi I is a stoichi ometric coefficient and Ai stands for a chemica] formula. The symbol Vi
itself is called a stoichiometdc number and by the sign convention of Sec. 4.6 it is:
positive (+) for a product and . negative (-) (or a reactanl
Thus for the reaction,

the stoichiometric numbers are:
VCJI.t =- I vco =
The stoichiometric number fo r an inert species is zero.
As the reaction represented by Eq. ( 13. 1) progresses, the changes in the numbers of
moJes of species present are in direct p\oportion to lhe stoichiometric numbers. Thus fo r the
preceding reactio n, if 0.5 mol of CH4 disappears by reaction, 0.5 moJ of H20 also di sappears~
simultaneously 0.5 mol of CO and 1.5 mol of H2 are formed. Applied to a differential amount
of reaction, this principle provides the equations:
-=- etc.
VJ VJ
The list continues to include all species. Comparison of these equations yields:
dn4
-=-=-=-=
VJ V"'_,
All terms being equal, they can be identified collectively by a single quantity representing an
amount of reaction. Thus a definition of de is given by the equation:
dn 1 dn2 dn3 dn4

- = - = - = - = =de ( 13.2
VJ V2 V3 IJ4
1For a comprehensive treatment of chemical-reaction equilibria. ee W. R. Smith and R. W. Missen, Chemic._.

Reacrion Equilibrium Analysis. John Wiley & Sons. New York. 1982.
13.1 . The Reaction Coordinate 485
The general relation connecting the differential change dni with de 1s therefore:
(i = 1, 2, . .. , N) I ( 13.3)
This new variable c, ca11ed the reaction coordinate, characterizes the extent or degree
to which a reaction has taken place.2 Only changes in c: with respect lo changes in a mole
number are defined by Eq. ( 13.3). The definition of c itself depends for a specific application
on setting it equal to zero for the initial state of the system prior to reaction. Thus, integration
of Eq. (!3.3) from an initial unreacted state where c = 0 and n; = n;0 to a state reached after
an arbitrary amount of reaction gives:
or (i = I , 2, ... , N) (13.4)
Summation over all species yields:
n = ~ ni = Z: 11 ; + c Z: v;
0
or n =no+ vc:
where n =b n; V =b Vj
Thus the mole fractions Yi of the species present are related to c: by:
n; n;0 + v;c:
Vi = - = ----=-- -- (13.5)
. n no+ vc:
Application of this equation is illustrated in the fo llowing examples.
Example 13.1
For a system in which the following reaction occurs,
assume there are present initially 2 mol CH4 , 1 mol H2 0 , 1 mol CO, and 4 mol H2 .
Determine expressions for the mole fractions y; as functions of t .
2The reaclion coordi nate s has been given various names. such as: degree of advancement. degree o f reaction,
extent of reaction, and progress variable.
486 CHAPTER 13. Chemical-Reaction Equilib1ja
Solution 13.1
For the reaction, .. V = ~ Vi = -1 - 1+ 1 + 3 =2
For the given numbers of moles of species initially present,
no = ~ nio = 2 + 1+ 1+4 = 8
.,
Equation (13.5) now yields:
2-e 1 -s
YCH4 = 8 + 28 YH20 = 8 + 28
l +e 4+3s
Yeo = 8 +2s YH2 = 8 + 2s
The mole fracti ons of the species in the reacting mixture are seen to be functions
of the single variable e.
Example 13.2
Consider a vessel which initially contains only no mol of water vapor. If decomposition
occurs according to the reaction,
H20 ~ H2 + ~ 02
find expressions which relate the number of moles and the mole fraction of each chem-
ical species to the reaction coordinate s.
Solution 13.2
For the given reaction, v = - 1+ 1+ ~ = ~- Application ofEqs. (13.4) and (J3.5)
yields:
no-s
YH20 = 1
no+ 2s
s
The fractional decomposition of water vapor is:

no- n1-12o no- (no-s) s
no no no
Thus when no J, s is di rectly relaLed to the fractional decomposition of the
water vapor.
13. 1. The Reaction Coordinate 487
The v; are pure numbers without units; Eq. (13.3) therefore requires s to be expressed
in moles. This leads to the concept of a mole of reaction, meaning a change in s of one mole.
When 6..& = 1 mol, the reaction proceeds to such an extent that the change in mole number of
each reactant and product is equal to its stoichiometric number.
Multireaction Stoichiometry
When two or more independent reactions proceed simultaneously, subscript j serves as the
reaction index. A separate reaction coordinate e j then applies to each reaction. The stoichio-
metric numbers are doubly subscripted to identify their association with both a species and a
reaction. Thus vi,j designates the stoichiometric number of species i in reaction j. Because the
number of moles of a species n; may change because of several reactions, the general equation
anal9gous to Eq. (13.3) includes a sum:
(i=1,2, ... ,N)
j
Integration from n; = n;0 and e j = 0 to arbitrary n; and s j gives:

....
n; = n;0 + I,; v;,j& j (i = 1, 2, ... , N) (13.6)

j
Summing over all species yields:
n = ~ n ;0 + ~ ~ v;,jEj = no+ ~ ( ~ v;.j ) Sj

I I j j I
The defi nition of a total stoichiometric number v (= L; v;) for a single reaction has its coun-
terpart here in the defin ition:
Vj =b Vi.j whence n =no+ I.; Vjej

j
Combination of this last equation with Eq. (13.6) gives the mole fraction:
(i = 1, 2, ... N)I (13.7)
Example 13.3
Consider a system in which the following reactions occur:
CH4 + H20 --7 CO+ 3H2 (1 )
C~ + 2H20 --7 C02 +4H2 (2)

where the numbers (1) and (2) indicate the value of j, the reaction index. If there
are present initially 2 mol CH4 and 3 mol H2 0, determine expressions for the y; as
functions of t: 1 and s2 .
488 CHAPTER 13. Chemical-Reaction Equilibria
Solution 13.3
The stoichiometric numbers vi.J can be arrayed as follows:
l=
- CH4 H20 co C0 2 H2
\)
J ~ J
"
1 -1 -I 1 0 3 2
2 - I -2 0 1 4 2
Application of Eq. ( 13.7) now gives:
2- eJ - e2 )
YCH-1 = 5 + 2) + 22 Yco=-----
5 + 2) + 22
3- cJ - 2e2 c?
JI I20 = 5 + 2C'J + 22 .reo..,
-
= 5 + 2e1-+ 2ez
3e J + 4ez
YH, =
- 5 + 2e 1 + 2e2
The composition of the system is a function of independent variables e, and e2.
13.2 APPLICATION OF EQUILIBRIUM CRITERIA TO

CHEMICAL REACTIONS
Tn Sec. 14.3 it is shown that the total Gibbs energy of a closed system at constant T and P
must decrease during an irreversible process and that the conditio n for equilibrium is reached
when G1 attains its mi nimum value. At this equilibrium state,
(14.68)
Thus if a mixture of chemical species is not in chemical equilibrium, any reaction that occur
at constant T and P must lead to a decrease in the total Gibbs energy of the system. The sig-
nificance of this for a single chemical reaction is seen in Fig. 13. 1, which shows a schematic
diagram of G' vs. e, the reaction coordinate. Because e is the single variable that characteri ze
the progress of the reaction, and therefore the composition of the system, the total Gibbs en-
ergy at constant T and P is determined by e. The arrows along the curve in Fig. 13.1 indicate
the directions of changes in ( G ') T. p that are pQssible on account of reaction. The reaction co-
ordinate has its equilibrium value ee at the minimum of the curve. The meaning of Eq. (14.68
is that differential displacements of the chemical reaction can occur at the equilibriu m stare
without causing changes in the total Gibbs energy of the system.
13.3. The Standard Gibbs-Energy Change and the Equilibrium Constant 489
Constant T and P
Figure 13.1: The total Gibbs energy in

relaLion to the reactio n coordinate.
Figure 13. 1 indicates the two disti nctive features of the equilibrium state for given tern-
perature and pressure: . .,
The total Gibbs energy G 1 is a minimum. Its differential is zero.
Each of these may serve as a criterion of equilibrium. Thus. we may write an expression for
G 1 as a function of s and seek the value of which minimizes G' , or we may differentiate the
expression, equate it to zero, and solve for . The latter procedure is almost always used for
single reactions (Fig. 13. 1), and leads to the method of equi librium constants. as described in
the following sections. It may also be extended to multiple reactions, but in this case the direct
mi nim ization of G' is often more convenient, and is considered in Sec. 13.9.
Although the equilibrium expressions are developed for closed systems at constant T
and P. they are not restricted in application to systems that are actually closed and reach
equilibrium states along paths of constant T and P. Once an equilibri um state is reached, no
further changes occur, and the system continues to exist in this state at fixed T and P. How this
state was actually attained does not matter. Once it is known that an equil ibrium state exists at
given T and P the criteria apply.
13.3 THE STANDARD GIBBS-ENERGY CHANGE AND THE

EQUILIBRIUM CONSTANT
Equation (I 1.2), the fundamental properLy relation for single-phase systems. provides an ex-
pression for the total differential of the Gibbs energy:
d(nG) = (n V)c/ P - (nS)dT +L J.J.i dn; ( I 1.2)
If changes in the mole numbers n; occur as the result of a single chemical reaction in a closed
system. then by Eq. ( 13.3) each dn; may be replaced by the product v; de. Equation ( 11.2)
then becomes:
cl(nG) = (nV)dP- (nS)dT + I:; Vill-i de
Because nG is a state function, the right side of this equation is an exact differential expression:
whence,
b v;JJ-; = [a(nG)J = [a(G'
O
)]
t O T.P T.P
Thus the quantity L; v; JJ-;.Jepresents, in general, the rate of change of total Gibbs energy of
the system with respect to the reaction coordinate at constant T and P . Figure 13.1 shows that
this quantity is zero at the equilibrium state. A criterion of chemical-reaction equibbrium i
therefore:
(13.8)
Recall the definition of the fugacity of a species in solution:

JL; = r ; (T ) + RT In }; ( 11.46)
In addition, Eq. (11.31) may be written for pure species i in its standard state3 at the same
temperature:
Gf = r; (T) + RT In /;0
The difference between these two equations is:
A
11 -
. G 0= RT 1n -f; (13.9
~~ 1 f;o
Combining Eq. (1 3.8) with Eq. (13.9) to eliminate /1-i gives for the equilibrium state of a
chemical reaction: '
b v; [Gf + RT ln (};j f t )J = 0
or
or
where Ti i signifies the product over all species i. In exponential form, this equation become :
(13.10
where the definition of K and its logarithm are given by:
~G )
0
- ~G o
K = exp ( RT (13.lla) InK= - - -
RT
(13.llb)
I'
3Standard states are introduced and discussed in Sec. 4.3.

13.3. The Standard Gibbs-Energy Change and the Equilibrium Constant 49 1
(
Also by defi~tion, 6.G 0 =Li viGj (13.12)
Because cr\, a property of pure species i in its standard state at fixed pressure, it depends
only on temperature. By Eq. ( 13. 12) it follows that 6.G 0 and hence K , are also functions of
temperature only.
In spite of its dependence on temperature, K is called the equilibrium

constant for the reaction; L;
v;Gf, represented by ~ G , is called the0
standard Gibbs-energy change of reaction.
The fugacity ratios in Eq. (13 .10) provide the connection between the equilibrium state
of interest and the standard states of the individual species, for which data are presumed avai l-
able;- as d iscussed in Sec. 13.5. The standard states are arbitrary, but must always be at the
equilibrium temperature T. The standard states selected need not be the same for all species
taking part in a reaction. However, for a particular species the standard state represented by
Gf must be the same state as for the fugacity f t .
The functio n 6.G 0 = Li viGj in Eq: ( 13.12) is the difference between the Gibbs en-
ergies of the products and reactants (weighted by their stoich iometric coefficients) when each
is in its standard state as a pure substance at the standard-state pressure, but at the system
temperature. Thus the value of 6.G 0 is fixed for a given reaction once the temperature is es-
tablished, and is independent of the equilibrium pressw-e and composition. O ther srandard
property changes of reaction are similarly defined. Thus, for the general property M:
In accord with this, 6.H 0 is defined by Eq. (4.14) and !:J.C $ by Eq. (4.16). These quantities are
functions of temperature only for a g iven reaction, and are related to one another by equations
analogous to property relations for pure species.
For example, the relation between the standard heat of reaction and the standard Gibbs-
energy change of reaction may be developed from Eq. (6.39) written for species i in its standard
state:
o d(G7/RT)
H =-RT 2
I dT
Total derivatives are appropriate here because the properties in the standard state are functions
of temperature only. Ylultiplication of both sides of this equation by v; and summation over all
species gives:
~ vH
.
I
I
0
I
= - RT
2 d(L; VjG7I RT )
dT
In view of the defin itions of Eqs. (4. 14) and (13. 12), thi s may be written:
(13. 13)
13.4 EFFECT OF TEMPERATURE ON THE

EQUILIBRIUM CONSTANT
"
Because the standard-state temperature is that of the equilibrium mixture, the standard prope1ty
changes of reaction, such as 6G 0 and 6 H 0 , vary with the equilibrium temperature. The
dependence of ~c o on T is given by Eq. ( I 3. 13), which may be rewritten:
,/
In view ofEq. ( 13 .1 Jb), this becomes:
d inK
(J3.14)
dT
Equation ( 13. I 4) gives the effect of temperature on the equilibrium constant, and hence on
the equi librium conversion. If ~H is negative, i.e., if the reaction is exothermic, the equi1ib-
0
Jium constant decreases as the temperature increases. Conversely, K increases with T for an
endothermic reaction.
If~ H , the standard enthalpy change (heat) of reaction , is assu med independent ofT,
0
integration of Eq. ( 13. 14) from a particular temperature T' to an arbitrary temperature T leads
to the simple result:
In!__ =- ~ Ho (_!__ - _J ) ( 13. 15)
K' R T T'
"
This approximate equation implies that a plot of ln K vs. the reciprocal of absolute temperature
is a straight li ne. Figure 13.2, a plot of InK vs. I I T for a number of common reactions,
illustrates this near linearity. Thus, Eq. ( 13.15) provides a reasonably accurate relation for the
interpolation and extrapolation of equilibrium-constant data.
The rigorous development of the effect of temperature on the equilibr(um constant is
based on the defini tion of the Gibbs energy, writlen fo r a chemical species in its standard state:
GC:I = H? -
I
TS?
I
Multiplication by v; and summation over all species gives:
As a result of the definition of a standard property change of reaction, this reduces o:
\ 6G 0 = 6.H
0
- Tt::.S
0
( J3. 16)
The standard heat of reaction is related to temperature:
(4.1 8)
13.4. Effect of Temperature on the Equilibrium Constant 493
oiJv
v lj ~
v
o~V'/~
28
0
~v
y.. 'V ~"'
)(
-
vl 1~
24
0
/c;/
20
c/('",~/
,_ v kt"'
/v 01 I
/ v ~'A'J
16
-,<;_/;;;v
~:Jv
12
~' ~/
"~
w
b-.... ~
8
;,~~ !'... /p 7
4 If
v; " ~ ~ s/
1,'1(\'1.
~
,..,...
~ ~~ t:;: ~~
" .~ ~v ~~
__..co2 + \-\ 2 -~~ /~
0
c::t:l -,
......-
co +
--
~~v
~Ot ~~~
~ ~0
:~02 :::;~
?.....,....
"l"~ r-.... c
-4
l>VVv
~ "'" ' N ~0
"*
1
_.. !'.. ~
~ v"'""'- <~< "' "~)( ,y 0<y..
"- 0~~:-
-8 '1- 1
K <'q
~ ~
'~o ~c co x ....,
0<> -)t
r--.... ~~<>
- 12
~'--r--
t---~ 2C + 2H
r---2r=::::-
. . . . . !'<
" ~c 0 :""
"~ K "
C2H
~ r--
- 16
~~
~
r--
- 20
4
2ooo
1
6
1510?
8
~2100
10
~~0 ~0? K
14 16
"'
18
~
~
20
F igu re 13.2: Equilibrium constants as a function of temperature.

T he temperature dependence of the standard entropy change of reaction is developed similarly.

Equation (6.21) is written for the standard-state entropy of species i at the constant standard-
state pressure P o:
o o dT
dS; CP;r =
Multiplying by v;, s umming over all species, and invoking the definition of a standard prope rty
change of reaction yields: ""
Integration gives:
b.C 0 dT
t::.So = t::.So +R
i T
To
__ P -
R T
(13. 17)
where t::.S 0 and t::.S are standard entropy changes of reaction at temperature T and at reference
0
temperature To respectively. Equations (13.16), (4. 18), and (13 .17) are combined to yield:
T_ _
~::.c o iT_ _~::.c o dT
t::.G 0 = D.H0 + R
i ~ R
P ciT- TD.S 0- RT
~ R
P-
T
However,
Whence,
t::.G 0 = b. H 0-
T
-(t::. H
0- b.G{))'+ R
iT t::.C o
__ P dT- RT
i r_ _
b.C o dT
P-
To To R To R T
Finally, division by RT yields:
b.G0 = t::.G 0- b.H 0 + b.H0 + _}_ { T D.C pdT _ { T b.C pdT (13.18)
RT RTo RT T 1To R 1r0 R T
0
Recall that by Eq. (13. 11b), InK= -t::.G / RT.
When the temperature de pendence of the heat capacity of each species is given by
Eq. (4.4), the first integral on the right side of Eq . (I 3.18) is given by Eq. (4. 19), repr\nted
for computational purposes by:
T b.C o
iTo
_ P dT
R
= IDCPH(TO,T;DA,DB,DC,DD)
where " D" denotes " b." . Similarly, the second integral is given by the analog ofEq. (5.15):
1 r _
I,0 R
0
P dT
t::.C_ - = b. A In r
T
+ [ b. 8 To + ( b. C T6" + -t::.D
2
? )
r T.-
(r + L)]
--
2
(r - I) (13. 19)
0
T
where r =-
To
13.4. Effect of Temperature on the Equilibrium Constant 495
The integral is evaluated by a function of exactly the same form as given by Eq. (5 . 15), and the
same computer program therefore serves for evaluation of either integral. The only difference
is in the name of the fu nction, here: IDCPS(TO,T;DA,DB,DC,DD). By definiti on,
T 6.C 0 dT
i To
_P-
R T
= IDCPS(TO,T;DA,DB,DC,DD)
Thus 6.G 0 I RT(= -InK) as given by Eq. (1 3.18) is readily calculated at any tempera-
ture from the standard heat of reaction and the standard Gibbs-energy change of reaction at a
reference temperature (us ually 298.15 K), and from two functions which can be evaluated by
standard computational procedures.
The preceeding equations may be reorgan ized so as to factor K into three terms, each
representing a basic contribution to its val ue:
,..
(13.20)
The first factor Ko represents the equilibrium constant at reference temperature To:
" 6-Go)
Ko =exp ( - 0
(13.2 1)
RTo
The second factor K 1 is a m ultiplier th at supplies the major effect of temperature, such that
the product KoK t is the equilibrium constant at temperature T w hen the heat of reaction is
assumed independent of temperature:
K1 =exp [ 6.H0 ( To) ]

RTo I - T (13.22)
The th ird factor K2 accounts for the much smaller temperature influence resulting from rhe
change of 6.H 0 with temperature :
K2 =exp ( - -1iT
T To
_
R
0
t::.C_
PdT + 1r__
To R
0
t::.C P -dT )
T
( 13.23)
With heat capacities g iven by Eq. (4.4), the expression for K2 b~comes:
J (r - 1)2
+ -t::.. BTo- - -
2 r
( I 3.24)
496 CHAPTER 13. Chemical-Reaction Equi libr ia
13.5 EVALUATION OF EQUILIBRIUM CONSTANTS
Values of l::. G 0 for many formation reactions are tabulated in standard references.4 T he re-
ported values of ~ G j are not measured ex pe1imentally, but are calculated by Eq. (1 3. 16).
The determination of t::.Sj may be based on the third law of thermodynamics, discussed in
Sec. 5.1 0. Combination of values from Eq. (5.40) for the absolute entropies of the species
laking part in the reattion gives the val ue of t::.Sj . Entropies (and heat capacities) are also
common ly de termined from statis-tical calcu lations based on spectroscopic data.5
Values of D.G 0 . for a limited number of chemical compounds are li sted in Table C.4
- 129&
of App. C. These are for a temperature of 298. 15 K, as are the values of t::. H.{ Listed in the
298
same table. Values of l::.G 0 for other reactions are calculated from form ation-reaction values
in exactl y the same way that l::. H 0 values for other reactions are determi ned from formation-
reacti on values (Sec. 4.4). In more extensive compilations of data, values of 6.Gj- and 6.HJ
are given fo r a wide range of temperatures, rather than j ust at 298.1 5 K. Where data are lacking,
methods of estimation are available; these are reviewed by Poling, Prausnitz, and O'Connell.6
Example 13.4
Calculate the equilibrium constant fo r the vapor-phase hydration of ethylene at 145
and at 320C from data given in App. C.
Solution 13.4
First determine values fo r !::.A, t::. B , 6.C, an~ 6. 0 for the reaction:
The meaning of D. is indicated by: 6. = (C2HsOH ) - (C2H4) - (H20 ). Thus, "'

from the heat-capacity data of Table C.l:
D.A = 3.5 18 - 1.424- 3.470 = -1.376

D. B = c2o.oo 1 - 14.394 - 1.450) x 10- 3 = 4. 157 x w-3
D..C = ( -6.002 + 4 .392 - 0.000) x 1o-6 = -1 .6 10 X I o- 6
6. 0 = (-0.000- 0.000- 0.121) X 10 5 = -0.121 X 105
4
For example. "TRC Thermod ynamic Tables- Hydrocarbons and "TRC Thermodynamic Tables-Non-hydro-
carbons." serial publications of the Thermodynamics Research Center, Texas A & M Univ. Sysrem, College Station.
Texas; "The NBS Tables of Chemical Thermodynamic Properties,'' J. Physical and Chemical Reference Daw, vol. 1I.
supp. 2, 1982.
5 K. S. Pirzer, Thermodynamics. 3d ed., chap. 5, McGraw-Hill , New York, 1995.
6B. E. Poling, J. M. PrausniLz, and J. P. O'Connell, The Properries of Gases wtd Liquids, 5th ed .. chap. 3, McGraw-
Hill. New York, 200 I.
13.5. Evaluation of Equilibrium Constants 497
Value. of 6 H298 and 6G298 at 298.15 K for the hydration reaction are found from
the heat-of-formation and Gibbs-energy-of-formation data of Table C.4:
= - 235,100- 52,510- (-24 1,8 18) = -45,792 1 mol - 1
6 H!f.98
6G298 = - 168,490 - 68,460- ( -228,572) = -8,378 J mol- 1
ForT = 145 + 273.15 = 418. 15 K, values of the integrals in Eq. ( 13. 18) are:
IDCP H(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-0. 121 E+5) = -23. 12 1
IDCPS(298. 15,418.15;-1 .376,4.157E-3,-1.61 OE-6,-0. 12 1 E+5) = -0.0692
Substitution of values into Eq. ( 13. 18) for a reference temperature of298.15 gives:
,.
6G~ 1 8 - 8,378+45,792 -45.792 - 23. 12 1
-...:..=
RT
=
(8.3 14)(298. 15)
+ (8.3 14)(4 18. 15) + 4 18. 15
+ 0069
. 2 = I. 9 356
ForT= 320 + 273.15 = 593.1~ K ,

IDCPH(298.15,593.15;-1.376,4.157E-3,-1 .61 OE-6,-0. 121 E+5) = 22.632
IDCPS (298.1 5 ,593.15;-1 .376,4.157E-3,-1.61 OE-6,-0. 121 E+5) = 0.0173
Whence,
-8,378 + 45 ,792 -45.792 22.632
"'
(8 ..> 14)(298.15)
+ (8.3 14)(593.1 5) + 593. 15 -0.0173 = 5.8286
Fin ally,
@ 4 18.15 K: In K= -1.9356 and K = 1.443 X 10- 1

@ 593. 15 K: InK = -5.8286 and K = 2.942 x lo-3
Application ofEqs. (13.21). ( 13.22), and ( 13.24) provides an alternative solu-
tion to thi s example. By Eq. (13.21).
8,378
Ko = exp = 29.366
(8.314)(298. 15)
6H00 -45,792
...
Moreover, = - 18.473
RTo (8.3 14)(298.1 5) ~
With these values, the following results are readily obtained:
T/K r Ko K1 K2 K
298.15 I 29.366 J I 29.366

4 18. 15 1.4025 29.366 4.985 x w- 3 0.9860 1.443 x w- 1
593.15 1.9894 29.366 1.023 X 10- 4 0.9794 2.942 X 10- 3
Clearly, the influence of K 1 is far greater than that of K2 . This is a typical result,
and accounts for the fact that the lines on Fig. 13.2 are nearly linear.
498 CHAPTER 13 . Chemical-Reaction Equilibria
13.6 RELATION OF EQUILIBRIUM CONSTANTS

TO COMPOSITION
Gas-Phase Reactions
T he standard state for a gas is the ideal-gas state of the pure gas at the standard-state pressure
P 0 of 1 bar. Because the fugacity of an ideal gas is equal to its pressure, ft = P for each
0
species i. Thus for gas-phase_;eactions ]; I f;0 = ]; 1P , and Eq. (13.1 0) becomes:

0
fi" )v;
.
I! ( po = K --"1 (1 3.25)
The equilibrium constant K is a function of temperature only. However, Eq. (13.25 )

relates K to fugacities of the reacting species as they exist in the real equilibrium mixture.
T hese fugacities reflect the nonidealities of the equilibrium mixture and are functions of tem-
perature, pressure, and composition. This means that for a fixed temperature the composition
at eq uilibrium must change with pressure in such a way that fl
(J'} I P 0 ) v; remains constant.
The fugacity is related to the fugacity coefficient by Eq. ( 11 .52):
Substitution of this equation into Eq. ( 13.25) provides an equilibrium expression displaying
the pressure and the composition:
.(1 3.26)
where v = L; v; and P 0 is the standard-state pressure of I bar, expressed in the same unirs
used for P. They; 's may be eliminated in favor of the equilibrium value of the reaction coor-
dinate ce Then, for a fixed temperature Eq. (13.26) relates ce to P. In principle, specification
of the pressure aJ_Iows solution force. However, the problem may be complicated by the de-
pendence of; on composition, i.e., on ce The methods of Sees. J 1.6 and 11 .7 can be applied
to the calculation of; values, for example, by Eq. (11.64). Because of the complexity of
the calc ulations, an iterative procedure, initiated by setting; = 1 and formulated for com-
puter solution, is indicated. Once the ini tial set {y;} is calculated, {;} is determined, and the
procedure is repeated to convergence.
If the assumption that the equilibrium mixture is an ideal solution is justified, then eacr
; becomes ;, the fugaci ty coefficient of pure species i at T and P [Eq. ( 11.84)]. In this case.
Eq. ( 13.26) becomes:
( 13.2-
Each ; for a pure species can be evaluated from a generalized correlation once the equilibrium
T and P are specified.
13.6. Relation of Equilibrium Constants to Composition 499
For pressures sufficiently low or temperatures sufficiently high, the equilibrium mixture
behaves essentially as an ideal gas. In this event, each; = I, and Eq. (13 .26) reduces to:
I! (y;) v; = (
p
po
)-vK (13.28)
In this equation the temperature-, pressure-, and composition-dependent terms are distinct and
separate, and solution for any one of Se, T , or P, given the other two, is straightforward.
Although Eq. (13.28) holds only for an ideal-gas reaction, we can base some concl usions
on it that are true in general:
According to Eq. (13.14), the effect of temperature on the equilibrium constant K is

determined by the sign of D. H 0 Thus when b. H 0 is positive, i.e., when the standard
reaction is endothermic, an increase in T results in an increase in K. Equation ( 13.28)
shows that an increase in K at constant P results in an increase in n ; (y;) v;; this implies a
shift of the reaction to the right and an increase in Se. Conversely, when D. H 0 is negative,
i.e., when the standard reaction is exothennic, an increase in T causes a decrease in K
and a decrease in ni (Yi) V; at constant p.~This implies a shift of the reaction to the left
and a decrease in Se.
If the total stoichiometric number v <= L; v;) is negative, Eq. (13.28) shows that an in-
crease in P at constant T causes an increase in n ; (y;) v;, implying a shift of the reaction
to the right and an increase in Se. If vis positive, an increase in P at constant T causes
a decrease in ni (y;) v; ' a shift of the reaction to the left, and a decrease in 8e .
Liquid-Phase Reactions
For a reaction occuning in .the liquid phase, we return to:
(13.10)
For the usual standard state for liquids ft is the fugacity of pure liquid i at' the temperature of
the system and at l bar.
According to Eq. (1 1.90), which defines the activity coefficient,
where .n is the fugacity of pure liquid i at the temperature and pressure of the equilibrium
mixture. The fugacity ratio can now be expressed:
it:.o -_ YiXi f;
+,o
_ . . ( fi )
- Yt X1 f.o (13.29)
JI JI I
Because the fugacities of liquids are weak functions of pressure, the ratio/; 1ft is often taken
as unity. However, it is readily evaluated. For pure liquid i Eq. (11.31) is written twice, first
for temperature T a nd pressure P , and second for the same temperature T but for the standard-
state pressure of P 0 . The difference between these two equations is:
G; - Gf = R T In ~~
Integration of Eq. (6. I 0) at constant temperature T for the change of state of pure liquid i from
P 0 to P yield~.;._
As a result,
J; =
R T 1n -:o
!,p V; d P
J; po
Because V; changes little with pressure for liquids (and solids), integration from P 0 to P gives
to an excellent approximation:
+.
./1 Y.(P-
I
p o)
1n - = - - - - - ( 13.30)
/;0 RT
With Eqs. ( 13.29) and (13.30), Eq. ( 13.1 0) may now be written:
(13.31)
Except for high pressures, the exponential term is close to unity and may be omitted. Then,
( 13.32)
and the only problem is determination of the activity coefficients. One may apply an equa6on
such as the wilson equation [Eq. ( 12. I 9) I, or the UNIFAC method [App. H], and th.e compo-
sitions can be found from Eq. ( 13.32) by a complex iterative computer program. However, the
relative ease of expetimental investigation for liquid mixtures has worked against the applica-
tion ofEq. (13.32).
lf the equilibrium mixture is an ideal solution, then y; is unity, and Eq. (13.32) becomes:
n (x;) Vi = K (13.33)
T his simple relation is known as the law of mass action. Because liquids often form nonideal
solu~ions, Eq. ( 13.33) can be expected in many instances to yield poor results.
l
For species known to be present in high concentration, the equation I J; = x; is usu-
ally nearly correct. The reason, as discussed in Sec. 12.1, is that the Lewis/Randall rule
[Eq. (11.83)] always becomes valid for a species as its concentration approaches x; = I.
For species at low concentration in aqueous solution, a different procedure has been widely
adopted, because in this case the equality of hIfi and Xi is usually far from correct. The
method is based on use of a fictitious or hypothetical standard state for the solute, taken as the
r
13.6. Relation of Equilibrium Constants to Composition 50 1
7
s late that wou ld exist if l'he solute obeyed Henry 's law up to a molality m of unity. In thi s
a pplication, Hen ry 's law is expressed as
]; = k;nt; (13 .34)
and it is always valid fo r a spec ies whose concentration approaches zero. This hypothetical
state is ilJustrated in Fig. 13.3. The dashed line drawn tangent to the curve at the origi n repre-
sents Henry'. law, and is valid in the case shown to a molality much less than unity. However,
one can calculate the properties the so lute would have if it obeyed Henry's law to a concen-
tration of I molal , and this hypothetical state often serves as a convenient standard state for
solutes.
Hypothetical 1
1
1-molal
solution/;
I I
II I
1 I
I I
I I
!; / I
I
I
Figure 13.3: Standard srarc for dilute
I
I aqueous solutions.
/
0
------~~------------~
m,, molal ity

1
The standard-state fugaci ty is

~0
f; = k;m; = k;
0
X I = k;
Hence, for any species at a concentration low enough ror Henry's law to hold,
j = k;m; = f t m;
and ( 13.35)
The advantage of this standard state is that it provides a very simple relation between fugacity
and concentration for cases in wh ich Henry 's law is at leas t approximately valid . Tts ra nge
does not common ly extend to a concentrati on of I molal. Tn the rare case where it does, the
0
standard s tate is a real state of the solule. This standard state is useful only where b.G data
are available for the standard state of a 1-molal so lution, for otherwise the equilibrium constant
cannot be evaluated by Eq. (13 .11 ).
7 Molality is a measure of solute concentration. expressed as moles of solute per kilogram of solvent.
502 CHA PTER 13. Chemical-Reaction Equilibria
13.7 EQUILIBRIUM CONVERSIONS FOR SINGLE REACTIONS
Suppose a single reaction occurs in a homogeneous system, and suppose the equilibrium con-
stant is known. In this event, the calculation of the phase composition at equilibtium is straight-
forward if the phase is assumed an ideal gas [Eq. (13.28)] or an ideal solution [Eq. (1 3.27)
or (13.33)]. When an assumption of ideality is not reasonable, the problem is still tractable
for gas-phase reactions through application of an equation of state and solution by computer.
For heterogeneous systems, where more ;
than one phase is present, the problem is more com-
plicated and requires the superposition of the criterion for phase equillbrium developed in
Sec. 11 .6. At equilibrium, there can be no tendency for change to occur, either by mass trans-
fer between phases or by chemical reaction. We present in what follows, mainJy by example,
the procedures in use for equ ilibrium calculations, first, for single-phase re actions, and second,
for heterogeneous reactions.
Single-Phase Reactions
The following examples illustrate application of equations developed jn the preceding section.
Example 13.5
The water-gas-shift reaction ,
CO(g) + H20 (g)--+ C02(g) + H 2(g)

"' described be!low. Calculate the
is carried out under the different sets of conditions
fraction of steam reacted in each case. Assume the mixture behaves as an ideal gas.
(a) The reactants consist of 1 mol of H2 0 vapor and 1 mol of CO. The temperature
is 1,100 K and the pressure is 1 bar.
(b) Same as (a) except that the pressure is 10 bar.
(c) Same as (a) except that 2 mol of N2 is included in the reactants.
(d) The reactants are 2 mol of H2 0 and 1 mol of CO. Other conditions are the
same as in (a) .
(e) The reactants are 1 mol of H2 0 and 2 mol of CO. Other conditions are the
same as in (a).
(f) The initial mixture consists of 1 mol of H2 0 , 1 mol of CO, and 1 mol of C0 2 .
Other conditions are the same as in (a) .
(g) Same as (a) except that the temperature is 1,650 K.

13. 7. Equilibrium Conversions for Single Reactions 503
Solution 13.5
(a)Forthegivenreactio natl,lOOK, 104 /T =9.05,andfromFig.l3 .2, lnK =0
and K = I . For this reaction v = L; v; = 1+ 1 - 1 - 1 = 0. Because the reaction
mixture is an ideal gas, Eq. (13.28) applies, and here becomes:
YHzYCOz = K = 1 (A)
YCOYH20
By Eq. (13.5),
1 - Se 1 - Se
YCO = 2 2
Substitution of these values into Eq. (A) gives:
2
,.. se = 1 or Se = 0.5
(1 - Se) 2
Therefore the fraction of the steam that reacts is 0.5.

'I
(b) Because v = 0, the increase in pressure has no effect on the ideal-gas reaction,
and Se is still 0.5.
(c) The N2 does not take part in the reaction, and serves only as a diluent. It does
increase the initial number of moles no from 2 to 4, and the mole fractions are all
reduced by a factor of2. However, Eq. (A) is unchanged and reduces to the same
expression as before. Therefore, te is again 0.5.
(d) In this case the mole fractions at equilibrium are:
I - Se
Yeo = 3
and Eq. (A) becomes:
s2
_ _____;;e_ _ _ = I or 8e = 0.667
(1 - 8e)(2- Se )
The fraction of steam that reacts is then 0.667/2 = 0.333.

,..
(e) Here the expressions for Yeo and YHzO are interchanged, but this leaves the
equilibrium equation the same as in (d). Therefore te = {).667, and the fraction of
steam that reacts is 0.667.
if) In this case Eq. (A) becomes:
Se(l + Se)
l or 8e = 0.333
---=-=
2
(1 - Se)
The fraction of steam reacted is 0.333.

504 CHAPTER 13. Cllemical-Rellclion Equilibria
(g) At I ,650 K, 10 4 jT = 6.06, and from F ig. 13.2. InK = -1.15 or K = 0.316.
T herefore Eq. (A) becomes:
or
The reaction is C)tothermi c, and conversion decreases with increasing temperature.
Example 13.6
Estimate the maximum conversion of ethylene to ethanol by vapor-phase hydration at
\.
250C and 35 bars for an initial steam-to-ethylene ratio of 5.
Solution 13.6
The calculation o f K for tllis reaction is treated in Ex. 13.4. For a tem perature of
250vc or 523. 15 K the calculation yields:
K = 10.02 X 10- 3
T he appropriate equilibrium expression is Eq. ( 13.26). This equation requires

eva luation of the fugacity coefficients of the species present in the equil ibrium
mi xrure. This may be accomplished w ith Eq. ( 11.64). However. the calcul ations
involve iteration, because the fugacity coefficients are fu nctions of compositio n.
For purposes of illustration , we ca1TY out OQIY the first iteration. based on the as-
sump tion that the reaction m ixture is an ideal solution. 1n this case Eq. ( 13.26)
reduces to Eq. (13.27), which req uires fugac ity coefficients of the pure gases of
the reacting mixture at the equi librium T and P. Because v = 2:; v; = - I , this
equation becomes:
(A)
Computatio ns based o n Eq. ( 11 .68) in conjunction with Eqs. (3.65) and (3.66)
provide values represented by:
PHIB(T R,PR,OMEGA) = i
The results of these calculatjon s are summaJized in the following table:
Tc!K Pclbar w; T,.; P,.; so B' i
C2H4 282.3 50.40 0.087 1.853 0.694 -0.074 0.126 0.977

H20 647 . 1 220.55 0.345 0.808 0. 159 -0.5 11 - 0.281 0. 887
EtOH 5 13.9 61.48 0.645 1.0 18 0.569 - 0.327 -0.021 0.827
The critical data and values of w; are from App. B. The temperature and pressure
in all cases are 523.15 K and 35 bar. Substitution of values for</>; and for ( P1P 0 )
into Eq. (A) gives:
YEtOH = (0.977)(0. 8S7) (35)( I 0.02 x 10- 3) = 0.367 (B)

YC2H4 .YH20 (0.827)
By Eq. ( 13.5),
Ee
YEtOH =
6- Ee
Substituting these into Eq. ( B) yields:
t:e(6 - Ee) = 0.367 ')
(5- E:e)( l - Se)

or e; - 6.000se + 1.342 = 0
The solution to this quadratic equation for the smaller root is Be = 0.233. Because
the larger root is greater than unity, 'i t does not represent a physically possible
result. The maximum conversion of ethylene to ethanol under the stated conditions
is therefore 23.3%.
In this reaction, increasing the temperature decreases K and hence the conver-
sion. Increasing the pressure increases the conversion. Equilibrium considerations
therefore suggest that the operating pressure be as high as possible (limited by con-
densation ), and the temperature as low as possible. However, even with the best
catalyst known, the minimum temperature for a reasonab le reaction rate is about
150C. This is an instance where both equilibrium and reaction rate influence the
commercializing of a reaction process.
The equ ilib1ium conversion is a function of temperature, pressure, and the
steam-to-ethy lene ratio in the feed. The effects of all three variables are shown
in Fig. 13.4. The curves in this figu re come from calculations just like those
illustrated in this example, except that a less precise relation forK as a function
of T was used.
Example 13.7
In a laboratory investigation , acetylene is catalytically hydrogenated to ethylene at
1,120C and 1 bar. If the feed is an equimolar mixture of acetylene and hydrogen,
what is the composition of the product stream at equilibrium?
Solution 13.7
The required reacti on is obtained by addition of the two forma tion reactions writ-
Len as follows:
100 , 14.7(psia)
/ ,,
// / /
300 I It / /
It I I
30
25
0 20
..c
0
- -.., 5
....0
QJ ~
c
QJ 10
>
..c
....
CJ.)
8
c
0 6
...
(/)
QJ 5
>
c
0 4
-...
()
c
QJ
() 3
QJ
0..
0.1~--L-~~--~--~--~----~--~~~--~~__J
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
1000/T, K- 1
1,.
Figure 13.4: Equi librium conversion of ethylene to ethyl alcohol in the vapor phase. Here, a = mole5
water/moles ethylene. Dashed lines indicate conditions of water condensation. Data based on equarion.
InK = 5200/ T - 15.0.
The sum of reaction s (I) and (ll) is the hydrogenation reaction:
Also,
ByEq. (13.11b),
-RTinK = -RTlnK1- RTlnKn or
Data for both reactions (I) and (II) are given by Fig. 13.2. For l,l20C (1,393 K),
104 / T = 7 .18, the following values are read from the graph:
In Kr = 12.9 Kt = 4.0 X 105
In Kn = -12.9 Kn = 2.5 X w-6

Therefore, K = KrKn = 1.0
At this elevated temperature and for a pressure of 1 bar, we can safely assume
ideal gases. Application of Eq. (13.28) leads to the expression:
YC2H4 =1
YH2YC2H2
On the basis of one mole initially of each reactant, Eq. (13.5) gives:
and
Se(2- Be)
Therefore, ----:::-'>=I
(I -Be) -
The smaller root of this quadratic expression (the larger is > 1) is: Be = 0.293.
T he equilibrium composition of the product gas is then:
1-0.293 " 0.293

YH2 = YC2H2 = _ _ = 0.414 YC2H4 = 2 - 0.293 = 0.172
2 0 293
Example 13.8
Acetic acid is esterified in the liquid phase with ethanol at 100 C and atmospheric
pressure to produce ethyl acetate and water according to the reaction:
If initially there is one mole each of acetic acid and ethanol, estimate the mole fraction
of ethyl acetate in the reacting mixture at equilibrium.
Solution 13.8
Data for tlHJ298 and 6.Gj298 are given for liquid acetic acid, ethanol, and water
in Table C.4. For liquid ethyl acetate, the corresponding values are:
'"
6.Hj 298 = -480,000 1 and 6.G~ = -332,200 J
.1298
The values of 6.H298 and 6.G298 for the reaction are therefore:
6. H2_98 = -480,000-285,830 + 484,500 + 277,690 = - 3,640 J
6.G298 = -332,200 -237, 130 + 389,900 + 174,780 = - 4,650 J

By Eq. (13. J I b),
4,650
8759 or K298 = 6.5266
(8.3 14)(298.15) = 1.
For the smal] temperature change from 298.15 to 373.1 5 K, Eq. ( 13. 15) is ade-
quate fo r esti mation of K . Thus,
- - -!:::.. H298 (
K 373
ln - I - -1- )
K 298 R 373. 15 298. 15
or I K373 = 3,640 ( I - 1 ) = -0.2951

n6.5266 8.3 14 373. 15 298. 15
./
and K 373 = (6.5266)(0.7444) = 4.8586
For the given r~action , Eq. (13.5), with x replacing y, yie lds:
I - ee
X AcH = XEtOH = 2
Because the pressure is low, Eq. ( 13.32) is applicable. In the absence of data
fo r lhe activity coefficients in this complex system, we assume thal the reacting
species form an ideal solution. In this case Eq. ( 13.33) is employed, givi ng:
K = X8tAcXH20
XAcHXEtOH
2
Thus, 4.8586 = ( ee )
I - ee
Sol uti on yields:
8e = 0.6879 and XEtAc = 0.6879/2 = 0.344
This result is in good agreement with experiment, even though the assum ption
of ideal solutions may be unrealistic. Carried out in the laboratory. the reaction
yields a meas ured mole fraction of ethyl acetate at equilibrium of about 0.33.
Example 13.9
The gas-phase oxidation of S02 to S0 3 is carried out at a pressure of 1 bar with 20/o
excess air in an adiabatic reactor. Assuming that the reactants enter at 25 C and that
equilibrium is attained at the exit, determine the composition and temperature of the
product stream from the reactor.
Solution 13.9
The reaction is:
for which, !:::.. HJ.98 = - 98.890 !:::..G298 = -70,866 1 mol- 1
On the basis of one mole of S02 entering the reactor,

I 3. 7. Equilibrium Conversions for Single Reactions 509
Moles 0 2 entering= (0.5)( 1.2) = 0.6

Moles N2 entering= (0.6)(79/2 1) = 2.257
Application of Eq. ( 13.4) yields the amounts of the species in the product stream:
Moles S02 = I - Ee
Moles 0 2 = 0.6 - 0.5"
Moles S03 = Ee
Moles N2 = 2.257
Total moles= 3.857 - 0.5Ee

Two equations must be written if we are to solve for both Ee and the temper-
ature. They are an energy balance and an equilibrium equation. For the energy
balance, we proceed as in Ex. 4.7:
D.H!j98 Ee + b.Hp = b.H =0 (A)
where all enthalpies arc on the basis of I mol S02 entering the reactor. The en-
tha lpy change of the products as they are heated from 298. 15 K to T is:
...
b.Hp = (C ~)H (T- 298. 15) (B)
where (C~)H is defined as the total heat capacity of the product stream:
Data from Table C. I provide {CP; }HI R values:
S02: MCPH(298.15,T;5.699,0.801 E-3,0.0,-1.015E+5)

0 2: MCPH(298.15,T;3.639,0.506E-3,0.0 ,-0.227E+5)
S03: MCPH(298.15, T;8.060,1.056E -3,0.0,-2.028E+ 5)
N2: MCPH(298.15, T;3.280,0.593E -3,0.0,0.040E+ 5)
Equations (A) and (B) combine to yield:
D.H298 ce + (C ?>Hcr- 298. 15) = o

-b. H 298 Ee
Solution forT gives: T = { + 298. 15 (C)
{Cp)H ~
.
At the conditions or temperature and pressure of the equilibrium state, the as-
sumption of ideal gases is fully justi fied, and the equilibrium constant is therefore
given by Eq. ( 13.28), which here becomes:
05
K= ( Ee ) ( 3.857- 0.5ce) (D)
I - Ee 0.6 - 0.5ce
Because - ln K = b.G0 I RT , Eq. (13. J8) can be written:
~Goo - D.Ho
o ~Hoo + -I
+ __ D.C o dT - h?" _
hr__ D.C_o dT
- InK = P P -
RTo RT T To R Tc> R T
5 10 CHAPTER 13. Chemical-Reaction Equilibria
Substitution of numerical values yields:
'~ .4 - ~
11 4
InK = -11..3054 + (IDCPH) + IDCPS (E)
IDCPH = IDCPH (298. 15,T;0.5415,0.002E-3,0.0,-0.8995E+5)

-
IDCPS = IDCPS(298.15,T;0.5415,0.002E-3,0.0,-0 .8995E+5)
~
These expressions for the computed values of the integrals show parameters ~A,
6 B, D. C, and D. D as evaluated from data of Table C. I .
An iteration scheme for solution of these equations for &e and T that converges
fairly rapidly is as follows:
1. Assume a starting value for T.
2. Evaluate IDCPH and IDCPS at this value ofT.
3. Solve Eq. (E) forK and Eq. (D) for e , probably by trial.
4. Evaluate (Cp }H and solve Eq. (C) forT.
5. Find a new value ofT as the arithmetic mean of the value just calculated and
the initial value; return to step 2.
This scheme converges on the values e = 0.77 and T = 855.7 K. For the product,
1 - 0.77 = 0.23 = 0.0662
2 3.472
YS0 = 3.857 - (0.5)(0.77)
...
0.6- (0.5)(0.77) - 0.2 15 - 0 0 9
y~ = - - . 6L
3.472 3.472
0.77 2.257
YSo3 = 3.472 = 0.2218 YN 2 - = 0.6501
= -3.472
Reactions in Heterogeneous Systems

When Liquid and gas phases are both present in an equilibrium mixture of reacting specie .
Eq. ( 11.48), a criterion of vapor/liquid equilibrium, must be satisfied along with the equation
of chemical-reaction equilibrium. Suppose, for example, that gas A reacts with liquid wate:-
B to form an aqueous solution C. Several methods of treatment exist. The reaction rna~
be considered to occur in the gas phase with transfer of material between phases to maintai::
phase equilibrium. In this case, the equilibrium constant is evaluated from ~G o data base<!
on standard states for the species as gases, i.e., the ideal-gas states at 1 bar and the reactioa
temperature. Alternatively, the reaction may be considered to occur in the liquid phase. i.::
0
which case ~G is based on standard states for the species as liquids. Finally, the reacric::
may be written:
A(g) + B([) -+ C(aq)
:. 7. Equilibrium Conversions for Single Reactions 5 11
c which case the 6G0 value is for mixed standard states: Cas a solute in an ideal 1-molal
~eous solution, Bas a pure liquid at 1 bar, and A as a pure ideal gas at 1 bar. For this choice
: srandard states, the equilibrium constant as given by Eq. (13.10) becomes:
fclfc
-:be second term arises from Eq. (13.35) applied to species C, Eq. (13.29) applied to B with
_:B/!8 = 1, and the fact that ! X= P 0 for species A in the gas phase. Because K depends on
~ standard states, this value of K is not the same as one obtains when the standard states are
:-hosen differently. However, all methods theoretically lead to the same equili.btium composi-
jon, provided Henry's law as applied to species C in solution is valid. In practice, a particular
.:boice of standard states may simplify calculations or yield more accurate results, because it
;:nakes better use of available data. The nature of the calculations required for heterogeneous
;-eactions is illustrated in the following example.
Example 13.1 0 '

=stimate the compositions of the liquid and vapor phases when ethylene reacts with
-mter to form ethanol at 200C and 34.5 bar, conditions which assure the presence
oi both liquid and vapor phases. The reaction vessel is maintained at 34.5 bar by
connection to a source of ethylene at this pressure. Assume no other reactions.
Solution 13.1 0
According to the phase rule (Sec. 13.8), the system has two degrees of freedom.
Specification of both T and P therefore fixes the intensive state of the system,
independent of the initial amounts of reactants. Material-balance equations are
irrelevant, and we can make no use of equations that relate compositions to the
reaction coordinate. Instead, phase-equilibrium relations must provide a sufficient
number of equations to allow solution for the unknown compositions.
The most convenient approach to this problem is to regard t_he chemical reac-
tion as occurring in the vapor phase. Thus,
,.,
and ithe standard states are those of the pure ideal gases at 1 bar. For these standard
states, the equilibrium expression is Eq. ( 13.25), which in this case becomes:
~
K = A fEtO~ po (A)
fc2~/H2o
where the standard-state pressure P o is 1 bar (expressed in appropriate units).
A general expression for ln K as a function of T is provided by the results of
Ex. 13.4. For 200C (473.15 K), this equation yields:
InK= -3.473 K = 0.0310
The task now is to incorporate the phase-equilibrium equations,/;" = into f/,

Eq. (A) and to relate the fugacities to the compositions in such a way that the
equatio ns can be readily solved. Equation (A ) may be written:
ft ~
K = ~ fEtOf;_l po = f EtOH pn (B)

.fc2H4.tP.2o fc2H.JJ~2o
The liquid-phase fu gacities are related to activity coeffi cients by Eq. (1 1.90), and
the vapoF-phase fugacities are related to fugacity coefficients by Eq. (11.52):
I
~
~/
..L
I
x;y;fi (C) I ];" = y,;p, p (D) I
Elimination of the fugacities in Eq. (B) by Eqs. (C) and (D) gives:
XEtOHYEtOH .f~tOH p
0
K = (E)
ft I
(yc2H4c2114 P)(xH20YH2ofH 2 o)
The fugacity f/
is for pure liquid i at the temperature and pressure of the system.
However, pressure has small effect on the fugacity of a liquid , and to a good
approximation, f/
= ~sat; whence by Eq. (1 1.40).
f,I.' = ..+. ~at P.sat

'f'I I
(F)
In this equation <Prat is the fugacity coefficient of pure sarurated liquid or vapor
evaluated at T of the system and at Pi sat , the vapor pres ure or pure species i. The
assumption that the vapor phase is an ideal solution allows su bstitution of 4>c2 H4
for c2 H 4 , where </>c2 H 4 is the fugacity coefficient of pure ethylene at the system
T and P. With this substitution and that of Eq. (F), Eq. () becomes:
sat p sat o
K = XEtOIIY~tOHEtOH EtOH p (G)
. (YCzH4C2H~ P)(xH2 0YH20cP~~O p~;o)
where the standard-state pressure P 0 is 1 bar, expressed in the units of P.
In addi tion to Eq. (G) the following expressions apply. Because Yi = l , L;
""
YC2H4 = I - YEtOII - Y ll20 (H )
Elim inate YEtOH and YH.,o from Eq. (H ) in favor of X&OIJ and XJhO by the va-
por/liquid equilibrium r;lation, ft
= !,'. Combination with Eqs. CC), (D), and
(F) then gives:
y;x;fat P/at
(f)
Yi = ; p
where 1 replaces 1 because of the assumption that the vapor phase is an ideal
sol ution. Equations ( H ) and (I) yield:
sat p sat
_ l _ XEtOHYEtOHEtOH EtOH
YC2H4 - ..+. p (J)
'VEtOH
Because ethyl ene is far more volatile than ethanol or water, let xc2 lil = 0. Then,
.. Equilibrium Conversions for Single Reactions 5 13
(K )
Equations (G), (J ), and (K) are the basis for solution of the problem. The
primary variables in these equations are: XH2 o, XELOH. and yc2H.t Other quantities
are either given or determined from correlations of data. The values of P; sat are:
p~;b = 15.55
The quantities <t>r' and </>; are found from the generalized correlation represented
by Eq. (1 1.68) with B0 and B 1 given by Eqs. (3.65) and (3.66). Computed results
are represented by PHIB(TR,PR ,OMEGA). With T = 473.15 K, P = 34.5 bar,
and c ritical data and acentric factors from App. B, computations provide:
TciK Pclbar w; Tr; Pr; P/at

I
so BJ ; ~at
I
EtOH 5l3.9 6 1.48 0.645 0.921 0.561 0.492 -0.399 -0. 104 0.753 0.780
H20 647.1 220.55 0.345 0.731 0.156 0.07 1 - 0.613 -0.502 0.846 0.926
C2H4 282.3 50.40 0.087 1.676 0.685 -0. 102 0.1 19 0.963
'
Substitution of values so far determined into Eqs. (G), (J), and (K) reduces
these three equations to the fol lowing:
K = 0.0493XEtOHYEtOH (L)
YC21i4XH20Yfi20
(M)
(K )
The only remaining undetermined thermodynamic properties are YH, o and YErOH
Because of the highly non ideal behavior of a liquid solution of ethanol and water,
these must be determined from experimental data. The required data, found from
VLE measurements, are given by Otsuki and Wil1iams. 8 From their results for
the ethanoJ/water system one can estimate values of YH 2 o and 'YEtOII at 200C.
(Pressure has little effect on the activity coefficients of liquids.)
A procedure for solution of the foregoing three equations is as follows.
I. Assume a value for XEtOH and calculate XH2 o by Eq. (K).
2. Determine YH2o and YEtOH from data in the reference cited.
3. Calculate yc2 H4 by Eq. (M).
4. Calculate K by Eq. (L ) and compare with the value of 0.0310 determined
from standard-reaction data.
5. If the two values agree, the assumed value of XErOH is correct. If they do not
agree. assume a new value of XEtOH and repeat the procedure.
8 H. Otsuki and F. C. Williams, Clzem. Eng1: Progr. Symp. Series No.6, vol. 49, pp. 55-67, 1953.
514 CHAPTER 13. Chemical-R eaction Equilibria
If XErOH = 0.06, then by Eq. (K), XH 2o = 0.94, and from the reference cited,
YEtOH = 3.34 and
By Eq. (M),
YC2 ft& = 1 - (0.907)(3.34)(0.06) - (0.493)(1.00)(0.94) = 0.355
The value of K given by Eq. (L) is then:
K = (0.0493)(0.06)(3.34) = 0 _0296
(0.355)(0.94)(1.00)
This result is in close enough agreement with the value, 0.03 10, found from
standard-reaction data to make further calculations pointless, and the liquid-phase
composition is essentially as assumed (XErOH = 0.06, XH 2 o = 0.94). The remain-
ing vapor-phase compositions (yc2 H.& has already been determined as 0.356) are
found by solution of Eq. (/)for YH 2 o or YEtOH All results are summarized in the
following table.
X; Yi
EtOH 0.060 0.180

H20 0.940 0.464
c2~ 0.000 0.356
L; X;= 1.000 Li Yi = 1.000

These results are probably reasonable estimates of actual values, provided no other
reactions take place.
13.8 PHASE RULE AND DUHEM'S THEOREM FOR

REACTING SYSTEMS
The phase rule (applicable to intensive properties) as discussed in Sees. 2.7 and 10.2 for non-
reacting systems of rr phases and N chemical species is:
F=2 - rc+N
It must be modified for application to systems in which chemical reactions occur. The phase-
rule variables are unchanged: temperature, pressure, and N - I mole fractions in each phase.
The total number of these variables is 2 + (N- l)(rr). The same phase-equilibrium equations
apply as before, and they number (rr -l) (N). However, Eq. (13.8) provides for each indepen-
dent reaction an additional relation that must be satisfied at equilibrium. Because the J.L; 's are
13.8. Phase Rule and Duhem 's Theorem for Reacting Systems 515
functions of temperature, pressure, and the phase compositions, Eq. (13.8) represents a relation
connecting phase-rule variables. If there are r independent chemical reactions at equilibrium
within the system, then there is a total of (rr - l)(N) + r independent equations relating the
phase-rule variables. Taking the difference between the number of variables and the number
of equations gives:
F = [2 + (N- l)(rr)]- [(rr- 1)(N) + r]
or I F=2-rr+N -r I (13.36)
This is the phase rule for reacting systems.

The only remaining problem for application is to determine the number of independent
chemical reactions. This can be done systematically as follows:
Write chemical equations for the formation, from the constituent elements, of each
chemical compound considered present in the system.
{!'
Combine these equations so as to eliminate from them all elements not considered
present as elements in the system. A systematic procedure is to select one equation
and combine it with each of the others of the set to eliminate a particular element. Then
the process is repeated to eliminate another element from the new set of equations. This
is done for each element eliminated [see Ex. 13.1 1(d)], and usually reduces the set by
one equation for each element eliminated. However, the simultaneous elimination of
two or more elements may occur.
The set of r equations resulting from this reduction procedure is a complete set of in-
dependent reactions for the N species considered present in the system. However, more than
one such set is possible, depending on how the reduction procedure is carried out, but all sets
number rand are equivalent. The reduction procedure also ensures the following relation:
r :::: number of compounds present in the system
- number of constituent elements not present as elements
The phase-equilibrium and chemical-reaction-equilibrium equations are the only ones
considered in the foregoing treatment as interrelating the phase-rule variables. However, in
certain situations special constraints may be placed on the system that allow additional equa-
tions to be written over and above those considered in the development of Eq. (13.36). If the
number of equations resulting from special constrajnts iss, then Eq. (13.36) must be modified
to take account of theses additional equations. The still more general form of the phase rule
that results is:
j F=2-rr+N -r- S""j (13.37)
Example 13.11 shows how Eqs. (13.36) and (13.37) may be applied to specific systems.
Example 13.11
Determine the number of degrees of freedom F for each of the following systems.
5 16 CHA PTER 13. Chemical-Reaction Equilibria
(a) A system of two miscible nonreacting species which exists as an azeotrope in

vapor/liquid equilibrium.
(b) A system prepare'd by partially decomposing CaC0 3 into an evacuated space.

(c) A system prepared by partially decomposing NH 4 CI into an evacuated space.
-
(d) A system consisting of the gases CO, C02 , H2 , H2 0 , and CH4 in chemical
equilibrium. ~
Solution 13.11
(a) The system consists of two nonreacting species in two phases . If there were
no azeotrope, Eq. ( 13.36) would apply:
F=2-rr+N-r=2-2+2-0=2
This is the usual result for binary VLE. However, a special constraint is imposed
on the system; it is an azeotrope. Thi s provides an equation, x1 = y 1, not con-
sidered in the development of Eq. (13.36). Thus, Eq. (13.37) with s = 1 yie lds
F = I . If the system is an az~otrope, then just one phase-rule variable- T , P , or
x 1 (= Y l )-may be arbitrarily specified.
(b) Here, a single chemical reaction occurs:
and r = I. Three chem ical species are'lJresent, ru1d three phases- sol id CaC03,
solid CaO, and gaseous C02. One might think a special constraint has been
imposed by the requirement that the system be prepared in a special way- by
decomposing CaC0 3. This is not the case, because no equation connecting the
phase-rule variables can be written as a result of th is requirement. Therefore, tJ
F=2-x+N - r -s=2-3+3- 1 - 0=1

and rhere is a single degree of freedom . T hi s is the reason that CaC03 exerts a
fixed decomposition pressure at fixed T.
(c) The che mical reaction here is:
Nli4Cl(s) -+ NH3(g) + HCl(g)
Three species, but onJy two phases, are present in this case: solid NH4Cl and
a gas mi xture of NH3 and HCL l n add ition , a special constraint is imposed by
the requirement that the system be formed by the decomposition of NH4Cl. Th is
means that the gas phase is equimolar in NH3 and HCl. Thus a special equa-
tion, YNH3 = YHCI (= 0.5), connec ting the phase-rule variab les can be written.
Application of Eq. (13.37) gives:
F=2 - x + N - r - s=2 - 2 + 3 - 1 -l=l

13.8. Phase Rule and Duhem 's Theorem for Reacting Systems 517
and the system has but one degree of freedom. This result is the same as that for
part (b), and it is a matter of expetience that Nt4Cl has a given decomposition
pressure at a given temperature. This conclusion is reached quite differently in the
two cases.
(d) This system contains five species, all in a single gas phase. There are no
special constraints. Only r remains to be determined. The formation reacti ons for
the compounds present are:
C+ ~02-+ CO (A) C + 0 2-+ C02 (B)
H2 + 102 --+ H20 (C) C+2H2 -7 CH4 (D)
Systematic elimi nation of C and 02, the elements not present in the system, leads
to two equations. One such pair of equations is obtained in the following way.
Eliminate C from the set of equations by combining Eq. (8), first with Eq. (A)
and then with Eq. (D). The two resulting reactions are:
From (B) and (A): CO+ ~02 --+ C02 ()

....
From (B) and (D): CH4 + 02 -+ 2H2 + C02 (F)
Equations (C), (E), and (F) are the new set, and we now eliminate 0 2 by com-
bining Eq. (C), first with Eq. (E) and then with Eq. ( F ). This gives:
From (C) and(): C02 + H2 .--+CO+ H20 (G)
From (C) and ( F): C~ + 2H20 -7 C02 + 4H2 (H)
Equations (G) and ( H ) are an independent set and indicate that r = 2. The use
of d ifferent elimination procedures produces other pairs of equations, but always
just two equations.
Application of Eq. ( 13.37) yields:
F=2-rr+N-r-s=2- 1+5-2- 0=4

This result means that one is free to specify four phase-rule variables, for example,
T, P , and two mole fractions, in an equilibrium mixture of these five c hemical
species, provided that nothing else is arbitrarily set. In other words, there can be
r
no special constraints, such as the specification that the system be prepared from
given amounts of Cf4 and H20. This imposes special constraints through material
balances that reduce the degrees of freedom to two. (Duhem 's theorem; see the
following paragraphs.)
Du hem's theorem for nonreacting systems was developed in Sec. I0.2. It states that
for any closed system formed initially from given masses of particular chemical species, the
equilibriu m state is completely determined (extensive as

weiJ as intensive properties) by spec-
ification of any two independent variables. This theor
em gives the differ ence between the
number of independe nt varia bles that comp letely deter
mine the state of the system and the
numb er of independent equations that can be writte n conn
ecting these varia bles:
r [2 + (N- l)(rr) + rr] - ((rr- l )(N) + NJ = 2
When chemical reactions occur,.p<t new variable Ej is introd
uced into the material-balance equa-
tions for each independen t reacti on. Furth ermo re, a new
equilibriu m re lation [Eq. (13 .8)1 can
be writt en for each independent reaction. There fore, when
chemical-reacti on equi librium is
supe1imposed on phase equilibrium , r new variables appea
r and r new equa tions can be writ-
ten. The difference between the number of variables
and number of equations there fore is
unch anged , and Duhe m's theor em as origi nally stated holds
for reacti ng systems as well as for
nonreacting systems.
Most chem ical-reactio n equilibrium problems are so posed
that it is Duhe m's theorem
that makes them determinate. The usual problem is to
find the comp osition of a syste m that
reaches equilibrium from an initial state of fixed amounts
of of reacting species when the two
vari ables T and P are specified.
13.9 MULTIREACTION EQUILIBRIA
When the equil ibtiu m state in a reacting sy tern depends

on two or more independent chemica.
reactions, the equil ibrium compositio n can be fo und
by a direct extension of the methods
developed for single reactions. One first determines a set
of independent reactions as discussee
in Sec. 13.8. With each independent reaction ther~ is ass.oc
iated a reaction coordi nate in accor d
with the treatment of Sec. 13.1. In addition, a separate
equilibrium const ant is evaluated fer
each reaction j, and Eq. ( 13.10) becomes:
with (j = I , 2, .. . , r)
For a gas-phase reaction Eq. ( 13.38) takes the form:
( 13..:
If the equilibrium mixture is an ideal gas,
p )-Vj
I) (y;) Vi.j = ( p0 Kj (13.-
I
For r indep enden t react ions Lhere are r separ ate equat
ions of this kind, and the y; 's c;:;::
eliminated by Eq. (13.7) in favor of the r reaction coord
inates EJ. The set of equations L -
solved simultaneously for the r reaction coord inates, as
illustrated in the follow ing ex~ _
13.9. Multireaction Equilibria
519
Example 13.12
A feed stock of pure n-butane is cracked at 750 K and 1 .2 bar to produc
e olefins. Only
two reactions have favorable equilibrium conversions at these conditions:
C4H10 ~ C2~ + C2 H6 (I)

C4H10 ~ C3H6 + C~ (II)
If these reactions reach equilibrium, what is the produc t composition?
With data from App. C and proced ures illustrated in Ex. 13.4, the equilib
rium
constants at 750 K are found to be:
Kr = 3.856 and Ku = 268.4

Solution 13.1 2
Equations relating the product composition to the reaction coordinates are de-
velped as in Ex. 13.3. With a b~sis of I mol of n-butane feed, they here become:
I - s1 - su
YC4Hto = l + cJ + en
The equilibrium relatio ns, by Eq. (13.40), are:
Combine these equilibrium equations with the mole-fraction equations:
_ __
(1-
__s_
I2_ _ _ _ -
sr- eu)( l + 8 1 + sn)
(-p-) -1
po
Kr
(A) "l
- - - -[)2- - - - - =
(-p )-1Ku (B )
(1 - sr - eu)(l + sr + eu) / P0
Divide Eq. (B) by Eq. (A) and solve f01: sn:
sn =K ey (C)
where
(D)
Combi ne Eqs. (A) and (C). After some reduction, sol ution for 8 1 gives:
0 112
Kr ( P /P) ]
81
= [ l + KI(P 0 j P)(K+ l) 2 (E)
Substi tu tion of numerical values in Eqs. (D ),(), and (C) yields:

112
K = ( 268.4) = 8.343
3.856
l j?
E =[ (3 .856)(1/ 1.2) ] - = 0.1068
- l l + (3 .856)(1/ 1.2)(9.343)2
; en = (8.343)(0.1 068) = 0.8914

The product-gas composition is then:
YC~H 10 = 0.00 I 0
For this simple reaction scheme. analytical solution is possible. More often,
solution of multireaction-eq uilibrium problems requires numerical techniques.
Example 13.13
A bed of coal (assume pure carbon) in a coal gasifier is fed with steam and air, and
produces a gas stream containing H2, CO, 0 2, H20 , C02, and N2. If the feed to
the gasifier consists of 1 mol of steam and 2.38 mol of air, calculate the equilibrium
composition of the gas stream at P = 20 bar for temperatures of 1 ,000, 1,100, 1 ,200,
1 ,300, 1 ,400, and 1,500 K. Available data are listed in the following table.
6.G 0 /J mol- l
" J
TIK H20 co C02
1,000 -192,420 -200,240 -395,790

I , 100 -187,000 -209,J 10 -395,960
J,200 -181,380 -2J7.830 -396,020
1,300 -175,720 -226,530 -396,080
1.400 -170,020 -235,130 -396, 130
1,500 -164,310 -243,740 -396, 160
Solution 13.13
The feed stream to the coal bed consists of I mol of steam and 2.38 mo l of air,
containing:
0 2 : (0.2 1)(2.38) = 0.5 mol N2 : (0.79)(2.38) = 1.88 mol
The species present at equilibrium are C, H2, CO, 02, H20. C02, and N2. The
formation reactions for the compounds present are:
13.9. Multireaclion Equilibria
521
H2 + ! 0 2 -* H20 (l)
C + !02- * CO (II)
C + 0 2 -* C0 2 (lli)
Becau se eleme nts hydrogen , oxygen, and carbon are thems elves presum
ed presen t
in the sy tern , thi s set of three indepe ndent reactions i. a complete
set.
All species are presen t as gases excep t carbon, which is a pure solid
phase.
In the equili brium express ion, Eq. ( 13.38), the fugacity ratio of the
pure carbon
is /c/fc = Jc/ fc, the fu gacity of carbon at 20 bar divided by the fugacity of
carbon at I bar. Becau se the effect of pressu re on the fugacity of
a solid is very
small, negl igible error is introd uced by the assum ption that thi s ratio
is unity. The
fugacity ratio for carbon is then /c/.fc = I , and it may be omitte d from the
equi libri um expression. With the assumption that the remain ing specie
s are ideal
gases, Eq. ( 13.40) is written for the gas phase onl y, and it provid es
the foll ow ing
,.equilibrium ex pre sions for reactio ns (I) through (lll ):
KI -
_ YH20
I /2
(_!_)-'
po
12
_ Yeo
KII -
(_!__)'
I /2 po
12
Yeo,
Krn = - --
Yo 2 YH2 Yo2 Yo2
The reaction coordinates for the three ' reactions are designated er, eu, and s m,
and they are here the equilibrium values . For the ini tia l state,
Moreo ver, becau se only the gas-ph ase species are considered,
I 1
VJ = - - Vfl = - VJlf = 0
2 2
Applying Eq. ( 13.7) to each species gives:
-e1 61(
YII = 3 .38 + (cu - cr)/2
2 )'CO = - - - - - --
3.38 + (en - ei)/2
~ (I - er- eu)- em I +e1

Y02 = J i hO = - - -----
3 .38 +(en - er)/2 - 3.38 + (c rJ - eJ) /2
l.88
YC02 = S
3.3 +(en
YN, = - - -- - - -
- cJ)/2 - 3.38+ (En- EJ)/2
Substi tution of these expressions for Yi into the equi liprium equati ons
.,. yie lds:
( 1 +eJ)( 2n)l f2 (P/ P o)-l f2
Kl = ~
( I - c J -En - 2t:w ) 112( -sJ)
2em
Krn = ---- ---- ---- ---
(1 - EI - eJI - 2em )
where n =3.38 + srr 2- t:I
Numerical values for the K j calculated by Eq. (13.1 1) are found to be very large.
For example, at 1,500 K,
- b. Go[ 164,3 10 = 13.2

lnKr = RT
(8.314)(1,500)
' - !:>.Go 243,740

In Ku = RT 11 - - - - - - -1 9. 6
(8.314)(1,500)
-b. Gin 396,160 - 3 8

1nKm = RT - - -- - - 1.
(8.31 4)(1,500)
With each K j so large, the quantity 1 - EI - err - 2sm in the denominator of
each equilibrium equation must be nearly zero. This means that the mole fraction
of oxygen in the equilibrium mixture is very small. For practical purposes, no
oxygen is present.
We therefore reformulate the problem by eliminating 02 from the formation
reactions. For this, Eq. (I) is combined, first with Eq. (II), and then wiLh Eq. (III).
This provides two equations:
C + C0 2 ~ 2CO (a)
H20 + C ~ H2 + CO (b)
The corresponding equilibrium equations are:
l ( p) ..
Ka = Y~~ p o
The input stream is specified to contain 1 mol H2, 0.5 mol 0 2, and 1.88 mol N2.
Because 0 2 has been eliminated from the set of reaction equations, we repl~ce the
0.5 mol of 0 2 in the feed by 0.5 mol of C0 2. The presumption is that this amount
of C02 has been fonned by prior reaction of the 0.5 mol 0 2 with carbon. Thus
the equi valent feed stream contains J mol Hz, 0.5 mol C0 2, and 1.88 mol N2, and
application of Eq. (13.7) to Eqs. (a) and (b) gives:
Sb
YHJ=---- - Y c o = - - -- -
2t:a + Eb
- 3.38+sa+sb 3 .38 + 0 + Eb
1- Eb 0.5- Ea
YH2o = -- - -- Yco2 = -- - --
3.38 + Ell+ ciJ 3.38 + Ea + Eb
1.88
YN2=-- - - -
3.38 + ca + cb
Because values of Yi must lie between zero and unity, the two expressions on the
left and the two on the right show that:
- 0.5 ~ Ea ~ 0.5
13.9. Multireaction Equilibria 523
Combining the expressions for the y; with the equilibrium equations gives:
2
(2t:a + cb) ( P )
Ka = (0.5- 0 )(3.38 + 0 + cb) P0 (A)
(B)
For reaction (a) at 1,000 K,
~Giooo = 2(-200,240)- ( -395,790) = - 4,690

and by Eq. (13.11),
6 0 4 9
In Ka =- - -'- - - - = 0.5641 Ka = 1.758
(8.31 4)(1,000)
Similarly, for reaction (b),
~Giooo '
= (-200,240)- (- 192,420) = -7,820
7 820
and In K
b
= (8.3 14)(1,000)
' = 0.9406 Kb = 2.561
Equations (A) and (B) with these values for Ka and Kb and with ( P I P 0 ) = 20
constitute two nonlinear equations in unknowns ea and C:b. An ad hoc iteration
scheme can be devised for their solution, but Newton's method for solving an
array of nonlinear algebraic equations is attractive. It is described and applied
to this example in App. I. Moreover, the Mathcad program for solving these
equations is included in App. D.2. The results of calculations fo r all temperatures
are shown in the following table.
T/K Ka Kb C:a C:b
1,000 1.758 2.561 -0.0506 0.5336

1, 100 l J.405 11.219 O.l2 10 0.7124
l,200 53. 155 38.609 0.3 168 0.8551
I ,300 l94.430 l l0.064 0.4301 0.9357
1,400 584.85 268.76 0.4739 0.97 l3
1,500 1,514.1 2 583.58 0.4896 0.9863
Values for the mole fractions y; of the species in the equilibrium mixture are
calculated by the equations already given. The results of all such calculations
appear in the following table and are shown graphically in Fig. 13.5.
524 CHAPTE R /3. Chemic al-Reaction Equilibria
TIK YH2 YCO YH20 YC02 YN2
1,000 0. 138 0.112 0.1 21 0.1 43 0.486

1, 100 0. 169 0.226 0.068 0.090 0.447
1,200 0.188 0.327 0.032 0 .040 0.413
1,300 0. 197 0.378 0.0 14 0.0 15 0.396
1,400 0.20 1 0.398 0.006 0.005 0.390
1,500 0.203 0.405 0.003 0.002 0 .387
At the higher tempera tures the values of ea and eb are approac hing their upper
limiting values of 0.5 and 1.0, indicati ng that reaction s (a) and (b) are proceeding
nearly to completion. In this limit, which..is approac hed e ven more closely at still
higher temperatures , the mole fraction s of C02 and H20 approac h zero. and for
the product species,
1
YH2 = = 0.205
3.38 + 0.5 + 1.0
I+I
Yeo= 3.38 + 0.5 + 1.0 = OAIO
. 1.88
=
+ 1.0 = 0.385
JN 2
3.38 + 0.5
0.5
~ co
0.4
0.3
_,
)'
Figure 13.5: Equ i l ibri um compositions of the

product gases in Ex. 13.13. 0.2
0.1
QL___L__ _L_~~~~~~
1000 1100 1200 1300 1400 1500
T/K
We have here assume d a sufficient depth of coal so that the gases reach equi-
libri um while in contact with incandescent carbon. This need not be the case; if
oxygen and steam are supplied at too hi gh a rate, the reactions may not attain equi -
librium or may reach equilibr ium after they have left the coal bed. In thjs event,
carbon is not present at equilibr ium, and the problem must again be refo1111ulated.
Although the Eqs. (A) and (B) of the preceding example are readily solved, the method of
equilibrium constants does not lend itself to standardizati on so as to allow a general program
to be written for computer soluti on. An alternative criterion of equi librium, mentioned in
Sec. 13.2, is based on the fact that at equilibrium the total Gibbs energy of the system has its
minimum value, as illustrated fo r a single reaction in Fig. 13.1. Applied to multiple reacti ons,
this criterion is the basis for a general scheme of computer solution.
The total Gibbs energy of a single-phase system as given by Eq. ( 11 .2) shows that:
1
(G )T.P = g(nl , IZ2, ll3, . , 11N)
The problem is lo find the set {ni} which minimizes G' for specified T and P , subject to
the constraints of the material balances. T he standard solution to this problem is based on
the method of Lagrange's undetermine d multipliers. The procedure for gas-phase reactions is
described as fo Llows.
l. The first step is to formulate the constraining equations, i.e., the material balances. Al-
.,. though reacting molecular species are not conserved in a closed system , the total number
of atoms of each element is constant. Let subscript k identify a particular atom. Then
define A.t: as the total number of atomic masses of the kth e lement in the system, as
determined by the initial constitution""of the system. Further, let a;k be the number of
atoms of the k th ele ment present in each molecule of chemi cal species i. The material
balance on each element k may then be written:
(k = I , 2, ... , w) I ( 13.4 1)
or (k = I, 2, ... , w)
i
where w is the total number of e lements comprising the system.
2. Next, we introduce the Lagrange multipliers Ak. one for each element, by multiplying
each element balance by its Ak:
(k = J, 2, .... w)
T hese equations are summed over k, giving:
1
3. Then a new function F is formed by addition of this last sum to G Thus,
F = G
1
+ 2:; Ak (
k
~ n;a;k- Ak)
I
This new function is identical with G'. because the summation term is zero. However,
the partial derivatives of F and G with respect to n; are different, because the function
1
F incorporates the constraints of the material balances.

4. The minimum value F (and G 1 ) occurs when all of the partial derivatives (8 F 18n;)r.P.ni
are zero. We therefore differentiate the preceding equation, and set the resulting deriva-
tive equal to zero:
(i = I, 2, ... , N)
-
Because the fi rst term on the right is the definition of the chemical potential [see Eq. ( 11.1 )],
this equation can be written:
JL; + ~ ). kaik = 0 (i = ] 2, ... N)

I I (13.42)
k
However, the chemical potential is given by Eq. ( 13.9):
JL; = Gj + RT ln(hl ft)

For gas-phase reactions and standard states as the pure ideal gases at 1 bar [or l(atm)):
JJ-i = Gj + RT In(/; I P 0
)
If Gj is arbitrarily set equal to zero for all elements in their standard states, then for
compounds Gj = !:::. Gj;, the standard Gibbs-energy change of formation for species i.
In addition, the fugacity is eliminated in favor of the fugacity coefficient by Eq. (1 1.52),
j~ = y;; P. With these substitutions, the equation for JJ-; becomes:
JL; = !:::.G/; + RT 1n(y;; PI P 0

)
Combination with Eq. (13.42) gives: "

(i = 1, 2, ... , N) (13.43)
Note that P o is I bar, expressed in the units used for pressure. If species i is an element,
!:::. G/; is zero.
Equation ( 13.43) represents N equilibtium equations, one for each chemical species,
and Eq. ( 13.41 ) repre ents w matetial-balance equations, one for each element- a total
or N t w equations. The unknowns arc the n; (note that y; = n; I L; n; ), of which
there are N, and the A.k 's, of which there are w- a total of N + w unknowns. Thu s the
number of equations is sufficient for the determination of all unknowns.
The foregoing discussion bas presumed that each ; is known. If the phase is an ideal
gas, then for each species ; = l. If the phase is an ideal solution, J>i = ;, and values can
at least be estimated. For real gases, (/J; is a function of the set {y;}, which is being calculated.
Thus an iterative procedure is indicated. The calculations are initiated with (/J; = 1 for all i.
Solution of the equations then provides a preliminary set of {y; }. For low pressures or high
temperatures this resu lt is usually adequate. Where it is not satisfactory, an equation of state
is used together with the calculated {y;} to give a new and more nearly correct set {(/J;} for use
in Eq. (13.43). Then a new set {y; } is determi ned. The process is repeated until successive
iterations produce no significant change in {y;}. All calculations are well suited to computer
solution, including the calculation of {d by equations such as Eq. ( 11.64).
In the p rocedure just described, the question of what chemical reactions are involved
never enters directly into any of the equations. However, the choice of a set of species is
entirely equivalent to the choice of a set of independent reactions among the species. In any
event, a set of species or an equivalent set of independent reactions must always be assumed,
and different assumpti ons produce different results.
Example 13.14
Calculate the equilibrium compositions at 1,000 K and 1 bar of a gas-phase system
containing the species CH4, H2 0 , CO, C02 , and H2. In the initial unreacted state there
are present 2 mol of CH4 and 3 mol of H2 0. Values of 6G/ ; at 1,000 K are:
6G 0
fcH4
= 19 720 J mot-
'
1
6G~
JCO
= - 200,240 J mol- 1
Solution 13.14
The required values of Ak are determined from the initial numbers of moles, and
the values of a;k come directly from the chemical fo rmul as of the species. These
a re shown in the following table.
Ele ment k
Carbon Oxygen Hydrogen
Ak = no. of alomic masses of k in the system
Ac=2 Ao =3 AH = 14
Species i a;k =no. of atoms of k per molecule of i
acf4.C = 1 acH4 ,o = 0 acli4.H =4

.
- =
a H?OC 0 a lf20.0 = 1 aH 2 0,H =2
aco.c = 1 aco.o =I aco.H = 0
aco2 .c = 1 aco2.o = 2 aco2 ,H = 0
aH2 .c = 0 al-h ,O = 0 al-b H ~ 2
-
At 1 bar a nd 1,000 K the assumption of ideal gases is justified, and each ; is
unity. Because P = I bar, PI p o = l , and Eq. (13.43) is written:
D.G f.. n.; Ak

' + In L .+ ~ -a;k = 0
RT ; n1 k RT
528 CHAPTER 13. Chemical-Reaction Equilib1ja
The five equations for the five species then become:
19,720 ncH 4 Ac 4).H

CH4 : RT +In _L, n; + RT + RT = 0
1-. - 192,420 n H?O 2),H ),o

H20:
RT
+ ln - --
L; n; +RT
- +RT
- =0
-200.240 nco Ac Ao
CO : RT + In L; n; + RT + RT = 0
-395,790 nco, Ac 2A.o
C02: +ln~+-+-=0
RT L..-i n; RT RT
The three atom-balance equations rEq. ( 13.41)] and the equation for L; n; are:
C : ncH4 + nco + nco2 = 2
1
With RT = 8,314 J mol - simultaneous computer solution of these nine equa-
,
rions9 produces the following results (y; = n; j L; n; ):
YOt4 = 0.0196
A.c = 0.7635
RT
Yeo= 0. 1743 ~~ = 25.068
.vco2 = 0.037 J
YH2 = 0.6710
~~ =0.1994
2:; y; = LOOOO
I
The values of ),kf RT are of no s ignificance, but are included for completeness.
9
Thc Malhcact formu lation of this problem is given in App. D.2.
13.1 0. Fuel Cells
529
13.10 FUEL CELLS
A fuel cell , similar in some respects to an e lectrolytic cell or battery, is a device in which
a fuel
is oxidized electroc hemical ly to produce electric power. It h as the characce ristics of
a battery
in that it consists of two electrod es, separate d by an electro lyte. However, the reactant
s are not
stored in the cell, but are fed to it continuo usly, and the product s of reaction are continu
ously
w ithdrawn. The fuel cell i thus not given an initial electric charge, and in operatio
n it doe.
not lose electric charge. It operates as a continuo us-flow system as long as fuel and
oxygen are
supplied , and produce a steady e lectric cunent.
A fuel, e.g., hydroge n, methane , butane, methano l. etc., makes intimate wntact w ith
an
anode or fuel electrod e, and oxygen (usuall y in air) makes intimate contact with
a cathode
or oxygen electrod e. Half-cell reaction s occur at each electrod e, and thei r sum is
the overall
reaction . Several types of fuel cell exist, each characte rized by a particu lar type of electroly 10
te.
Cells operatin g with hydroge n as the fuel are the simples t such dev ices, and . erve
to
"' ill ustrate basic principles. Schema tic diagram s of hydroge n/oxyge n cells appear in
Fig. 13.6.
When the electroly te is acidic [Fig. 13.6(a) 1. the half-cell reaction occurrin g at the
hydrogen
electrod e (anode) is:
'H2 --+ 2 H+ + 2e-
and that at the oxygen electrod e (cathode ) is:
~02 + 2e - + 2H+--+ H20 (g)
When the electrol yte is alkali ne [Fig. 13.6(b)], the half-cell reaction at the anode is:
and at the cathode:

~ 02 + 2e- + H20(g) --+ 2 OH-
Io either case, the sum of the half-cell reaction s is the overall reaction of the cell:
This of course is the combustion reaction of hydroge n, but combus tion in the sen e :\ .
of bu rni ng
does not occur in the cel l.
In both cells electron s with negative charge (e- ) are released at the anode, produce
an
electric cu1rent in an external circu it, and are taken up by the reaction occurring at the
cathode .
The electroly te does not allow passage of electrons, but provides a path for migratio
n of an ion
from one electrod e to the other. With an acid electroly te cation ~H+ migrate s from
anode to
cathode , whereas w ith an alkaline electrolyte anion oH- migrates from caU1ode to
anode.
For many practical applications the most sati sfacto ry hydroge n/oxyge n fuel ceJJ is
buill
around a sol id polymer that serves as an acid e lectrolyt e. Because it is very thin and
conducts
H+ ions or protons, it is known as a proton-e xchange membra ne. Each si de of the
membra ne
is bonded to a porous carbon electrod e impregn ated with finely divided p latinum w hich
serves
1
Con!>trucrion derails or the various types of fuel <.:ells and cxfonsive explanatio
ns of rhcir operation arc gi ven by
J. Larminie and A. Dicks. Fuel Cell Systems Explained. John Wi(ey & Sons, Ltd .. Chichester,
England, 2000.
Anode
Electrolyte
...Cathode
Load
(a)
Anode
Electrolyte
Cathode
Load
... (b)
Figure 13.6: Schematic diagrams of fuel cells. (a) Acid electrolyte; (b) alkaline electrolyte.
as a catalyst. T he porous electrodes provide a very large surface area for reaction and accom-
modate the diffusion of hydrogen and oxygen into and water vapor out of the cell. Cells can
be stacked and connected in series to make very compact units with the required terminal emf.
They typically operate at tempertures near 60C.
Because fuel-cell operation is a steady-flow process, the first law takes the form:
D. H = Q + Welcct
where potential- and kinetic-energy terms are omitted as negligible and shaft work has been
replaced by electrical work. If the cell operates reversibly and isothermally,
Q = Tt::.S and t::.H = T t::.S + Wclect

The electrical work of a reversible cell is therefore:
Welect = t::.H- T D.S = D.G (13.44)

13.1 0. Fuel Cells 531
where ~ denotes a property change of reaction. The heat transfer to the surroundings required
for isothermal operation is:
Q = ~H- ~G (13.45)
With reference to Fig. J3.6(a), we note that for each molecule of hydrogen consumed, 2 elec-
trons pass to the external circuit. On the basis of 1 mol of H2, the charge (q) transferred
between electrodes is:
q = 2NA (-e) coulomb
where -e is the charge on each electron and N A is Avogadro's number. Because the product
N A e is Faraday's constant :F, q =-
2:F. 11 The e lectrical work is then the product of the
charge transferred and the emf( volt) of the cell:
Welect = -2:F E joule
The emf of a reversible cell is therefore:

-Welect -~G
E= 2F = _2_F_ ( 13.46)
,.. These equations may be applied to a hydrogen/oxygen fuel cell operating at 25C and
I bar with pure H2 and pure 0 2 as reactants and pure H20 vapor as product. (f these species are
assumed ideal gases, then the reaction occurring is the standard formation reaction for H20(g)
at 298.15 K, for which values from Tab\e C.4 are:
~H = ~Hj
298 = -241,8 18 1 mol-l and ~G = 6G j298 = -228,572 J mol - 1
Equations (13.44) through (13.46) then yield:
Wetect = -228,572 J mol- 1

Q =- 13,246 J mol - 1 E = 1.184 volts
If, as is more commonly the case, air is the source of oxygen, the cell receives 0 2 at
ts partial pressure in air. Because the enthalpy of ideal gases is independent of pressure, the
mthalpy change of reaction for the cell is unchanged. However, the Gibbs-energy change of
eaction is affected. By Eq. ( I 1.24),
ig - ig
G; - G; = - RT ln y;
herefore, on the basis of l mol of H20 formed,
~G = ~G/298 + (0.5)(G~2 - G~)

= ~Gj298 - 0.5RT ln yo2 ,r
= -228,572- (0.5)(8.3 14) (298. l5)(ln 0.21) = -226,638 ~
uations (l3.44) through (13.46) now yield:
Wetect = -226,638 J mol- 1 Q = - 15,180 J mol- 1

E = 1.174 volts
Faraday's constant is equal to 96,485 coulomb mol- 1.

The use of air rather than pure oxygen does not significantl y reduce the emf and work output
of a reversible cell.
The enthalpy and G ibbs-energy changes of reaction are given as f unctions of temperature
by Eqs. (4. 18) and ( 13. I 8). For a cell temperature of 60C (333 .1 5 K ), the integrals in these
equ a ti on ~ are eva l u~ted as: _
333. 15 !::.C o
1298. 15
P dT =
__
R
IDCPH(298. 15,333.15;-1.5985,0.775E-3,0.0,0 .151 5E+5)
= - 42.0472
333.1 5 tlC p dT
1
298. 15 R T
= IDCPS(298.15,333. 15;-1.5985,0 .775E-3 ,0.0,0.15 15 E+5}
= - 0. 13334
Equatio ns (4.1 8) and (13.18) then yield:
tl H_f.u.l = -242, 168 J mol- 1 and llGJ:m = -226,997 J mol- 1
With cell operation at 1 bar and oxygen extracted from air, 6 H = tl H ~

1.U3 , and
llG = -226,997- (0.5)(8.3 14)(333.15)(ln 0.2 1) = -224,836 J mol - 1
Equati ons ( 13.44) throug h ( 13.46) now yield:
1
Weloct = -224,836 ] mol- Q = ~ 1 7.332 J mol- 1
E = 1. 165 volts
T hus cell operation at 60C rather than aL 25C reduces the voltage and work output of a
reversible cejl by o nly a smal l amount. w
T hese calculations for a reversible cell show that the e lectricaJ work output i more th an
90% of the heat that would be released (6 H) by actual combustion of the fuel. Were this heat
supplied to a Carnot engine operating at practical temperature levels, a much smaller fraction
would be converted into work. The reversible operation of a fue l cell implies that a poten-
tiometer exactly balances its emf. with the result that its current output is negligible. In actual
operation under reasonable load, internal irreversibil itie inevitably reduce the emf of the cell
and decrease its production of e lectrical work, while increasing the amount of heat transfer to
the surroundings. The operati ng emf of hydrogen/oxy gen fuel cells is 0.6-0.7 volts, and its
work output is closer ro 50% of the heating value of the fuel. Nevertheless, the irreversibilities
of a fuel cell arc far less than those inherent in combustion of the fuel. It has the additioDa l
advamages of simplicity, of c lean and quiet operation, and of directly produci ng electrical
energy. Fuels othe r than hydrogen may well be appropriate for fuel-cell use, but require devel-
opment o r effective catalysts. MethanoL for example. reacts at the anode of a proton-excha nge
membrane f uel cell according to the equation:
The usual reaction of oxygen to form water vapor occurs at the catbode.
Problems 533
PROBLEMS
13.1. Develop expressions for the mole fractions of reacting species as functions of the re-
action coordinate for:
(a) A system initially containing 2 mol NH3 and 5 mol 0 2 and undergoing the reac-
tion:
(b) A system initially containing 3 mol H2S and 5 mol 0 2 and undergoing the reaction:
(c) A system initially containing 3 mol N02, 4 mol NH3 , and 1 mol N2 and undergo-
ing the reaction:
13.2. A system initial1y containing 2 mol C2H4 and 3 mol 0 2 undergoes the reactions:
C2H4(g) + ~ 02 (g) ---7 {(CH2)2}0(g)
C2H4(g) + 30 2(8) ---7 2C0 2(g) + 2H20(g)

Develop expressions for the mole fractions of the reacting species as functions of the
reaction coordinates for the two reactions.
13.3. A system formed initially of 2 mol C02, 5 mol H2, and I mol CO undergoes the
reactions:
C02(g) + 3H2(g) ---7 CH30H(g) + H20 (g)
C02(g) + H2(g) ---7 CO(g) + H20(g)
Develop ex pressions fo r the mole fractions of the reacting species as functions of the
reaction coordinates for the two reactions.
13.4. Consider the water-gas-shift reaction:
At high temperatures and low to moderate pressures the reacting species form an ideal-
gas mixture. By Eq. ( 11 .27):
G = b y;G; + RT b y; In y;
When the Gibbs energies of the clements in their standard states are set equal to zero,
G; = t:J. G[; fo r each species, and then:
G = b y; 6G }; + RT b y; ln y; (A)
At the beginn ing of Sec. 13.2 we noted that Eq. (14.68) is a criterion of equilibrium.
Applied to the water-gas-shift reaction with the understanding that T and P are con-
stant, this equation becomes:
dG dn
dG' = d(nG) = ndG + Gcin = 0 n-+G-=0
de de
Here, however, dnjde = 0. The equilibrium criterion therefore becomes:
ciG =O (B)
ds
Once the Yi are eliminated in favor of e, Eq. (A) relates G to e . Data for b..G~. for
the compounds of interest are given with Ex. 13.13. For a temperature of 1,000 K (the
reaction is unaffected by P) and for a feed of 1 mol H2 and 1 mol C02:
(a) Determine the equilibrium value of c by application of Eq. (B).

(b) Plot G vs. e, indicating the location of the equihbrium value of e determined in
(a) .
13.5. Rework Pb. 13.4 for a temperature of:
(a) 1,100 K; (b) 1,200 K; (c) 1,300 K.
13.6. Use the method of equi librium constants to verify the value of e fou nd as an answer in
one of the following:
(a) Pb. 13.4; (b) Pb. 13.5(a); (c) Pb. 13.5(b); (d) Pb. 13.5(c).
~
0
13.7. Develop a general equation for the standard Gibbs-energy change of reaction b..G as
a function of temperature for one of the reactions given in parts (a), (f), (i), (n). (r) ,
(t), (u), (x), and (y) of Pb. 4.21.
13.8. For ideal gases, exact mathematical expressions can be developed for the effect ofT
and p on Be. For conciseness, let n
(yi)Vi
i
=
Ky. Then:
( ase) = (aKy) dec and Bee) =

( aP
(aKy) .:!!!._
BT p BT p dKy 7 aP 7 dK.r
Use Eqs. (13.28) and ( 13.14), to show that:
(a) (aee)
fJT p
= Ky dse b.. H e
RT 2 dKy
(h) ( -
ase) _ Kr dse
- - --(-v)
8P T P dKy
(c) dee/dKy is always posi tive. (Note: It is equally valid and perhaps easier to show
that the reciprocal is positive.)
Problems
535
13.9. For the ammo nia synthesis reaction written:
with 0.5 moJ N2 and 1.5 mol H2 as the initial amoun ts of reactants
and with the as-
sumption that the eq uilibri um mixtu re is an ideal gas,. show thar:
ce = I - ( 1 + J.299K p 0
p )-1/2
13.10. Peter, Paul, and Mary, members of a therm odyna mics class,
are asked to find the equi-
librium compo sition al a particu lar T and P and for given ini tial amoun
ts of reactants
for the fol1owing gas-ph ase reaction:
2NH3 + 3NO ---7 3Hz0 + ~ N2 (A)

,. Each solves the proble m correctly in a differe nt way. Mary bases her
solution on reac-
tion ( A) as wtitten. Paul, who prefers whole numbers, multiplies reactio
n (A) by 2:
4NH3 + 6NO ---7 6H20 + 5Nz (B)
Peter, who usually does things back\vard, deals with the reactio n:
3Hz0 + ~Nz ---7 2NH3 + 3NO (C)

Write the c hemical-equ ilibrium equati ons for the three reactions,
indicate how the
equilibrium constants are related, and show why Peter, Paul, and Mary
all obtain the
same result.
13.11. The following reaction reaches equilib rium at 500C and 2 bar:
4HCI (g) + Oz(g) -7 2H2 0 (g) + 2C]z(g)

Tf the system initially contain s 5 mol HCl for each mole of oxygen, what
is the com-
positio n of the system at equilib rium? Assum e ideal gases.
13.12. The following reaction reaches equilibri um at 650 C and atmos

pheric pressure:
If the system initially is an equim olar mixtu re of nitrogen and acetyl

ene, what is the
compo sition of the system at equi librium ? What would be the effect
of doubli ng the
pressu re? Assume ideal gases.
13.13. The following reaction reaches equilibrium at 350C and 3 bar:
If the system initiall y contai ns 1.5 mol H2 for each mole of acetaldehyd
e, what is the
compo sition of the system al equilibriu m? What would be the effect
of reduci ng the
pressure to 'I bar? Assum e ideal gases .
.. .. .
13.14. The following reaction reaches equilibrium at 650C and atmospheric pressure:
[f the system initiall y contains 1.5 mol H2 for each mole of styrene, what is the com-
position of the system at equilibrium? Assume ideal gases.
,
13.15. The gas stream from a sulfur burner is composed of I5-mol-% S02, 20-mol-% 02 , and
65-mol-% N2. This gas stream at l bar and 480C enters a catalytic converter, where
the S02 is further oxidized to S03. Assuming that the reaction reaches equilibrium,
how much heat must be removed from the converter to maintain isothermal conditions?
Base your answer on I mol of entering gas.
13.16. For the cracking reaction ,
the equilibrium conversion is negligible at 300 K, but becomes appreciable at temper-

atures above 500 K. For a pressure of I bar, determine:
(a) The fractional conversion of propane at 625 K.

(b) The temperature at which the fractional conversion is 85%.
13.17. Ethylene is produced by the dehydrogenation of ethane. If the feed includes 0.5 mol
of steam (an inert diluen t) per mol~ of ethane and if the reaction reaches equilibrium
at .I, 100 K and l bar, what is the composition of the product gas on a water-free basis?
13.18. The production of I ,3-butadiene can be carried out by the dehydrogenation of l -

butene: tol
C2HsCH:CH2(g) ~ CH2:CHCH:CH2(g) + H2(g)

S ide reactions are suppressed by the introduction of steam. Jf equilibrium is attained
at 950 K and I bar and if Lhe reactor product contains I 0-moJ-% 1,3-butadjene, find:
(a) The mole fractions of the other species in the product gas.
(b) The mole fraction of steam required in the feed.
13.19. The production of 1,3-butadiene can be carried out by the dehydrogenation of n-

butane:
S ide reactions are suppressed by the introduction of steam. If equilibrium is attai ned
at 925 K and J bar and if the reactor product contains J2-mol-% I ,3-butadiene, find:
(a) The mole fractions of the other species in the product gas.
(b) The mole fraction of steam required in the feed.
Problems
537
13.20. For the ammoni a synthes is reaction ,
the equilibr ium conversion to ammon ia is large at 300 K, but decreases rapidly with
increasi ng T. However, reaction rates become apprecia ble only at higher tempera tures.
For a feed mixture of hydrogen and nitrogen in the stoichio metric proportions,
(a) What is the equilibrium mole fract ion of ammoni a at I bar and 300 K?
(b) At what temperature does the equilibrium mole fraction of ammoni a equal 0.50
for a pressure of 1 bar?
(c) At what temperature does the equilibr ium mole fraction of ammoni a equal 0.50
for a pressure of J 00 bm, assumin g the equilibrium mixture is an ideal gas?
(d) At what temperatu re does the equilibr ium mole fraction of ammoni a
equal 0.50
for a pressure of 100 bar, assumin g the equ ilibrium mixture is an ideal solution of
gases?
13.21. For the methanol synthes is reaction ,

..
CO(g) + 2H2(g) ~ CH30H (g)
the equil ibrium conversion to methanol is large at 300 K, but decreases rapidly with
increasing T. However, reaction rates become apprecia ble only at higher tempera tures.
For a feed mixture of carbon monoxi de and hydrogen in the stoich iometri c proportions,
(a) What is the equilibr ium mole fraction of methanol at I bar and 300 K.
(b) At what tempera ture does the equ ilibrium mole tiaction of methano l
equal 0.50
for a pressure of I bar?
(c) At what temperature does the equilibr ium mole fraction of methanol equal 0.50
for a pressure of I00 bar, ac;sumin g the equilibr ium mixture is an ideal gas?
(d) At what tempera ture does the equilibrium mole fraction of methanol equal 0.50
for a pressure of 100 bar, assumin g the equilibri um mixture is an ideal solution of
gases?
13.22. Limesto ne (CaC03 ) decomp oses upon heating to yield qu icklime (CaO) and carbon
dioxide. At what tempera ture is the decomposition pressure of limeston e I (atm)?
13.23. Ammon ium chloride rN ~Cl (s)] decomp oses upon heating to yield a gas mixture
of
ammon ia and hydrochloric acid. At what tempera ture docs ammon ium ch loride ex-
ert a decomposition pressure of 1.5 bar? For NH4Cl(s), t1Hj H = -314,43 0 J and
29
t1G j 298 = -202,87 0 J.
13.24. A chemica lly reactive system contains the following species in the gas phase:
NH3,
NO, N02 , 02, and H20. Dete1mine a complet e set of indepen dent reaction s for this
system. How many degrees of freedom does the system have?
538 CHAPTER 13. Cbemical-Reaction Equilibria
13.25. The relative compositions of the pollutants NO and N02 in air are governed by the
reaction,
NO+ ~ 02 ---7 N02
For air containing 2 1-mol-% 02 at 25C and 1.0133 bar, what is the concentration of
NO in p<:[ts per million if the total concentration of the two nitrogen oxides is 5 ppm?
13.26. Consider the gas-phase oxidation of ethylene to ethylene oxide at a pressure of I bar
with 25% excess air. If the reactants enter the process at 25C, if the reaction pro-
ceeds adiabatically to equilibrium, and if there are no side reac6ons, determine the
composition and temperature of theproduct stream from the reactor.
13.27. Carbon black is produced by the decomposition of methane:
For equilibrium at 650C and I bar,
(a) What is the gas-phase composition if pure methane enters the reactor, and what
fraction of the methane decomposes?
(b) Repeat part (a) if the feed is an equimolar mixture of methane and nitrogen.
13.28. Consider the reactions,

1N2(g) + ~ 02(g) ---7 NO(g)
~N2(g) + 02(g) --+ N02(g)
\
If these reactions come to equilibrium after combustion in an internal-combustjon en-
gine at 2,000 K and 200 bar, estimate the mole fractions of NO and N02 present for
mole frac tions of nitrogen and oxygen in the combustion products of 0.70 and 0.05.
13.29. OH refineries frequently have both H2S and S02 to dispose of. The followfng reaction
suggests a means of getting rid of both at once:
For reactants in the stoichiometric proportion, estimate the percent conversion of each
reactant if the reaction comes to equilibrium at 450C and 8 bar.
13.30. Species N204 and N02 as gases come to equilibrium by the reaction: N204 ---7 2N02.
(a) For T = 350 K and P = 5 bar, calculate the mole fractio ns of these species in the
equilibrium mixture. Assume ideal gases.
(b) If an equilibrium mixture ofN204 and N02 at conditions of part (a) flows through
a throttle valve to a pressure of 1 bar and through a heat exchanger that restores its
initial temperature, how much heat is exchanged, assuming chemical equilibrium
is again attained in the final state? Base the answer on an amount of mixture
equivalent to 1 mol of N204, i.e., as though the N02 were present as N204.
Problems 539
13.31. The following isometization reaction occurs in the liquid phase: A --+ B, where A and
B aremiscibleliquidsforwhich: GE/RT = O.lxAX. Tf .6.G298 = -1,000 1, what
is the equilibrium composition of the mixture at 25C? How much error is introduced
if one assumes that A and B form an ideal solution?
13.32. Hydrogen gas is produced by the reaction of steam with "water gas," an equimolar
mixture of H2 and CO obtained by the reaction of steam with coal. A stream of "water
gas" mixed with steam is passed over a catalyst to convert CO to C02 by the reaction:
Subsequently, unreacted water is condensed and carbon dioxide is absorbed, leaving a

product that is mostly hydrogen. The equilibrium conditions are 1 bar and 800 K.
(cr/ Is /ltlY /ldV/ltlt/lge gtlined oy caaying Ol/t toe re/lction tit p!eSSl/res obove } 0/l.T?
(b) Would increasing the equilibrium temperatu re increase the conversion of CO?
(c) For the given equilibrium conditions, determine the molar ratio of steam to "water
gas" (H 2 + CO) required to produce a product gas containing only 2-mol-% CO
after cooling to 20C, where the unreacted H20 has been virtually all condensed.
(d) Is there any danger that solid carbon will form at the equilibrium conditions by the
....
reaction
2CO(g) ---+ C02(g) + C(s)
13.33. The feed gas to a methanol synthesis reactor is composed of 75-mol-% H2, 15-mol-%
CO, 5-mol-% C02, and 5-mol-% N2. The system comes to equilibrium at 550 K and
100 bar with respect to the reactions:
Assuming ideal gases, determine the composition of the equilibrium mixture.
13.34. "Synthesis gas" may be produced by the catalytic reforming of methane with steam.
The reactions are:
CH4(g) + HzO(g)--+ CO(g) + 3Hz(g) CO(g) + HzO(g) --+ C02(g) + Hz(g)

"\ .
Assmne equilibrium is attained for both reactions at 1 bar and 1,300 K.
(a) Would it be better to carry out the reaction at pressures above 1 bar?
(b) Would it be better to carry out the reaction at.temperatures below J ,300 K?
(c) Estimate the molar ratio of hydrogen to carbon monoxide in the synthesis gas if
the feed consists of an equimolar mixture ot7team and methane.
(d) Repeat part (c) for a steam to methane mole rati o in the feed of 2.
(e) How could the feed composition be altered to yield a lower ratio of hydrogen to
carbon monoxide in the synthesis gas than is obtained in part (c)?
(f) Is there any danger that carbon will deposit by the reaction 2CO --+ C+COz under
conditions of part (c)? Part (d)? If so, how could the feed be altered to prevent
carbon deposition?
CHAPTER 13. Chemical-Reaction Equilibricl
540
13.35. Consider the gas-phase isom

erization reaction: A-+ B.
equilibrium
(a) Assuming idea l gases, develop
ftom Eq. ( 13.28) the chemical-reaction
equation for the system. dom for the
(b) The result of part (a) should
sugge. t that there is one degree of free
of
the phase rule indicates two degrees
equilibrium state. Upon verifying that
freedom. explain the discrepa ncy.
such
-pr~ S:<>u re, ation reaction, A-+ B, occurs at conditions
13.3 6. A low gas -ph ase isomeriz
that vapor and liquidjlhases are present.
(a) Prove that the equilibri um stat

e is univariant.
y, and
Sup pos e T. is specifi ed. Show how to calculate XA, YA, and P. State care full
(b)
justify, any assumptions.
of equilib rium
13.37. Set up the equations requ ired
for solution of Ex. 13. 14 by the method
e equilibrium compositions as give n
constants.Verify that your equations yield the sam
in the example.
positions
Rea cti on- equ ilib rium calculation s may be useful for estimation of the com
13.3 8. gas at
feedstock, ava ilable as a low-pressure
of hydrocarbon feed . tacks. A particular isomers:
K, is iden tified as "aJo mat ic C8." Tt could in principle contain the CsHJO
500 e how
e (PX ), and ethylbenzene (EB ). Estimat
o-xylene (OX). m-xylene (MX). p-xylen um at
h of eac h pec ies is present. assu min g the gas nuxture has come to equil ibri
muc
is a set of independent reactions (why?):
500 K and low pressure. The foll owing
I OX -+ MX (J) I ox ~ PX (II) I ox -+ EB (Ill )
clearly
ns for each equatio n of the set. State
(a) Wri te reac tion-equilibrium equatio
any assu mptions. equ ilibrium
(b) Solve the set of equatio ns
to obtain algebraic expression s for the -
species in relation to the equ ilibrium con
vapor-phase mole frac tions of the fou r
stants, Kt , K11 , Km. constan ts at
(c) Use the data below to determi
ne numerical values fo r the equilibrium
500 K. State clearly any assump tions.
mole frac tions of the four species.
(d) Determine numerical values for the
Species /).H.f:.9'S
0 /J mol- l /). Gj 29/J mol - 1
OX (g) 19,000 122,200

17,250 J 18,900
MX (g)
PX (g) J7,960 121,200
EB(g) 29,920 130,890
Problem s 541
react to
13.39. Ethylen e oxide as a vapor and water as liquid, both at 25C a nd 101.33 kPa,
form a liquid solution containing e thylene glycol ( l ,2-etha ned iol) at the same condi-
tions:
If the initial molar ratio of ethylene oxide to water is 3.0, estimat e the equilib rium
convers ion of ethylen e oxide to ethylene g lycol.
e
At equilib rium the system consist s of liquid and vapor in equilibrium, and the intensiv
state of the system is fixed by the specification of T and P. T herefore, one must
first determ ine the phase compo sitions. indepen dent of the ratio of reactan ts. These
results may then be applied in the materia l-balance equatio ns to fi nd the equili brium
conversion.
Choose as standard states for water and ethy lene glyco l the pure liquids at I bar and
for ethylen e oxide the pure ideal gas at J bar. Assum e any water present in the liquid
f!' phase has an activity coeffic ient of unity and that the vapor phase is an ideal gas. The
partial pressur e of ethylene oxide over the liquid phase is given by:
p;/kPa = 4 15x;
'
The vapor pressure of ethylene glycol at 25C is so low that its concentration in the
vapor phase is negligible.
13.40. In chemic al-reac tion enginee ring special measures of produc t distribution arc some-
times used when multipl e reactio ns occu r. Two of these are yield Yj and selectivity
12
Sj/k We adopt the following definitions :
moles fo rmed of desired produc t j

Yj =---------------------------------------------
moles of j that would be formed with no side reaction s and
with comple te consum ption of the limiting reactan t species
S. k = moles formed of desired produc t j

11 moles formed of undesired prod uct k
For any particu lar applicatio n yield and selectiv ity can be related to compo nent rates
and reactio n coordin ates. For two-reaction scheme s the two reaction coordin ates can
.
be found from Yj and S.ifk> allow ing the usual materia l-balan ce equatio ns to be wrillen
Consider the gas-pha se reactions:
(I) A+C~D (II)
He re, C is the desired product, and Dis the undesired byproduct. If the feed to a steady-
flow reactor contains 10 kmol hr- of A and 15 kmol hr- of B, and if Yc = 0.40 and
1 1
ScJD = 2.0, detenn ine com plete produc t rates and the produc t composition (mole
fractio ns), usi ng reactio n coordin ates.
12 R. M. Felder and R. W. Rousseau. Elementary Principles of Chemical Processes, 3rd ed .. Sec. 4.6d. Wi ley. New
York, 2000.
13.41. The following problems invol ving chemical-reaction stoichiometry are to be solved
through use of reactio n coordinates.
(a) Feed to a gas-phase reactor comprises 50 kmol hr- 1 of species A, and 50 kmol hr- 1
of species B. Two independent reactions occur:
A + B ---7 C (I) A + C ---7 D (II)
Analysis of the gaseous effluent shows mole fractions: YA = 0.05 and YB = 0.1 0.
(.i) What is the reactor effluent rate in kmol hr- 1?
(ii) ~hat are the mole fractions yc and YO in the e ffluent?
(b) Feed to a gas-phase reactor comprises 40 kmol hr- 1 of species A, and 40 kmol hr- 1
of species B. Two independent reactions occur:
A + B ---7 C (I) A + 2B ---7 D (II)
Analysis of the gaseous effluent shows mole fractions: YC = 0.52 and YD = 0.04.
Determine the rates (kmol hr- 1) of all species in the effluent stream.
(c) Feed to a gas-phase reactor is 100 kmol hr- 1 of pure species A. Two independent
reactions occur:
A --+ B + C (I) A + 8 --+ D (II)
Reactio n (I) produces valuable species C and coproduct B. The side reaction (II)
produces byproduct D. Analysis of the gaseous effluent shows mole fractions:
Yc = 0.30 and Yo = 0.10. 'Determine the rates (kmol he 1) of all species in
the effluent stream.
(d) The feed to a gas-phase reactor is 100 kmol hr- 1, containing 40 mol-% species A
and 60 mol-% species B. Two independent reactions occur:
A + B --+ C (I) A +B ---7 D +E (IT)
Analysis of the gaseous effluent shows mole frac tions: Yc = 0.25 and YD = 0.20.
Determine:
(i) Rates in kmol hr- 1 of a ll species in the effluent stream.
(ii) Mole fractio ns of all species in the effluent stream.
13.42. The following is an industrial-safety rule-of-thu mb: compounds with large positive
f),G j must be handJ ed and stored carefully. Explai n.
13.43. Two important classes of reactions are oxidation reactions and cracking reactions. O ne
class is invariably endothermi c; the other, exothermic. Which is which? For which
class of reactions (oxidation or cracking) does equilibrium conversion increase with
increasing T?
Qlllllll II lllmlll,lh I II llil.llllllhill i lltrnl:l I 1

11 1!
1
Problems 543
13.44. The standard heat of reaction D. Ho for gas-phase reactions is independent of the choice
0
of standard-state pressure P 0 . (Why?) However, the numerical value of D.G fo r
such reactions does depend on P 0 . Two choices of P o are conventional: 1 bar (the
0
basis adopted in this text), and 1.01325 bar. Show how to convert D.G for gas-phase
0
reactions from values based on P 0 = 1 bar to those based on P = 1.01325 bar.
13.45. Ethanol is produced from ethylene via the gas-phase reaction:
Reaction conditions are 400 K and 2 bar.
(a) Determine a numerical value for the equilibrium constant K for this reaction at
298.15 K.
(b) Determine a numerical value forK for this reaction at 400 K.
(c) Determine the composition of the equilibrium gas mixture for an equimolar feed
containing only ethylene and H20. State all assumptions.
(d) For the same feed as in part (c), but for P = 1 bar, would the equilibrium mole
fraction of ethanol be higher or lower? Explain.
13.46. A good source for formation data for compounds is the NIST Chemistry WebBook
site. Values of D. H j , but not of D.G j , are reported. Instead, values of absolute standard
entropies soare listed for compounds and elements. To illustrate the use of NIST data,
let H20 2 be the compound of interest. Values provided by the Chemistry WebBook:
D.Hj[H20z(g)] =- L36.1064 kJ mol- 1
S 0 [H202(g)) = 232.95 J mol- 1 K- 1

S 0 [H2(g)] = 130.6801 mol- 1 K- 1
S 0 [02(g)] = 205.152 J mol- 1 K- 1
0
All data are for the ideal-gas state at 298. 15 K a nd 1 bar. Determine a value for D.G f.298
for H20 2(g).
13.47. Reagent-grade, liquid-phase chemicals often contain as impurities isomers of the nom-
inal compound, with a consequent effect on the vapor~ressure. This can be quantified
by phase-equil ibrium/reaction-equilibr ium analysis. Consider a system containing iso-
mers A and B in vapor/liquid equilibrium, and also in equilibrium with respect to the
reaction A -----+ B at relatively low pressure.
(a) For the reaction in the liquid phase, determine an expression for P (the "mixture
vapor pressure,) in terms of P;.at, PJtat, and K1,
the reaction equilibrium constant.
Check the result for the limits K = 0 and K = oo.
1 1
(b) For the reaction in the vapor phase, repeat part (a). Here, the relevant reaction
equilibrium constant is Kv.
CHA PTER 13 . Chemical-Reaction
Equilibria
544
ur
ter whe ther the reaction is assumed to occ
(c) If equ ilibrium prevails, it doesn ' t mat
for parts (a) and (b) mu t be equivalent.
in one phase or the other. Thu s the results
een K 1 and Kv through the pure-species
Use thi s idea to show the connec tion betw
vapor pressures. b le and
(d) Why is the assumption of idea
l gases and idea l solution s both reasona
~ prudent?
Sho w that
(e) Res ults for part s (a) and (h) sho
uld suggest that P depends on T on ly.
this is ina cco rd with the phase rule.
king
ck.ing propane is a rou te to light olefin producti on. Suppose that two crac
13.48. Cra
reactions occ ur in a steady-flow reac tor:
C3H g(g ) ---r C3H6(g) + H2(g)
(I)
C3Hs (g) ---r C2H 4(g ) + CH.t(g)

(11)
reactions go to equilibrium at 1.2 bar and

Calculate the product composition if both
(a) 750 K; (b) I,000 K; (c) 1,250 'K

n reac-
established for the gas -phase isomerizatio
13.49. Equilibrium at 42.5 K and 15 bar is
tion :
n-C4H10(g) ---r iso- C4H to(g )
rium mix ture by two procedures :
Estimate the composaition of the equilib
(a) Ass ume an ideal-gas mixture

.
the equation of state given by Eq. (3.38).
(b) Ass ume an ideal solULioh with
Compare and disc uss the resu lts. 1

iso-butane, b. H c = - 134,180 J mo l- 1; D. G0/298 = -20 ' 760 J mo r
Dat a: For 1298 til
Chapter 14
Topics in Phase Equilibria
The simplest models for vapor/liquid equi librium, based on Raoul t's law and Henry's law, are
presented in Chap. I 0, largely from an empirical point of view. The calculations by modi-
fied Raoult's law, described in Sec. 10.5, are adequate for many purposes, but are limited to
low pressures. The ini tial secbons of thi s chapter therefore present two general calculational
'
procedures for VLE, the first by an extension of modified Raoult's law and the second by equa-
tions of state. The theoretical foundation for both procedures is presented in Chap. l I. The
remainder of this chapter deals more generall y with phase equilibria, with consideration given
in separate sections to liquid/liquid, vapor/liquid/liquid, solid/liquid, solid/vapor, adsorption,
and osmotic equilibtia.
14.1 THE GAMMA/PHI FORMULATION OF VLE
Modified Raoult's law includes the activity coefficient to account for liquid-phase nonideali-
ties, but is limited by the assumption of vapor-phase ideality. This is overcome by introduction
of the vapor-phase fugacity coefficient. For species i in a vapor mixture, Eq. ( 11.52) is written:
For species i in the liquid phase, Eq. (11.90) becomes:

~, .
fi = XiYi li
....
Equation (11.48) req uires these two expressions to be equal; whence,
(i = l , 2, ... , N)
Superscripts v and l are not used here because of a presumption that /Pi refers to the vapor
phase and that y; and f; are liquid-phase properties. Substituting for fi by Eq. ( 11.44) gives:
(i = 1, 2, .. . , N) (14.1 )
545
546 CHAPTER 14. Topics in Phase Equilibria
where
Because the Poynting factor (represented by the exponential) at low to moderate pressures
differs from unity by only a few parts per thousand, its omission introduces negligible etTor,
and this equation is often simplified:
' ,..
<1> - .!!._ (14.2)
~- <Prl
Equation (14.1 ), called the gamma/phi formulation of VLE, reduces to Raoult's law when
; = y; = 1, and to modHied Raoult's law when ; = 1.
Systematic application of Eqs. (14. 1) and (14.2) depends on the availability of correla-
tions of data from which values may be obtained for P; sat, ;, and y;. T he vapor pressure of a
pure species js most commonly given by the Antoine equation, Eq. (6.76):
B1
lnP.sat =A- (14.3)
I I T+C;
At moderate pressures Eq. (3.38), the two-term vi rial expansion in P, is usually adequate for
property calculations, and the fugacity coefficients of Eq. (14.2) are then given by Eq. (11.64),
here written:
(14.4)
where
with 8ii = 0, 8 jj = 0, etc., and Oij = 8ji, etc. Values of the virial coefficients come fr om
a generalized conelation, as represented for e~ample by Eqs. (11.69) through (1 1.74). The
fugacity coefficient for pure i as a saturated vapor <Prr is obtained from Eq. (14.4) with 8ji and
8jk set equal to zero:
sat
sat B ii P;
; = exp RT ""(14.5)
Combination of Eqs. (14.2), (14.4), and (14.5) gives:
sat 1 ~ ~
Bii (P- P; ) + 2_P LJ LJ YjYk(28j;- Ojk)
j k
i=~p RT (14 .6)
For a binary system comprised of species 1 and 2, this becomes:

B t t (P - p ;sat) + Py?812
<l>t = exp RT ( J4.7a)
B22(P- P2sat) + Pyf8t2

2 = exp RT (14.7b)
Activity coefficients [y; in Eq. ( 14.1 )] are evaluated from models for GE as discussed in
Sec. 12.2. Thus for data at constant T we presume the availability of a conelation giving:
cE
RT = g(xJ, x2, .. . , XN-J) (const T)
14.1. The Gamma/Phi Formulation ofVLE 547
Dewpoint and Bubblepoint Calculations

The nature of dewpoint and bubblepoint calculations is evident from the examples of Sees. 10.4
and 10.5 for Raoult's law and modified Raoult's law. All such calculations made by the
gamma/phi formulation require iteration because of its complex functionality:
; = (T, P , Yl , Y2 . , YN-I)

Yi = y(T, XJ, X2, ... , XN - I)
pi sat = f(T)
At the moderate pressures where the gamma/phi approach to VLE is appropriate, activity co-
efficients are assumed independent of pressure. The need for iteration is evident. For example,
a BUBL P calculation to yield {y; } and P requires values of i , which depend on P and {y; },
the quantities being found. Simple iterative procedures, described in the following paragraphs,
apply to BUBL P, DEW P, BUBL T, and DEW T calculations.
Equation ( 14.1) may be solved for either y; or x;:
y; ; p
(14.8.) x; = .p sut (14.9)
y, i
Because L;y; = 1 and L; x; = 1, these equations may be summed to give:

sat
"'\' x;y; P;
1= L.,.. 1= L )H~P
I I
. ;P v p .sat
I j rl I
'~o
Solved for P, they become: . y\) ll\.J (.)
1\")
P=L: xy<l>;p
I I i
sat
(14.1 0) P = - - - - --
1
( l4.ll)
i ~ y; ;/Yi P/at
i
BUBL P Calculations : Figure 14.1 shows an iteration scheme to be implemented by

computer. Input consists of the given values, T and {xi}, and the P.arameters for evaluation
of {P/at}, {yi}, and {<t> d. Because the values of {y;} required for calculation of <l>; are not
yet known, sel <l>; = I. Each P/at is evaluated at the given T by Eq. (14.3) and values of y;
come from an activity-coefficient correlation. Equations (14).0) and (14.8) yield P and {y;}.
Equation (14.6) then provides {<1>;}; substitution in Eq. (14.10) provides a new value for P.
o
Iteration proceeds until P, the change in P from one iteration to the next, is less than some
tolerance e, thus converging on final values for P and {y; }.
DEW P Calculations : Figure 14.2 shows a calculation scheme with input: T , {yi},
and appropriate parameters. Neither {;} nor {Yi} can be evaluated initially, and all values are
sel equal to unity. Equation ( 14.3) yields {P;sat}, and Eqs. (14.1 1) and ( 14.9) are solved for
P and {xi}. Evaluation of {y;) and substitution into Eq. (14.11) gives an improved value of
P from which to determine {;} by Eq. (14.6). The inner iteration loop lhen converges on
interim values for {x;} and {y;}. Because the calculated values of x; are not constrained to sum
548 CHAPTER 14. Topics in Pbase Equilibria
. ( " -
Read T, {x,}, consta nts. ..

Set all <1>; = 1.0. Calc. {)) by Eq. (14.8).
Evaluate {P;58t}, {y;}. Evaluate {ct>;}.
Calc. P by Eq. (M.10). '
; No
Yes
Print P, {y 1}. Is BP < s ? ~ Calc. P by Eq. (14.10). I
Figure 14.1: Block diagram for the calculation BUBL P.
to unity, the set is normalized by setting x; = xi/ L 1 x;. Subsequent recalculation of P by

Eq. ( 14.11) leads to the outer loop and iteration to convergence on final values for P and {x; }.
Read T, {y 1}, constants.

Set all .>, = 1.0, all 'Y; = 1.0.
Evaluate {P/ 81}. Calc. {x;} by Eq. (14.9).
Calc. P by Eq. (14. 11 ).
Calc. {x;} by Eq. (14.9). H Evaluate {<T>;}
~ Normalize the x; values .
Evaluate {y1}.
.......
Evaluate {y1}.
Calc. P by Eq. (14. 11). " No
No l is each 8y; < nl

Yes
Yes I
I Print P, {x;}.
I I
Is 8P < s ? Calc. P by Eq. (14.11) .
Figure 14.2: Block diagram for the calculation DEW P.
In BUBL P and DEW P calculations, temperature is gi ven, allowi ng immediate and fin-
calculation of {P/ 31 } . This is not the case for procedures BUBL T and DEW T, where th~
temperature is unknown. Because iteration is controlled by T, an initial estimate is requ irc'-
Depending on whether {x;} or {y; } is known, it is given by:
or
BI CI
where T1. sat _
-
_ '--
(I -r.
A; -In P
14.1. The Gamma/P hi Formulation of VLE 549
Although individual vapor pressures are suong functions of temperatu re, vapor-pressure
ratios are not, and calculations are faci litated by their introduction. Mu ltiplying the right sides
of Eqs. (14.1 0) and (14. ll ) by P/al (outside the summatio n), di viding by P/ 31 (inside the
summation), and solving for the 31
P/
appearing outside the summation gives the two results:
p . at = ____ _P_____
(14.13)
J ~ (x; Yi / <P;)( P/ at/ P/at)
i
.. <t> . P .sat )
p _sat=P ~~ _J_ (14.14)
J ~ v ( p _sat
j rt I
The summatio ns are over all species including j, which is an arbitrarily selected species. Once
:al
P1 is known, the cotTesponding value ofT is found from Eq. (14.3), written:
B1
T == Aj - In p jsat
-C (14.15)
J
BUBL T Calculations : Figure 14.3 shows an iterative scheme with input, P , {x;}, and
parameters. In the absence ofT and {y;} values, set <t>; = 1. The simple iteration scheme that
follows is clear from the figu re.
Read Pl h), constants. Set all <1>1 = 1.0. Evaluate {P;sat}.

Calc. <rr } by Eq. (14.16). Ca lc. T = l 1x1 T1sat. Calc. {y1} by Eq. { 14.8).
Evaluate {P;sat}, h;}. Identify species j . Evaluate {<1>1}, {'Y;} ~
Calc. P/at by E_g. (14.13). Calc. T by Eq. (14.15). Calc. P/at by Eq. (14.13).
Calc. Tby Eq. (14.15).
No
I Print T, {)";}.~ _...._.. Yes I

1

lsoT < s ?
I
1
"..;'
Figure 14.3: Block diagram for the calculati on BUBL T.
DEW T Calculations : Here, neither T nor {x; } is know n. The iteration scheme is shown
in detai l by Fig. 14.4 . As in the DEW P procedure, the set {x;} calculated within the inner loop
is not constraine d to sum to un ity, and is therefore normalized by setting x; = x; I x;. Li
Dewpoint and bubblepoi nt calculations are readily made with software packages such as
Mathcad and Maple, in which iteration is an integral parl of an equation- solving routine.
Calculations for multicomponent systems made either with the iteration schemes detailed here
or with software packages are readil y carried out by computer.
Read P, {y1}, constants.

Set all ~; = 1.0, all -y, = 1.0.
Calc. {T;531} by Eq. (14.12).
Ca lc. T = '2. 1y1T1581
Evaluate {P15 a1} .. 1dentify species). Calc. {x;} by Eq. (14.9).
calc. Pr1 by Eq. (14.14).
Ca lc. Tby Eq. (14.15}.

-..lEvaluate <Pr 1
}, {<l';lt-+- Normalize the x; values .
Evaluate {-y1}.
.........
Eva luate {P,sat}, {cJ>;}.

Calc. {x;} by Eq. (14.9).
Evaluate {y;}. Calc. prtby
.. t
l is each 5-y1 < g? !
No
Eq. (14. 14}, Tby"Eq. (14.15). No
~Yes
Yes calc. Pr 1 by Eq. (14.14),
~
Print T, {x). I I Is 8T < e 7
I I I Calc. T by Eq. ( 14.15).
Figure 14.4: Block diagram for the calculation DEW T.
The results for a complete BUBL T calculation are shown in Table 14.1 for the sy te.--
n-hexane(l)/e thanol(2)/me thylcyclopen tane(3)/benzc ne(4). The given pressure P is l (ac::
and the given liquid-phase mole fractions Xi are listed in the second column of Table 1.!
Parameters for the Antoine equations 1 fT in kelvins, P in (atm)], supplied as input data. are
..
At= 9.2033 Ct =
81 = 2 ,697.55 -48.78
=
A2 12.2786 82 =3,803.98 c2 = -4 J.68
A3 = 9. 1690 8 3 = 2,73 1.00 c3 = -47.11
A4 = 9.2675 8 4 = 2,788.51 c4= -52.36
1)
In addition, the following viria1 coefficients 2 (in cm3 mol- are provided:
8 11 = -1,360. 1 8 12 = -657.0 8 13 = -1 ,274.2 814 =- 1,218.8

8 22 = -1,174.7 8 23 = -62 1.8 8 24 = -589.7
B 33 = -1,191.9 8 34 = - 1,137.9
8 44 = - 1,086.9
Finally, input information includes parame ters for the UNJFAC method (App. H). Thr
lated values ofT and the vapor-phase mole fractions Yi compare favorably wi th exnP"...-po-~
values .3 Also listed in Table 14.1 are final computed values of P/at, <t>i, and Yi
1R. C. Reid, J. M. Prausni1z, and T. K. Sherwood, Tire Properties of Gases and Liquids, 3d ed .. app _-\...
Hill, New York, 1977.
2From the correlation of J. G. Hayden and J.P. O'Connell, f/1(1. Eng. Chem. Proc. Des. Dev., vol. (-1_ ;r _
1975 .
3J. E. Sinor and J. H. Weber, J. Chem. Eng. Daw, vol. 5, pp. 243-247, 1960.
14.1. The Gamma/Phi Formulation of VLE 551
Table 14.1: System: n-Hexane/Ethanol!Methylcyclopentane(MCP)/Benzene

BUBL T calculations at l(atm).
Species k .x; Yi(calc) y;(exp) P; sat/(atm) <l>; Yi

n-Hexane( I) 0.162 0.139 0.140 0.797 0.993 1.073
Ethano1(2) 0.068 0.279 0.274 0.498 0.999 8.241
MCP(3) 0.656 0.500 0.503 0.725 0.990 ] .042
Benzene(4) 0.114 0.082 0.083 0.547 0.983 1.289
T(calc) = 334.82 K T(exp) = 334.85 K Iterations= 4
The BUBL T calculations for which results are given in Table 14.1 are for a pressure of
I (atm), a pressure for which vapor phases are often assumed to be ideaJ gases and for which <l>;
is unity for each species. Indeed, these values here lie between 0.98 and 1.00. This illustrates
the fact that at pressures of 1 bar and less, the assumption of ideal gases usually introduces
little error. The additional assumption of liquid-phase ideality (y; = I ), on the other hand, is
j ustified only infrequently. We note that 'o/i for ethanol in Table 14.1 is greater than 8.
Values of parameters for the Margules, van Laar, Wilson, NRTL, and UNIQUAC equa-
tions are given for many binary pajrs by Gmchling et al. 4 in a su mmary collection of the
world's published VLE data for low to moderate pressures. These values are based on reduc-
tion of experimental data through application of modified Raoult's law, Eq. (10.5). On the
other hand, data reduction for determination of parameters in the UNIFAC method (App. H)
does not include the ideal-gas assumption, and is carried out with Eq. (14.1 ).
Flash Calculations
The treatment of flash calculations in Sec. 10.6 led to calculations based on Raoult's law and
K -value correlations. Use of the gamma/phi formulation of YLE makes the calculations some-
what more complex, but the primary equation is unchanged:
Z; K;
(i = 1, 2 , ... , N) (I 0.16)
y; = 1 + V(K; - l )
With .x; = y; I K;, an alternative equation is:
Z;
X ; = -- - - - (i = I )C'"~, N) (14. 16)
l + V(K;- l)
,
Because both sets of mole fractions must sum to unity, x; = L; L; ),;

= 1. Thus, if we sum
Eq. (10. 16) over all species and subtract unity from this sum, the difference Fy is zero:
F.= " z; K; - 1= 0 ( 14.17)

> ~ 1 + V(K; - l)
I
4 J. Gmehling, U. Onken. and

W. Arlt. Vttpor-Liquid Equilibrium Data Collection, Chemistry Data Series, vol. I,
part 1-8, DECHEMA, Frankfurt/Main, 1977-1990.
Simila r treatm ent of Eq. ( 14.16) yields the differe nce F.r, which is also zero:
~i
F.= L. - 1= 0
.\ 1 + V ( K; - 1) ( 14.18)
I
Soluti on to a P , T- flash proble m is accom plishe d when a value of V is found

that makes
either functio n F_r or F.r equal to zero for known T, P , and overal l com positio
n. Howeve r, a
more conve nient functio n for a genera l solutio n proced ure5 is the differe
nce Fy - F.r = F:
F= ~ ... 1 (KI - 1) =0
7
~ (14.19)
I
J + V(K; - 1)
The advant age of thi s functio n is appare nt from its deriva tive :
dF ~ z;(K; -1)-?
dV = - ~ [l + V(K; - l ) J2 ( 14.20)
I
Becau se d F I dV is always negati ve, the F vs. V relatio n is monot onic,

and this makes New-
ton's metho d (App. 1), a rapidly conver ging iteratio n proced ure, well suit
e d to solutio n for V.
Equati on (I. I ) for the nth iteratio n here becom es:
F+
(-dF)
dV
b.V= O (14.21
where b. V = V11 + 1 - V 11 , and F and (d F I dV) are found by Eqs. ( 14.19)

and ( 14.20) . In the e
equations the K -value s come from Eq. ( l 4.1 ), written :
,.. v p _sat
. _ :..!_ _ rl
K1-
x;
-
1
<P; p
(i = I. 2.... , N) (14. 2 ~
where <1>; is given by Eq. (14.2). The K -values contai n alJ of the thermo
dynam ic inform ation..
and are related in a complex way toT. P, {J; }. and (x;}. Becau se solutio
n is for {y;} and {.r, .
the P. T -flash calcul ation inevita bly requir es iteratio n.
A genera l solutio n schem e is shown by the block diagra m of Fig. 14.5.
The given infor-
mation is read and stored . Becau se it is not known in advanc e wheth er
the system of stare.:
compo sition at the stated T and P is in fact a mixture of satura ted liquid
and satura ted vapc:
and not entirel y liquid or entirel y vapor. prelim inary calcul ations are made
to establi sh the n~-
ture of the system . At the given T and overall compo sition, the syste m exists
as a superh eme....
vapor if its pressu re is less than the dewpo int pressu re Pdew On the other
hand , it exist a:- _
subcoo led liquid if its pressu re is greate r than the bubb lepoin l pressu re
Pbubl Only for pre--
sures betwe en Pdew and Pbubl is the system an equilib rium mixtur e of
vapor and liquid. V e
there fore determ ine Pdew by a DEW P calcul ation (Fig. 14.2) at the given
T and for {y;} = :
and Pbubl by a BUBL P calculation (Fig. 14.1 ) at the given T and for {xi}=
{zd. The P . -:-
flas h calculation is perfor med only if the given pressu re P lies between
Pdew and Pbubl If 1.:"
is the case, we make use of the results of the prelim inary DEW P and BUBL
P calcul ation
5 H. H. Rachfor
d. Jr.. and J.D. Rice. J. Petrol. Techno/.. vol. ~( I 0). sec. I. p. 19 and sec. 2, p. 3.
October. 195:
:-4. 1. The Gamma I Phi Fonnulalion of VLE
553
,---- --
1
Read T, P, { z;}, constants.
I
I DEW P calculation with {y;} = {:1}. I
I
t
JJUBL P calcula tion with {.t";} = {::;}. j
I
t
I
I
I
: I
1 Is Pdew -1
'----- t,--------1I
Estima te {Y;}, {<1>,), V.
Figur e 14.5: Block
diagra m for a P ,T -flash
calculation.
Evaluate {K;} by Eq. (14.22).
Evaluate F and dF/ fN by Eqs. (14.19) and (14.20).
Find V by Ne\'Vton's metho d. 'I ~-.......
Evaluate {x1} by Eq. (14.16) and {y;} by y == K x
1 1 1
Evaluate { y;}, {<f>,}.
No
IAre 8V, each fix,, and each l5y1 < s? ,[ ___ _ __,
! Yes
I Print V, {x;}. {y;}. j
provide initial estimates of {y;}, {;},and V. For the dewpoint, V

= 1, with calcu lated values
of Pdew. Yi.dew. and i.dew ; for the bubblepoi nt, V = 0, with calcu
lated values of P bub!, Yi.bubl ,
and i.bub l The simplest procedure is to interpolate between dewp
oint and bubblepoint values
in relation to lhe location of P between Pdew and Pbubl:
Yi- Yi.dew P- Pdew

Yi.bubl - Yi.dcw
- -
i.bubl - i.dew Pbub l- Pdew
V-I P- Pdew
and ---
0
= ---- ---- -- or V= Pbub l- P
- I Pbubl - Pdew Pbubl - Pdcw
With these initial values of the y; and ;, initial values of the K;
can be calcu lated by
Eq. (14.22 ). The P/at and r' values are already available from
the preliminary DEW P
and BUBL P calculations. Equations (14. 19) and ( 14.20 ) now
provide sta11ing values of F
and d F jdV for Newton's method as represented by Eq. (14.21 ).
Repeated application of this
equation leads to the value of V for which Eq. ( 14.19 ) is satisfied
for the present estimates of
{K; }. The remai ning calculations serve to provide new estimates
of {yi} and {>;} from which
to reevaluate {K;}. Thi s sequence of steps (an outer iteration) is repeated until there is no
significant change in results from one iteration to the next. After the fi rst outer iteration, the
values of V and (d F jdV) used to start Newton's method (an inner iteration) are simply the
most recently calculated values. Once a value of V is established, values of x; are calculated
by Eq. ( 14.16) and values of y; are given by y; = K;x;.
Multicomponent flash calculations based on the gamma/phi formulation are readi ly car-
ried out by compt,!ter as outlined in Fig. 14.5. Table 14.2 shows the results of a P, T-fiash
calculation for the system n-hexane(l)/ethanol(2)/methylcyclopentane(3)/benzene(4). This is
the same system for which results of a BUBL T calculation are presented in Table 14. 1, and
the_same correlations and parameter values are used here. The given P and Tare here l (atm)
and 334.15 K. The given overall mole fractions for lhe system {z;} are listed in Table 14.2
along with the calculated val ues of the liq uid-phase and vapor-phase mole fractions and the
K -values. The molar fraction of the system that is vapor is found to be V = 0.8166.
Table 14.2: System: n -Hexane/Eth a nol!MetbyJcyclopentane(MCP )/Benzene

Calculation of P ,T -flash at 1(atm) and 334. 15 K.
Species(i) Xi Yi K;
n-Hexane(l) 0.250 0.160 0.270 l.694

Ethanol(2) 0.400 0.569 0.362 0.636
MCP(3) 0.200 0.129 0.216 1.668
Benzene(4) 0. 150 0.142 0.1 52 1.070
P =I (atm) T = 334.15 K V =0.8166
Solute (1) I Solvent (2) Systems

The gamma/phi approach to VLE calculations, based on Eq. ( 14.1 ), presumes knowledge .
the vapor pressure of each species at the temperature of interest. Situations do arise ho--
ever where a species is either unstable at the system temperatw-e or is supercritical, i.e.. :!:.e
system temperature exceeds its critical temperature. Therefore its vapor pressw-e cannot ~
measured, and its fugacity !1 as a pure liquid at the system temperature cannot be calcula:a5
by Eq. ( 11.44).
Consider a bjnary system wherein species I, de ignated the solute, cannot exist asa p ...... !'
liquid at the system temperature. Although Eqs. (14. 1) and ( 14.2) can be applied to species.::.
designated lhe sol vent, they are not applicable to the solute, and an alternative approact
req uired. Figure 14 .6 shows a typical plot of the liquid-phase fugacity of the solute /1
,s. ~
mole fractio n X t at constant temperature. This figure differs from Fig. 12.3 in that the cu.~_
representing ft does not extend all the way to .x1 = 1. Thus the location of j 1, the liquid-ph::....-
fu gacity of pure species 1, is not established, and the line representing the Lewis/Randall ~
cannot be drawn. The tangent line at the origin, representing Henry's law (Sec. 12.1 ), pro -:
alternative information. Recall that the slope of the tangent line is Henry's constant, de:r::....
I4.1. The Gamma I Phi Formulation of VLE 555
by Eq. (12.2). Thus,

Ji 1 = lim /J
,q -+ 0 XJ
( 14.23)
Henry's constant is a strong function of temperature, but only weakly dependent on pressure.
Note, however, that the definition of 1-t 1 at temperature T presumes the pressure is the equilib-
rium value at XJ ---* 0, i.e., the vapor pressure of the pure solvent P2sat.
Henry's law
],
Figure 14.6: Solute fugacity j, vs. XJ.
0 1
The activity coefficient of the solute is related to its fugacity by Eq. (11.90), which may
be written: A
-ft = Ytf1
XJ
(14.24)
Combining this with Eq. ( 14.23) yields:
rt, =YFft
where yj represents the infinite-dilution value of the activity coefficient of the solute. Because
both 1-t 1 andyr are evaluated at P/at, this pressure also applies to ! 1 However, the effect of P
on a liquid-phase fugacity, given by a Poynting factor, is very small, and for practical purposes
may usually be neglected. Elimination of / 1 from Eq. (14.24) gives on rearrangement:
(14.25)
For vapor/liquid equilibrium,

,... "'/ "u "
ft = ft = / 1 = Yl P 1
~
where the final term comes from Eq. (11.52). Combining the... two expressions for j, gives,
after rearrangement:
(14.26)
For the solute, trus equation takes the place ofEqs. (14.1) and ( 14.2). For species 2, the solvent,
Eq. (14.8) becomes:
( 14.27)
Because Yl + Y2 = 1, a BUBL P calculation for a binary system is based on the equation:
( 14.28)
The same correlation that provides for the evaluation of Yl also allows evaluation of rr.
.,
As a simple example, consider a system for whi ch:
~
</>J = 1.0
By Eqs. (12.15), YI = exp (A xi) Y2 = exp (Axf)

Whence, and (yJ/yr) = exp [A (xi- 1)]
Equation (14.28) here becomes:
(
Yt X11t 1 exp [A (X~ - 1)]
= ___
and by Eq. (14.26), ___;;;._~-~
For comparison, if P 1sat were known, the for mulation would be:
x1 P at exp (Ax 2 )
P = XJ P 1sm exp ( Axi ) + x2 P 2sat exp ( Axf) Yl = I 2
p
...
The difference in the input data for the two formulatjons is that Henry's constant for specie
is requjrcd in the former case whereas the vapor pressure of species I appears in the latter.
There remajns the problem of finding Henry's constant from the available VLE data. f -
equilibrium ,
Division by x1 gives:
Henry 's constant is defined as the limit as x1 -r 0 of the ratio on the left; therefore,
'1.1 _ p sal~OO . Yl
1lill -
1 L) - 2 If')
X1-+0 X)
The limiting value of Yt/XJ can be found by plotting y,jx, vs. Xt and extrapolating to ze:--
14.2 VLE FROM CUBIC EQUATIONS OF STATE
As shown in Sec. 11 .6, phases at the same T and P are in equilibrium when the fuga... -_
each species is the same in all phases. For VLE, this requirement is written:
14.2. VLE from Cubic Equations of St.ale 557
r.~IJ
I
= i!
JI (i = l. 2 .... , N) ( I 1.48)
An alternative form resu lts from introduction of the fugacity coefficient, defi ned by Eq. ( 11.52):
A A I
y; P(/>j' = x; P</>;
or (i = I, 2, ... , N) (14.29)
Vapor Pressures for a Pure Species

Allhough vapor pressures for a pure species P/a1 are subject to experimental measurement , it
is also true that vapor pressures are implicit in a cubic equation of state. Indeed, the simplest
application of equation of stale fo r VLE calculations i. to find the vapor pressure of a pure
species at given temperature T.
p
r
'
Figure 14.7: Isotherm for

T < Tc on P V diagram for
a pure fluid.
The subcritical P V isotherm of Fig. 3.1 I labeled T2 < Tc is reproduced here as Fig. 14.7.
As generated by a cubic equation of state, it cons ists of three segments. The very steep segme nt
on the left (rs) is characteristic of liquids; in the limit as P ~ oo, the molar volume V
'"\ .
approaches the constant b lEq. 3.42]. T he segment on the ri ght (tu) with gentle downward
slope is characteristic of vapors: in the limit as P ~ 0 molar volume V approache. infiojty.
The middle segment (sl), containing both a minimum (note here that P < 0) and a maximum,
provides a smooth transition from liqu id to vapor, but has no phy ical meaning. The actual
transition from liquid to vapor occurs at the vapor pressure along a horizontal line, such as
connects points M and W.
For pure . pecies i, Eq. (14.29) reduces to Eq. ( 11.41 ). (N =</>{,which may be written:
In <l>f -In <N = 0 (14.30)

T he fugacity coefficient of a pure liquid or vapor is a function of its temperature and pres-
sure. For a salurared liquid or vapor, the equi librium pressu re is P/a1 Therefore Eq. (14.30)
implicitly expresses the functional relation,

g(T, P/at) = 0 or P;sat = f(T)
An isotherm generated by a cubic equation of state, as represented in Fig. 14.7, has three
volume roots for a speci fic pressure between P = 0 and P = P' . The smallest root lies on
the left line segment, and is a liqujd-li ke volume, e.g., at point M. The largest root lies on the
right line segment, and is a vapor-l ike volume, e.g., at point W. If these points lie at the vapor
pressurel..then M represents saturated liquid, W represents saturated vapor, and they exist in
phase equilibrium. The root lying on the m[ddle line segment has no physical significance.
Two widely used cubic equations of state, developed specifically for YLE calculations,
are the Soave/Redlich/Kwong (SRK) equation6 and the Peng/Robin son (PR) equation .? Both
are special cases of Eq. (3.52) for a vapor phase and Eq. (3.56) for a liquid phase. Equation-
of-state parameters are independent of phase, and in accord with Eqs. ((3.45), (3.46), (3.50),
and (3.51) are given by:
cx(Tr) R2 T/
a; (T) = \11 ' (14.3 1) b; = n -RTc
-' (14.32)
Pc; Pc;
/3- = b; P
a; (T )
I- RT (14.33) q; = b;RT
(14.34)
Written for pure species i as a liquid, Eq. (3.56) becomes:
Z;' = {:J; + (Z;' + E{3;)(Z;, + af3;) ( 1 + /3; -

q; f3i
zf ) ( 14.35)
For pure species i as a vapor, Eq. (3.52) is written:
zu - 1 + {3" -
; - '
(( P..
7WI
z~ - f3
I
(Zj + E/J;)(Z j
I
+ af3;)
( 14.36)
The pure numbers E, a, w, and nand expressions for cx(Tr;) are specific to the equation of
state, and are given in Table 3.1 (p. 98). ..,
As shown in Sec. 11.5, and applicable to both vapor and liquid phases:
In; = Z;- I - ln (Z;- {3;) - q; l; (1 1.37)
Values for ln ; arc therefore imp Iied by each of the equations of state considered here. In
Eq. ( I 1.37), q; is given by Eq. (14.34), and 1;, by Eq. (6.65b). For given T and P, the liquid-
phase value Zf at point M of Fig. 14.7 is found by solution of Eq. ( 14.35). The vapor-phase
value Zj at point W comes fro m Eq. (14.36). Values for In f and In j are then found b)
Eq. (1 1.37). If they satisfy Eq. ( 14.30), then Pis the vapor pressure P/at at temperature T.
and M and W represent the states of aturated liquid and vapor implied by the equation of
state. If Eq. (j4.30) is not satisfied, P/at is found by trial, by iteration, or by the solve routine
of a software pack age. The eight equations solved for eight unknowns are listed in Table 14. 3.
6G. Soave, Chem. En~. Sci., vol. 27. pp. 11 97-1203, 1972.
7 D.- Y. Peng and D. B. Robinson. Ind. Eng. Chem. Fwrdam., vol. 15, pp. 59-64. 1976.
14.2. VLE from Cubic Equations of State 559
Table 14.3: Equations for Calculating Vapor Pressures
f 1.= 1 Zf +_
In.......:,._ a/3;_ f. =
v 1 zr + a{3;
In ~---
1
(J - E 2~ + E /3; ' (J - E zr + {3;
E
lnf = zf- 1 -lnCZ1- {J;)- q; rf

"'
In 'Y1
A.~= z~-
l
1- Jn(Z ~ -
I
/3;)- q; J.V
I
The calculation of pure-species vapor pressures as just described may be reversed to

allow evaluation of an equation-of-state parameter from a known vapor-pressure P; sat at tem-
perature T. Thus, Eq. (11.37) may be written for each phase of pure-species i and combined
in accord with Eq. (14.30). Solving the resulting expression for q; yields:
Z!l- z{
z'-
+ 1n zy-
;
/3'
I I /3i
q; = ----------~--- (14.37)
J.U-
I
J!I
where {3; = b; P/at; RT. For the PR and SRK equations, /; is given by Eq. (6.65b) written for
pure species i:
Z; + a/3;
!; = - - In ,;-
a - E Z; + E/3;
This equation yields If with Zf
from Eq. (14.35), and It with zy from Eq. (14.36). However,
the equations for Zf and zycontajn q;. the quantity sought. Thus, an iterative procedure is
indicated, with an initial vaJue of q; from a generalized correlation as g iven by Eqs. (14.31 ),
( 14.32), and (14.34).
Mixture VLE
The fundamental assumption when an equation of state is ,written for m ~xtures is that it has
exactly the same fonn as when written for pure species. Thus for mixtures Eqs. (14.35) and
560 CHAPTER 14. Topics i n Phase Equilibria
( 14.36), written without subscripts, become:
Liq uid: .. zl = {3 1+ (Z1+ E/31)(Z1+ a/31) ( 1 + !3' - zl ) (14.38)

q'fJ'
Vapor:
lot..
zu= ] + f3 v -
zu
c.7. ll f3 v -(Z_"_+_E_/3-")_(_
{3"
14.39)
Z_"_+_a_f3_"_)
~
Here~ {3 1, /3", q 1, and c/ are for mixtures, with definitions:
b"P aP
f3P =--
RT
( p=l, v) ( 14.40) qP=--
bPRT
(p=l,v) (14.41)
The complication is that mixture parameters aP and bP, and therefore fJP and qP, are functions
of composition. Systems in vapor/liquid equilibrium consist in genera] of two phases with dif-
ferent compositions. The PV isotherms generated by an equation of state for these two fixed
compositions are represented in Fig. 14.8 by two similar li nes: the solid line for the liquid-
phase composition and tbe dashed line for the vapor-phase composition. They are displaced
from one another because the equation-of-state parameters are different for the two composi-
tions. However, each 11ne includes three segments as described in connection with the isotherm
of Fig. 14.7. Thus, we distinguish between the composition which characterizes a complete
line, and the phases, all of the same composition, which are associated with the segments of
an isotherm.
I
I
Figure 14.8: Two P V isotherms at the same T I
I
for mixtures. The solid line is for a I
I
liquid-phase composition; the dashed line is I
I
for a vapor-phase composition. Point B I
I
B
represents a bubblepoint with the liquid-phase
composition; Point D represent a dewpoint 0
v
with the vapor-phase composition. When these
points lie at the same P (as shown) they
represent phases in equilibrium.
Each line contains a bubblepoint on its left segment representing saturated liq uid, and a
dewpoint of the same composition on its right segment representing saturated vapor8 . Because
these points for a given line are for the same composition, they do no t represent phases in
equilibrium and do not lie at the same pressure. (Sec Fig. I 0.3 , where for a given constant-
composition loop and a given T saturated liquid and saturated vapor are at different pressures.)
For a BUBL P calculation, the temperature and the liquid composilion are known, and
this fixes the location of the P V isotherm for the composition of the liquid phase (solid line).
8 Note that bubblepoint 8 und dewpoint D in Fig. 14.8 are on different lines.
The BUBL P calculation then fi nds the compos ition for a second (dashed) line that contain
sa
dewpoint D on its va_por se.zment that lies at the,.pressure of .the bJJJJhJJf.D.D.ivJ..B .m>.Jl'
)..i:pJJ).&J
segmen t of the solid line. This pressure is then the phase-equilibrium pressu re and the compo-
sition for the dashed line is that of the cquiliblium vapor. Thi equilibrium condition is
shown
by Fig. 14.8, where bubblepoint Band dewpoin t D lie at the same P on isotherms for the
same
T but representing the different compos itions of two phases in equilibrium.
Becaus e no established theory prescrib es the form of the composition depende nce of
the equation-of-state parameters, empirical mixing rules have been proposed to relate mixture
parame ters to pure-species parame ters. The simples t realistic express ions are a linear
mi xi ng
rule for parame ter hand a quadrat ic mixi ng rule for parameter a:
( 14.43)
with Clij = a Ji . The general mole-fraction variable Xi is used here because applica
tion is
to both liquid and vapor mixtures. The aiJ are of two types: pure-species parameters
(like
subscripts) and interaction parameters (unlike subscripts). Parame ter b; is fo r pure species
i.
The interaction parameter aiJ is often evaluate d from pure-species parame ters by combin
ing
rules, e.g., a geometric-mea n rule:
"'
Clij = (a;aj) 112 (14.44)
These equations, known as van der Waals prescriptions, provide for the evaluation of mixture
parameters solely from parame ters for the pure constituent species. Althoug h they are
sati s-
factory onJy for mixtures comprised of simple and chemically simil ar molecules, they
allow
straight -forward calculations that illustrate how complex VLE problems may be solved.
Also useful for application of equations of state to mixtures are partial equation-of-state
parame ters, defined by:
_ [a(na) ] b; - [ o(nb) ] q; =[a(nq) ]

Cli = a;;:- T.11
1
(14.45)
on; T.nj
( 14.46)
dl'l; T ,nl
(14.47)
Because equation-of-state parameters are, at most, fun ctions of tempera ture and compos
i tion,
these defini tions are in accord with Eq. (L 1.7). They are general equations, valid regardle
ss of
the particular mixing or combining ru les adopled for the composition depend ence of mixture
parameters.
Values of[ and [ are implicit in an equation of state, and with Eq. (14.29) allow
calculation of mixture VLE. The same basic principle applies as for pure-species VLE,
but the
calculations are more complex. With fa fu nction ofT, P, and {xi}, and ;u a fun ction
ofT ,
P , and {y; }, Eq. ( 14.29) represeol N relations among the 2N vruiables: T , P , (N -
1) XiS and
(N - I) y;s. Thus. specification of N of these variables, usually either T or P and
either the
liquid- or vapor-phase compos ition, allows solution for the remaini ng N vatiables by BUBL
P,
DEW P, BUBL T, and DEW T calculation .
Cubic equations of state give Z a~.; a function ~f the indepen dent variab les T and p (or V ).
Use of such an equation in VLE calculations therefore requires ; to be given by an equatio
n
suited to these variables. The derivation of such an equation starts with Eq. ( 11.56), written for
a mi xture with V R replaced by Eq. (6.40):
nCR) n(Z- 1) nHR ...

d(- = A-dn
d P- - - dT + "ln \f'l
~
..... RT p RT2 I
I
Division by dn; and restriction to constant T , nlp(= n V) , and nj (j =f. i) leads to:
... [ o(nGRIRT)] n(Z - 1) ( a p) ( 14.48)

In ;= - -
on; T ,njp,nj p on; T.njp ,llj
For simplicity of notation, the partial derivatives in the following development are written
without subscripts, and are understood to be at constant T, nlp(= n V), and n j . Thus, with
P = (nZ) RTl(nl p),
ap RT a(nZ) P o(nZ)
- = - (14.49)
on; nlp an; nZ on;
Combination of Eqs. (14.48) and ( 14.49) yields:
In cP; = o(nGR I RT) -

an;
(z z- 1) o(nZ) = o(nGR I RT) - o(nZ)
an; an; an;
+~
z
(n az
an;
+ z)
Equation (6.66a), written for the mixture and multiplied by n , is differentiated to give the firs
term on the ri ght:
nGR "
- - = nZ- n - n ln(l - pb)Z- (nq)l
RT
o(nGR 1RT)
----=
o(nZ) ,.,
- 1 - ln(l -pb)Z-n
[aIn(l - pb)
+
atn z] ril aI
, - - 1q;
-nq-
_
on; on; on; on; an;
where use has been made ofEq. ( 14.47). The equation for In ; now becomes:
,. o(nZ) a In( I - pb)

In ;= - 1 - ln(l - pb)Z- n- - - -
on; on;
_ !!_ az _ nq ol
z on; on;
_ l q; _ o(nZ)
on;
+~
z
(n az +
on;
z)
... n a(pb) a1
This reduces to: ln ; = - nq-- ln( l - pb)Z- q;f
1 - pb on; an;
All that remains is evaluation of the two paLtial derivatives. The first is:
a(pb)
~)
a ( nl p p-
_:...........;._~=-b;
on; on; 11
The second fo1lows from differentiation of Eq. (6.65a). After algebraic reduction this yields:
a1 a(pb) b; pb
-- - ---------
an; an; (1 + apb)(l + Ep b) nb (1 + apb)(l + Epb)
Substitution of these derivatives in the preceding equation for ln ; reduces it to:
" = -b;
ln ; [ pb - q pb -
] - In[( I - pb)Z] - q;f
b 1 - pb (l + Epb) (l + apb)
Reference to Eq. (6.64) shows that the term in square brackets is Z - I. Therefore,
" b;
In; = b(Z- 1) - ln[( l - pb)Z]- ih I
bP p f3
However, /3=-
RT
and Z =pRT; whence pb = Z
Thus,
,.
ln ; = -b; (Z - 1) - ln(Z - {3) - q; I
b
Because experience has shown that Eq. ( 14.42) is an acceptable mixing rule for parame-
ter b, it is here adopted as appropr~ate for present purposes. Whence,
and b; =[ a(nb) ] = [ a(n;b;) ] +L [a(n j bj) ] = b;

an; T' " J an; T n.J 1
. an; T , II ).
The equation for ln ; is therefore written:
,. b;
In ;= -(Z- 1) - ln(Z- {3)- ij; l ( 14.50)
b
where 1 is evaluated by Eq. (6.65b). Equation ( 11.37) is a special case for pure species i.
Application of Eq. (14.50) requires prior evaluation of Z at the conditions of interest by
an equation of state. This may be accomplished for a liquid phase by solution of Eq. ( 14.38) ~
and for a vapor phase by solution ofEq. ( 14.39).

Parameter q is defined i~ relation to parameters a and b by Eq. (14.41 ). The relation of
a;
partial parameter q; to and b; is found by differentiation of this equation, written:
n(na)
nq = RT(nb)
Whence, q; = [a(nq) ] =q ( 1 +a;_ b; ) =q ( 1 +a;_ b;) (14.51)

an; T.IIJ a b a b
Any two of the three partial parameters form an independent pair, and any one of them can be
found from the other two. 9
9secau~c q, a, and bare not linearly related, iii ::/= ii; /b; RT.
Example 14.1
A vapor mixture of N2 (1) and CH4 (2) at 200 K and 30 bar contains 40 mol-o/o N2 . De-
termine the fugacity coefficients of nitrogen and methane in the mixture by Eq . (14.50)
and the Redlich/Kwong equation of state.
Solution 14.1 ,..

For the Redlich/Kwong equation. E = 0 and a = I, and Eq. ( 14.39) becomes:
Z-{3
qf3 Z(Z + {3) (A)
z = I + f3 -
w here f3 and q are given by Eqs. (14.40) and (1 4.41). Superscripts are here omit-
ted, because all calculations are for a vapor phase. The mixing rules most com-
monly used wi th the Redlich/Kwong equati on for parameters a(T) and bare given
by Eqs. ( 14.42) through ( 14.44). For a binary mixture they become:
(B)
(C)
In Eq. (B), a 1 and a2 are pure-species parameters given by Eq . ( 14.3 1) written for
the Redlich/Kwong equation:
In Eq. (C), b 1 and b2 are pure-species.JJarameters , given by Eq. ( 14.32):

83 .1 4 Tc
b; = 0.08664 ' em3 mol- 1 (E)
Pc;
Critical constants for nitrogen and methane from Table B. I and calculated
values for bi and ai fro m Eqs. ( D ) and() are:
126.2 1.5848 34.00 26.737 10.995

1.90.6 1.0493 45.99 29.853 22.786
Mixture parameters by Eqs. ( B ), (C), and ( 14.41) are:
a= 17.560 x 105 barcm 6 mol- 2 b = 28.607 cm 3 mol- 1
q = 3.69 16
Equation (A) becomes:
Z = 1 + {3- 3.69 16 {3(Z- {3) with {3 = 0.05 161 2

Z(Z + {3)
where {3 comes from Eq. (14.40). Iterati ve solution y ields Z = 0.85393. More-
over, Eq. (6.65 b) red uces to:
Z+/3
I = In z = 0.05868
Applicalion of Eq. ( 14.45) to Eq. (B) yields:
8(na)]
a, = [- - = 2 y,cq + 2y2.JlilG2- a
8nl T.n2
By Eq. ( 14.46) applied to Eq. (C),
- [8(n.b)J
bl =
-- =b) - [&(nb)J
b2 =
-- =b?
Dnt T.n2 8n.z T.n, -
Whence, by Eq . ( J4.5 1):

-
Cf l =q
(2)'t Cl l + 2y2.jCi]Ci2 - - b,) (F)
a b
(G)
Substitution of numerical values into these eq uations and into Eq. ( 14.50) leads lo
the following results:
q;
N2(1) 2.39 194 - 0.05664 0.94493
CH4(2) 4.55795 - 0. 19966 0.81901
The values of (/J; agree reasonably well with those found in Ex. 11.7.
Equation ( 14.50) provides the means to evaluate(/;;, and is the basis for VLE calculations.
A common procedure makes use of Eq. (14.29), rewritten as Yi = K;x; . Because L; y; = I,
,-
~ K;Xi = I ( 14.52)
....
where K; , the K -value, is given by:
A'
KI. -- </>;
A ( 14.53)
cJ>f
Thus for bubblepoint calculations, where the liquid-phase compos ition is known, the problem
is to find the set of K -values that satisfies Eq. (14.52). A block diagram of a computer program
for BUBL P calculations is shown by Fig. 14.9.
Read T, {x;},
EOS parameters, Print
estimates of P, {y).
P, {y;}.
-
!
Evaluate {r,b~},
Yes
I Adjust P. ,
{r,b'j}, {K;}. No Is
o(
Calculate { K;x;} "i.K;X; = 1?
Figure 14.9: Block and "i.K;x;.
diagram for BUBL P
calculalion.
!
Calculate all
No
Yes Has
K;X;
y= - - LK; x; changed?
I kK;X;
!
Reevaluate {cjJj}, {K;},
{K;x;}, and LK;x;.
Example 14.2
Develop the P -x -y diagram at 100(F) for the methane(1)/n-butane(2) binary"" system.
Base calculations on the Soave/Redlich/Kwong equation with mixing rules given by
Eqs. (14.42) through (14.44). Experimental data at this temperature for comparison
are given by Sage et al. 10
Solution 14.2
The procedure here is to do a BUBL P calculation for each experimental data
poi nt. Reference to Fig. 14.9 indicates that for each calculation estimated values
of P and Yl are required to initiate iteration. These estimates are here provided
by the experimental data. Where no such data are available, several trials may be
required to find values for which the iterative procedure of Fig. 14.9 converges.
Pure-species parameters ai and bi are found fro m Eqs. (14.3 1) and ( 14.32)
with constants and an expression for cx(I;.) from Table 3.1 (p. 98). For a temper-
ature of 310.93 K [100(F)] and with critical constants and w; from Table B.l ,
calculations provide the following pure-species values:
lOB. H. Sage, B. L. Hicks, and W. N. Lacey, Industrial and Engineering Chemist1y, vol. 32, pp. 1085- 1092. 19-!-
Tc,. IK w; b;
Crf.t(l) 190.6 1.6313 0.012 0. 7425 45.99 29.853 1.7331

n-C4H10(2) 425.1 0.7314 0.200 1.2411 37.96 80.667 17.458
The uni L~ of b; are cm3 mol- 1, and for a;, bar cm6 mol- 2 .
Note that the temperature of interest is greater than the critkal temperature of
methane. The P-x-y diagram will therefore be of the type shown by Fig. 10.2(a)
for temperature Tb. The equations for a(T,.) given in Table 3. 1 are based on vapor-
pressure data, which extend only to the critical temperature. However, they may
be applied to temperatures modestly above the critical temperature.
The mix ing rul es adopted here are the same as in Ex. 14. 1, where Eqs. (B),
(C), (F), and (G) give mixture parameters for the vapor phase. When applied ro
the liquid phase, x; replaces y; as the mole-fraction variable:
where qt is given by Eq. (14.41 ).

For the SRK equation, E = 0 and a = 1; Eqs. (14.38) and (14. 39) reduce to:
zt = fit + zt cz' +fit) ( 1 + fi' - zt )
qlfil
where fi 1, ~v, q 1, and qv are given by Eqs. (14.40) and (14.41). Each BUBL P
calculation proceeds as indicated in Fig. 14.9. The first set of calculations is made
for the assumed pressure. With the given liquid-phase composition and assumed
vapor-phase composition, values for zt and zv are detennined by the preced-
ing equations, and fugacity coefficients f
and~ then follow from Eq. (14.50).
Values of K 1 and K 2 come from Eq. ( 14.53). The constraint Yl + Y2 = 1
has not been imposed, and Eq. (14.52) is unlikely to be satisfied. In this event,
K 1x 1 + K 2x2 "# I , and a new vapor composition for the next iteration is given by
the normalizing equation:
with ~ Y2 = 1 - Yl
This new vapor composition allows reevaluation of{{}, (K; }, and {K;xi}. If
the sum K 1x1 + K2x2 has changed, a new vapor composition i found and the se-
quence of calculations is repeated. Continued iteration leads to stable values of all
quantities. If the sum K 1x 1 + K 2X2 is not unity, the assumed pressure is incorrect,
and must be adjusted according to some rational scheme. When L;
K; .xi > 1, P
is too low; when L; K;x; < l , P is too high. The entire iterative procedure is
then repealed with a new pressure P. The last calculated values of y; are used for
the initial estimate of {y;}. The process continues until K 1x 1 + K 2x2 = 1.
568 CHAPTER I 4. Topics in PJw~e Equilibria
140 .---------.---------.---------.---------.---------~
+ Critical Point
120
100
80
'-
1'0
.0
ii:
60
40
20
0 L-------~~------------------~--------~--------~
0 0.2 0.4 0.6 0.8 1
Figure 14.10: Pxy diagram at 100( F) for metha11e(J )/n-butane(2). Lines represent values from
BUBL P calculations with the SRK equation; point are experimental values.
The results of all calculations are shown by the solid lines of Fig. 14.10. Ex-
perimental values appear as points. The root-mean-square percentage difference
between experimental and calculated pressures is 3.9%, and the root-mean-square
deviation between experimental and calculated Yl values is 0.0 13. These results,
based on the simple mixing rules of Eqs. (14.42) and ( 14.43), are representalive
for systems that exhibit modest and well-behaved deviations from ideal-, olution
behavior, e .g., to syste ms comprised of hydrocarbons and cryogenic fluids.
14.2. VLE from Cubic Equations of State
569
Summability Equation as a Mixing Rule

Although the linear mixing rule for b [Eq. ( l4.42)J is usually
acceptable, the quadratic mix-
ing rule for a [Eq. (14.43)] is often unsatisfacto ry. An alternative
i, a mixing rule for q that
incorporates activity-coe fficien t data. Equation-of-state param
eters are related to activity co-
efficients by the definitions of the activity coefficient and the fugac
ity coefficienr:
y;=-. =
J; ./;/x;P /f>;
= -
x; ./1 fi I P </>;
Whence, In y; = ln ; - In; (14.54)
where y;, ; , and</>; are all liquid -phas e prope rties evalu ated at
the same T and P. Subtracting
Eq. ( 11.37) from Eq. ( 14.50 ) in accord with this equation gives:
b
lnv = ....!...(z - l ) - Z + I -In (Z -ft) - q-1 +q J
Tl b I ( Z; _ /3;) I I I
where symbols without subscripts are mixture properties. Solut

ion for q; yields:
_ 1[
q = - 1 - Z + -b;"(Z - I ) - In (Z-{ J) + tt J. - In ,.,.
]
I I I b (Z; - /3;) 11 I rl
(14.55 )
For a pure species, thi s equat ion correc tl y reduces to the identi
partial property, the summability equation applies:
ty, q; =q;. Because ij; is a
q = :2:; x;ql ( 14.56 )
Equations (14.55) and (14.56) together constitute a

thermodynami-
cally sound mixing rule for q.
Equations (14.5 5) and ( 14.56) apply to both ljquid and vapor phase
s. For a liquid phase,
application is direct , because the activity coefficients y; and the
mixture properties b, Z , {3 , and
I are for exactly the same phase. Tn Fig. 14.8, the solid
line is for the composition of the Liquid
phase, and point B on this li ne lies on its Liquid segment; there
is here no confusion. Thus,
1
-1
q. =-1 [l
- h; I
z.tI + -(2 - 1) - In (2 -/3 1) + q.J.I - In y- ]
1 Jf b' (Z~-{3;) It
( 14.57 )
I
and q' = I; x;qf -. (14.5 8)
Application of Eq. (14.57) requires prior evaluation of Zf and 1

Z by Eqs. (14.35) and
( 14.38). These quantities are also required for evalu alion of 1 t/
and 1 by Eq. (6.65b). How-
ever. the equation of state contain q 1, evaluated from the value
tions (14.57) and (14.58), together with Eq. ( l4.38) and the
qf
s through Eq. (14.58). Equa-
necessary auxiliary equ ations ,
must therefore be solved simultaneously for {Zf}, Z 1, {!{}, 11,
{qf}, and q1. The results make
f
possible the calculation of values by Eq. ( l4. 50).
In Fig. 14.8 the entire dashed line and its parameters qt and q v are for the coinposi tion of
the vapor phase. However, its left segment represents a liquid with this composition. Because
all properties in Eqs. 14.55 and 14.56 are liquid-p hase properties, the activity coefficients are
associate d with this segment, and are values for a liquid phase with the vapor composition,
denoted by the superscript l , v. Thus:
~
l [ b czt.v - /3/ ,v)

- ln y! v
]
- l - Z~ +~(zt,v- 1) - In
q-~I =f l,V czf _ /3;)
+ q-J!
I I I
(14.59)
I bf,V
and (14.60)
These equations, together with Eq. (14.39) and the necessary auxiliary equations, must
therefore be solved simultan eously for {Zf}, zt.v, {1(}, I v, {qt}, and qv, either by iteration or
1
by the equation-solving feature of a software package. The results make possible calculati on
of t values by Eq. (14.50).
A choice must be made of an equation of state. Only the Soave/Redlich/Kwong and
Peng!Ro binson equation s are treated here, and they usually give comparable results. A choice
must also be made of a correlating equation fo r the liquid-phase compos ition dependence of
In y;. The Wilson, NRTL, and UNIQUAC equations (Sec. I 2.2) are of general applicability~ for
binary systems the Margules and van Laar equation s may also be used. The equation selected
depends on evidence of its suitability to the particular system treated.
The required input informa tion includes not only the known values ofT and {x;}, but
also estimates of P and {Yi }, the quantities to be evaluated. These estimates may be provided
by preliminary calculations:
"
1. For the chosen equation of state (with appropri ate values of n, \11 , E, and rr), fo r each
species find values of b; and q; by Eqs. (14.32) and (14.34).
2. If the vapor pressure P;sat for species i at temperature T is known, determin ~a new
value for q; by iterative solution of Eq. ( 14.37) with Z; and /; for both liquid and vapor
phases from Eqs. ( 14.35), ( 14.36), and (6.65b).
3. A reasonable estimate of P is given by the sum of known or estimated P;sat values, each
weighted by its known liquid-phase mole fraction.
4. For each pure species i at the given T and estimated P , fi nd liquid-p hase values zf and
If fro m Eqs. ( 14.35) and (6.65b).
5. For each pure species i at the given T and estimated P , find vapor-p hase values Zj and
I;v from Eqs. ( 14.36) and (6.65b).
6. For each pure species i eval uate f and <PT by Eq. (11.37).
7. An initial estimate of the vapor-phase composition is based on the assumption that both
the liquid and vapor phases are ideal solutions. Each fugacity coefficie nt is then given
by;= ;, and Eq. ( 14.53) can be written (K; = y;Jx;):
4>f
Yi =X; 4>j
Because these val ues are not constrained to sum to unity, they should be normalized to
yield the initial estimate of vapor-phase composition.
The essential step in the iterative process of Fig. 14.9 is evaluation of {fl and {Yl by
Eq. ( 14.50). This is a complex iterative step, consisti ng of a number of parts. For a specific
phase (liquid or vapor), application of Eq. (14.50) requires prior calculation of mixture prop-
enies Z, /3, and I and partial properties iii. The mixture properties come fro m sol ut ion of the
equation of state, Eq. (1 4.38) or ( 14.39), but th is requires knowledge of q 1 or qv as ca1cu1ated
from qf or q}) values by Eq. (14.58) or Eq. ( 14.60). Moreover, Eqs. (14.57) and (14 .59) fo r qf
and Cit include the pure-species properties zf and qf or Zj and qj, which must therefore be
determined first. The sequence of calculations is as follows:
1. For each pure species at the current value of P (initial estimate or adjusted value) deter-
mine fh by Eq. (14.33). Then for each pure species as a liquid at the current value of P
determine zf
and If by Eqs. (14.35) and (6.65b).
2. For the liquid mixture at known T and composition calculate {In y;} (assumed indepen-
dent of P). For th is liquid mixture at the current value of P, determine z', 11, q 1, and
{qf} by iterative solution of Eqs. (14.38), (6.65b), (14.57), and (14.58). The process is
implemented with an ini tial value, q 1 ~ L; x ;qf. This allows solution of Eqs. (14.38)
and (6.65b) fo r Z 1 and 11, which are used with Eq. ( 14.57) to yield values ofqf.
Equation
1
( 14.58) then provides a new value of q , and the process is repeated to convergence.
3. Evaluate the set fl by Eq. (14.50). Values of Z 1, {3 1, and I 1 for the liquid mixture are
known from the preceding item.
4. Repeal the calculations of item 2 for a liquid phase with the current vapor-phase com-
position (initial estimates or updated values) so as to determine q v and {ijn appropriate
to the vapor phase. This requires iterative solution of Eqs. ( 14.38), (6.65b), (14.59), and
(14.50) to evaluate zl.v, I 1v, qv and {qn.
5. Determine vapor-phase-mixture values for zv, 13v, and I u by Eqs. (14.39), (14.40), a nd
(6.65b) at the current vapor composition.
6. Evaluate the set n by Eq. (14.50), with z v, f3 v, and l u for the vapor-phase mixture
from the preceding item.
Values for {K;} now come from Eq. (14.53). These allow calculation of {K;x; }. The
constraint L; y; = 1 has not yet been imposed; most likely L; K;x; # 1, and Eq. (14.52) is
therefore not satisfied. However, a new set of y; values is given by the normalizing equation:
thus insuring that they; values for the next iteration do sum to unily.
This new set {y;} is used to reevaluate fn, { K;}, and {K;xi}. lf L; K;x; has changed,
{y;} is again calculated and the sequence of calculations is repeated. Iteration leads to a sta-
ble value of L; K; x;. If this su m is not unity, the assumed pressure is inconect, and must
be adjusted according to some rational scheme. When L; K; x; > I , P is too low~ when
L ; Ki x; < I, P is too high. The entire iterative procedure is then repeated with a new pres-
sure P. The last calculated values of y; are used for the initial estimate of {yi}. The process
continues until L ; K;x; = I.
Extrapolation of Data to Higher Temperatures

A vast store of liquid-(iliase exce~property data for binary systems aL Lemperatures near 30C
and somewhat higher is available in the literature. Effective use of these data to extend cE cor-
relations to higher temperatures i~criti cal to the procedure considered here. The key relations
are Eg . (1 1.95), written:
. (G)
d RT = - RT2dT
HE (const P , x)
and the excess-property analog of Eq. (2.21 ):
d H = C~dT (const P ,x)
Integration of Lhe first of these equations from To toT gives:
G
- =
(G) i T
- -
HE
--?ciT ( 14.61 )
RT RT To To RT-
Similarly, the second equati on may be inlegrated from T, to T:
HE = H(~ + { T C~ dT (14.62)
Ir,
act:)'
In addition,
dC~ = ( a! P.x dT
Integration from T2 toT yields:

Cp = Cp2
rr(ac;
+ J T2ar
c) P.x dT
Combining this equation with Eqs. ( 14.61) and ( 14.62) leads to:
GE ( G E) ( HE) ( T 1) T
1
RT = RT To - RT T, 7() - T
- CR~2 [1n !_
To
- (2:. - 1) r, J-
To T
.1 (14.63)
where J -
1T - I
r;, RT- r 1
? JTi T(aCE )
Tz
_P
oT P .x
dT dT dT
This general equation makes use of excess Gibbs-energy data at temperature To. excess en-
thalpy (heat-of-mixing) data at T 1, and excess heat-capacity data at T2
Evaluation of integral J requires information with respect to the temperature dependence
of C~. Because of the relative paucity of excess-heat-capacity data, the usual assumption is
that this property is constant, independent of T. In this event, in tegral J is zero, and the closer
To and T1 are toT , the less the infl uence of this assumption. When no information is available
wi th respect to C~. and excess enthalpy data are available at only a single temperature. the
excess heat capacity must be assumed zero. ln this case only the first two terms on the right
side of Eq. (14.63) are retained, and it more rapidly becomes imprecise as T increases.
Because the parameters of 2-parameter correlations of G data are directly related to
infinite-dilution values of the activity coefficients, our primary interest in Eq. ( 14.63) is its
application to binary systems at infini te dilution of one of the constituent species. For this
purpose, we divide Eq. (14.63) by the product XtX2. For c~ independent ofT (and thus with
J = 0), it then becomes:
- C% [In -T - ( -T - 1) -Tt ]
x1x2 R To To T
As shown in Sec. 12. I , GE ) = In y.oo

( X1X2RT x,=O
1
The preceding eq uation appl ied at infinite dilution of species i may therefore be written:
(
C ~ ) T - 1) -T1 ]
[ InT- - ( - (14.64)
X JX2 R x;=O To To T
Data for the ethanol( l )/water(2) binary system provide a specific iiJustration. At a base
1
temperature To of 363. 15 K (90C), the VLE data of Pemberton and Mash 1 yield accurate
values for infinite-dilution activity coefficients:
(In y~)r0 = 1.7720 and (In Yi)r0 = 0.9042

...
Correlation of the excess enthalpy data of J. A. Larkin 12 at I 1ooc yields the values:
and
11 R. C. Pemberton and C. J. Mash, Int. DATA Series, Se1: 8, vol. I, p. 66, 1978.
12 As reportedin Hears of Mixing Data Collection. Chemistry Data Series, vol. III, part I , pp. 457-459. DECHEMA.
Frankfurt/Main, 1984.
Correlations of the excess enthalpy for the temperature range from 50 to 11 0C lead to infinite-
dilution values of C~fxtxzR, which are nearly constant and equa] to
and
Equation (14.64) may be directl~applied with these data to estimate In yr and In yy> for
temperatures greater than 90C. The van Laar equations [Eqs. (12.17)] are appropriate here,
with parameters directly related to the infinite-dilution activity coefficients:
A't2 =In yf' and
These data allow prediction of VLE by an equation of state at 90C and at two higher
temperatures, 423. 15 and 473.15 K (150 and 200C), for which measured VLE data are given
by Barr-David and Dodge. 13 Pemberton and Mash report pure-species vapor pressures at 90C
for both ethanol and water, but the data of Barr-David and Dodge (at 150 and 200C) do
not include these values. They are therefore calculated from reliable correlations. Results of
calculations based on the Peng/Robinson equation of state are given in Table 14.4. Shown for
the three temperatures are values of the van Laar parameters A~ 2 and A~ I' the pure-species
vapor pressures P 1sat and P2sal, the equation of state parameters bi and qi, and root-mean-
square (RMS) deviations between computed and experimental values for P and Yt
Table 14.4: VLE Results for Etbanol(l)/Water(2)

p sat P. sat
T/C A~z A~l I 2 ql qz RMS RMS
bar bar ' %8 P OY I
90 1.7720 0.9042 1.5789 0.7012 12.0364 15.4551 0.29 *****

150 1.7356 0.7796 9.825 4.760 8.8905 12.2158 2.54 0.005
200 1.5204 0.600 1 29.861 15.547 7.0268 10.2080 1.40 0.005
bt = 54.0645 b2 = 18.9772
***** Vapor-phase compositions not measured.
The small value of RMS % 8 P shown for 90C indicates both the suitability of the van
Laar equation for correlation of the VLE data and the capability of the equation of state to
reproduce the data. A direct fit of these data with the van Laar equation by the gamma/phi
procedure yields RMS % 8P = 0.19. 14 The results at 150 and 200C are based only on vapor-
pressure data for the pure species and on mixture data at lower temperatures. The quality of
prediction is indicated by the P-x-y diagram of Fig. 14.1 J, which reflects the uncertainty of
the data as well.
13 F. H. Barr-David and B. F. Dodge. J. Chen1. Eng. Data, vol. 4, pp. 107-121, 1959.
14
As reported in Vapor-Liquid Equilibrium Data Collecrion, Chemistry Data Series, vol. I, part Ia, p. 145,
DECHEMA, Frankfurt/Main, 198 1.
14.3. Equilibrium and Stability 575
30
25
20
15
10
0 0.2 0.4 0.6 0.8
Figure 14.11: Pxy diagram for ethanol( I )/water(2). The lines represent predicted values; the points are
experimental values.
14.3 EQUILIBRIUM AND STABILITY
Consider a closed system containing an arbitrary number of species and comprised of an arbi-
trary number of phases in which the temperature and pressure are uniform (though not neces-
sarily constant). The system is initially in a nonequilibrium state with respect to mass transfer
between phases and chemical reaction. Changes which occur in the system are necessarily
irreversible, and they take the system ever closer to an equilibrium state. V.fe imagine that the
system js placed in surroundi ngs such that the system and surroundings are always in ther-
mal and mechanical equilibrium. Heat exchange and expansi9n work are then accomplished
reversibly. Under these circumstances the entropy change of the surroundings is:
_ dQsurr _ - dQ
dssurr - -
Tsurr T
The final term applies to the system, for which the heat transfer d Q has a sign opposite to that
of d Q surr , and the temperature of the system T replaces Tsurr. because both must have the same
value for reversible heat transfer. The second Jaw requires:
dS 1 + dSsurr > 0
576 CHAPTER I 4. Topics in Phase Equilibri::.
where S 1 is the total entropy of the system. Combination of these expression s yields. upoc
reanangem ent:
c/Q < T ciS' (14.65
Application of the fi!st law ptovJdes:
dV' =dQ +dW = dQ- PdV'

or dQ=dU '+PdV 1
Combinin g this equation with Eq. (14.65) gives:
dU 1 + PdV 1
< TdS 1
or Iu+
d I p d vI - T d S' ~0 I ( I-L6C
Because this relation involves properties only, it must be satisfied for changes in tar.e
of an.y closed system of uniform T and P , without restriction to the condition s of mechani~
and thennal reversibili ty assumed in its deri vation. The inequality applies to every incremem::a:.
change of the system between nonequilib lium states, and it dictates the direction of chang~
that leads toward equilibriu m. The equality holds for changes between equilibriu m state (:-e-
versible processes) . Thus Eq. (6. 1) is just a special case of Eq. ( 14.66).
Equation (14.66) is so general that applicatio n to practical problems is difficult; restricre.1
versions are much more useful. For example, by inspection:
(dU 1 )s,. v':- < 0

where the subscripts specify properties held constant. Similarly, for processes that occur:::
constan t V 1 and V 1 '
(c/S 1 )ut.Vt > 0
An isolated system is necessarily constraine d to constant internal energy and vo lume, and ~~
such a syste m it fo1lows directly fro m the second law that the last equation is valid.
Jf a process is restricted to occur at constant T and P , then Eq. ( 14.66) may be wrinea:
dU~.P +d(PV 1 )T,P- d(TS 1 )T.P < 0
or d(U 1 + PV 1 - TS 1 )T.P < 0

From the de finition of the Gibbs energy I Eq. (6.3)],
G1 = H' - T s' = V 1 + P V1 - T S1
Therefore , I (dG')r.P =::: 0 j

Of the possible specializa tions ofEq. (14.66), this is the most useful , because T and P, whi'"-
are easily measured and controlled , are more logical as constants than are oth er pairs of ,a::-
ables, such as U1 and V'.
Equation (14.67) indicates that all ineversibl e processes occurring at constant T and P
proceed in such a direction as to cause a decrease in the Gibbs energy of the system. Therefo:c
14.3. Equilibrium and Stability 577
The equilibrium state of a closed system is that state for which the
total Gibbs energy is a minimum with respect to all possible changes
at the given T and P.
Thls criterion of equilibriu m provides a general method for determina tion of equilibriu m states.
One w1ites an expression for G 1 as a function of the numbers of moles (mole numbers) of
the species in the several phases, and then finds the set of values for the mole numbers that
minimizes C' , subject to the constrain ts of mass conservat ion. This procedure can be applied to
p roblems o f phase, chemical -reaction , or combined phase and chemical -reaction equilibriu m;
it is most usefu l for complex equilibriu m problems , and is illustrated for chemical -reaction
equilibriu m in Sec. 13.9.
At the equilibrium state differential variations can occur in the system at constant T and
P without producin g any change in G1 This is the meaning of the equality in Eq. ( 14.67).
Thus another form of this criterion of equilibriu m is (See Fig. 13.1.):
(14.68)
To apply this equation, one develops an expre'ssion for dG' as a fu nction of the mole numbers
of the species in the various phases, and sets it equal to zero. The resulting equation along
with those represent ing the conserva tion of mass provide working equations for the solutio n of
equi lib1ium problems . Equation (14.68) leads directly to Eq. (11.6) for p hase equi librium and
it is applied to chemical -reaction equilibriu m in Sec. 13.3.
0 xf
Figure 14.12: Gibbs-energy

change of mixing. Curve l,
t.C complete miscibility ; curve If,
two phases between ex and {3.
Equation (J4.67) provides a crilerion that must be satisfied by any single phase chat is
stabLe with respect to the alternativ e that it spli t into two phases. It requires that the Gibbs
energy of an equ ilibrium state be the minimum value with respect to all possible changes at the
given T and P. Thus, e.g., when mixing of two liquids occurs at constant T and P , the total
Gibbs energy must decrease, because the mixed state must be the one of lower Gibbs energy
l
578 CHAPTER 14. Topics in Phase Equi libria
wi th respect to the unmixed state. As a result:
G' =nG < ~ n; G; from which
or (const T , P)
.,
According to the defi nition of Eq. (12.29), the quantity on the left is the Gibbs energy change
of mixing. Therefore, D.G < 0. Thus, as noted in Sec. 12.3, the Gibbs-energy change of
mixing must always be negative, and a plot of G vs. x1 for a binary system must appear
as shown by one of the curves of Fig. 14. 12. With respect to curve II, however, there is a
\. further considerati on. If, when mixing occurs, a system can achieve a lower value of the Gibbs
energy by forming two phases than by forming a single phase, then the system splits into
two phases. This is in fact the situation represented between points a and fJ on curve II of
Fig. 14.1 2, because the straight dashed line connecting points a and {3 represents the G that
would obtain for the range of states consisting of two phases of compositio ns xf and xf in
various proportions. Thus the solid curve shown between points a and {3 cannot represent
stable phases with respect to phase splitting. The equilibrium states between a and {3 consist
of rwo phases.
These considerati ons lead to the following criterion of stability for a single-phase binary
=
system for which b.G G - X i G 1 - x2G2:
At constant temperature and pressure, A G and its first and second
derivatives must be continuous functions of x 1, and the second de-
rivative must everywhere be positive.
d 2 A.G
Thus, ---=-2- > 0 (co'nst T , P )
dx 1
1
(const T , P )
Crv ,- ..: 0 ,;r ' '(14.69)
and
This requirement has a number of consequences. Equation (J2.30), ream1nged and written for
a binary ystem, becomes:
t::. G G~
- = x1 ln x1 + x2 ln x2 + -
RT RT
d (A. G / RT ) I I d(GE / R T)
from which
dx1
= ll XJ- 11 X2 + d
.x1
and
Hence, equi valent to Eq. ( 14.69), stability requires:
(const T, P ) (1 4_70)
I I I I ' ' :11 ,1111 i,ll llj. it! ,JIJir~lll !Liiii
14.3. Equilibrium and S tability 579
F urlher, for a binary mixture Eq. (12.6) is:

oE
-RT = x 1 In Y l + x2 ln Y2
d(G / RT ) d ln yt d ln y2
and - - - - = ln y1 -ln }'2 +x1 +x2 - -
dx1 dxt dx1
According to Eq. (12.7), the activity-coeffi c ie nt form of the G ibbs/Duhem equation, the last
two terms sum to zero; whence:
d(G EI RT )
- - - - = ln Yl - In Y2
dx 1
A second differentiation and a second application of the Gibbs/Duhem equation gives:
d ln y1
dx 2I x2 dx 1
This equation in combination with Eq. (1 4.70) y ields:
d In Yt , I
- - >-- (const T, P )
dx l XJ
which is yet another cond ition for stability. It is equivalent to Eq. (14.69), from wh ich it
ultimately derives. Other stability criteria fo llow directly, e.g.,
(const T , P )
The last three stability conditions can equally well be written for species 2; thus for either
species in a binary mixture:
d ln y; l
--> - - (const T, P) (14.71)
dx; x;
dt
-> 0 (const T, P ) (1 4.72) df,.l;
- >
0 (const T , P ) ( 14.73)
dx; dx;
Example 14.3
The stability criteria apply to a particular phase. However, there is nothing to preclude
their application to problems in phase equilibria, where the phase of interest (e.g., a
liquid mixture) is in equilibrium with another phase (e.g., a vapor mixture). Consider
binary isothermal vapor/liquid equilibria at pressures low enough that the vapor phase
may be considered an ideal-gas mixture . What are the implications of liquid-phase
stability to the features of isothermal P-x-y diagrams such as those in Fig. 10.8?
Solution 14.3
Focus initially on the liquid phase. By Eq. ( 14.72) appl ied to species I ,
.... - d/, =!1-: d Jn j,

- > 0
~ dx1 dx1
whence, becaus e j, cannot be negative,
dln/1
- - >0
d;q
Similar ly, wi th Eq. {14.72) applied to specie 2 and dx2 = -dx, :
dJ n j2 <
0
dx ,
Combi nation of the last two inequalities gives:

d In j, _ d In J2 >
0 (const T , P) (A)
dx 1 dx,
which is the basis fo r the first part of this analysis. Becaus e ju = y; P

for an
ideal-g as mixture and becaus e!/ = f/ for VLE, the left side of Eq. (A) may
be
written:
dlny,P di n"'n P din y , d ln y2

dx , dx 1 dx, dx1 dx1 dx1
I dy 1 I dy2 1 d y, 1 dy, l dy,

= --- --= --+--= --
Yl dx1 YIY2 dx1Y2 dx1 )1 1 dx 1 Y2 dx 1
dy, > 0 (B)

Thus, Eq. (A) yields:
dx 1
t
which is an essenti al feature of binary VLE. Note that, although P is not constan
tion is
for isother mal V LE, Eq. (A) is sti ll approx imately valid, becaus e its applica
to the liquid phase, for which properties are insensi tive to pressu re.
The next part of this analysis draw on the fugacit y form of the Gibbs/ Duhem
equalion. Eq. (12.4), applied again to the liquid phase:
d In j,
+x2
d ln j; = 0 (constT .P) ( 12.4)
x,
dx1 dx ,
e
Note again that the restriction here to constant P is of no signi ficance, becaus
of the insensitivity of liquid-phase properties to pressure. With j = y;
P for
low-pressure VLE,
. d ln y ,P . dln n P
,\I d + X2 dx 1 = 0
x,
14.4. Liquid I Liquid Equilibrium (LLE) 58 1
Manipulations similar to those used to develop Eq. (B) yield:

J dP (YJ - xi) dy1
(C)
P dx1 Yl Y2 dx1
Because by Eq. ( B ) dy , jdx, > 0 , Eq. (C) asse1ts that the sign of d P jdx 1 is the
same as the sign of the quantity Y1 - x,.
The last part of this analysis is based on simple mathematics, according to
which, at constant T ,
c/P c/ p j dXJ
-= (D)
dy1 dy,jdXJ
But by Eq. (B), dy 1 j c/x 1 > 0. Thus d P jdy, has the same sign as d P jdx 1
In summary, the stability requirement implies the following for VLE in binary
systems at constant temperature:
dP
-,and (y, - Xt) have the same sign
d y,
'
At an azeotrope, where Yl = x 1,
c/ P
-= 0 and
dx1
Although derived for conditions of low pressure, these results are of general va-
Jidity, as illustrated by the VLE data shown in Fig. 10.8.
14.4 LIQUID I LIQUID EQUILIBRIUM (LLE)
Ma ny pairs of chemical species, were they to mix to form a singl e liquid phase in a certai n com-
position range, would not sati sfy the stability criterion of Eq. (14.69). Suclh systems therefore
split in this composition range into two liquid phases of different compositions. If the phases
are at thermodynamic equilibrium, the phenomenon is an e~mpl e of liquid/liquid equilibrium
(LLE), which is important for industrial operations such as solvent extraction.
The equilibrium criteria for LLE are the same as for LE, na mely, uniformity of T, P,
and of the fugacity i for each chemical species throughout both phases. For LLE in a system
of N species at uniform T and P , we denote the liqu id phases by superscripts a and /3, and
write the equilibrium critelia as: ~
(i = 1, 2, ... , N)
With the introduction of activity coefficie nts, this becomes:
x~y~ +.a = x~yf3J.. 13

I I J I I I I
2 ~ If each pufe spt?cfes exists as' liquid at the system temperature, ft = J/ = f;; whence,
(i =l ,2, ... ,N) I (14.74)
In Eq. (14.74), activity coefficients rt andy( derive from the same function G EI RT ;
thus they are functionally identlfal, distinguished mathematically only by the mole fractions
to which they apply. For a liquid/liquid system containing N chemical species:
Yt = y;(xf,x2, .. -,xN-lT, P) (14.75a)
13 13 f3 1 T ' P) (14.75b)
Y; -- Yt (x /31 X2 ' x N-
According to Eqs. (14.74) and ( 14.75), N equilibrium equations can be written in 2N inten-
sive variables (T , P , and N - 1 independent mole fractions for each phase). Solution of
the equilibrium equations for LLE therefore requires prior specification of numerical values
for N of the intensive variables. This is in accord with the phase rule, Eq. (2.7), for which
F = 2- n + N = 2- 2 + N = N. The same result is obtained for VLE with no special
constrain ts on the equilibrium state.
In the general description of LLE, any number of species may be considered, and pres-
sure may be a significant variable. We treat here a simpler (but important) special case, that of
binary LLE either at constant pressure or at reduced temperatures low enough that the effect of
pressure on the activity coefficients may be ignored. With but one independent mole fraction
per phase, Eq. (14.74) gives:
(l4.76a) (1 - xf)yf = (l - xf)yf (14.76b)
where Y;cx = y; (xf, T) (14.77a) yf = y; (xf, T ) (14.77b)
With two equations and three variables (xf, xf,

and T), fixing one of the variables allows
solution of Eqs. (14.76) for the remaining two. Because In Yi. rather than y;, is a more natural
thermodynamic function , application of Eqs. (14.76) often proceeds from the rearrangements:
(14.78a) (14.78b)
For conditions of constant pressure, or when pressure effects are negligible, binary LLE
is conveniently displayed on a solubility diagram, a plot ofT vs. x1. Figure 14.13 shows binary
solubility diagrams of three types. The first, Fig. 14.1 3(a), shows curves (binodal curves) that
define an "island." They represent the compositions of coexisting phases: curve UAL for the
a phase (rich in species 2), and curve UBL for the f3 phase (rich in species 1). Equilibrium
compositions xf and xf at a particular Tare defined by the intersections of a horizontal tie line
with the binodal curves. Temperature Tr is a lower consolute temperature, or lower critical
solution temperature (LCST); temperature Tu is an upper consolute temperature, or upper
14.4. Liquid/Liquid Equilibrium (LLE) 583
u
Two liquid phases
I
I
I
I
Tt.. --t----
I L
I
I
I
I
I
I
I
0 xf ,.(J
'1 Oxf 0 xf x'f 1
XI
(a) (b) (c)
Figure 14.13: Three types of constant-pressure Jiquid/liquicl solubiLity diagram.
critical solution temperature (UCST). At temper~tures between TL and Tv, LLE is possible;
forT < TL and T > Tv, a single liquid phase is obtained for the full range of compositions.
The consolute points are limiting states of two-phase equilibrium for which all properties of
the two equil ibrium phases are identicaL
Actually, the behavior shown on Fig. 14.13(a) is infrequently observed; the LLE binodal
curves are often interrupted by curves for yet another phase transition. When they intersect the
freezing curve, only a UCST exists [Fig. 14.13(b)]; when they intersect the VLE bubblepoint
curve, only an LCST exists [Fig. 14.13(c)]; when they intersect both, no consolute point exists,
and yet another behavior is observed. 15
Thus it is apparent that real systems exhibit a diversity of LLE behavior. The thermo-
dynamic basis for calculation or correlation of LLE is an expression forGE j RT , from which
activity coefficients are derived. The suitability of a particular expression is determined by its
ability to accommodate the various featu res illustrated by Fig. 14.13. This is a severe test, be-
cause, unlike their role in Jow-press01:e VLE where they represent corrections to Raoult's law,
the activity coefficients here are the only thermodynamic contribution to an LLE calculation.
Example 14.4
Develop equations that apply to the limiting case of binary LLE for which the <X phase
is very dilute in species 1 and the f3 phase is very dilute in species 2.
15 A comprehensive treatment of LLE is given by J. M. Srensen, T. Magnussen, P. Rasmussen, and Aa. Fredenslund,
Fluid Phase Equilibria, vol. 2, pp. 297-309. 1979; vol. 3, pp. 47-82, 1979; vot. 4, pp. 15 1- 163, 1980. For a com-
pilation of data see W. Arll, M. E. A Macedo, P. Rasmussen, and J. M. Sli5rensen, Liquid-Liquid Equilibrium Data
Collection, Chemistry Data Series, vot. V, Parts 1-4, DECHEMA, Frankfurt/Main, J 979-1987.
Solution 14.4
For the case described, to a good approximation,
a ~ y oo yf:::::: I Y2/3 "' yoo
YI - I - 2
Substitution into the equ ilibrium equations, Eqs. (14.76), gives:
xfy~:::::: xf I - xf:::::: ( I - xf)yf'

...
and solution for the mole fractions yields the approximate expressions:
(A) (B)
Alternatively, solution for the infinite-dilution activ ity coefficients gives:
oo I - xf
(C) Yz = (D)
I -x 13
1
Equations ( A ) and ( B ) provide order-of- magnitude estimates of equilibrium com-

positions from two-parameter expressions for C I R T, where Y;00 is usually re-
lated to the parameters in a simple way. Equations (C) and ( D ) serve the opposite
function; they provide simple explicit expressions for Y;oc in relation to measur-
able equi librium compositions. Equations (C) and ( D ) show that positive devia-
tions fro m ideal-solution behavior promote LLE:
oc I
YJ :::::: -CI > and
X
I
....
The extreme example of binary LLE is that of cmnplete immiscibility of the
two species. W hen xf = x~ =
0, yf and y.f are unity. and Eqs. ( 14.76) therefore
require:
Y ICI -- y/3-
2 -
00
Strictly speaking, probabl y no two liquids are completely immiscible. However,

actual solubilities may be so small (e.g., fo r some hydrocarbon/water syste ms)
that the idealizations xf = x: =
0 provide suitable approximations for practical
calcul ations (Ex. 14 .9).
Example 14.5
The simplest expression for c 1R T capable of predicting LLE is:
ce
-R T = Ax1x2
Derive the equations resulting from application of this equation to l LE.
14.4. Liquid I Liquid Equilibrium (LLE) 585
Solution 14.5
The activity coefficients implied by the given equation are:
and ln y2 = Axf
Specializing these two expressions to the a and f3 phases a nd combining them
with Eqs. ( 14.78) gives:
x/1
[
A ( I - xa)
1
2
- (1 - xfi) 2
I
= In - 1
J xa (B)
I
[ ? R ?]
A (xa)- - (x"')- = In ----'-
)- xf (C)
1 1 1 -xa
I
Given a vaJ ue of parameter A, one finds equilibrium compositions xf and as xf

the solution to Eqs. (B) and (C).
Solubility curves implied by Eq. (A) are symmetrical about Xt = 0.5, because
substitution of the relation,
'
X~= I -xf (D)
into Eqs. (B) and (C) reduces them both to the same equation:
l -x,
A(l-2xt) = ln - - (E)
Xt
When A > 2, this equation has three real roots: Xt 1/2, Xt =

r , andx, 1- r , = =
where 0 < r < I /2. The latter two roots are the equilibrium compositions (xf
a nd x~), w hereas the first root is a trivial solution. For A < 2 onl y the trivial
solution exists; the value A = 2 corresponds to a consolute point, where the three
roots converge to the value 1/2. Table 14.5 shows values of A as calc ulated from
Eq. (E) for various values of xf (= I - x~). Note partic ularl y the sensitivity of
xf to small increases in A from its limiting value of 2.
The actual shape of a solubili ty curve is determined by the temperature de-
pendence of G E I R T. Assume the fo llowing T dependence of parameter A in
Eq. (A):
a
A = - + b - c In T ~ ( F)
T
where a, b, and care constants. By Eq. (11.95 ), this requires the excess enthalpy
H E to be linear in T , and the excess heat capacity C~ to be independent ofT:
H E = R(a + cT)x tX2 ~ (G)
c~
aH-E)
= (- = R cxt X2 ( H)
aT P.x
The excess e nthalpy and the temperature dependence of A are directly related.
Table 14.5: Liquid/liquid equilibrium compositions implied by Eq. (A)
A xa A xa
I I
.,; 2.0 0.5 2.4780 0.15
2.0067 0.45 2.7465 0.1
2.0273 0.4 3.2716 0.05
2 .0635 0.35 4.6889 0.01
2. 1182 0.3 5.3468 0.005
2. 1972 0.25 6.9206 0.001
2.3105 0.2 7.6080 0.0005
dA I
From Eq. (F), -=--(a+cT)
dT T2
Combination of this equation with Eq. (G) yields:
dA HE
-- ---~
dT X1X2RT 2
Thus d A/dT is negative for an endothermic system (positive HE) and positive for
an exothermic system (negative HE). A negative value of dA/dT at a consolute
point implies a UCST, because A decreases to 2.0 as T increases. Conversely,
a positive value implies an LCST, because A decreases to 2.0 as T decreases.
Hence a system described by Eqs. (A) and (F) exhibits a UCST if endothermic at
the consolute poin t and an LCST if exothermic at the consolute point. Equation
(F) written for a consolute point (A = 2) becomes: w
T lnT = a~- (2 -c b) T (!)
Depending on the values of a, b, and c, this equation has zero, one, or two tem-
perature roots.
Consider hypothetical binary systems described by Eqs. (A) and (F) and for
which LLE obtains in the temperature range 250 to 450 K. Setting c = 3.0 makes
the excess heat capacity positive, independent of T, for which by Eq. (H) the
maximum value (at .x1 = x2 = 0.5) is 6.24 J mol- 1 K- 1. For the first case, let
-975
A= + 22.4 - 3 In T
T
Here, Eq. (I) has two roots, corresponding to an LCST and a UCST:
TL = 272.9 and Tu = 391.2 K

Values of A are plotted vs. T in Fig. 14. J4(a) and the solubility curve [from
Eq. ()]is shown by Fig. 14.J4(b). This case- that of a closed solubility loop-
14.4. Liquid / Liquid Equilibrium (LLB) 587
is of the type shown by Fig. 14.1 2(a). It requires that H E change sign in the
temperature interval for which LLE obtains.
450
2.0
A 77K 350
1.9 .____ __,___ ___.___ _.....___ ____._,.

250 350 450
T/K
~) (b)
Figure 14.14: (a) A vs. T. (b) Solubility diagram for a binary system described by a I RT = AXtX2
with A =-915fT+ 22.4- 3Jn T. (H changes sign.)
As a second case, let
-540
A= T +2 1.1 -3 lnT
Here, Eq. (/) has only one root in the temperature range 250 to 450 K . It is a
UCST, Tu = 346.0 K, because Eq. (G) yie lds positive H E at this temperature.
Values of A and the corresponding solubility curve are given by Fig. 14.15.
Finally, let "
- 1,500
A= T + 23.9 - 3 ln T
This case is similar to the second, there being only one T (339.7 K) that solves
Eq. (/)for the temperature range considered. However, this is an LCST, because
H E is now negative. Values of A and the solubility cur.;'e are shown in Fig. 14. 16 .
..
Example 14.5 demonstrales in a "brute-force " way that LLE cannot be predicted by the
expression c I RT = AXJX2 for values of A < 2. If the goal is merely to determine under
what conditions LLE can occur, but not to fi nd the composition s of the coexisting phases, then
one may instead invoke the stability criteria of Sec. 14.3, and determine under what conditions
they are satisfied.
2.4
450
2.2
I I
A
2.0
T/K 350 I I
1.8
I I
1.6
250 350 450

250 L__,___ _ __.___J
0 1
I
T/K
(a) (b)
Figure 14.15: (a) A vs. T; (b) Solubility diagram for a binary system described by c / RT = AXJX2
with A= -540/T + 2 1.1 - 31n T. (HE is positive.)
450
T/K 350
250 1...----"""'---....J
250 350 450 0 1
T/K
(a) (IJ)
15 = A.q x2
Figure 14.16: (a) A vs. T; (b) Solubility diagram fo r a binary system described by G I RT
wi th A= - 1,500/ T + 23.9- 3 In T. (HE is negative.)
14.4. Liquid I Liquid Equilibrium (LLE) 589
Example 14.6
If GEl RT = Ax 1x2 for a liquid phase, show by stability analysis that LLE is predicted
for A > 2.
Solution 14.6
Application of inequality ( 14 .70) requires evaluation of the derivative:
d 2(c 1RT) _ d 2(Ax1x2) _
2
dx2 - dx 2 -- A
I I
I
Thus, stability requires: 2A < - -
X!X2
When X J = x2 = I12, the right side of this inequality has its minimum value of 4;
thus A < 2 yie lds stability of single-phase mixtures over the e ntire composition
range. Conversely, if A > 2, then binary mixtures described by I RT AXJX2 c =
form two liquid phases over some part of the composition range.
Example 14.7 '

Some expressions for G 1:: 1RT are incapable of representing LLE. An example is the
Wilson equation:
(12.18)
Show that the stability criteria are satisfied for all values of A 12 , A 21 , and x 1.
Solution 14.7
A n equivalent form of inequality ( 14.71) for species 1 is:
d ln (XJYJ) > O
( A)
dx1
For the Wilson equation, ln YJ is given by Eq. ( 12. I 9a). Addition of ln x 1 to both
sides of that equation yields:
X? ) ( A1 2 A21 )
ln (X!YJ)=- ln I +-=-A12 +x2 ~ -
(
XI XJ + 2 A 12 X2 + X I A2 1
? 2 ....
from which:
d Jn(xt Yf) = x2A i2 + A2 I
cl.Xt XJ (Xt + X2A 12)2 (X2 + Xf A 21 ) 2
All quantities on the right side of this equation are positi ve, and therefore Eq. (A)
x,
is satisfied fo r aU and for all nonzero J\ 12 and A2 1. 16 Thus inequality (14.71 )
is a lways satisfied, and LLE cannot be represented by the Wi lson equ ation.
16
Both A 12 and /\21 are positive definite. because A 12 = A21 = 0 yields infinite values for Yr' and y.f.
14.5 VAPOR/LIQUID/LIQUID EQUILIBRIUM (VLLE)
As noted in Sec. 14.4, the binodal curves representing LLE can intersect the VLE bubblepoint
curve. This gives rise-to the phenomenon of vapor/liquid/liquid equilibrium (VLLE). A binary
system of two liquid phases and one vapor phase in equilibrium has (by the phase rule) but
one degr~ee of freedom . For a given pressure, the temperature and the compositions of all three
phases are therefore fixed. On a temperature/composition diagram the points representing the
states of the three phases in equilibrium fall on a horizontal line at T *. In Fig. 14. 17, points
C and D represent th~ two liquid phases, and point E represents the vapor phase. If more
of either species is added to a system whose overall composition lies between points C and
D , and if the three-phase equilibrium pressure is maintained, the phase rule requires that the
temperature and the compositions of the phases be unchanged. However, the relative amounts
of the phases adjust themselves to reflect the change in overall composition of the system.
At temperatures above T* in Fig. I 4. 17, the system may be a single liquid phase, two
phases (liquid and vapor), or a single vapor phase, depending on the overall composition. In
region a the system is a single liquid, rich in species 2; in region f3 it is a single liquid, rich
in species I. In region a- V , Iiquid and vapor are in equilibrium. The states of the individual
phases fall on lines A C and A E. In region {3- V, liquid and vapor phases, described by lines
B D and BE, also exist at equilibrium. Finally, in the region designated V, the system is a
single vapor phase. Below the three-phase temperature T *, the system is entirely liquid, wid:
features described in Sec. 14.4~ this is the region of LLE.
Locus of
k

A"
A
T
T
A'
r
A
0 1
0
Figure 14.17: T xy diagram at constant P for Figure 14.18: T xy diagram for several
a binary system exhibiting YLLE. pressures.
When a vapor is cooled at constant pressure, it follows a path represented on Fig. 1-t ! -
by a vertical line. Several such lines are shown. If one starts at point k , the vapor first reache :~
dewpoint at line BE and then its bubblepoint at line B D, where condensation into single liqc._
phase f3 is complete. This is the same process that takes place when the species are complee__
miscible. If one starts at point n , no condensation of the vapor occurs until temperature ~
is reached. Then condensation occurs entirely at this temperature, producing the two liqc :-
phases represented by points C and D. If one stmts at an intermediate point m, the process _
14.5. Vapor/Liquid / Liquid Equilibrium (VLLE) 591
a combination of the two just described. After the dewpoint is reached, the vapor, tracing a
path along line BE , is in equilibrium with a liquid tracing a path along line B D. However, at
temperature T* the vapor phase is at point E. All remaining condensation therefore occurs at
this temperature, producing the two liquids of points C and D .
Figure 14.17 is drawn for a single constant pressure; equilibrium phase compositions,
and hence the locations of the lines, change with pressure, but the general nature of the diagram
is the same over a range of pressures. For most systems the species become more soluble in one
another as the temperature increases, as indicated by lines CG and DH of Fig. 14.17. If th is
diagram is drawn for successively higher pressures, the corresponding three-phase equilibrium
temperatwes increase, and lines C G and D H extend further and fu rther until they meet at the
liquid/liquid consolute point M , as shown by Fig. 14.18.
As the pressure increases, line CD becomes shorter and shorter (indicated in Fig. 14.18
by lines C' D' and C" D"), until at point M it diminishes to a differential length. For still
higher pressures ( P4) the temperature is above the ciitical-solution temperature, and there is
but a single liquid phase. The diagram then represents two-phase VLE, and it has the form of
Fig. 10.9(d), exhibiting a minimum-boiling azeotrope.
For an intermediate range of pressures, the vapor phase in equilibrium with the two liquid
phases has a composition that does not lie between the compos itions of the two liquids. This
is illustrated in Fig. 14.18 by the curves for ? 3, which terminate at A" and B". The vapor in
equilibrium with the two liquids at C" and D" is at point F. In addition the system exhibits an
azeotrope, as indicated at point J .
Not all systems behave as described in the preceding paragraphs. Sometimes the upper
critical-solution temperature is never attained, because a vapor/liquid critical temperature is
reached first. In other cases the liquid solubilities decrease with an increase in temperature. In
this event a lower critical-solu tion temperature exists, unless solid phases appear first. There
17
are also systems which exhibit both upper and lower critical-solution temperatures.
Figure 14.19 is the phase diagram drawn at constant T corresponding to the constant-?
diagram of Fig. 14.17. On it we identify the three-phase-equilibri um pressure as P *, the three-
phase-equilibrium vapor composition as yf, and the compositions of the two liquid phases that
contribute to the vapor/liquid/liquid equilibrium state as xf and xf.
T he phase boundaries
separating the three liquid-phase regions are nearly vertical, because pressure has only a weak
influence on liquid solubilities.
The compositions of the vapor and liquid phases in equilibrium for partially "!iscible
systems are calculated in the same way as for miscible systems. In the regions where a single
liquid is in equilibrium with its vapor, the general nature of;;<ig. 14.19 is not different in any
essential way from that of Fig. 10.8(d). Because limited miscibility implies highl y nonideal
behavior, any general assumption of liquid-phase ideality is excluded. Even a combination of
Henry's law, valid for a species at infinite dilution, and Raoult's law, valid for a species as it ap-
proaches purity, is not very useful, because each approximates actual behavior for only a very
small composition range. Thus a is large, and its composition dependence is often not ad-
equately represented by simple eq uations. Nevertheless, the NRTL and UNIQUAC equations
and the UNIFAC method (App. H) provide suitable correlations for activity coefficients.
17 For a comprehensive d iscussion of binary fluid-phase behavior. see J; S. Rowlinson and F. L. Swinton, Liquids
and Uquid Mixtures, 3d ed., Butterworth Scientific, London, 1982.
592 CHAPTER 14. Topics in Phase Eq uili bha
Const T
.(J
.\ 1
()(-{3
p
1.,.
p
Figure 14.19: Pxy diagram at
cons tant T for two partially miscible
liquids.
Example 14.8
Careful equilibrium measurements for the diethyl ether(1 )/water(2) system at sscc
have been reported. 18 Discuss the correlation and behavior of the phase-equilibrium
data for this system.
Solution 14.8
The P-x -y behavior of this system is shown by Fig. 14.20, where the very rapid
rise in pressure wi th increasing liquid-ph..ase ether concentration in the dilute-ether
region is apparent. The three-phase pressure, P* = I 04.6 kPa, is reached at an
ether mole fraction of only 0.011 7. Here, .Y I also increases very rapidly to its
three-phase value of yf = 0.946. l n the dilute-water region, on the other hand,
rates of change are quite small. as shown to an expanded scale in Fig. 14.20(b).
T he curves in Fig. 14.20 provide an excellent correlation of the VLE data.
They result from BUBL P calculations carried out as indicated in Fig. 14.1. The
excess Gibbs energy and activity coefficients are here expressed as functi ons of
liquid-phase composition by a 4-parameter modified Margules equation [see Eqs.
(12.9) and ( 12. 10)1:
?[
1n Y2 =X( A21 dQ, ]
+ 2(A 12- A2 1)x2- Q + x2 dx
18 M. A. Villamanan, A. J. Allawi, and H. C. Van Ness. .1. Chem. Eng. Data. vol. 29. pp. 431-435, 1984.
14.5. Vapor/ Liquid /Liquid Equilibrium (VLLE) 593
120 ((l'
p
1 x1
-.;P
1
p
100
-
104.8
p*
80 I
Scale
change
co co
Q.. Q..
.::.!
Q::-
60 .::.!
x1 Q::-
104.0
40
,..
20
,.
1
103.2
0.8 0.9' 1.0 0.92 1

0 0.01 0.02 0.7
(a) (b)
h region.
Figure 14.20: (a) P xy diagram at 35C for diethy1 ether( 1)/water(2); (b) Detail of ether-ric
O!t2X ta2!X2 _ _ O!t20!2 J(0!2 JX~

_dQ - CJ2Xf)
Q= -- - - - + 2
at2XJ + 0!2JX2 (O!J2XJ 0!2 JX2)
A21 = 3.3562 9 At 2 = 4.62424 0!}2 = 3.78608 a21 = 1.81775
The BUBL P calcula tions also require values of 2, which come from
Eqs. (14.7) with viriaJ coefficients:
= -567 cm3 mol-

1
Brr = -996 8 22 =- 1245 81 2
~
In additio n, the vapor pressur es of the pure species at 35C are:
P 1sat = 103.264 P 2sat = 5.633 kPa
The high degree of nonideality of the liquid phase is indicat ed by the values
of the activity coeffic ients of the dilute species, which range for diethyJ ether from
Yr = 81 .8 atxf = 0.0117 to YF = 101.9 atx1 = 0 and for water from Y2 = 19.8
at x~ = 0.9500 to y200 = 28.7 at x 1 = l.
594 CHAPTER I 4. Topics in Phase Equilibria
Thermodynamic insight into the phenomenon of low-pressure YLLE is provided by

the modified Raou lt's-law expression, Eq. (10.5). For temperature T and the three-phase-
equiljbrium pressure P *, Eq. (10.5) has a double application (See Fig. 14.19):
x~y.a p .sat = y"! p * and x~y.P p, sat = )P~ p *

I I I I I I I I
Implicit in these equations is the LLE requirement of Eq. (14.74). Thus four equations can be
written for a binary system:
xaya p sat_ y* p * (A) '({3 y{J p Sal _ y* p * (B )

I I I - I " I I I - I
xaya p sal _ y* p * (C) x/3 y/3 p2sat _ y* p* (D )

2 2 2 - 2 2 2 - 2
All of these equations are correct, but two of them are preferred over the others. Consider the
expressions for Y7 P *:
X aya
p sat _ .... tJY/3 p sat_ y*P*
I I I - "" 1 I I - I
For the case of two species that approach complete immiscibility (Ex. 14.4),
xf ~ 0 x/JI -+ I
Thus,
T his equation implies that rr
-+ CXJ; a similar derivation shows that -+ oo. Thus Eqs. ( B r-r
and (C), which include neither yf nor yf, are chosen as the more useful expressions. The~
may be added to give the three-phase pressure:
p * _ x{Jyfi p sal.. + xaya p sat (14.79
-Ill ' 222
In addition, the three-phase vapor composition is given by Eq. (B):

x/3 yfi p sat
yf = I I I (l..t.
P*
For the diethyl ether( l)/water(2) system at 35C (Ex. 14.8), the correlation for oE f R T pro-
vides the values:
y 1fJ -- .1 .0095 yf = 1.0013
T hese allow calculation of P* and yj by Eqs. (14.79) and (14.80):
P* = (0.9500)( 1.0095)(.103.264) + (0.9883)(1.0013)(5.633) = 104.6 kPa
and
yf = (0.9500) ( 1.0095)( 103.264) = 0.946
104.6
Although no two liquids are totall y immiscible, this condition is so closely approu~
in some instances that the assumption of complete immiscibility does not lead to app:e...
ble error. The phase characteristics of an immiscible system are iJiustrated by the ter:-. -
ature/composition diagram of Fig. 14.21 (a). This diagram is a special case of Fig. :- -
14.5. Vapor I Liquid I Liquid Equilibrium (VLLE) 595
Const P Const T
B
Ill

p ~---------r--------------~
T p
,.
B
0 1 0 1
' x,, >'1
(a) (b)
Figure 14.21: Binary system of immjscible liquids. (a) T xy diagram; (b) P xy d iagram.
wherein phase a is pure species 2 and phase f3 is pure species 1. Thus lines ACG and BDH
of Fig. 14.17 become in Fig. 14.2 L(a) vertical lines at x1 =
0 and x1 = l.
In region I, vapor phases with compositions represented by line BE are in equilibrium
with pure liquid L. Similarly, in region II, vapor phases whose compositions lie along line
A E are in equilibrium with pure liquid 2. Liquid/liquid equilibrium exists in region III, where
the two phases are pure liquids 1 and 2. If one cools a vapor mixture starting at point m,
the constant-composition path is represented by the vertical line shown in the figure. At the
dewpoint, where this line crosses line BE , pure l iquid J begins to condense. Further reduction
in temperature toward T* causes continued condensation of pure liquid L; the vapor-phase
composition progresses along line BE until it reaches point E. Here, the remaining vapor
condenses at temperature T*, producing two liquid phases, ont"of pure species 1 and the other
of pure species 2. A sirrlilar process, caiTied out to the left of point E, is the same, except that
pure liquid 2 condenses initially. The constant-temperature phase diagram for an immiscible
system is represented by Fig. 14.2l(b).
Numerical calculations for immiscible systems are particularl y simple, because of the
following identities:
x2 = L Yi = l
The three-phase-equilibrium pressure P* as given by Eq. (14.79) is therefore:
Substitution of this equation and xf = yf = 1 into Eq. (14.80) gives:

p Sal
y* - I
I - p sat
I
+ p2sat
For region T where vapor is in equilibrium with pure liquid l, Eq. ( J 0.5) becomes:
or YtCI) =
p sat
+
Similarly, for region TI where vapor is in equilibrium with pure liquid 2,
p sal
Y2 (1I)P = [1 - Yt (Il)]P = P 2sal or Yl (ll) = 1 - _L_
p
Example 14.9
Prepare a table of temperature/composition data for the benzene(1 )/water(2) system
at a pressure of 101.33 kPa (1 atm) from the vapor-pressure data in the accompany-
ing table.
Solution 14.9
Assume that benzene and water are completely immiscibl e as liquids. Then the
three-pha se equilibrium temperature t* is estimated as:
P (t*) = P1sat + P2531 = 10 I .33 kPa
t/ C p sal/ kPa p 2sat/ kPa p sat

I
+ P.2sat
I
60 52.22 19.92 72.14

70 73.47 3 1.16 104.63
75 86.40 38.55 J24.95
80 101.05 47.36 148.41
80.1 101.33 47.56 148.89
90 136.14 70. 1 1 206.25
100.0 180.04 101.33 28 ] .37
The last column of the preceding table of vapor pressures shows that t* lies
between 60 and 70C , and interpolation yields t* = 69 .0C. At this temperatu re,
=
again by interpolation: P 1sat(t*) 71.31 kPa. Thus,
p sat
y* - 7 1.31 0 0
I
+ p sat - - = .7 4
I - p sat 101.33
J 2
14.6. Solid/Liquid Equilibrium (SLE) 597
For the two regions of vapor/liquid eq uilibrium,

p sat p sal
)'I (I) = _!_ = __:1_
p 101.33
p sat
P2sat ?
and Vt (II) = I - - = I - l 01.33
-
. p
Applicatio n of these equations for a number of temperatu res gives the resulls sum-
marized in the table that follows.
t/C Yl (II) Yt (I)
100.0 0.000
90 0.308
80.1 0.531 1.000
80 0.533 0.997
75 0.620 0.853
70 0.693 0.725
69.0 0.704 0.704
..
-
14.6 SOLID I LIQUID EQUILIBRIUM (SLE)
Phase behavior involving Lhe solid and liquid states is the basis for separation processes (e.g.,
crystallization) in chemical and materials eng ineering. Indeed, a wide variety of binary phase
behavior is observed for systems exhibiting solid/solid . solid/liquid, and solid/solid/liquid equi-
libria. We develop here a rigorous formu lation of solid/liqui d eq uilibrium (SLE), and present
as applicatio ns analyses of two limiting classes of behavior. Comprehe nsive treatments can be
fou nd e lsewhere. 19
The basis for representing SLE is:
-1/=l t (all i)
A
where uniformity ofT and P is understood. As wilh LLE, each f; is eliminated in favor of an
activity coefficient. Thus, r
I -r:l s -r:s (all i)
- Xj Y; J i = Zi Y; J i
where x; and z; are, respectively, the mole fractions of species i in the liquid and solid solu-
tions. Equ ivalently,
(all i) (t4.8 1)
t9see, e.g.. R. T. DeHoff, 11rermodyncunic:s in Materials Science, chaps. 9 and 10, McG,aw-Hill , New York, 1993.
A data compilation is given by H. Knapp. M. Teller. and R. Langhorst, Solid-Liquid Equilibrium Data Collection,
Chemistry Data Series. vol. VII I. DECHEMA , Frankfurt/M ain, 1987.
..
where 1/1; = !,.S I J/ (14.82)
The right side of this,equation, defining l/J; as the ratio of fugacities at the T and P of
the system, may be written in expanded form:
,_ f/ (T , /{J. f/ (T, P) f/ (Tm;, P) J/ (Tm ;, P)

J/ (T, P) - f/ (Ttn.;, P) J/ (T,n;, P) J/ (T , P)
where Tm; is the melting temperature ("freezing point") of pure species i, i.e., the temperature
at which pure-species SLE obtains. Thus the second ratio on the right side is unity because
J/ = f/ at the melting point of pure species i. Hence,
1/1 _
1
f/ (T, P ) ~ f/ (Tm;, P) (14.83)
- f/(~ni' P) J/(T , P)
According to Eq. (14.83), evaluation of 1/Ji requires expressions for the effect of temper-
ature on fugacity. By Eq. (11.33) , with <Pi = f; I P ,
j; Gf G1R.
ln - = - In ).r:.I = -RT + ln P
p RT
Whence, 8ln/;) =[8(GfiRT)] ___

H_/
( aT p BT P- RT2
where the second equality comes from Eq. Q1.58). Integration of this equation for a phase
from Ttn; toT gives:
j;(T, P) = exp { T - H/ dT ( 14 .84)
.f;(T,n;.P) Jr
111 I
RT2
Equation (14.84) is applied separately to the solid and liquid phases. The resulting expressions
are substituted into Eq. (14.83), which is then reduced by the identity:
-(H/s - H/ J) = -[(Hf - H~ 8 )- (Hj - H~g)] = Hj - Hf
This yields the exact expression:
H!- H:~
i
T
1/1; = exp
1 1
dT (14.85)
T,,i RT2
Evaluation of the integral proceeds as follows :
and
14.6. Solid/Liquid Equilibrium (SLE) 599
Hence, for a phase,
H;(T) = H; (Tm;) + Cp;(~n)(T- ~~~) +

( r { T ( aCp.)
ar' ciT dT (14.86)
11T,"i 11Tm; p
Applying Eq. (14.86) separately to the solid and liquid phases and performing the integration
required by Eq. (14.85) yields:
TH!- H~
= _t;,._H.:. .,_/' ( T - Tm; )
!,
'0n I
I
RT2
I dT
RTm; T
+
/),. csl
R
p.
I
[
ln _!_-
I;n;
(T -T Tm;)] +I (14.87)
where integral I is defined by:
1 = !, T-l- !,T
' !,T[a(C~. - Cf,.) ] I I dT dT dT
1;"; RT2 0u; T,; 8T P
In Eq. (14.87), t;,.Hl' is the e nthalpy change of melti ng ("heat of fusion") and .6-C~.I is the
heat-capacity change of melting. Both quantities are evaluated at the melting temperature T,111
Equations (14.81), (14.85), and (14.87) provide a formal basis for solution of problems
in solid/liquid equilibria. The full rigor of Eq. (14.87) is rarely maintained. For purposes of
development, pressure has been canied through as a thermodynamic variable. However, its
effect is rarely included in engineering applications. The triple integral represented by I is a
second-order contribution, and is normally neglected. The heat-capacity change of melting can
be signifi cant, but is not always available; moreover, inclusion of the term involvi ng .6-C Pl'
1
adds little to a qualitative understanding of SLE. With the assumptions that I and t;,.C pf are
negligible, Eqs. ( 14.85) and ( 14.87) together yield:
.6. H/' ( T - T, 11;

1/f; = exp --'--
)
(14.88)
RTm; T
With 1/f; given by Eq. (14.88), all that is req uired for formulating an SLE problem is a set
of statements about the temperature and composition .d'ependence of the activity coefficients
yj and yj'. In the general case, this requires algebraic ex,2ressions __for G E (T, composition) for
both liquid and solid sol utions. Consider two limiting special cases:
I. Assume ideal-solution behavior for both phases, i.e., let yj = l and Y/ = 1 for all T
and compositions.
II. Assume ideal-solu tion behavior for the liquid phase (y/ = 1), and complete immiscibil-
ity for all species in the solid state (i.e., set z; y/ = l ).
These two cases, restricted to binary systems, are considered in the following.
easel
The two equilibr ium equation s which follow from Eq. (14.8 1) are:
I X ) = <Jlf/J ( 14.89a) I x 2 = <2lf/2 ' (14.89b)
where lfrt and 1/12 are given by Eq. (14.88) with i = 1, 2. Because x2 = I -Xt and Z2 I -z t. =
Eqs. (14.89) can be solved...fo give x 1 and ZI as explicit function s of the lfr; s and thus ofT:
1 -1/12
(14.90) Zt = (14.91)
1/11 - 1/12
with
D. H~ ( T - ~n., )
1
' (14.92b)
(14.92a) 1./f2 = exp RT. T -
m2
Inspecti on of these results verifies that x; = z ; = 1 forT = Tm ; Moreov er, analysi

shows that both x; and z; vary monoton ically with T . Hence systems described by Eqs. (14.89 l
exhibi t lens-sha ped SLE diagrams, as shown on Fig. 14.22(a), where the upper line is the
freezing c urve and the lowe r line is the melting c urve. The liquid-soluti on region lies abme
the freezi ng c urve, and the solid-so lution region lies below the melting curve. Example s of
system s exhibitin g d iagrams of this type range from nitrogen /carbon monoxid e at low temper-
ature to copper/n ickel at hi gh tempera ture. Comparison of this fi gure with Fig. ( I 0.12) sugge ~
that Case I-SLE behavio r is analogo us to }\aoult's -law behavio r for VLE. Compar ison of the
assumpt ions leading to Eqs. (1 4 .89) and ( I 0. 1) confirms the analogy. As with Raoult's ]a\ .
Eq. (14.89) rarely describe s the behavio r of actual systems . Howeve r, it is an importa nt limi -
ing case. and serves as a standard agai nst which observed SLE can be compare d.
CaseD
The two equilibri um equation s resulting from Eq. (14.81) are here:
I XJ= lf/J ( 14.93) I X2 = lf/2 ( 14.94)
where 1/ft and 1fr2 are given as functions solely of tempera ture by Eqs. ( 14.92). Thus XI an!!
x2 are also solely fu nctions of tempera ture, and Eqs. (14.93) and (14.94) can
apply simultan-=-
ously only for the particula r tempera ture where 1/11 + 1./f2 I and hence Xt + x2
= l. Tn =
is the eutectic tempera ture Te. Thus, three distinct equilibr ium situations exist: one wh.:~
Eq. (14.93 ) alone applies, one where Eq. (14.94) alone appl ies, and the special case wh.:-~
they apply together at Te.
Equatio n (14.93) alone applies. By this equation and Eq. (14.92a),

1
D. H f ( T - T111 1 )
Xt = exp -~
RTm 1 T
14.6. Solid/ Liquid Equilibrium (SLE) 601
This equation is valid only from T = Tm 1, where XI = l, toT = Te, where XI = X!e,
x,
the eutectic composition. (Note that = 0 only forT = 0.) Equation (14.95) therefore
applies where a liquid solution is in equilibrium with pure species 1 as a solid phase. This
is represented by region I on Fig. l4.22(b), where liquid solutions with compositions x 1
given by line BE are in equilibrium with pure solid I .
B Tm,
Tm, Liquid
Liquid
II
Solid
~~c----~r---------------~0
t h
I i \
I i \
i
Solid 1/Solid 2
0
' 1 0 1
(a) (b)
Figure 14.22: Tx z diagrams.(a) Case I, ideal liquid and solid solutions; (b) Case II, ideal liquid
solution ; immiscible solids.
Equation (14.94) alone applies. By this equation and Eq. (14.92b), with x2 = I - XJ:
1
6H?_ ( T- T,, 2 )
x 1 = 1 -exp -~ (14.96)
RT,n 2 T
This equation is valid only from T = T,112 , where X t = 0, toT= Te, where x 1 = X!e.
the eutectic composition. Equation ( 14.96) therefore applies where a liquid solution is
in equilibrium with pure species 2 as a solid phase. This is represented by region II
on Fig. 14.22(b), where liquid solutions with compositions x 1 given by lineAE are in
equilibrium with pure solid 2. ?
Equations ( 14.93) and ( 14.94) apply simultaneously, and are set equal because they must
both give the eutectic composition Xle The resulting expression,
1 1
exp 6Ht (T- T 1111 )
= 1- exp --=- (T - T,n 2 )
6Hi (14.97)
RTm1 T RT,n2 T
is satisfied for the single temperature T = Te. Substitution of Te into either Eq. (14.~- -.
or (14.96) yields the eutectic composition. Coordinates Te and Xt e define a eutettic
(
state, a special state of three-p hase equilibri um, lying along line CED on Fig. 14.22(b ),
a
for which liquid of compo sition XJe coexists with pure soJid 1 and pure solid 2. This is
state of solid/so lid/liquid equ.Iibrium. At temperatures below Te the two p ure immiscible
solids coexist.
for
Figure I4.22(b ), the phase djagram for Cac;e II, is an exact analog of Fig. J4.2 1(a)
are
immisci ble liquids, becaus e the assump tions upon which its generat ing equations are based
analog s of the corresp onding VLLE assump tions.
14.7 SOLID/VAPOR EQUILIBRIUM (SVE) J

rium for
At temper atures below its triple poi nt, a pure solid can vaporize. Solid/v apor equjlib
); here,
a pure species is represe nted on a P T diagram by the sublimation curve (see Fig. 3.1
apor)
as for VLE, the equilib rium pressur e for a particu lar temper ature is called the (solid/v
saturat ion pressur e P sat.
We consider in this section the equilibrium of a p ure solid (species 1) with a binary
le in
vapor mixture contain ing species 1 and a second species (specie s 2), assume d insolub
2 is
the solid phase. Because it is usually the major constitu ent of the vapor phase, specjes
its mole
conven tionally called the solvent species. Hence species J is the solute species, and
ure
fraction Yl in the vapor phase is its solubility in the solvent. The goal is to develop a proced
for compu ting Yl as a fu nction ofT and P for vapor solvents.
2,
Only one phase-e quilibrium equatio n can be written for this system, becaus e species
1. Thus,
by assumption, does not distribute between the two phases . The solid is pure specjes
s A
- fl = Jt
Equation (J 1.44) fo r a pure liquid is, with minor change of notation, appropriate here:
-' I
rs = sat p sat exp vs(PRT_ p sat)
I I
l I
where Pt"1t is the solid/vapor saturation pressur e at temperature T and V{ is the molar volume
of the soJ id. For the vapor phase, by Eq. (J 1.52),
I

Combi ning the three preceding equatio ns and solving fo r Yl gives:

p sat
I (14.98)
Yl = -p- F,
sat
1
vs1 (P _ p sat)
1
where FI = - -exp
A RT
( 14.99)
1
Functio n F1 reflects vapor-phase non idealities through fat and 1 and the effect of pres-
ntJy low
sure on the fugacity of the solid through the expone ntial Poynting factor. For sufficie
14. 7. Solid! Vapor Equilibrium (SVE) 603
pressures, both effects are negligible, in which case F, ~ I and Yl ~ P,sat; P. At moderate
and high pressures, vapor-phase nonidealities become important, and for very high pressures
even the Poynting factor cannot be ignored. Because F1 is generally observed to be greater
than unity, it is sometimes called an "enhancement factor," because according to Eq. (14.98) it
leads to a solid solubility greater than would obtain in the absence of these pressure-induced
effects.
Estimation of Solid Solubility at High Pressure

Solubilities at temperatures and pressures above the critical values of the solvent have impor-
tant applications for supercritical separation processes. Examples are extraction of caffeine
from coffee beans and separation of asphaltenes from heavy petroleum fractions. For a typical
solid/vapor equilibrium (SVE) problem, the solid/vapor saturation pressure P 1sat is very small,
and the saturated vapor is for practical purposes an ideal gas. Hence ~at for pure solute vapor
at this pressure is close to unity. Moreover, except for very low values of the system pressure
P, the sol id solubility YI is small, and , can be approximated by f, the vapor-phase fugac-
ily coefficient of the solute at infinite dilution. Finally, because P 1sal is very s mall, the pressure
difference P- P 1sat in the Poynting factor is nearly equal to Pat any pressure where this factor
is important. With these usually reasonable approximations, Eq. (14.99) red uces to:
' I
F1 =-A- exp --
PVt
(14.1 00)
f RT
an expression suitable for enginee1ing applications. In this equation, P,sat and V{ arc pure-
species properties, found in a handbook or estimated from a suitable correlation. Quantity f,
on the other hand, must be computed from a P VT equation of state- one suitable for vapor
mixtures at high pressures.
Cubic eq uations of state, such as the Soave/Redlich/Kwong (SRK) and Peng!Robinson A
(PR) equations, are usuall y satisfactory for this kind of calculation. Equation (14.50) for;,
developed in Sec. 14.2, is applicable here, but with a slightly modified combining rule for
interaction parameter aij used in calculation of q;. Thus, Eq. (14.44) is replaced by:
(14.101)
The additional binary interaction parameter lij must be found for each ij pair (i f:. j) from
experimental data. By convention, lij = 1ji and l;; = l jj = 0.
Partial parameter a; is found by application ofEq. (14.45) with a from Eq. (14.43):
,.
a;= -a +2 h Yjaji
j
Substitution of this expression into Eq. (14.51) yields:
-
2 ~J Yjaj; b( )
q; = q -- (14.102)
( a b
0
--
SR~K~E:O:S~,w
o~ ith-1~,2~=-_____
a,~ ~ro~
\
$; from SRK EOS, with 112 == 0.088
Ideal solubility
__ + Poynting effect
--------------------
10- ~----~~~~------~----~----~------~
6
0 200 300
' P/bar
F igure 14.23: Solubility of naphthalene( I) in carbon dioxide(2) at 35 C. Circles are data. Curves are
computed from Eqs. ( 14.98) and ( 14.100) under various assumptions. "
where band q are given by Eqs. (14.42) and (14.41).

For species I at infinite dilution in a binary system, the " mixture" is pure species 2. In
this event, Eqs. ( l4.50), (14.10 1), and (14. 102) yield an expression for F:
(14. 103)
where by Eq. (6.65b),
Equation (14.103) is used in conjunction with Eqs. (14.33) and (14.36), which provide
values of fh and Z2 correspondin g to a particular T and P.
As an example, consider the calculation of the solubility of naphthalene (!) in carbon
dioxide(2) at 35C (308.15 K) and pressures up to 300 bar. Strictly, th is is not soli d/vapor
14. 7. Solid/ Vapor Equiliblium (SVE) 605
equilibrium, because the critical temperature of C02 is 31. 1C. However, tbe development of
this section remains valid.
The basis is Eg. (14. I00), with f determined from Eq. ( 14.1 03) written for the SRK
equation of state. For solid naphthalene at 35C,
P1sat = 2.9 x 10- 4 bar and
Equations ( 14.103) and (14.36) reduce to the SRK expressions on assignment of the values
a = l and E = 0. Evaluation of parameters 01, a2, b t, and b2 requires values for Tc. Pc, and
(JJ, which are found in App. B. Thus Eqs. (l4.31) and (l4.32) give:
02 = 3.664 X I 06 bar cm 6 mol-2
0?
By Eq. (14.34), q? =
-
-
b2RT
= 4.819
With these values, Eqs. (14.103), ( 14.33), and ( 14.36) become:
Aoo ' Z2 + fh
In 1 = 4.485(22 - l) - ln(Z2 - f3z) + [21.6 L - 43.02(1 -/12)] In (A)
22
f32 = 1.1585 x l0- 3P . (P / bar) (B)
(C)
To find f for a given l12 and P, one first evaluates f32 by Eq. (B) and solves Eq. (C) for
Z2. Substitution of these values into Eq. ( A) gives f. For example, for P = 200 bar and
l12 = 0, Eq. (B) gives fh = 0.2317 and sol ution of Eq. (C) yields Z2 = 0.4426. By Eq. (A),
f' = 4.74 x 10- 5 . This small value leads by Eq. (14.1 00) to a large enhancement factor Ft.
Tsekhanskaya et al. 20 report solubility data for naphthalene in carbon dioxide at 35C
and high pressures, given as circles on Fig. J4.23 . The sharp increase in solubility a& the
pressure approaches the critical value (73.83 bar for C02) is typical of supercritical systems.
Shown for comparison are the results of calculations based on Eqs. ( 14.98) and ( 14.1 00), under
various assumptions. The lowest curve shows the "ideal solubil ity" P 1sar; P , for which the
enhancement factor F 1 is unity. The dashed<"curve incorporates the Poynti ng effect, which is
significant at the higher pressures. The topmost curve includes the Poy nting effect as well as
r, esti mated from Eq. (14.103) with SRK constants and with l1 2 = 0; th is purely predictive
result captures the general trends of the data, but overestimates the solubility at the higher
pressures. Correlation of the data requires a [IOnzero value for the interaction parameter; the
value l 12 = 0.088 produces the semi-quantitative representation shown on Fig. 14.23 as the
second curve from the top.
20 Y. V. Tsekhanskaya, M. B. Tomtev, and E. V. Mushkina, Russian J. Phys. Ghent, vol. 38, pp. 1173-J 176, 1964.
14.8 EQUILIBRIUM ADSORPTION OF GASES ON SOLIDS
The process by which certain.. porous solids bind large numbers of molecules to their surfaces
is known as adsorption. Not only does it serve as a separation process, but it is aJso a vital
part of catalytic-reaction processes. As a separation process, adsorption is used most often for
removal of low-concentrationimpurities and pollutants from fluid streams. It is also the basis
for chron1atograpby. In surlace-catalyzed reactions, the initial step is adsorption of reactant
species; the final step is the ...feverse process, desorption of product specjes. Because most
industrially important reactions are catalytic, adsorption plays a fundamental role in reaction
engmeenng.
The nature of the adsorbing surface is the determining factor in adsorption. The molec-
ular characterization of solid surfaces is not yet fully developed; however, current knowledge
allows a helpful description. To be useful as an adsorbent, a solid must present a large sur-
face area per unit mass (up to 1,500 m2 per gram). This can only be achieved with porous
solids such as activated carbon, silica gels, al uminas, and zeolites, which contain many cavi-
ties or pores with diameters as small as a fraction of a nanometer. Sl11faces of such solids are
necessarily irregular at the molecular level, and they contain sites of particular attraction for
adsorbing molecules. If the sites are close together, the adsorbed molecules may interact with
one another; if they are sufficientl y dispersed, the adsorbed molecules may interact only with
the sites. Depending upon the strength of the forces binding them to the sites, these adsorbate
molecules may be mobile or fixed in position. The relatively weak electrostatic, induction,
and dispersion forces discussed in Sec. 16.1 favor mobility and result in physical adsorption.
On the other hand, much stronger quasichemical forces can act to fix molecules to the sur-
face, promoting chemisorption. Although adsorption may be classified in several ways, the
usual distinction is between physical adsorption and chemisorption. Based on the strength of
the binding forces , this division is observed'experimentally in the magnitudes of the heat of
adsorption.
In the adsorption of gases, the number of molecules attracted to a solid surface depends
on conclitions in the gas phase. For very low pressures, relatively few molecules are adsorbed,
and only a fraction of the solid smface is covered. As the gas pressure increases at a given tem-
perature, smface coverage increases. When all sites become occupied, the adsorbed molecules
are said to form a monolayer. Further increase in pressure promotes multilayer adsorption. It
is also possible for multilayer adsorption to occur onone part of a porous surface when vacant
sites still remain on another part.
The complexities of solid smfaces and our inability to characterize exactly their interac-
tions with adsorbed molecules limits our understanding of the adsorption process. It does not.
however, prevent development of an exact thermodynamic description of adsorption equilib-
rium, applicable alike to physical adsorption and chemisorption and equally to monolayer and
multilayer adsorption. The thermodynamic framework is independent of any particular theo-
retical or empirical description of material behavior. However, jn application such a description
is essential, and meaningful results require appropriate models of behavior.
The thermodynamic treatment of gas/adsorbate equilibrium is in many respects analo-
gous to that of vapor/liquid equilibrium. However, the defirution of a system to which the r
equations of thetmodynamics apply presents a problem. The force fieJd of the solid adsorben t
influences properties in the adjacent gas phase, but j ts effect decreases rapidly with distance.
607
14.8. Equilibrium Adsorption of Gases on Solids
immediate neighborhood of the solid sur-

Thus the properties of the gas change rapidly in the
chan ge exists which contains gradients in
face, but they do not chan ge abruptly. A region of
phase that the solid makes its influence
the properties of the gas, but the distance into the gas
felt cannot be precisely established.
ed by J. vV. Gibbs. Imagine that the
This problem is circumvented by a cons truct devis
id urface. Differences between the actual
gas-phase prope11ies extend unchange d up to the sol
to a mathematical surface, treated as a two-
and the unch anged propertie s can then be attributed
erties. Thjs provides not only a precisely
dimensional phase with its own thermodynamic prop
of the interfacial region, but il also extracts
defined su1face phase to acco unt fo r the singularities
it too may be treated precisely. The solid,
them from the three-dimensional gas phase so that
inert and not otherwise to participate in
despite the influence of its force field, is presumed
therm odynamic analysis the adsorbate is
the gas/adsorbate equi librium. Thus for purposes of
syste m beca use it is in equilibrium with
treated as a Lwo-dimensional phase, inherently an open
the gas phase.
system is given by Eq. (11.2):
The fundamental property relation for an open P VT
d(nG ) = (nV )dP - (nS) dT + "JJ-; dni
nsional phase. The only diffe rence is

An anaJogous equation may be written for a two-dime
appropriate variables. Pres sure is replaced
that pressure and molar volume., are not in th is case
by the mola r area a:
by the spreading pressure n, and Lhe molar volume
d(n G ) = (na )dn - (nS) dT + "
JJ-i dn; (14.104)
, usually a gram or a kilogram, of so lid

This equation is written on the basis of a unil mass
i.e., the number of moles of adsorbate per
adso rbent. Thus n is the spec(fic amount adsorbed,
unit mass of adso rbent. Moreover, area A is defin
ed as the specific surface area, i.e., the area
of a particular adsorbent. The molar area,
per unit mass of adsorbent, a quantity characteristic
a = Ajn , is the surface area per mole of adsorbate
.
g of pressure, having uruts of force
The sprearung pressure is the two-rumensional analo
pictured as the force in the pJane of the
per unit length, akin to surface tension. It can be
lengt h of edge to keep the smfa ce from
surface that must be exerted perpendicular Lo each unit
m. It is not subje ct to djrect experimental
spreading, i.e., to keep it in mechanical equil ibriu
complicating the treatment of adsorbed-
meas urem ent, and must be calculated, significantly
phase equilibrium.
the num ber of degrees of freedom
Because the spreading press ure adds an extra variabJe,
version of the phase rule. For gas/a dsorb ate
for gas/adsorbate equilibrium is gjven by an altered
equilibrium, n = 2; there fore, ,
F= N- n+3 ..N -2+ 3_= N + .I
Thus for adsorptio n of a pure species,

F= l + l =2
n, must be fixed independently to e tabli sh
and two phase-rule variables, e.g., T and Por T and
e is counted neither as a phas e nor as a
an equiljbriurn state . Note that the inert solid phas
species.
CHAPTER 14. Topics in Phase Equilibria
608
ich follows from Eqs. ( 11.8)

Recall the summability relati on for the Gibb s energy, wh
and ( 11. 12):
nG == ~ n;JL;
....
Differentiation gives:
,.
- d (n G ) = ~ JLi dn; + ~ l'li dJJ.,i
Comparison with Eq. ( 14. 104) shows:
(nS) dT- (na)d n + ~ n; dJJ.,; == 0
or s dT- a d n + ~ x; dJL; = 0
icting it to constant temperature

This is the Gibbs/Duhem equation for the adsorbate. Restr
produces the Gibbs adsorption isotherm:
(const T) ( 14.105)
-ad n + ~ x;dJL; == 0
mes the same temperature

The condition of equilibrium betw een adsorbate and gas presu
for the two phases and req uires: g
/-Li = JL;
where JJ..f represents the gas-phase chemical poten tial. For

a change in equilibrium condi tions,
'I(( JJ..i == d JJ..f

differentiation of Eq. ( I I .29) at
If the gas phase is an ideal gas (the usual assumption), then
constant temperature yield s:
dJLf = RTd ln y; P
isotherm gives:
Combining the last two equations with the Gibbs adsorption
a (const T) (14.106)
- - d n +dI n P + ~ x; dIn Yi = 0
RT I
.
ons respectively.
where .Xi and y; represent adsorbate and gas-p hase mole fracti
Pure-G as Ads orp tion

measuremenLc;; at constant temper-
Basic to the exper imental study of pure-gas adsorption are
pressure in the gas phase. Each
ature of n , the moles of gas adsorbed, as a function of P , the
gas on a partic ular solid adsorbcnr.
set of data represents an adsorption isotherm fo r Lhe pure 21
The correlation of such data re-
Available data are summ arized by Valenzuela and Mycrs.
relation should be consistent with
quires an analytical relation between n and P , and such a
Eq. (14. 106).
Handbook, Prentice Hall, Englewood C liffs. :\J.

21 D.P. VaJenzucla and A. L. Myers, Adsorption Equilibrium Data
1989.
14.8. Equilibrium Adsorption of Gases on Solids 609
written for a pure chemical species, this equation becomes:

a
- dn =d lnP (canst T ) (14.107)
RT
The compressibility-factor analog for an adsorbate is defined by the equation:
z=-
na (14. 108)
RT
Differe ntiation at constant T yields:
n a
dz = RTcla + RTdn
Replace the last term by Eq. ( 14. 107) and eliminate D j RT in favor of zj a in accord with
Eq. (14.108) to yield:
da
- d ln P = ~- - dz
a
Substituting a= Ajn and da =-A'dnjn 2 gives:
dn
- d l nP = - z- - dz
n
Adding dn f n to both sides of th is equation and rearranging,
n dn
d ln - = (1 - z)- - dz
p n
Integration fTom P = 0 (where n = 0 and z = 1) to P = P and n = n yields:
In -n - ln lim -n =
P P~o P
Ia" (1 - z) -dn
n
+I- z
0
The limiting value of n j P as n ~ 0 and P ~ 0 must be fou nd by extrapolation of
experimental data. Applying l'Hopital's ru le to thi s limit gives:
n dn
lim - = lim - =k
P~O P P-> 0 d ?_,.
Thus k is defined as the li miting slope of an i sorh crm ~'l P -+ O, ~nd is known as Henry's con-
stant for adsorption. It is a fu nction of temperature only for a given adsorbent and adsorbate,
and is characteristic of the specific interaction between a particular adsorbent and a particular
adsorbate.
The preceding equation may therefore be written:
n =
In-
kP
1 0
11
(1 - z) -dn
n
+ 1- z
dn + 1 - zJ
11
or n = k P exp [
Jo
(
(1 - z)-;;: (14.J09)
This general relation between n, the moles adsorbed, and P , the gas-phase pressure,
includes z, the adsorbate compressibility factor, which may be represented by an equation of
state for the adsorbate. The simplest such equation is the ideal-gas anaJog, z = l , and in this
case Eq. ( 14. 109) yields n = k P , which is Henry's law for adsorption.
An equatjon of state known as the ideal-lattice-gas equation22 has been developed specif-
ically for an adsoibate:
z =-
- ln l - -
n
m ( n)
m
where m is a constant. This equation is based on the presumptions that the surface of the
adsorbent is a two-dimensional lattice of energeticall y equivalent sites, each of which may
bind an adsorbate molecule, and that the bound molecules do not interact with each other. The
validity of thi s model is therefore limited to no more than monolayer coverage. Substitution of
this equation into Eq. ( 14.1 09) and integration leads to the Langmuir isotherm:23
n = (m-n )m
kP
1nP
Solution fo r n yields: n= m (14.11 0)
k+P
kbP
Alternatively, n = --,-- 14.111 )
b+.P
where b = mf k, and k is Henry's constant. Note that when P ~ 0, nf P properly approache
k. At the other extreme, where P ~ oo, n approaches m., the saturation value of the specific
amount absorbed, representing full monola-yer coverage.
Based on the same assumptions as for the ideal-lattice-gas equation, Langmuir in 191 8
derived Eq. (14.110) by noting that at equil ibrium the rate of adsorption and the rate of desorp-
tion of gas molecules must be the same. 24 For monolayer adsorption, the number of sites rna~
be divided into the fraction occupied 8 and the fraction vacant J - 8. By definition,
m- ll
and l -8=--
m
where m is the value of n fo r full monolayer coverage. For the assumed conditions, the rate
of adsorption is proportional to the rate at which molecules strike the surface, which in tum i
proport1 onal to both the pressure and the fraction J - 8 of unoccupied smface sites. The rate
of desorption is propo1tional to the occupied fraction 8 of sites. Equating the two rates give :
m -n ,n
KP =K -
111 m
22See,
e.g., T. L. Hill , An Introduction ro Statistical Mechanics, sec. 7- 1. Addison-Wesley, Reading. MA, 1960.
21 Irving Langmuir
( 1881- 1957), the second American to receive the Nobel Prize in ehemisLry, awarded for ~
contributions in rhe field of surface chemistry.
24 I. Langmuir,
J. Am. Chem. Soc. , vol. 40, p. 1361. 1918.
14.8. Equilibrium Adsorption of Gases on Solids 6 11
where K and K 1 arc proportionality (rate) constants. Solving for nand rearranging yields:
Km P mP
n = --:----
KP +K' ~+p
K
where K = t( I K 1 , the ratio of the forward and reverse adsorption rate constants, is the con-
ventional adsorption equilibrium constant. The second equality in this equation is equivalent
to Eq. (14.11 0), and indicates that the adsorption equilibrium constant is equal to Henry's
constant divided by m, i.e., K = kj m.
Because the assumptions upon which it is based are fu lfilled at low surface coverage,
e
the Langmuir isotherm is always valid as -+ 0 and as n --+ 0. Even though these assump-
tions become unrealistic at higher surface coverage, the Langmuir isotherm may provide an
approximate overall fit ton vs. P data; however, it does not lead to reasonable values form.
Substituting a= Ajn in Eq. (14.107) gives:
Adn
- - =ndlnP
RT
Integration at constant temperature from p = 0 (where n = 0) top = p and n = n yields:
ITA
-=
lop -dP
n
(14.112)
RT o P
This equation provides the only means for evaluation of spread ing pressure. The integration
may be carried out numerically or graphically with experimental data, or the data may be fit to
an equation for an isotherm. For example, if the integrand nf P is given by Eq. ( 14.111 ), the
Langmuir isotherm, then:
TI A P +b
- =kb l n - - ( 14. 11 3)
RT b
an equation valid for n --+ 0.
o equation of state is known that leads to an adsorption isotherm which in general fits
experimental data over the entire range of n from zero to full monolayer coverage. Isotherms
that find practical use are often 3-parametcr empirical extensions of the Langmuir isotherm.
An example is the Toth equation: 25
mP
..
n = - - -...,...,- (14. 11 4)
(b+P')l / t
which reduces to the Langmuir equation fort = I. W;hen the integrand of Eq. (14.112) is
expressed by the Toth equation and most other 3-parameter equation s, its integration requjres
numerical methods. Moreover, the empirical element of such equations often introduces a
singu larity that makes them behave improperly in the limit as P -+ 0. Thus for the Toth
equation (l < 1) the second derivative d 2n.jd P 2 approaches -oo in this limit, making values
of Henry's constant as calculated by this equation too large. Neve1theless, the Toth equation
finds frequent practical use as an adsorption isotherm. However, it is not always suitable , and
25valenzuela and Myers, op. cit.

1.5 ""-
.,... ~ ~
/"
. , ;t#
/.
j v
I
/
v
... 1.0
I
0) i
~
0 !
I
E
"'?
0.5
IJ
II _,_ /
/
-- ---- --- -
---- ---- ---- ----
'/
r
0 10 20 30 40
P/kPa
Figure 14.24: Adsorption isotherm for ethylene on a carbon molecular sieve at 50C.
Legend: experimental data; -~- - Henry's law; Toth equation;
- - -Langmuir equation n ~ 0.
26 Among them. the

a number of other adsorption isotherms are in use, as d iscussed by Suzuki.
Freundlich equation, ..~
() = !!.. =a pl //3 (/3 > 1) ( 14. 115)

m
is a 2-par ameter (a and {3) isotherm that often successfully correJates experimental data for
low and intermediate values of e.
Example 14.1 0
Nakahara et al. 27 report data for ethylene adsorbed on a carbon molecular sieve
(A = 650 m2 g- 1) at 50C. The data, shown as filled circles on Fig. 14.24, consist of
pairs of values (n, P ). where n is moles of adsorbate per kg of adsorbent and P is
the equilibrium gas pressure in kPa. Trends shown by the data are typical for physical
26M. Suzuki, Adsorption Engineering. pp. 35-5 1, Elsevier. Amsterdam. 1990.
27T. Nakahara, M. Hirata, and H. Mori, J. Chem. Eng. Dara, vol. 27, pp. 317-320, 1982.
14.8. Equilibiium Ads01ption of Gases on Solids 613
adsorption on a heterogeneous adsorbent at low-to-moderate surface coverage. Use

these data to illustrate numerically the concepts developed for pure-gas adsorption.
Solution 14.1 0
The solid line on Fig. 14.24 represents a curve-fit to the data by Eq. (14.11 4),
the Toth equation, with parameter values as reported by Valenzuela and Myers
(loc. cit.):
m = 4.7087 b = 2.194 1 I = 0.3984
These imply an apparent value of Henry's constant:

n
k(Toth) = lim -
P- 0 p
= -bm1-1
1
= 0.6551 mol kg- 1 kPa- 1
Although the overaJ l quality of the fit is excellent, the value of Henry's constant is
too large, as we will show.
'
- - - Toth equation
0. 4 ~---- - -He nry' s law
Figure 14.25: PloL of n/ P

I 0.3 vs. n for ethylene on a carbon
C"O
c.. molecular sieve at 50C.
-
~
I
Cl experimental data;
~
0 - - - cubic polynomial fit

E 0.2
--
:::IQ.
ofn/P vs. n ;
- - - Langmuir equation
for n--+ 0;
- - -Henry 's law;
0.1 Toth equation for
small n.
Langmuir equation
for n-O
0
n/mol kg - 1
Extraction of Henry 's constant from an adsorption isotherm is facilitated when

n.j P (rather than n.) is considered the dependent variable and n (rather than P ) the
independent variable. The data plotted in this form are shown by Fig. 14.25. On
614 CHAPTER J4. Topics in Phase Equilibria
this plot, Henry's constan t is the extrapolated intercept:

n n
k = lim - = lim -
p_.o P n ..... o P
where the second equality follows from the first because n -+ 0 as P -+ 0.

Evaluation of the intercept (and hence of k) is done in this case by fitting all of the
n f P data by a cubic polynom
.,. ial in n:
The evaluated parame ters are:
Co= 0.4016 c1 = - 0.6471 c2 = -0.4567 C3 = -0. 12oo

1
W hence, k =Co= 0.4016 mol kg-L kPa-
Represe ntation of nf P by the cubic polynomial appears as the solid curve on

Fig. 14.25, and the extrapo lated intercept (Co = k = 0.40 16) is indicate d by an
open circle. For comparison, the dotted line is the !ow-n portion of then 1P curve
g iven by the Toth equation. Here it is apparen t that the extrapolated intercep t
k(Toth), off-scal e on this fig ure, is too high. The Toth equatio n cannot provide an
accurat e representation of adsorption behavio r at very low values of n or P.
The Langmu ir equation on the other hand , is always suitable for sufficie ntly
s mall nor P. Rearran gement of Eq. ( 14 .111 ) gives:
n 1
- = k- -n
p b
....
which shows that the Langmu ir equatio n impJies a linear variation of nf P with n.
Hence the limiting tangent to the "true" isotherm on a plot of n/ P vs. n represe nts
the Langmu ir approxi mation to the isotherm for small n. and is shown by the
dashed lines on Figs. 14.24 and 14.25. It is given by the equation:
/1
p =0.40 t6-0.6 47 ln
0.6206 ?
or, equivale ntly, by n=----
1.5454 + p
Figures 14.24 and 14.25 show that Henry's law (represented by the dot-dash lines)
and the limiting fo rm of the Langmu ir equatio n provide , respectively. in this ex-
ample upper and lower bounds for the actual isotherm. The Langmu ir isotherm
when fit to all the experim ental data yields a cur ve (not shown) in Fig. 14.24 that
fits the data reasona bly well, but not so well as the 3-parameter Toth expression.
Neither the spreadi ng pressur e nor the adsorba te equatio n of state is required
for an empirical correlation of single-s pecies ad sorption data. However, a et
of (n, P) data implies an equatio n of state for the adsorbe d phase, and hence
a relationship between the spreadi ng pressur e n and rhc moles adsorbed. B~
Eq. (14.112 ),
nA { P n (' 1 n d P
RT = loPdP= } 0 P dn dn
Fquilibrium Adsorption of Gases on Solids 615
E{juation (14.1 08) may be written:

TIA
z= - -
nRT
\Vhence, z =-I loP

n
-dP
n o P
=- n dP
--dn
n o P dn
11 11
Finding numerical values for z and n depends on evaluation of the integral:
I=
l0
pn
-dP=
P
1o
11
ndP
--dn
P dn
Choice of the form depends on whether P or n is the independent variable. The

Toth equation gives the integrand n f P as a function of P, and therefore:
,.
p mdP
I Toth =
( ) lo0 (b + pt) 1f t
The cubic poJynomial gives nf P as a function of n; whence,
'
These two expressions permit numerical determination of z (n) and n (n) as are-
sult of correlations presented in this example. Thus, for n = 1 mol kg- 1 and
A = 650m2 g- 1, both the Toth and cubic-polynomial equations yield z = 1.69.
From this result,
1
nRT 1 molkg- 1 x 83.14cm3 barmol- 1 K- x 323. 15 K
TI=--z =
A 650,000 m2 kg- 1
x 1.69 x 10- 6 m 3 cm- 3 x I 05 N m- 2 bar- 1
1
= 6.99 x 10-3 N m- 1 = 6.99 mN rn- 1 = 6.99 dyn cm-
The adsorptive capacity of an adsorbent depends directly on its specific surface area A,
but determination of these large values is not a trivial matter. The means is provided by the
adso1ptioo process itself. The basic idea is to measure the quantity of a gas adsorbed at fu ll
monolayer coverage and to multiply the number of molecules adsorbed by the area occupied
by a single molecule. Two difficulties attend this procedure. First is the problem of detecting
the point of full monolayer coverage. Second, one finds that with djfferent gases as adsorbates
different area values result. The latter problem is circumvented by the adoption of nitrogen
as a standard adsorbate. The procedure is to make measurements of the (physical) adsorption
of N2 at its normal boiling point (-195.8C) for pressures up to its vapor pressure of l(atm).
The result is a curve the first part of which is like that in Fig. 14.24. When monolayer cov-
erage is nearly complete, multilayer adsorption begins, and the curve changes direction, with
616 CHAPTER 14. Topics in PJJase Equilibria
n increasing ever more rapidly with pressure. Finally, as the pressure approaches I (atm), the
vapor pressure of the N2 adsorbate, the curve becomes nearly vertical because of condensation
in the pores of the adsorbent. The problem is to identify the point on the curve that represents
full monolayer coverage. The usual procedure is to fit the Brunauer/Emmett/Teller (BET)
equation, a 2-parameter extension of the Langmuir isotherm to multilayer adsorption, to the n
vs. P data. From this, one can determine a value for m. 28 Once m is known, multiplication by
Avogadro 's number and 'by the area occupied by one adsorbed N2 molecule (16.2 A2 ) yields
the surface area. The method has its uncertainties, particularly for molecular sieves where the
pores may contain unadsorbed molecu les. Nevertheless, it is a useful and widely used tool for
characterizing..and comparing adsorption capacities.
""'
Heat of Adsorption
The Clapeyron equation, derived in See:.. 6.4 for the latent heat of phase transition of pure
chemjcal species, is also applicable to pure-gas adsorption equilibrium. Here, however, the
two-phase equilibrium pressure depends not only on temperature, but on surface coverage or
the amount adsorbed. Thus the analogous equation for adsorption is written
( 14.116)
where subscript n signifies that the derivative is taken at constant amount adsorbed. Super-
script av denotes a property change of deso1ption, i.e., the difference between the vapor-phase
and the adsorbed-phase property. The quantity 6 Hav - H 11 - Ha is defined as the isosteric
heaL of adsorption, and is usually a positive quantity. 29 The heat of adsorption is a useful indi-
cation of the strength of the forces binding adsorbed molecules to the surface of the adsorbent.
and its magnitude can therefore often be used to distinguish between physical adsorption and
chemisorption.
The dependence of heats of aclsorptiQn on surface coverage has its basis in the energet ic
heterogeneity of most solid surfaces. The first sites on a surface to be occupied are those which
attract adsorbate molecules most strongly and with the greatest release of energy. Thus the
heat of adsorption decreases with surface coverage. Once all sites are occupied and mu~ti layer
adsorption begins, the dominant forces become those between adsorbate molecu4es, and for
subcrilical species the decreasing heat of adsorption approaches the heat of vaporization.
Assumed in the derivation of the Langmuir isotherm is the energeti.c equivalence of all
adsorption sites, implyi ng that the heat of adsorption is independent of surface coverage. This
explains in pa1t the inability of the Langmuir isotherm to provide a close fit to most experimen-
tal data over a wide range of surface coverage. The Freundlich isotherm, Eq. ( 14.115), implies
a logarithmic decrease in the heat of adsorption with surface coverage.
As in the development of the Clausius/Clapeyron equation (Example 6.5), if for low
pressures one assumes that the gas phase is ideal and that the adsorbate is of negligible volume
28 .r. M. Smith, Chemical Kinetics. 3d ed .. sec. 8- 1. McGraw-Hill, New York, 1981.

290ther heats of adsorption. defined differently. are also in use. However. the i sosteric heat is the most common.
and is the one needed for energy balances on adsorption co lumns.
14.8. Equilibrium Adso1ption of Gases on Solids 6 17
compared with the gas-phase volume, Eq. ( 14.1 16) becomes:
a ln
( ar
P) II
= ~H:v
RT
( 14.117)
Application of this equation requires the measureme nt of isotherms, such as the one at 50C in
Fig. 14.24, at several temperatures. Cross plottjng yields sets of P vs. T relations at constant n,
from which val ues for the partial derivative of Eq. ( 14.117) can be obtained. For chemisorption,
b.. H av values usually range from 60 to 170 kJ mol- 1 For physical adsorption, they are smaller.
For example, measured values at very low coverage for the physical adsorption of nitrogen and
n-butane on SA zeolite are 18.0 and 43.1 kJ mol - 1, respective1y. 30
Mixed-Gas Adsorption
Mi xed-gas adsorption is treated simUarly to the gamma/phi form ulation of VLE (Sec. 14.1 ).
With a gas-phase property denoted by superscript g, Eqs. ( 11.31) and ( I 1.46), which define
fugacity, are rewritten:
Gf = rf(T) + RT ln f/ (14.1 J 8) ~Lf = rf (T) + RT In .f/ (14. 119)
Note as a result of Eqs. (I L.32) and (I I .53) that:

g ' "g
. J:
Ilffi - = 1
i . f;
l Im - = I
and
P--+ 0 P P~O y; P
For the adsorbate analogous equations are:
( 14.120) /Li = r ; (T) + RT In /; ( 14.121)
with .
Ilffi -f; =l and li
li m - = l
n -+O TI n-+O X; TI
The Gibbs energies as given by Eqs. (l4.118) and (l4. 120) may be equated for pure-
gas/adsorbate equilibrium:
rf(T) + RT ln f/ = f ;(T) + RT ln .fi

Rearrangement gives:
J; -_ exp [ r f (T ) - r ; (T )
8fi
J=_F,(T
.) ( 14. 122)
RT r
The limiting value off; 1 f/ as both P and n approach zero can be used to evaluate F; (T):
. J; . n . n; . n
1rm -, = hm - = hm - hm -
P-+0 ft P-+O P 1/j-o P n ->O n ;
n-+0 I n -+O P- o n;->0
30 N. Hashimoto and J. M . Smith, Ind. Eng. Chem. Fund. , vol. 12, p. 353, 1973.
618 CHAPTER 14. Topics in Pbase Equilibria
The first limit of the last member is Henry's constant k;; the second limit is evaluated from
Eq. ( 14.108), written TI / n; = z; RT/ A; thus,
. TI RT
hm - = -
n ---+0 n; A
n;---+ 0
In combination with Eq. (14.122) these equations give:

;
F;(T) = k;RT (14.123) +l.

JJ -- k;ART JJ+,.8 (14.124)
A
Similarly, equating Eqs. ( 14. 119) and (14.121) yields:
rf (T) + RT In fl = f ;(T ) + RT In ];
];,. [r~(T) - r;(T)J

1
=F; (T)
from which = exp
f;8 RT
Then by Eq. (14.123), (14.1 2:
These equations show that equality of fugacities is not a proper criterion for gas/adsorb-
ate equilibrium. This is also evident from the fact that the units of gas-phase fugacities are
those of pressure, while the units of adsorbate fugacities are those of spreadjng pressure. In
most applications the fugacities appear as ratios, aQd the factor k; RT1A cancels. Neverthele-
it is instructive to note that equality of chemical potentials, not fugacities, is the fundamenL..
c1iterion of phase equilibrium.
An activjty coefficient for the constituent species of a mixed-gas adsorbate is defined ' .
the equation:
f;"
y;=--
x I. f,.o
I
where]; and /;0 are evaluated at the same T and spreading pressure n. T he degree sign
denotes values for the equilibrium adsorption of pure i at the spreading pressure of the mi.n:~
Substitution for the fugacities by Eqs. (14.124) and (14.125) gives:
The fugacities are evaluated at the pressures indjcated in parentheses, where P js the equ:.n
rium mixed-gas pressure and Pi0 is the equilibrium pure-gas pressure that produces the ~-:e
spreading pressure. 1f the gas-phase fugacities are eliminated in favor of fugacity coeffic1~
[Eqs. (J 1.34) and (11.52)], then:
619
14.8. Bquilib1ium A dsorptio n of Gases on Solids
y;/JJ;P = x;; P;0 Yi (14.126)

or
are then unity:
The usual assumption is thar the gas phase is ideal; the fugacity coeffic ients
(14.1 27)
from mixed-
These equalio ns provide the means for calculation of activity coeffic ients
low calculation of
gas adsorpt ion data . Alternatively, if y; values can be predicted, they al
ideal so lu tion , then
adsorbate compos itio n. In particu lar, if the mixed-gas adsorba te form s an
y; = 1, and the resulting equation is the adsorption analog of Raoult' s law:
(14. 128)
which Henry' s law

This equation is alway valid as P --+ 0 and within the pressure range for
is a suitable approximation.
adsorpt ion
Equation ( 14. 11 2) is applica ble not only for pure-gas adsorption but also for
it yields:
of a constan t-comp os ition gas mixture . Applied where Henry's law is valid,
TI A =k P (14. 129)
RT
' i at the same
where k is the mixed- gas Henry' s constant. For adsorption of pure species
spreadi ng pressure, this becomes:
flA
-RT =kI P.I 0
Combin ing these two equatio ns with Eq. ( 14.128) gives:
(14.1 30)
Summi ng over al l i,
Eliminati ng k betwee n these two equatio ns yields:

y;k; (14. 13 1)
X;=
adsorbate compo -
This simple equation, requirin g only data for pure-gas adsorpt ion, provides
sitions in the limi t as P --+ 0. ,
For an ideal adsorbe d solution, in analogy with Eq. (11.8 1) for volumes,
of the pure-ga s
where a is the molar area for the mixed-gas adsorba te and a~ is the molar area
and af = A/ nj,
adsorba te at the same temperature and spreading pressure. Becaus e a = A/n
this equatio n may be written:
1 X;
;; = 4=
n?
l I
or n=---- ( 14.132)
(x;fnj)b
;
where n is the specific amount of mixed-gas adsorbate and nr

is the specific amount of pure-i
adsorbate at the .same spreading pressure. The amount of species i in the mixed-gas adsorbate
is of course n; = x; n.
31
The prediction of mixed-gas adsorption equilibria by ideal-adsorb ed-solution theory
is based on Eqs. (14.128) and (14.132). The fo11owing is a brief outline of the procedure. Be-
cause there are N + 1 degrees of freedom, both T and P , as well as the gas-phase composition,
must be specified. Solution is for the adsorbate composition and the specific amount adsorbed.
Adsorption isotherms for each pure species must be known over Lhe pressure range from zero
to the value that produces the spreading pressure of the rruxed-gas adsorbate. For purposes of
illustration we assume Eq. ( 14.1 11), the Langmuir isotherm , to apply for each pure species.
writing it:
(A)
The inverse of Eq. ( 14.11 3) provides an expression for Pt, which yields values of P;!
corresponding to the spreadjng pressure of the mixed-gas adsorbate:
P; 0 = b; ( exp _j_ - 1) (B )
k;b;
TI A
where -
1/1 =RT
..
The following steps then constitute a solution procedure:
An initial estimate of 1/f is found from the Henry's-law equations. Combining the defi-
nition of1/f with Eqs. (14. 129) and ( 14.130) yields:
1/1 = p ~ y;k;
With this estimate of 1/f, calculate P; for each species i by Eg. ( B) and
0
nf for ea.:!:
species i by Eq. (A).
One can show that the error in 1/1 is approximated by:
p:z= l!_-1
. p_o
I I
8''
.,.,
= ---. )'; -
p 2;::: p.on~
I I I
Moreover, the approximation becomes increasingly exact as 81/f decreases. If 8

7
smaller than some preset tolerance (say 81/f < 1/f x 10- ), the calculation goe tc
31 A. L. Myers and J. M. Prausnitz, A/ChE 1. , vol. II , pp. 12 1- 127, 1965; D.P. Valenzuela and A. L. Myer.... ~
- .9. Osmotic Equilibrium and Osmotic Pressure 621
final step; if not, a new value, l/1 = ljr + 81/f, is determined, and the calculation returns
to the preceding step.
Calculate x; for each species i by Eq. ( 14.128):

y; P
x- --
1 - p_ o
I
Calculate the specific amount absorbed by Eq. (14. 132).
Use of the Langmuir isotherm has made this computational scheme appear quite si mple,
because direct solution for P; 0 (step 2) is possib le. However, most equations fo r the adsorption
i otherm are less tractable, and this calculation must be done numerically. This s ign ificantly
increases the computational ta k, but does not alter the general procedure.
Predictions of adsorption equilibria by idea1-adsorbed-so lution theory are usually saLis-
facto ry when the specific amount adsorbed is less than a third of the saturation val ue for mono-
layer coverage. At higher adsorbed amounts, appreciable negative deviations from ideality are
promoted by differences in size of the adsorbate molecules and by adsorbent heterogeneity.
One must then have recourse to Eq. (14.127). The difficulty is in obtaining values of the ac tiv-
ity coefficients, which are strong functions of both spreading pressure and temperature. This i.
in contrast to activity coefficients for liquid phases, which for most applications are insensitive
32
to pressure. Th is topic is treated b~ Tal u et al.
14.9 OSMOTIC EQUILIBRIUM AND OSMOTIC PRESSURE
Most of the earth's water resides in the oceans, as seawater. For some regions, this is the ul-
timate source of fresh water fo r pub lic and commercial use. Conversion of seawater to fresh
water requires the separation of more-or-less pure water from an aqueous solution contain-
ing dissolved solute species. About 65% of such conversion is currently done by distillation
schemes. But another 30% is effected by reverse osmosis. Central to an understanding of os-
motic separations are the concepts of osmotic equilibrium and osmotic pressure, the topics of
this section.
Consider the idealized physical situation represented by Fig. 14.26. A chamber is divided
into two compa rtments by a rigid semipermeable partition. The left comparLment contains a
binary solute( I)/solvenr(2) liquid mixture. and the right contains pure solvent; the prutition
is permeable to so lvent species 2 only. Temperature is uniform and constant throughout, but
moveable pistons permit independent adjustment of the pressures in the two compartments .
Suppose that pressure is the same in the two compartments: P' = P. This implies
inequality of the fugacity /2
of the only di stributecfSpecies (the solvent), for by Eq. (14.72),
d/2 > 0 (const T. P)

dxz
meaning that f2(T, P'= P , x2 < I) < .f2(T, P , xz =I)= /2(T, P)
32 0 . Talu. J. Li, and A. L. Myers_ Adsorption. voL I. pp. 103- 112. 1995.
. . - - - - - - - P i s t ons - - - - - - - ,
Mixture of
Pure 2
P' ~ ~ 1 and 2
@T,P
Figure 14.26: Idealized @T,P'
osmotic system.
Rigid
semipermeable
J
partition
Thus, if P' = P, the solvent fugacity is smaller in the left compartment than in the right. The
difference in solvent fugacities represents a driving force for mass transfer, and solvent diffuses
through the partition, from right to left.
Equilibrium is established when pressure P' is increased to an appropriate value P*,
such that
h<T. P'= p *' X2 < 1) = /2(T , P)
The pressure difference, TI = P*- P , is the osmotic pressure of the solution, defined implicitly
through the equilibrium equation for species 2, which in abbreviated form is:
(14.133)
...
Equation (l4.133) is a basis for developing explicit expressions for osmotic pressure n.
Development is faci litated by the identity:
f;(P + n, x 2) =12 (P). /2CP. x2) . J2u:_ + n, x2) (14.134)

fz( P ) fz( P , xz)
The first ratio on the right is, by Eq. (1 1.90),
/2(P , x2)
f2(P) = X2Y2
where Y2 is the activity coefficient of solvent in the mixture at pressure P . The second ratio is
a Poynting factor, representing here a pressure effect on the fugacity of a species in solution.
An expression for this factor is readily found from Eq. (1 1.46):
aIn /; ) = _1 ( aJ.J. ; )
( aP T,x RT aP T .x
By Eqs. (11.18) and (11.8), ( aJ.aPJ. ; ) r x = V;

'
Thus, for solvent species 2,

14.9. Osmotic Equilibrium and Osmotic Pressure 623
W hence,
.f2( P+TI ,x2)
~ = exp
1P+n-dP
V2
f2(P, x2) p RT
Equation (14.134) therefore becomes:
h( P + n , x2) = x2Y2h(P ) exp } P

rP+nRTd
V?
P
Combination with Eq. (1 4. J 33) yields:
P+0 V2
X?Y2 exp
- - 1p
-dP = l
RT
or (14. 135)
Equation (14.135) is exact; working expressions for 11 follow by rational approximation.

If we ignore the effect of pressure on v2.
the integral b ecomes V2/ RT. Solution forn rr
then yields: '
RT
TI = - -_- ln(X2Y2) (1 4.136)
v2
lf in addition the solution is sufficiently dilute in solute I ,
and
With these approximations, Eq. (14.136) becomes:
n = x 1RT (14. 137)

v2
Equation ( 14.1 37) is the celebrated van 't Hoff equalion. 33
Equation (14.135) is valid when species 1 is a nonelectrolyte. If the solute is a strong
(completely dissociated) e lectrolyte containing m ions, then the right side is:
and the van 't Hoff equation becomes:

;"
mx1RT
TI = - - -
V2
Osmotic pressure can be quite large, even for very dilute solutions. Consider an aqueous
solution containing mole fraclion x 1 = 0.00 I of a nonelectrolyte solute species at 25C. Then
I cm3 (atm)
mol
n = 0.001 x - - - -3 x 82.06 K x 298.15 K = 1.36(atm)
18.02 em mol
33 Jacobus Henricus van ' t lolr ( 1852-1 91 1), Dutch chemist who won the first Nobel prize for chemistry in 190 I .
With reference to Fig. 14.26, this means that for a pure solvent pressure P = I (atm), the
pressure P' on the solution must be 2.36(atm) to prevent diffusion of solvent from right to left,
i.e., to establish osnwtic equilibrium.34 Pressures P' greater than this value make:
and a dJi ving force exists for transfer of water (solvent) from left to right. This observation
serves as motivation for the process called reverse osmosis, wherein a solvent (commonly
water) is segarated from a solution by application of sufficient pressure to provide the driving
force necessa~y for solvent transfer through a membrane which for practical purposes is perme-
able only to the solvent. The minimum pressure difference (solution pressure vs. pure-solvent
pressure) is just the osmotic pressure TI.
In practice, pressure differences significantly greater than IT are used to effect osmotic
separations. For example, seawater has an osmotic pressure of about 25 bar, but working
pressures of 50 to 80 bar are employed to enhance the rate of recovery of fresh water. A feature
of such separations is that they require mechanical power only, for pumping the solution to an
appropriate pressure level. This contrasts with distillation schemes, where steam is the usual
35
source of energy. A brief overview of reverse osmosis is given by Perry and Green.
PROBLEMS
14.1. The excess Gibbs energy fo r the system chloroform( 1)/ethanol(2) at 55C is well rep-
resented by the Margules equation, written:
cE I RT = ( 1.42XJ + 0.59x2)XJX2
The vapor pressures of chloroform and ethanol at 55C are:
P2sat = 37.31 k.Pa
(a) Assuming the validity ofEq. (I 0.5), makeBUBL P calculations at 55C for liquid-
phase mole fractions of 0.25, 0.50, and 0.75.
(b) For comparison, repeat the calculations using Eqs. (14.1) and {)4.2) with virial
coefficients:
B1 2 =52 cm 3 moJ
14.2. F ind expressions for 1 and </J2 for a binary gas mixture described by Eq. (3.40). The
mixing rule forB is given by Eq. (1 1.62). The mixing rule for Cis given by the general
equation:
C= ~ ~ b YiYjYk Cijk
j k
34 Note that. unlike conventional phase equilibrium. pressures are unequal for osmotic equilibrium, owing to the
special constraints imposed by the rigid semipermeable partition.
35 R. H. Perry and D. Green, Perry's Chemical Engineers' Handbook. 7th ed .. pp. 22-37-22-42 and 22-48- 22.56.
McGraw-H ill, New York, 1997.
Problems
625
where Cs with the same subscripts, regardless of order, are equal. For a binary mixture,
this becomes:
14.3. A system formed of methane( !) and a light oit(2) at 200 K and 30 bar consists of
a vapor phase containing 95 mol-% methane and a liquid phase containin g oil and
di ssolved methane. The fugacity of the methane is given by Henry's law, and at the
temperature of interest Henry's constant is 7-iJ = 200 bar. Stating any assumptions,
estimate the equilibrium mole fraction of methane in the liquid phase. The second
virial coefficien t of pure methane at 200 K is -105 cm3 mol- 1.
14.4. Assume that the last three data points (includin g the value of P 53 t) of Table 12.1,
,. 1
p. 43 1, cannot be measu red. Nevertheless, a conelatio n based on the remaining data
points is required. Ass uming the validity ofEq. ( 10.5), Eq. (14.28) may be written:
p = X J (YI/Y~)7-iJ +X2Y2 p2sat

'
Data reduction may be based on Barker's method , i.e., minim izing the sum of squares
of the residuals bet\een the experimental values of P and the values predicted by
this equation (see Ex. 12.1). Assume that the activity coefficients can be adequate ly
represent ed by the Margules equation.
(a) Show that: ln(yJ j y~) = xi[A 12 + 2(AzJ - A 12)x1] - A 12

(b) Find a value for Henry's constant 7-it.
(c) Determine values for paramete rs A12 and A21 by Barker's method.
(d) Find values for OYJ for the data points.
How could the regression be done so as to minimize the sum of squares of the residuals
in G I RT, thus including the Yl values in the data-reduction process?
14.5. Assume that the first three data points (including the value of p sat) of Table 12.1 ,
2
p. 431 , cannot be measured. Nevertheless, a correlation based on the remainin g data
points is required. Assumin g the validity of Eq. (1 0.5), Eq. ( 14.28) may be written:
P= XJ YJ P 1 sa~+ X2(Y2/Y2)7-i2
Data reduction may be based on Barker's method, i.e., minimizing the sum of squares
of the residuals between the experimenl~1 values of P and the values predicted by
this equation (see Ex. 12.1 ). Assume thal the activity coefficients can be adeq uately
represented by the Margules equation.
(a) Show that: ln (Y2/Y~) = xf LA21 + 2(A 12 - A 2 1)xz]- Azl

(b) Find a value for Henry's constant 7-i2-
(c) Determin e values for parameters A 12 and A21
(d) Find values for O)IJ for the data points.
'y Barker's method.
How could the regression be done so as to minimize the sum of squares of the residuals
in cE I RT) thus including the Yl values in the data-reduction process?
14.6. Work Pb. 14.4 with the data set of Table 12.3, p. 439.
14.7. Work Pb. 14.5 with the $ata set of Table 12.3, p. 439.
14.8. Use Eq. (14.1 ) to reduce one of the isothermal data sets identified below, and compare
the result with that obtained by application of Eq. (10.5). Recall that reduction means
developing a numerical expression forGE I RT as a function of composition.
(a) Methylethylket one(l)/toluene(2) at 50C: Table 12.1, p. 431.

(b) Acetone(l)/meth anol(2) at 55C: Pb. 12.3, p. 470.
(c) Methyl tert-butyl ether(l)/dichloromethane(2) at 35C: Pb. 12.6, p. 471.
(d) Acetonitrile(! )/benzene(2) at 45C: Pb. 12.9, p. 472.
Second-virial-coefficient data are as follows:
Part (a) Part (b) Part (c) Part (d)
Bl I -1,840 -1,440 -2,060 -4,500

B22 - 1,800 -1,150 -860 -1,300
B12 - 1,150 - 1,040 -790 -1,000
14.9. For one of the substances listed belo~ determine P sat/bar from the Redlich/Kwong
equation at two temperatures: T = T,, (the normal boiling point), and T = 0.85Tc.
For the second temperature, compare your result with a value from the literature (e.g.,
Perry's Chemical Engineers' Handbook). Discuss your results.
(a) Acetylene~ (b) Argon~ (c) Benzene; (d) n-Butane; (e) Carbon monoxide; -~
(f) n-Decane; (g) Ethylene; (h) n-Heptane; (i) Methane; (j) Nitrogen.
14.10. Work Pb. 14.9 for one of the following:
(a) The Soave/Redlich/Kwong equation; (b) The Peng!Robinson equation.
14.11. Departures from Raoult's law are primarily from liquid-phase nonidealities (y; =f: 1).
But vapor-phase nonidealities (; =f: 1) also contribute. Consider the special case
where the liquid phase is an ideal solution, and the vapor phase a non ideal gas mixture
described by Eq. (3.38). Show that departures from Raoult's law at constant tempera-
ture are likely to be negative. State clearly any assumptions and approximations.
14.12. Determine a numerical value for the acentric factor w implied by:
(a) The van der Waals equation; (b) The Redlich/Kwong equation.
14.13.. Starting with Eq. (14.71), derive the stability criteria of Eqs. (1 4.72) and (14.73).
627
Problems
of an equi mola r binar y mixt ure is G =

14.14. An abso lute uppe r boun d on GE for stabi lity
boun d for an equi mola r mix-
RT In 2. Deve lop this result. Wha t is the corre spon ding
ture containin g N spec ies?
. Dete rmin e from each of the follo wing

14.15. A binary liquid syste m exhib its LLE at 25C
12 and A 2 1 in the Margu1es equation
sets of miscibilit y data estim ates for para mete rs A
at 25 C:
; (c) xf = 0.10 , x~ = 0.80 .
(a) xf = 0.10 , x~ = 0.90 ; (b) xf = 0.20 , xf = 0.90
14.16. Wor k Pb. 14.15 for the van L aar equa tion.
ribed by Eqs. (3.38) and (11.62). Und er

14.17. Cons ider a bina ry vapo r-pha se mixt ure desc split into two im-
what (high ly unlikely) cond itio ns woul d one expe ct the mixt ure to
miscible vapo r phas es?
Eqs. (A) and (F) of Ex. 14.5 wi th C~

14.18. Figu res 14. 14, 14.15, and 14. 16 are based on
Grap h the corre spon ding figur es for
assu med positive and give n by C~/ R = 3xtxz.
the fo llow ing case s, in whic h C~ is assu med nega
tive:
975 '
(a) A = T - 18.4 + 3 In T
540
(b) A= --1 7.1 +3 lnT
T
1,500
(c) A = --y:-- 19.9 + 3 1n T
least 0.5 RT is requ ired for liqui d/liq uid

14.19. lt has been sugg ested that a value forG E of at ment.
fication for this state
phas e split ting in a bina ry syste m. Offe r some justi
oses imm iscib le in one anot her. Liqu id

14.20. Pure liqui d species 2 and 3 are for prac 6cal purp
One mole each of liquids l, 2, and
spec ies 1 is soluble in both liqui d 2 and liqui d 3.
ure of two liqui d phas es: an a-
3 are shaken toge ther to form an equil ibriu m mixt
cont ainin g spec ies 1 and 3. Wha t
phas e containi ng spec ies I and 2, and a ,8-ph ase
phas es, if at the temperatlLre of the
are the mol e fract ions of spec ies 1 in the a and ,8
es are given by:
expe rime nt, the exce ss Gibbs ener gies of the phas
,
and
on equa tion forG E is incap able of repre -

14.21. It is dem onstrated in Ex. 14.7 that the Wils
Wi lson 's equa tion given by:
senti ng LLE . Show that the simp le modification of
GE / RT = -C[x t ln(xt + x2l\J 2) + x2 ln(x2 + Xt A21)]

can repre sent LLE . Here, C is a cons tant.
14.22. Vapor sulfur hexafluoride SF6 at pressures of about 1,600 kPa is used as a dielectric in
large primary circuit breakers for electric transmission systems. As liquids, SF6 and
H20 are essentiall y immiscible, and it is therefore necessary to specify a low enough
moisture content in the vapor SF6 so that if condensation occurs in cold weather a
liquid-water phase will not form first in the system. For a preliminary determination,
assume the vapor phase an ideal gas and prepare the phase diagram [Fig. 14.21(a)]
for H20 (1)/Sf.0 (2) at 1,600 kPa in the composition range up to 1,000 parts per million
of water (mole basis). The following approximate equations for vapor pressure are
adequate: /
2 048 97
ln plsaL/kPa = 19.1478- 5,363.70 ln P2satjkPa = 14.6511 - '
Tj K T/K
14.23. In Ex. 14.4 a plausibility argument was developed from the LLE equilibrium equations
to demonstrate that positive deviations from ideal-solution behavior are conducive to
liquid/1iquid phase splitting.
(a) Use one of the binary stability criteria to reach this same conclusion.
(b) Is it possible in principle for a system exhibiting negative deviations from ideality
to form two liquid phases?
14.24. Toluene(l) and water(2) are essentially immiscible as liquids. Determine the dew-
point temperatures and the compositions of the first drops of liquid formed when vapor
mixtures of these species with mole fractions zt = 0.2 and zt = 0.7 are cooled at
the constant pressure of l 01.33 kPa. What is the bubble-point temperature and the
composition of the last drop of vapor in each case? See Table B.2, App. B, for vapor-
pressure equations. \
14.25. n-Heptane(l) and water(2) are essentially immiscible as liquids. A vapor mixture con-
taining 65-mol-% water at I 00C and l 01.33 kPa is cooled slowJy at constant pressure
until condensation is complete. Construct a plot for the process showing temperature
vs. the equilibrium mole fraction of heptane in the residual vapor. See Table B.2,
App. B, for vapor-pressure equations.
14.26. Consider a binary system of species 1 and 2 in which the liquid phase exhibi ts par-
tial miscibility. In the regions of miscibility, the excess Gibbs energy at a particular
temperature is expressed by the equation:
cE 1RT = 2.25 x 1x2
In addition, the vapor pressures of the pure species are:
and
Making the usual assumptions for low-pressure VLE, prepare a P-x-y diagram for thi
system at the given temperatu re.
Problems 629
14.27. The system water(l)/n-p entane(2)/n- heptane(3) exists as a vapor at 101.33 kPa and
100C with mole fractions ZJ = 0.45, Z2 = 0.30, Z3 = 0.25. The system is slowly
cooled at constant pressure until it is completely condensed into a water phase and a
hydrocarbon phase. Assuming that the two liquid phases are immiscible, that the vapor
phase is an ideal gas, and that the hydrocarbons obey Raoult's law, determine:
(a) The dew-point temperature of the mixture and composition of the first condensate.
(b) The temperature at which the second liquid phase appears and its initial composi-
tion.
(c) The bubble-point temperature and the composition of the last bubble of vapor.
See Table B.2, App. B, for vapor-pressure equations.
14.28. Work the preceding problem for mole fractions z t = 0.32, Z2 = 0.45, Z3 = 0.23.
14.29. The Case I behavior for SLE (Sec. 14.6) has an analog for VLE. Develop the analogy.
'
14.30. An assertion with respect to Case II behavior for SLE (Sec. 14.6) was that the condition
z;yt = I corresponds to complete immiscibility for all species in the solid state. Prove
this.
14.31. Use results of Sec. 14.6 to develop the following (approximate) rules of thumb:
(a) The solubility of a solid in a liquid solvent increases with increasing T .

(b) The solubility of a solid in a liquid solvent is independent of the identity of the
solvent species.
(c) Of two solids with roughly the same heat of fusion, that solid with the lower melt-
ing point is the more soluble in a given liquid solvent at a gjven T.
(d) Of two solids with similar melting points, that solid with the smaller heat of fusion
is the more soluble in a given liquid solvent at a given T.
14.32. Estimate the solubility of naphthalene (!) in carbon diox ide(2) at a temperature of 80C
at pressures up to 300 bar. Use the procedure described in Sec. 14.7, with l12 = 0.088.
Compare the results with those shown b~ Fig. 14.23. Discuss any differences. P{'at =
0.0102 bar at 80C. ..,
14.33. Estimate the solubility of naphthalene (!) in nitrogen(2) at a temperature of 35C at
pressures up to 300 bar. Use the procedure described in Sec. 14.7, with / 12 = 0.
Compare the results with those shown by Fig. 14.23 for the naphthalene /C02 system
at 35C with l 12 = 0. Discuss any differences.
14.34. The qualitative features of SVE at high pressures shown by Fig. 14.23 are determined
by the equation of state for the gas. To what extent can these features be represented
by the two-tetm virial equation in pressure, Eq. (3.38)?
14.35. The UNILAN equation for pure-species adsorption is:
n= -m In ( c + Pes )
2s c +Pe-s
where m, s, and c are positive empirical constants .
..
(a) Show that the UNILAN equation reduces to the Langmuir isotherm for s = 0.
(Hint: Apply l' Hopital's rule.) .;
(b) Show that Henry's constant k for the UNILAN equation is:
m
k (UNILAN) = - sinh s
cs
(c) Examine the detailed behavior of the UNILAN equation at zero pressure (P ---+ 0,
n ---+ 0).
14.36. In Ex. 14.10, Henry's constant for adsorption k, identified as the intercept on a plot
of n f P vs. n, was found from a polynomial curve-fit of nf P vs. n. An alternative
procedure is based on a plot of Jn(P I n) vs. n.. Suppose that the adsorbate equation of
state is a power series inn: z = 1 + Bn + Cn.2 + . Show how from a plot (or a
polynomial curve-fi t) of ln (P fn) vs. none can extract values of k and B. [Hint: Start
with Eq. (14. 109).]
14.37. It was assumed in the development of Eq. ( 14.109) that the gas phase is ideal, with
Z = 1. Suppose for a real gas phase that Z = Z(T, P ). Determine the analogous
expression to Eq. ( 14.109) approptiate for a real (nonideal) gas phase. [Hint: Start
.
WlthEq. (14. 105).] '
14.38. Use results reported in Ex. 14.10 to prepare plots of n vs. n and z vs. n for ethylene
adsorbed on a carbon molecular sieve. Discuss the plots.
14.39. Suppose that the adsorbate equation of state is given by z = (1 - bn)- 1, where b is
a constant. Find the implied adsorption isotherm, and show under what conditions it
reduces to the Langmuir isotherm.
14.40. Suppose that the adsorbate equation of state is given by z = I + f3n, where f3 is
a fu nction of T only. Find the implied adsorption isotherm, and show under what
conditions it reduces to the Langmuir isotherm.
14.41. Derive the result given in the third step of the procedure for predicting adsorption
equilibria by ideal-adsorbed-solution theory allhe end of Sec. 14.8.
14.42. Consider a ternary system comprising solute species 1 and a mixed solvent (species 2
and 3). Assume that:
Problems 631
Show that Henry's constant 1-tt for species 1 in the mjxed solvent is related to Henry's
constants 1-tt,2 and 1it,3 for species 1 in the pure solvents by:
ln 1i1 = x~ In 1it,2 + x~ In 1it ,3- A23x~x~

Here x~ and x3 are solute-free mole fractions:
14.43. It is possible in principle for a binary liquid system to show more than one region of
LLE for a particular temperature. For example, the solubility diagram might have two
side-by-side "islands" of partial miscibility separated by a homogeneous phase. What
would the D..G vs. Xt diagram at constant T look like for this case? Suggestion: See
Fig. 14.12 for a mixture showing normal LLE behavior.
14.44. With V2 = V2, Eq. (14.136) for the osmotic pressure may be represented as a power
senesmx1:
nv2 = 1 + Bx 1 + Cx 2 +
' 1
XtRT
Reminiscent of Eqs. (3.1 1) and (3.12), this series is called an osmotic vi rial expansion.
Show that the second osmotic virial coefficient B is:
What is B for an ideal solution? What is B if G = Ax1x2?

14.45. A liquid-process feed stream F contains 99 mol-% of species 1 and 1 mol-% of impu-
rity, species 2. The impurity level is to be reduced to 0.1 mol-% by contacting the feed
stream with a stream S of pure liquid solvent, species 3, in a mixer/settler. Species
1 and 3 are essentially immiscible. Owing to "good chemistry," it is expected that
species 2 will selectively concentrate in the solvent phase.
(a) With the equations given below, determine the required solvent-to-feed rations In F.
(b) What is mole fraction x2 of impurity in the solvent phase leaving the mixer/settler?
(c) What is "good" about the chemistry here? With respect to liquid-phase nonideali-
ties, what would be "bad" chemistry f.or..the prop.osed operation?
Given:
14.46. At 25C the solubility of n-hexane in water is 2 ppm (molar basis), and the solubility
of water in n-hexane is 520 ppm. Estimate the activity coefficients for the two species
in the two phases.
14.47. A binary liquid mixture is only partially miscible at 298 K. If the mixture is to be made
homogeneous by increasing the temperature, what must be the sign of HE?
14.48. The relative volatility a12 is commonly used in applicationas involvi ng binary VLE.
In particular (see Ex. 10.3), it serves as a basis for assessing the possibility of binary
azeotropy.
(a) Develop an expression for a 12 based on Eqs. (14.1) and ( 14.2).
(b) Specialize the expression to the composition limits XJ = Yt = 0 and Xt = Yl = l.
Compare with the result obtained from modified Raoult's law, Eq. (10.5). The
difference between the results reflects the effects of vapor-phase nonidealities.
(c) Further specialize the results of part (b) to the case where the vapor phase is an
ideal solution of r~ gases.
14.49. Although isothermal VLE data are prefened for extraction of activity coefiicients, a
large body of good isobaric data exists in the literature. For a binary isobaric T -x 1- Yl
data set, one can extract point values of y; via Eq. (14.1 ):
y; ct>;(Tk. P , y) P
Yi(X, Tk) = . p Sal(T.)
Xr ; k
Here, the variable list for Yi recognizes a primaty dependence on x and T; pressure
dependence is normally negligible. The notation Tk emphasizes that temperature varies
with data point across the composition range, and the calculated activity coefficients
are at different temperatures. However, the usual goal of VLE data reduction and
correlation is to develop an appropriate expression for Gel RT at a single temperature
T. A procedure is needed to correct each activity coefficient to such a T chosen near
the average for the data set. If a correlation for HE (x) is available at or near this T ,
show that the values of Yi corrected to T can be estimated by the expression:
y;(x,T)=y;(x,T~)exp [ R;
- fi. .E ( T
Tk - 1
)]
14.50. What are the relative contributions of the various terms in the gamma/phi expression
for VLE? One way to address the question is through calculation of the activity coef-
ficients for a si ngle binary VLE data point via Eq. (14.1): ..~
Yip /fii trt

Yi = p sat -""~-at --r-,.
Xj , \f/ J I
______.. ~ '-v-"
(A) (B) (C)
Term (A) is the value that would follow from modified Raoult's law; term (B) accounts
for vapor-phase nonidealities; term (C) is the Poynting factor [see Eq. (1 1.44)]. Use
the single-point data below for the butanenitrile(l)/benzene(2) system at 3 J8.15 K to
evaluate aH terms fori = 1 and i = 2. Discuss the results.
VLE Data: P = 0.20941 bar, XJ = 0.4819, Yl = 0.1813
Ancillary data: P 1sat = 0.07287 bar, P2sat = 0.29871 bar
3 1
B11 = - 7 , 993 cm3 mol- 1, B 22 = -1,247 cm mol- ,
B1 2 = -2,089 cm3 mol- 1
, vf = 90 cm3 mol- 1 Vi= 92 cm3 mol- 1
Problems 633
14.51. The spinodal curve for a binary liquid system is the locus of states for which
d 2 (~G I RT) =0 (const T , P)

dxf
Thus it separates regions of stability from instability with respect to liquid/liquid phase
splitting. For a given T, there are normally two spinodal compositions (if any). They
are the same at a consolute temperature. On curve II of Fig. 14.12 they are a pair of
compositions between xf and xf, corresponding to zero curvature.
Suppose a liquid mixture is described by the symmetrical equation
(a) Find an expression for the spinodal compositions as a function of A (T ).

(b) Assume that A (T) is the expression used to generate Fig. 14.15. Plot on a single
graph the solubility curve and the spinodal curve. Discuss.
14.52. Two special models of iiquid-solution behavior are the regular solution, for which
sE = 0 everywhere, and the athermal solution, for which HE = 0 everywhere.
(a) Ignoring the ? -dependence of GE, show that for a regular solution,
GE
--
RT
(b) Ignoring the ? -dependence of cE, show that for an athermal solution,
cE
RT = FA(x)
(c) Suppose that GE/ RT is described by the symmetrical equation
c
RT = A(T)x1x2
From parts (a) and (b), we conclude lhat

GE a ;
- = -x1x2 (regular) (A)
RT RT.
cE
RT = f3x1x2 (athermal) (B)
where a and f3 are constants. What are the implications of Eqs. (A) and (B) with
respect to the shapes of predicted solubility diagrams for LLE? Find from Eq. ( A )
an expression for the consolute temperature, and show that il must be an upper
consolute temperature.
Suggestion: See Ex. 14.5 for numerical guidance.
14.53. Many flu ids could be used as solvent species for supercritical separation processes
(Sec. 14.7). But the two most popu lar choices seem to be carbon dioxide and water.
Why? Discuss the pros and cons of using C02 vs. HzO as a supercritical solvent.
14.54. Generate P -x 1-y1 diagrams at 100C for one of the systems identified below. Base
activity coefficien ts on the Wilson equation, Eqs. (1 2.19). Use two procedures: (i)
modified Raoult's law, Eq. (I 0.5), and (ii) the gamma/p hi approach , Eq. (l4.1), with
4>; given by Eq. ( 14.2). Plot the results for both procedures on the same graph. Com-
pare and discuss them. "'
Data sources: For P/at use Table B.2. For vapor-phase nonidealities, use material
from Chap. 3; assume that the vapor phase is an (approximately) ideal solution. Esti-
mated parameters for the Wilson equation are given for each system.
(a) Benzene(l)/Carbon tetrachloride(2): A 12 = 1.0372, A 21 = 0.8637

(b) Benzene( l )/Cyclohexane(2): i\1 2 = 1.0773, i\21 = 0.7100
(c) Benzene( l)/n-Heptane(2): A1 2 = 1.2908, 1h1 = 0.50 11
(d) Benzene(l)/n-Hexane(2): A 12 = 1.3684, i\21 = 0.4530
(e) Carbon tetrachloride(l)/Cy clohexan e(2): A 12 = 1. 1619, A21 = 0.7757
(/) Carbon tetrachloride(l )/n-Heptane(2): A 12 = 1.5410, i\21 = 0.5197
(g) Carbon tetrachloride(l)/n-Hexane(2): A 12 = 1.2839, A21 = 0.601 1
(h) Cyclohexane( 1)/n-Heptane(2): A 12 = 1.2996, A21 = 0.7046
(i) Cyclohexane( l)/n-Hexane(2): i\12 = 1.4187, i\21 = 0.5901
'
Chapter 15
Thermodynamic Analysis of
Processes
The purpose of this chapter is to present a procedure for the analysis of practical processes
from the thermodynamic point of view. It is an extension of the ideal work and lost work
concepts presented in Sees. 5.8 and 5.9.
Real irreversible processes are amenable to thermodynamic analysis. The goal of such an
analysis is to determine how efficiently energy is used or produced and to show quantitatively
the effect of inefficiencies in each step of a process. The cost of energy is of concern in
any manufacturing operation, and the first step in any attempt to reduce energy requirements
is to determine where and to what extent energy is wasted through process irreversibilities.
The treatment here is limited to steady-state flow processes, because of their predominance in
industrial practice.
15.1 THERMODYNAMIC ANALYSIS OF STEADY-STATE

FLOW PROCESSES
Many processes consist of a number of steps, and lost-work calculations are then made for
each step separately. By Eq. (5.34),
. .
= Tu Sc
Wtost
,
For a single surroundings temperature Tu, summing over the steps of a process gives:
...
Dividing the former equation by the latter yields:
Wtost Sc
:LWtost - :LSc
Thus an analysis of the lost work, made by calculation of the fraction that each individual lost-
work term represents of the total, is the same as an analysis of the rate of entropy generation.
635
636 CHAPTER 15. Therm odyna mic Analy sis of Processes
made by expre ssing each indivi dual entrop y-gen eratio n term
as a fractio n of the sum of a ll
entrop y-gen eratio n terms. Recal l that all terms in these equat
ions are positive (p. 182).
An altern ative to the lost-w ork or entrop y-gen eratio n analy
sis is a work analysis. For
this, Eq . (5.31) becom es:
( 15.1)
For a work- requ iring proce ss, all of these work quan tities
preceding equat ion is then writte n:
are positi ve and Ws > Wideal The
(15.2 )
A work analy sis expresses each individual work term on the

right as a fracti on of W.t
For a work-produ cing proce ss, Ws and Wideal are negative,
and I widead > I Ws I. Equ a-
tion (15 .1) is theref ore best writte n:
A work analysis expre sses each indivi dual work term on

the right as a fracti on of J"Widead Such
an analy sis canno t be carrie d out if a proce ss is so inefficient
that wideal is negat ive, indicating
that the proce ss shoul d produ ce work, but Ws is positive,
indica ting that the proce ss in fact
requi res work. A lost-w ork or entrop y gener ation analy sis
is alway s possi ble.
Example 15.1
'
The operating conditions of a practical steam power plant
are described in Ex. 8.1,
parts (b) and (c). In addition, steam is generated in
a furnace/boiler unit where
methane is burned completely to C02 and H 0 with 25%
2 excess air. The.., flue gas
leaving the furnace has a temperature of 460 K, and T(}' =
298.15 K. Make a thermo-
dynamic analysis of the power plant.
Solution 15.1
A fl ow diag ram of the powe r plant is shown in Fig. I5.1. The
condi tions and
prope rties for key points in the steam cycle , taken from
Ex. 8. I, are listed as
follow s:
Point State of steam t/C P/kPa HlkJ kg- 1 S/kJ kg- l K- I
1 Subco oled liquid 45.83 8,600 203.4 0.658 0

2 Super heate d vapor 500 8,600 3,39 1.6 6.685 8
3 Wet vapor, x = 0.937 8 45.83 10 2,436 .0 7.684 6
4 Satur ated Iiqu id 45.83 10 191.8 0.649 3
15.1. Thermodynamic Analysis of Steady-State Flow Processes 637
CH 4 and air at 298.15 K Flue gases at 460 K

--------------~- ------ -------- r---------------~
Furnace/boiler
--------~~ ---------------~--~
1 2
Pump
,..
4 3
Condenser
Heat discarded to
surroundings at 298.15 K
Figure 15.1: Power cycle of Ex. !5.1.
S ince the steam undergoes a cyclic process, rbe only changes that need be
considered for calculation of rhe ideal work are those of the gases passing through
the fwnace. The reaction occuning is:
For this reaction, data from Table C.4 g ive:
b.H?_98 = -393,509 + (2)( -241 ,8 18) - (- 74,520) = -802,625 J

b.G29& = - 394,359 + (2)( - 228,572) -...( -50,460) = - 801,043 J
b.Ho - b.Go
Whence, b.So = 298 298 = -5.306 J k - 1
298 298. 15
On the basis of 1 mol of methane burned with 25% excess air, the air entering
the furnace contains:
~: (2)( 1.25) = 2.5 mol
N2: (2.5)(79/21) = 9.405 mol
Total: 11.905 mol air
After complete combustion of the methane, the flue gas contains:

638 CHAPTER 15. Thermodynamic Analysis of Processes
C02: l mol Yco2 = 0.0775

H20: 2mol YH2 o = 0. 1550
0 2: 0.5 mol Yo2 = 0.0387
N2: 9.405 mol YN2 = 0.7288
Total: 12.9~ mol flue gas LYi = 1.0000
The change of state that occurs in the furnace is from methane and air at atmo-
spheric pressure and 298.15 K, the temperature of the surroundings, to flue gas at
atmospheric pressure and 460 K. For this change of state, 6. H and D.S are calcu-
lated for the path shown in Fig. 15.2. The assumption of ideal gases is reasonable
here, and is the basis of calculation for 6.H and 6.S for each of the four steps
shown in Fig. 15.2.
1 mol CH 4 11.905 mol air

298.15 K 298.15 K
!
(b) Standard reaction at 298.15 K
9 .405 N2
Figure 15.2: Calculation path
for combustion process of
Ex. 15.1.
(c) Mix at 298.15 K
(d) Heat to 460 K
12.905 mol flue gas

460 K
Step a: For unmixing the entering air, Eqs. (12.37) and (12.35) with changes of
sign give:
D.Ha =0
6.Sa = nR Li )I; ln Yi
= (11.905)(8.314 )(0.2lln0.21 +0.79ln0.79) = -50.870J K- 1
15.1. Thermodynamic Analys is of Steady-State Flow Proces ses 639
Step b: For the standar d reaction at 298.15 K,
b. Hb = b.H~98 = -802,625 J
Step c: For mixing to form the flue gas,
b.Hc = 0
tlSc = - nR L;Yi In Yi
= -(12.90 5)(8.31 4)(0.07 75 ln 0.0775 + 0.1550 In 0.1550
+ 0.0387 ln0.0387 + 0.7288 ln0.7288) = 90.510 J K - 1
Step d: For the heating step, the mean heat capacities between 298. 15 and 460 K
are calculated by Eqs. (4.8) and (5 .17) with data from Table C.J. The
results in J mol- 1 K- 1are summa rized as follows:
(Cp )H (Cp )s
C02 41.649 41.377

H20 34.153 34.106
N2 29.381 29.360
0 2- 30.473 30.405
Each individual heat capacity is multiplied by the numbe r of moles of

that species in the flue gas, and the products are summe d over all species.
This gives total mean heat capacities for the 12.905 mol of mixtu re:
(C~)H = 401.520 and

Then,
b.Hd = ( C~ )H (T2- Tt) = (401.520)(460 - 298.15 ) = 64,986 J

T2 460
b.St~ = (C~)s ln- = 400.92 2 1n
298.15
= 173.85 2 J K - 1
Tt
For the total process on the basis of 1 mol CH4 burned ,
b. H = ~ b. H; =0 - 802,625 + 0 + 64,986 = -737,6 39 J

5.306 + 9Q 510 + 173.852 = 208.18 6 J K-
1
b.S = ~ b.S; = -50.870 -
1
Thus, b.H = -737. 64 kJ b.S = 0.2082 kJ K-
1
The steam rate fou nd in Ex. 8. 1 ism = 84.75 kg s- An energy balanc e for
the furnace/boiler unit, where heat is transfe rred from the combu stion gases to the
steam, allows calculation of the enterin g methane rate ticH 4 :
(84.75 )(3,39 1.6- 203.4) + liCH.$ (-737. 64) = 0

whence licH4 = 366.30 mol s- 1

The ideal work for the process, given by Eq. (5.26):
Wideal = 366.30(-737.64- (298.15)(0.2082)] = -292.94 X 103 kJ S- 1
or Wideal = -292.94 X 103 kW
"'
The rate of entropy generation in each of the four units of the power plant is
calculated by Eq. (5.22), and the lost work is then given by Eq. (5.34).
Furnace/boiler: We have assumed no heat transfer from the furnace/boiler to

the surroundings; therefore Q = 0. The term L:::.(Sm)rs is simply the sum of the
entropy changes of the two streams mu ltiplied by their rates:
Sc = (366.30)(0.2082) + (84.75)(6.6858- 0.6580) = 587.12 kJ s- 1 K-L
or Sc = 587.12 kW K- 1
and W1ost = TtrSc = (298.15)(587.12) = 175.05 x 103 kW
Turbine: For adiabatic operation,
Sc = (84.75)(7.6846- 6.6858) = 84.65 kW K - 1
Wlost = (298.15)(84.65) = 25.24 X 10 kW
3
and
Condenser: The condenser transfers heat from the condensing steam to the
surroundings at 298.15 Kin an amount determin'ed in Ex. 8.1:
Q(condenser) = - 190.2 x 103 kJ s- 1
200
+ ~ .15
29
19 1
Thus Sc = (84.75)(0.6493- 7.6846) = 4 1.69 kW K -
and Wlost = (298.1 5)(41.69) = 12.32 X 103 kW

Pump: Since the pump operates adiabatically,
1
Sc = (84.75)(0.6580 - 0.6493) = 0.74 kW K -
. 3
and Wlost = 0.22 X I 0 kW
The entropy-generation analysis is:
kWK- 1 Percent of :L Sc
Sc (furnace/boiler) 587.12 82.2

Sc(turbine) 84.65 11.9
Sc(condenser) 4 1.69 5.8
. 0.74 0.1
Sc(pump)
l:Sc 714.20 100.0

: _-.1. Thermodynamic Analysis of Steady-State Flow Processes 6-H
A work analysis is carried out in accord with Eq. (15.3):
The results of this analysis are:

.
kW Percent of IWideall
IWsl (from Ex. 8. 1) 80.00 X J03 27 .3(==TJt)

W1ost (furnace/boiler) 175.05 X 103 59.8
. 25.24 103 8.6
WJost(turbine) X
W1ost(condenser) 12.43 X 103 4.2

Wlost(pump) 0.22 X 103 0.1
Iwidea! l 292.94 X 103 100.0
The thermodynamic effi ciency of the power plant is 27 .3%, and the major source
of inefficiency is the furnacelboile~. The combustion process itself accounts for
most of the entropy generation in this unit, and the remainder is the result of heat
transfer across finite temperature differences.
Example 15.2
Methane is liquefied in a simple Linde system, as shown in Fig. 15.3. The methane
enters the compressor at 1 bar and 300 K, and after compression to 60 bar is cooled
back to 300 K. The product is saturated liquid methane at 1 bar. The unliquefied
methane, also at 1 bar, is returned through a heat exchanger where it is heated to
295 K by the high-pressure methane. A heat leak into the heat exchanger of 5 kJ is
assumed for each kilogram of methane entering the compressor. Heat leaks to other
parts of the liquefier are assumed negligible. Make a thermodynamic analysis of the
process for a surroundings temperature of Tu == 300 K.
Solution 15.2
Methane compression from 1 to 60 bar is assumed to be C{lrried out in a three-
stage machine with inter- and after-cooling to 300 K and a compressor efficiency
of75%. The actual work of this compression is estimated as 1,000 kJ per kilogram
of methane. The fraction of the methane that is liquefied z is calculated by an
energy balance:
where Q is the heat leak from the surroundings. Solution for z gives
_ H 6 - H2 - Q _ 1,188.9 - l , 140.0 - 5 _ O O
z- - - . 486
H6- H4 1, 188.9 - 285.4
642 CHAPTER 15. Thermodynamic Analysis of Procn.
Q from cooling Q from heat

leak= + 5 kJ
CH 4 feed
1.00 kg
_ _(b_a_s_is_) ---i~ Compression/ ._,.;..__2_ ..._ _________ .,___3_-.....
1 Throttle
cooling Exchanger r---+----:"" valve
- - - -- - ---~--i
5
w:f = 1,000 kJ
, 6
Unliquefied CH 4
.. 0.9514 kg 4
Liquid CH 4
0.0486 kg
Figure 15.3: Linde liquefaction system for Ex. 15.2.
This result may be compared with the value of 0.0541 obtained in Ex. 9.3 for the
same operating conditions, but no heat leak.
The properties at the various key points of the process, given in the accom-
panying table, are either available as data or are calculated by standard methods.
Data are from Perry and Green. 1 The basis of all calculations is I kg of methane
entering the process, and all rates are expressed on this basis.
Point State of the Ct4 TIK Plbar ' HikJ kg- 1 SfkJ kg- 1K- 1
1 Superheated vapor 300.0 1 1, 199.8 11.629

2 Superheated vapor 300.0 60 1,140.0 9.359
3 Superheated vapor 207.1 60 772.0 7.798
4 Saturated liquid 111.5 1 285.4 4.962
5 Saturated vapor 111.5 1 796.9 9.523
6 Superheated vapor 295.0 1 1,188.9 11.589
The ideal work depends on the overall changes in the methane passing through
the liquefier. Application of Eq. (5.25) gives:
Wideal = Ll(Hrn)fs- Tall(Srn)fs

= l(0.0486)(285.4) + (0.9514)(1,188.9)- 1,199.8]
- (300)[(0.0486)(4.962) + (0.9514)(11.589)- 11.629] = 53.8 kJ
1R. H. Perry and D. Green, Perry's Chemical Engineers' Handbook, 7th ed., pp. 2-25 1
and 2-253. McG:z
New York, 1997.
_aermodynamic Analysis of Steady-State Flow Processes 643
The rate of entropy generation and the lost work for each of the individual
~eps of the process are calculated by Eqs. (5.33) and (5.34).
Compression/cooling: Heat transfer for this step is given by an energy balance:

Q = D.. H - Ws = ( H2 - H1) - Ws
= (1,140.0- 1,199.8)- 1,000 = -1 ,059.8 kJ
. Q
Then, SG = S2 - St - Ta
= 9.359- 11.629 + ! ,~~~ 8 = 1.2627 kJ kg- 1 K- 1

Wlost = (300) (1.2627) = 378.8 kJ kg- I
Exchanger: With Q equal to the heat leak,

. Q
SG = (S6- Ss)(l - z) + (S3 - S2)(l) - -
Ta
. 5
Then, Sa = (11.589- 9.523)(0.9514) + (7.798- 9.359) - 300
' 0.3879 kJ kg- 1 K - 1
Wtost = (300)(0.3879) = 116.4 kJ kg- l
Throttle: For adiabatic operation of the throttle and separator,

Sc = S4z + Ss (1 - z) - S3
= (4.962)(0.0486) + (9.523)(0.95 14) -7.798

= 1.5033 kJ kg- 1 K- 1
Wtost = (300)(1.5033) = 451.0 kJ kg- I
The entropy-generation analysis is:

'\
kJ kg- 1 K- 1 Percent of L Sc
-
Sc (compression/cooling) .9"1.2627 40.0
.
SG (exchanger) ~.3879 12.3
~
SG(throttle) 1.5033 47.7
LSc 3.1 539 100.0

The work analysis, based on Eq. (15.2), is:
Percent of Ws
w ideal 53.8 5.4(=1Jt)

WlostCcompression/cooling) 378.8 37.9
WtostCexchanger) 116.4 11.6
WlostCthrottle) .r 451.0 45.1
Ws 1,000.0 100.0
The largest loss occurs in the throttling step. Replacing this highly irreversible
process by a turbine results in a considerable increase in efficiency.
From the standpoint of energy conservation, the thermodynamic efficiency of a process

should be as high as possible, and the entropy generation or lost work as low as possible.
The final design depends largely on economic considerations, and the cost of energy is an
important factor. The thermodynamic analysis of a specific process shows the locations of the
major inefficiencies, and hence the pieces of equipment or steps in the process that could be
altered or replaced to advantage. However, this sort of analysis gives no hint as to the nature
of the changes that might be made. It merely shows that the present design is wasteful of
energy and that there is room for improvement. One function of the chemical engineer is to
try to devise a better process and to use ingenuity to keep operating costs, as well as capital
expendjtures, low. Each newly devised process may, of course, be analyzed to determine what
improvement has been made. '
PROBLEMS
15.1. A plant takes in water at 70(F), cools it to 32(F), and freezes it at this temperature.
producing 1(lbm)(s)- 1 of ice. Heat rejection is at 70(F). The heat of fusion of wa ter
is 143.3(Btu)(lbm)- 1.
(a) What is Wideal for the process?

(b) 'vVhat is the power requirement of a single Carnot heat pump operating bet,, ee-
32 and 70(F)? What is the thermodynamic efficiency of this process? What i :_
irreversible feature?
(c) What is the power requirement if an ideal tetrafluoroethane vapor-compre _! -
refrigeration cycle is used? Ideal here implies isentropic compression, infir~
cooling-water rate in the condenser, and minimum heat-transfer driving forc6 -
evaporator and condenser of 0(F). What is the thermodynamic efficiency of~
process? What are its irreversible features?
Problem s
645
(d) What is the power requirem ent of a tetrafluoroethane vapor-compression cyc

le for
whi ch the compressor efficiency is 75%, the minimum temperature differences in
evaporator and condenser are 8(F), and the temperature rise of the cooling water
in the condenser is 20(F)? Make a thermodynamic analysis of this process.
15.2. Con ider a steady-flow process in which the following gas-phase reaction takes place:
CO+ ~ 02 ~ C02. The surroundings are at 300 K.
(a) What is Wideal when the reactant e nter the process as pure carbon monoxide and
as air containi ng the stoichiometri c amount of oxygen, both at 25C and I bar, and
the products of complete combustion leave the process at the same conditions?
(b) The overall process is exactly the same as in (a), but the CO is here burned
in
an adiabatic reactor at I bar. What is Wideal fo r the process of cooling the flue
gases to 25C? What is the irreversible feature of the overall process? What is its
thermodynamic efficiency? What has increased in entropy, and by how much?
15.3. A plant has saturated steam availabl e at 2,700 kPa, but there is little use for this steam.
Rather, steam at 1,000 k.Pa is required. Also available is saturated steam at 275 k.Pa.
A suggesti on is that the 275-kPa steam be compressed to 1,000 kPa, using the work of
expanding of the 2,700-kPa steam to 1,000 kPa. The two streams at 1,000 k.Pa would
then be mi xed. Determine the rates at which steam at each initial pressure must be
supplied to provide enough steam at 1,000 kPa so that upon condensation to saturated
1
liquid heat in d1e amount of 300 kJ s- is released ,
(a) If the process is carried out in a completely reversib le manne r.

(b) If the higher-pressure steam expands in a turbine of 78% efficiency and the
lower-
pressure steam is compressed in a machine of 75% efficiency. Make a thermody-
namic analy is of this process.
15.4. Make a thermod ynamic analysis of the reftigeration cycle of Ex. 9.1 (b).
15.5. Make a thermodynamic analysis of me refri geration cycle describe d in one of the parts
of Pb. 9.9. Assume that the refrigeration effect maintains a heat reservoi r at a tem-
perature I 0(F) above the evaporation temperature and that Ta is I 0(F) below the
condensation temperature.
15.6. Make a Lhermodynamic analysis of the refrigeration cycJe describe d in the first para-
graph of Pb. 9.12. Assume that the refrigeration effect maintains a heat reservoi r at a
temperature 10(F) above the evaporation temperature and that Ta is 10( F) below the
condensation temperature.
d
15.7. A colloidal solution enters a single-e ffect evaporator at 100C. Water is 1vaporize
.
from the soluti on, producing a more concentrated olu tion and 0.5 kg s- of steam
at 100C. Th is steam is compressed and sent to the heati ng coils of the evaporator
to supply the heat requ ired for its operation. For a min imum heat-tran sfer driving
force across the evaporator coils of 10C, for a compressor efficiency of 75%, and
646 CHAPTER 15. Thermodynamic Analysis of ~
for adiabatic operation, what is the state of the steam leaving the heating coils _
evaporator? For a surroundings temperature of 300 K, make a thermodynamic ~
of the process.
15.8. Make a thermodynarruc anaJysis of the process described in Pb. 8.8. Ta = 80CF
15.9. Make a thermodynamic analysis of the process described in Ex. 9.3. Ta = 295 :-
'
'
Chapt er 16
Introduction to Molecular
Thermodynamics
Classical thermodynamics is a deductive science, in which the general features of macroscopic-

system behavior follow from a few laws and postulates. However, the practical application of
thermodynamics requi res values for the properties of individual chemical species and their
mixtures. These may be presented either as numerical data (e.g., the steam tables for water)
or as con-elating equations (e.g., a P VT equation of state and expressions for the temperature
dependence of ideal-gas heat capacities). '
The usual source of property values is experiment. For example, the ideal-gas equation
of state evolved as a statement of observed volumetric behavior of gases at low pressures.
Similarly, the rule of thumb that Cp ~ 291 mol- 1 K- 1 for diatomic gases at normal temper-
atures is based on experimentaJ observation. However, macroscopic experiments provide no
insight into why substances exhibit their observed property values. The basis for insight is a
microscopic view of matter.
A central dogma of modern physics is that matter is particulate. The quest for the ul-
timate elementary particles is still in progress, but for engineering purposes we may adopt
the following picture: ordinary matter consists of molecules; molecu les consist of atoms; and
atoms consist of a positively charged nucleus (comprising neutrons and protons), surrounded
by negatively charged electrons. Atoms and molecules with equal numbers of electrons and
protons have no net charge and are neutra l.
16.1 MOLECULAR THEORY OF FLUIDS
Molecules are small and light: typical linear dimension~ are 10- to 10- m, and typical
10 8
masses are I o- 27 to w- 25 kg. Hence the number of molecules in a macroscopic system is

23
enormous. For example, one mole of matter contains ro22 X I 0 molecules (Avogadro's
number). Because of these features- smallness, lightness, and numerical abundance- the
proper description of behavior at the molecular level and)ts extrapolation to a macroscopic
scale require the special methods of quantum mechanics and statistical mechanics. We pursue
neither of these topics here. Instead, we present material useful fo r relating molecular concepts
to observed thermodynamic properties.
647
~ - - - - - - - - - --- ---------
648 CHAPTER I 6. In troduction to Molecular Thermodynamics
Intermolecular Forces and the Pair-Potential Function

As noted in Sec. 3.3, an ideal gas is characterized by the absence of molecular interactions:
nevertheless, it still possesses internal energy. This energy is associated with the individ-
.. their motion. Real gases and other fluids are comprised of
ual molecules, and results from
molecules that have not only the energ~of individual molecules, but also energy that is shared
among them because of intermoleculcy: forces. This intermolecular potential energy is asso-
ciated with qollections of molecules, and is the form of energy that reflects the existence of
such forces. Well established is the fact that two molecules attract each other when they are
far apart and repel one another when close together. Electromagnetic in origin, intermolecular
forces represent interactions among the charge distributions of neighboring molecules.
Figure 16.1: The intermolecular

potentiaJ energy U for a pair of
structureless, neutral molecules.
(Not to scale.)
Figure 16.1 is a sketch of the intermolecular potential energy U for an isolated pair of
spherically symmetric neutral molecules, for which U depends only on the distance between
the molecular centers, i.e., on the intermolecular separation r. (More generally, U is also a
function of the relative orientations of the two molecules.) The intermolecular force F is
proportional to the r-derivative of U:
F (r) = _ _d_U_(,_
')
dr
By convention, a positive F represents an intermolecular repulsion, and a negative Fan inter-

molecular attraction. Hence (Fig. 16.1) molecules repel each other at small separations, and
attract each other at modest-to-large separations.
An algebraic expression for the pair-potential function U is one of the tools of the trade
of the molecu1ar scientist or engineer. The methods of statistical mechanics provide for Hs
relation to both thermodynamic and transport properties. Shown in Fig. 16.1 are specific values
for U and r that may appear as species-dependent parameters in a pair-potential function.
The hard-core diameter d is a measure of the center-to-center separation for which U,
and hence F, becomes infinite. It is not subject to precise determination, but plays the role
16.1. Molecular Theory of Fluids 649
of a modeling parameter in some expressions for U. The collision diameter a is defined as

the separation for which U = 0. The equilibrium separation ro is the separation for which U
attains its minimum value of - E. At r = ro, the net intermolecular force is zero. Quantity E
is called the well depth. For a particular class of chemical species (e.g., noble gases, or cyclic
alkanes), each of these special quantities increases with increasing molecular size. Typical
20 J.
ranges of values for a and E are a ~ 3 to 8 >< 10- 10 m and ~ ~ 0.1 to 1.0 x 10-
Commonly, ro is about 10 to 15% greater than a.
1
Scores of expressions have been proposed for U. All are essentially empirical, although
their functional forms often have some basis in theory. The most widely used is the Lennard-
lones (LJ) 12/6 pair-potentiaLfimction:
(16.1)
Equation (16.1) provides semiquantitative representations of thermodynamic and transport

properties for nonpolar substances of relatively simple molecular structure. In Eq. ( 16.1),
6
the r - 12 term is supposed to represent bimolecular repulsions, and the ,.- term bimolecular
12
attractions. Although tlie attraction term has significant theoretical justification, the ,.- de-
pendence for repulsions is chosen primarily for mathematical convenience. Table 16.1 shows
some values of the dimensionless potential energy U I E as a function of the dimensionless sepa-
ration r fa, as implied by Eq. (16. 1). Clearly, the effects of intermolecular forces are s ignificant
only over a modest range of separations. Although they operate over an infinite range (U and
F together approach zero only in the limit as r ~ oo), both U and F for neutral molecular
pairs are numerically negligible for separations greater than about 10 molecular diameters.
Contributions to the Intermolecular Potential Energy 2

The origins of intermolecular forces stem from the essential concept that a molecule is a dis-
tribution of charges: a colleclion of positively charged nuclei, surrounded by a cloud of neg-
atively charged electrons. Intermolecu]ar repu lsions at sufficie ntly small separations therefore
result from the overlap of electron clouds of interacting molecules, giving rise to a Coulombic
repulsion. At still smaller separations the positively charged nuclei "see" each other: again
promoting repulsion.
The origins of intermolecular attractions are less obvious, and several mechanisms can
contribute. First, consider the electrostatic interaction of two rigid charge distributions A and
B. By Coulomb's law, the electrostatic potential energy of interaction U(el) is:
U(el) = _ 1_ LA LB. q; qj (16.2)

4nEo l
. J
r; 1
1 Fora compilation of expressions for Usee G. C. Maitland, M. Rigby, E. B. Smith, and W. A. Wakeham, !mer-
molecular Forces: Their Origin and Determination , app. I, Clarendon Press, Oxford, 198 t.
2 A comprehensive discussion of these contributions to U(r) is given by J. 0. Hirschfelder, C. F. Curtiss, and

R. B. Bird, Moleculctr Theory of Gases and Liquids, pp. 25-30, 209, 983- 1020, John Wi ley and Sons, New York,
1954.
650 CHAPTER 16. Introduction to Molecular Thermodynamics
Table 16.1: Bimolecular Potential Energy as a Function of Separation for the Leonard-
Jones 12/6 Potential.
rju U jE rja U jE
'--
0.0000 00 1.0267 -0.5
0.6279 1000 1.1225 - 1
0.7521 100 J .8413 - 0.1
0.8797 10 2.7 133 -0.01
0.9691 J 3.9841 - 0.001
j .0000 0 00 0
Here, q; is a charge in distribution A , q j is a charge in <listribution B, and r ;j is the separation

between charges q; and qj. Quantity Eo is the electric permittivity of vacuum, a physical
constant3 equal to 8.85419 x 10- 12 C y - l m- 1 . (The unit of electric charge is the coulomb C,
and the unit of electric potential difference is the volt V.) The sums are taken over all charges
in the distributions.
Equation (16.2) is exact, but awkward to use as it stands. Application is facilitated when
the charge separation r ij is replaced by the center-of-mass separation r of the two distributions.
Statistical averaging of contributions from all orientations of charge distribution yields the
4
foJlowing approximate expression for U(el) for two neutral rigid charge distributions:
2 /);2jJ.2 1
U (el) =- - A B - . ( 16.3)
'3 k T (4nEo) 2 r6
1
Quantity k is Boltzmann's constant, equal to 1.381 x 10- 23 J K- ; /J-A and f.LB are the per-
manent dipole moments for charge distributions A and B associated with the molecules. Thi
contribution to the pair-potential function varushes only when one of the permanent 9 ipole mo-
ments is zero. The averaging procedure which leads to Eq. (16.3) produces several remarkable
results:
Even though the distributions are electrically neutral, there is a net attraction between
them.
The dependence of U(el) on charge-distribution orientation becomes on averaging an

r - 6 dependence.
As given by Eq. (16.3) U (el) varies wi th T - 1 Hence the magnitude of the permanen-
dipole interaction decreases with increasing temperature.
Equation (16.3) is the simplest example of a direct electrostatic potential for two ne_-
tral molecules; here, the dipole moment emerges as an important physical property. D ip<h~
3unrelated to the well depth of Fig. 16.1.
4-rhis result is only valid for modest dipole moments. For a discussion, see T. M. Reed and K. E. Gubbins. A;,
Starisrica/ Mechanics, sec. 5-7, McGraw-Hill, New York, 1973.
16. 1. Molecular Theory of Fluids 651
moments are measures of the net separation of charge within a molecule. For a spherically
symmetric neutral charge distribution (e.g., an atom of argon), f.L is zero. For a molecule in
which charge+ lq I is separated from charge -lq I by distance l , the dipole moment is f.L = lq 11.
Hence f.L has dimensions of charge x length; its SI unit is the coulomb(C)-meter(m). How-
3
ever, values are usually reported in debyes (D); I D = 3.3357 x 10- C m. A molecule with
a nonzero dipole moment is called polar. Water (fL = l.9 D), acetone (J.L = 2.9 D), and ace-
tonitrile (J.L = 4.0 D) are strongly polar molecules. Carbon monoxide (J.L = 0.1 D), propylene
(J.L = 0.4 D), and toluene (J.L = 0.4 D) are slightly polar. Carbon dioxide, neon, nitrogen, and
n-octane are nonpolar (J.L = 0).
The dipole moments just discussed are permanent dipole moments, intrinsic properties
of a molecule. A net separation of charge may also be induced in any molecule by application
of an external electric field. The induced dipole moment J,L(ind) so created is approximately
proportional to the strength of the applied field. Thus, for molecule A, J.L A (ind) = a A E, where
E is the applied field strength and aA is the polarizability of A. If the source of the electric
field is a permanent dipole in a neighboring molecule B , then the contribution to U from the
permanent dipole/induced dipole interaction is:
J.L1aA I
U=- -
(4rrEo) 2 r 6
'
If molecules A and B are both polar (J.LA, J.L n =f. 0), then the complete expression for the
potential energy of induction U(ind) is: 5
U(ind) = _ (J.L~ao + J.L~aA) _I (J 6.4)

(4rrEo) 2 r6
The polarizability a, like the permanent dipole moment J.L, is an intrinsic property of
a molecule. SI units for a are C m2 y - l , but values are usuall y reported for the quantity
& = aj4rrEo, in cm3 . The volumetric uni ts for & suggest a possible connection between
polarizability and molecular volume. Typically, & increases with molecular volume: very
a a
roughly, ~ 0.05 a 3 , where a is the molecular collision diameter. Hence normally falls in
the range of about 1 to 25 x 10- 24 cm3.
The two types of dipole (and dipole moment) so far discussed, permanent and induced,
can both be rationalized and treated by the methods of classical e lectrostatics, and both produce
a contribution to U proportional to r- 6 . There is yet a third kind of dipole, an instantaneous
dipole, whose calculation requires the methods of quantum mechanics. However, its existence
can be rationalized on semi-classical grounds. If we picture a molecule A as nuclei with orbit-
ing (i.e., moving) electrons, then we can imagine that a snapshot might show an instantaneous
but temporary net separation of molecular charge~ This is manifested as an instantaneous
dipole, which induces a dipole in a neighboring molecule B. Interaction of the dipoles results
in the intermolecular dispersion force, with corresponding dispersion potential U(disp) given
for large separations as:
(16.5)
5see Reed and Gubbins, op. cit.

652 CHAPTER 16. Introduction to lv!olecular Thermodyna mics
Here, I is the first ionization potential, the energy required to remove one electron from a
neutral molecule. Typically, I is of magnitude 1 to 4 x 1o-J8 J. All molecules possess nonzero
ionization potentials and p~larizabilities; hence all molecular pairs experience the dispersion
interaction.
6
Th~ dispersion potentiaJ U(disg); like U(el) and U(ind), varies as ,.- . When molecules
6
A and B are identical, these three special results Jend justification for the r- attraction
term in empirical intermolecu lar potential functions such as the Lennard-Jan es 12/6 poten-
tial, Eq. (16.1). For identical molecules A and B , f.J.A = f.J.B = J-'-, and Eqs. (16.3), (16.4), and
(16.5) produce the expressions:
4
2 f.J- 1
U(el) = ( 16.6)
3 kT(4nEo) 2 r6
2JJ-2 Ct 1
U(ind) = - - ( 16.7)
(4nEo) 2 r6
3 a21 I
U(disp) = - - - (J 6.8)
4 (4nEo)2 r6
These equations provide estimates of the contributions of di rect-electros tatic, induction, and
dispersion forces to the intermolecu lar potential for pairs of identical molecules. Thus, if
C6
U(long range) = - - 6
r '
then C6 = 1 2
(2
- - + 2!-'-
3 kT
f.J-
4
2 et
4
3
+ -a 2I ) (16.9
(4nEo)
Quantity C6 is a measure of the strength of long-range intermolecu lar attractions. Fractional

contributions of the three mechanis ms to long-range forces are:
f(el) = U(el)/ lJ f (ind) = U(ind)/~ f(disp) = U(disp)/Z:
where ~ = U(el) + U(ind) + U(disp)

and the U's are given by Eqs. (16.6), (16.7), and ( J6.8).
Values of C6 calculated by Eq. (16.9) and the fractional contribution s made by elec~
static, induction, and dispersion interactions to U are summarized in Table 16.2 for 15 pc:=
substances, illustrating concepts just developed. Also shown are values of f-1-, &, and I for etr::!
species, and, in the last column, the ratio of the direct electrostatic to dispersion contributi
f(el) U(el) 8 1-'-4

- =- --=---
f(disp) U(disp) 9 a 2 lkT
The dimensionless ratio f (el)If (disp) is a measure of the effective polarity of a specie . _-
the following:
In alJ cases, the magnitude of the dispersion interaction is substantial, even when _:
is small. These interactions can rarely be ignored.
-
~
.._
~
......
~
-
c:
...,~
Table 16.2: Long-range Attra ctions for Poljlr Mole cules at ;1
298 K nl
0
~
Comp ound pJD &/10- 24 cm3 I I lo-18 1 C6/I0 -78 J m6 f(cl)
0
,.....,
.f<ind ) .f(disp ) .f(el)lf(disp )
~
co
C3H6
0.1
0.4
2.0
6.0
2.2
1.6
6.6
43.4
2.45 x lo-5
9.55 x to- 4
0.001 0.999 2.45 x lo-5 -
c:
~
0.004 0.995 9.60 X 10- 4
C6 H5 CH:o ,oA 12.3 1.4 159.3 2.60 x 10-4 0.003 0.997 2.61 X 10-4
HI 0.5 5.5 1.7 38.9 0.003 0.007 0.990 0.0026
HBr 0.8 3.6 l.9 19.6 0.034 0.024 0.942 0.0359
CHCI3' l.O 9.0 1.8 112.8 0.014 0.016 0.970 0.0148
HCJ , 1. 1 2.6 2.1 13.7 0.174 0.046 0.780 0.223
(C2H shO 1.2 8.7 1.5 9 1.0 0.037 0.028 0.935 0.0394
NH3 1.5 2.4 1.6 16.2 0.506 0.067 0.427 1.19
HF 1.9 0.8 2.5 22.9 0.922 0.025 0.053 17.6
H20 1.9 1.5 2.0 25.6 0.826 0.042 0.132 6.26
Cs HsN 2.5 9.4 1.5 174.4 0.363 0.067 0.570 0.637
(CH3)2CO 2.9 6.4 1.6 174.5 0.656 0.062 0.282 2.33
HCN 3.2 2.6 2.2 186.3 0.912 0.029 0.059 15.2
CH3C N 4.0 4.5 2.0 459.5 0.903 0.031 0.066 13.7
"'
t;)\
til
I iJ
654 CHAPTE R 16. Introduction to Molecular Thermodynamics
The fractional contribution f(i nd) of inductio n interactions is generall y small, never
exceedin g about 7%.
Contribu tions from permane nt dipoles at near-am bient temperatures, through U(el) and
U(ind), are small (less than about 5% of the total) for values of JJ- less than 1 D. Hence
substanc es such as propylen e (C3H6) and toluene (C6HsC H3) are common ly classified
as nonpolar, even though they have significant dipole moment s .
..
;
16.2 SECOND VIRIAL COEFFICIENTS FROM
POTENTIAL FUNCTIONS
The molar volume of a fluid depends on the behavior of its constitu ent molecule s, and is
therefore influenced by intermolecular forces. Thus a gas becomes more dense as the attractiv e
forces between molecul es become stronger. The referenc e point is an ideal gas, for which the
intermol ecular forces are zero. The nature and strength of these forces in an actual gas therefore
determin e the departur e of its molar volume from that of an ideal gas.
In the virial equation as given by Eq. (3.12), the first term on the right is unity, and
by itself provides the ideal-ga s value for Z. The remainin g terms provide correctio ns to the
ideal-ga s value, and of these the term 8 IV is the most importan t. As the two-bod y-interac tion
term, it is evidentl y related to the pair-potential function discusse d in the precedin g section.
For spherica lly sy mmetric intermol ecular force fields, statistica l mechani cs provides 6an exact
expressi on relating the second virial coefficie nt 8 to the pair-pote ntial function U(r):
B = -2rc N A fo"" (e-UV)/ kT - I) r 2 dr (16.10)
Quantity N A is Avogadr o's number, and k = R / N A is Boltzmann's constant. By assumpt ion.

U(r) depends only on the intermol ecular separatio n r between pairs of molecu les. Given an
expressi on for the pair-pote ntial function U (r), one determin es 8 (T) by evaluatio n of the inte-
gral in Eq. (16.10). For realistic potential functio ns (Fig. 16. 1), the integration must generall y
be done numeric ally or by series techniqu es. Howeve r, for rectilinear potential functio ns-
those in which U(r) is defined by a collectio n of straight- line segment <;- one can obtain
closed-f orm analytica l expressi ons for B(T).
The simplest realistic rectiline ar potentia l function is the square-w ell potentia l U(sw ).
shown in Fig. J6.2. It consists of four segments, producin g the followin g piecewis e contribu-
tions to U:
U (sw) = oo for r < d }
U(sw) = -E for d < r ~ l d ( 16.1 1
U(sw) = 0 for l d < r
Here, d = a, and the hard-cor e and collision diamete rs are identica l; E is the well depth; and
l is a constant which defines the width of the well. Compar ison of Fig. 16.2 with Fig. 16.:
shows that U(sw) mimics many of the features of the " true" intermol ecular potentia l ener~
for which repu lsions prevail for sufficiently small separatio ns, and attractio ns dominate fc-
intermed iate separatio ns. For sufficien tly large separations, U becomes negligible.
60 . A. McQuarrie, Statistical Mechanics, p. 228, Harper and Row, New York, 1976.
16.2. Second Virial Coefficients from Potential Functions 655
U(sw)
Figure 16.2: The

-+- d -+
square-well potentia) U(sw)
ld for a pair of molecules.
0~~~,----------~
- E r-
,..
With U (sw) given by Eq. (16.11), evaluation of B by Eq. (16.10) is a straightforward
exercise in integration. The result is:
(16.12)
where the first term in the square brackets (i.e., 1) arises from the repulsion part of the poten-
tial and the remaining tetm from the attraction part. Equation (16.12) therefore provides the
fo llowing insights into the behavior of the second virial coefficient:
The sign and magnitude of B are determined by the relative contributions of attractions
and repulsions.
At low temperatures, attractions dominate, producing negative values of B . The stronger

the attractions (as determined by the magnitudes of E and l ), the more negative is B at
fixed T .
At high temperatures , repulsions dominate, producing positive values of B. In the (hy-

pothetical) limit of infinite temperature, B approaches the value:
. 2 3 ..
lim B (sw) = -nNAd = 4vm
T-400 3
where Vm
,.
is the volume occupied by a m9 Ie of hard spheres of diameter d.
At the Boyle temperature Te, the contributions of attractions are exactly balanced by
those of repulsions, and B is zero. For the square-wetlpotential, according to Eq. (16. 12),
j_ Ejk
Ts(sw)- ~ ( [3 )
ln -:,.,--
p - 1
Hence, the stronger the attractions, the higher is the Boyle temperature.
656 CHAPTER 16. Introduction to M olecular Thermodynamic
,_ 70 2000 T/K
I -100
0
E
M
E
u
~
- 200
- 300
Figure 16.3: Second vi rial coefficients for argon by the square-well potential. Circles are data: ll!1~
given by Eq. (16.12).
Although Eq. (J 6.12) is based on an intermolecular potential function that i ii:

unrealistic, it nevertheless often provides an excellent fit of second-virial-coefficiem dz.:...:...
example is provided by argon, for which reliable data forB are available over a wide re~
ture range, from about 85 to l ,000 K. 7 The correlation of these data by Eq. ( L6.1 2) a ~r-
Fig. 16.3 results from the parameter values E/ k = 95.2 K, l = l.69, and d = 3.07 x IC-,;;;-
This empirical success depends at least in part on the availabi lity of three adjustable ~
ters, and is no more than a limited validation of the square-wen potential. Use of th.i pc:.=
does illustrate by a very simple calculation how the second virial coefficient (and heru:_
volume of a gas) may be related to molecular parameters.
7J. H. Dymond and E. B. Smilh, Tlze Virial Coej]iciems of Pure Gases and Mixtures, pp. 1- 10. Claren:b:.
Oxford, 1980.
16.3. Internal Energy of Ideal Gases: Microscopic View 657
Such calculations carried out for more-realistic potential functions, though of greater
complexity, also lead to values for molecular parameters. For example, experimental volumet-
ric data for many gases have been regressed to yield values of u and E for the Lennard-l ones
8
potential [Eq. (16.1 )]. Values from several potential functions are given by R. L. Rowley. Th is
is an essential source of vaJues, because theory does not provide the means for their prediction.
One must remember, however, that potential functions are empirical models, and as such are
approximations. The deficiency of a model is reflected by the values of the molecular param-
eters regressed from the model, and they must therefore be regarded as effective values of the
parameters. Different effective values result from the use of different potential functions.
Since transport properties, such as viscosity and diffusivity, are also related to these same
polential functions, data for the transport properties, particularly viscosity, are also used to pro-
vide values forE and a. Note, however, that any deficiency in the potential function influences
the calculation of values in different ways, and the same molecular parameters obtained from
different data sources are rarely in exact agreement.
16.3 INTERNAL ENERGY OF IDEAL GASES:

MICROSCOPIC VIEW
'
Thermodynamic properties such as internal energy and enthalpy arc manifestations on a gross
scale of the positions, motions, and in teractions of the countless molecules comprising a
macroscopic system. The two theories that relate the behavior of molecules to macroscopic
properties are kinetic theory and statistical mechanics. These theories together represent a
very large body of extra-thermodynamic knowledge, well beyond the scope of this text. Our
purpose here is to indicate in a very elementary fashion how the energy associated with the
individual molecules of an ideal gas relates to the macroscopic internal energy of the ideal-gas
state.
A fundamental postulate of quantum theory is that energy is quantized, that energy on
the microscopic scale comes in very small discrete units. Thus a macroscopic system has
associated with it an enormous number of quanta of energy, which sum to delermine its energy
level. Quantum theory specifies that the set of energy levels "allowed" to a closed system is
determ ined by its volu me. This does not mean that fixing the volume of a system fixes its
energy; it just determines the discrete set of energy levels permilted to it. When a system is
isolated (constrained from exchanging either mass or energy with its surroundings), it exists at
one of the energy levels allowed to it. Each energy level of a system has associated with it a
number of quantum. states. This number g is known as the degeneracy of the level. Although
an isolated system exists at a particular~nergy level, it passes over time through all of the g
quantum states characterized by this same energy . ..
A large number of quantum states is accessible to a system of given volume in equilib-
rium with surroundings at fixed temperature. From the thetmodynamic point of view, fix ing T
and V establishes the state of lhe system, including Its internal energy. However, macroscopic
equilibrium does not imply a static situation on the microscopic scale. The ceaseless motion of
8 R. L. Rowley, Srmislica/ Meclumics for Thermophysica/ Property Calculations, app. 5, PTR Prentice Hall. En-
glewood Clilffs, NJ, 1994.
the molecules and their collisions with the walls of the container result in exchanges of energy
with the surroundings, which cause momentary fluctuations in the energy of the system. Thus
the internal energy of thermodynamics is an average over the discrete set of energy levels of
the allowed quantum states. Statistical mechanics provides the means for arriving at the proper
average value.
The fundamental postulate of statistical mechanics for a system of g iven volume in equi-
librium with surround ings at fixed temperature is that the probability of a quantum state de-
pends only on its energy, and all quantum states with the same energy have the same probabil-
ity. A value for the thermodynamic internal energy is found as the average of the energies of
the accessible quantum states, each weighted by its probability. The quantity of fundamental
importance to come out of this procedure is- the partitionfunction: 9
Z = """"'
LJ g;e -EfkTI (J6.13
where Ei is the energy of level i , g; is the degeneracy of the level, and k is Boltzmann .
constant. This quantity is a state function , from which all thermodynamic properties may be
found once it is known as a function of T and V. In particular, the internal energy is given b~ :
U =kT2 (aiaTn Z)v (16. 1-+)
Equations (16.13) and (16. 14) are written for the total energy of a macroscopic system.
The problem of their application is greatly simpJified for ideal gases, which (because of the
absence of molecular interactions) do not possess intermolecular potential energy. The inter-
nal energy of ideal gases is therefore associated with individual molecules, and results frorr:
translation and rotation of each molecule a~ a w hole and from rotations and vibrations intem a:
to the molecule. Energy is also associated with the electrons and nuclei of atoms. For idea:
gases all of these forms of energy are usually treated as separable, and this allows the parti tio~
function to be factored and written as a product of partition functions, each of which relate l
a particular form of molecular energy. It suffices for present purposes to treat the translationaJ
kinetic energy as separable from all other contributions. These other contributions together
constitute the intramolecular energy of a molecule, and they depend on molecular strucrur~.
We therefore write:
z = ZtranslationZintramolccuJar
N!
whence ln Z = In Zrranslation + ln Z intramolecular - In N! (16. 15
ln these equations the quantity N! arises because in the summation process the molecules are
treated as distinguishable from one another, whereas in fact they are indistinguishable. The
translational contribution comes from kinetic theory, whereas the intramolecular contributi or~
derive from quantum mechanics, w ith the quantized energy levels determined from appropriate
spectroscopic measurements.
9The name implies a sum over states partitioned according to energy levels. and
the symbol comes from ...--e
German word, Zustandssumme. sum-over-states. The other commonly used symbol is Q. which is used in this oo
ro represent heat.
16.3. Internal Energy of Ideal Gases: Microscopic View 659
For one mole of an ideal gas, the equation for the translational partition function is: 10
2TC mkT) (3/Z)NA

Ztranslation = v NA ( h2
where N A = Avogadro's number; m = mass of the molecule; and h = Planck's constant. In

logarithmic form this becomes:
3 2nmkT
ln Ztranslation = N A In V +-2 N A ln h2
Substitution into Eq. (16.15) gives:
3 2nmkT
ln Z = NA ln V + -NA
2
In ?
h-
- In NA! + lnZintramolecular (16.16)
where Zinrramolecular is evaluated by equations of the form of Eq. (16.13).
Differentiation of Eq. ( 16.16) with respect to temperature at constant V (and N A) yields:
In Z) ' = ~ N + ( aln
(8ar v 2 T
A Zintramolecular)
aT v
whence by Eq. ( 16.14) applied to the ideal-gas state,
Uig = ~N kT +kT2 ((JlnZimramolecular )

2 A ()T
v
Representing the final term by :F(T) and noting that N Ak = R reduces this to:
. 3
U'8 = - RT + :F(T) (16.17)
2
where R is the universal gas constant. Since Hig = Uig + RT ,
. 5
H'8 = - RT + :F(T)
2
In view of Eq. (2.20),
ct = c:;g)p= ~R~c~~)t (16.18)
The molecules of an ideal monatomic gas have no energy of rotation or vibration, and
:F(T) in Eq. (16.18) is therefore zero except at high temperatures where electronic energy
contributions become important. Thus in Fig. 4.1 the value of C ~8 j R for argon is constant at a
value of 5/2. For diatomic and polyatomic gases, :F(T) in Eq. (16.18) contributes importantly
at all temperatures of practical importance. The contribution becomes larger the more complex
the molecule and increases monotonically with temperatuJe, as is evident from the curves
shown in Fig. 4. 1 for Nz, H20, and COz.
10 0. A. McQuarrie, Swtislical Mechanics, pp. 81-82, Harper & Row, New York, 1976.
660 CHAPTER 16. Introduction to Molecular Thermo dynami cs
16.4 THERMODYNAMIC PROPERTIES AND

STATISTICAL MECHANICS
num-
The equatio ns of statistical mechanics are derived by application of Eq. (5.4 I) to a large
ber of macrosc opically identical systems (an ensemb le) in a11 of their many allowed quantum
ensem-
states. The entropy S as given by Eq. (5.42) is then a statistical average value for the
ble.11 Ultimately, the result is an equatio n for the entropy:
u
S = k lnZ + T (16.19)
given
where Z is the partition function, given by Eq. (16.13), and U is the internal energy as
by Eg. ( 16.14).
For an ideal gas, combin ation of Eqs. (16.16) and ( 16.17) with Eq. (16.19) yields:
i 3 2mnkT 3 F(T )
S g = kN A ln V + -kN A ln -k In N A! + In Zinrrarnolecular 1- - R + - T-
2 h2 2
Accord ing to Stirling 's formula ln NA! = NA lnNA- NA; also kNA = R. Maki ng these
substitutions gives:
. 3 2rrmkT 3 F(T)
S 1
g = R In V + 2 R ln h2 - R InNA+ R +In ZintramoJecular + 2R + -T-
...
Upon rearrang ement, this may be written:
. [(2rrmkT) 1 VeNA1
S = R
1
g In
h2
3 2 5 2
--
]
+In Zintramolccular +
F(T)
- -
T
(16.20
Equation (16.20) for the molar entropy of an ideal gas allows calculation of absolute
on the
entropies for the ideal-ga s state. The data required for evaluation of the last two terms
ci6
right are the bond distances and bond angles in the molecu les, and the vibratio n frequen
re
associated with the various bonds, as determi ned from spectToscopic data. The procedu
atomi ...
has been very success ful in the evaluation of ideal-gas entropie s for molecules whose
structures are known.
Both the classical and statistical equations fEqs. (5.40) and ( 16.20)1 yield absolute value-.:
12 calcula-
of entropy. As is evident from Table 16.3, good agreem ent between the statistical
i' e
tions and those based on calorimet1ic data is obtained. Results such as these provide impress
s result:
evidenc e for the validity of statistical mechanics and quantum theory. In some instance
acit:_
based on Eq. (16.20) are considered more reliable because of uncertainties in heat-cap
prmi&
data or about the crystallinity of the substance near absolute zero. Absolut e entropie s
11 Th1s mathematical development is lengthy but not unduly difficult. An elementary treatment is given by H. C. \
York, 1983. Much re-:
Ness, Understanding Thermodynamics. chap. 7, McGraw-Hill, New York. 1969; Dover, New
s, Harper & Row, New York. 1976, and R. L. Ro\\
comprehe nsive arc D. A. McQuarrie, Statistical Mechanic
Calculati ons. PTR Prentice Hall. Englewoo d Cliffs, NJ , 199.!.
Statistical Mechanics for Th ermophys ical Pmperty
12 From D. A. McQuarrie, op. cit .. p. 138.

16.4. Thermodynamic Properties and S tatistical Mechanics 661
Table 16.3: Absolute Entropies, Ideal-Gas State at 25 C and l(atm)
SiBfJ mol- 1 K- 1
Eq. (5.40) Eq. (I 6.20)

C0 2 21 3.4 2 13.8
NH3 192.5 192.9
N0 2 240.6 240.6
CH4 186.2 186.2
CH3Cl 234.3 233.5
C6H6 269.5 269.9
much of the dala base for calculation of the equilibri um conversions of chemical reaclions, as
discussed in Chap. 13.
The fundamental property relation most intimately connected with statistical mechan-
ics is Eq. (6.9), which expresses the differential of the Helmholtz energy as a function of its
canonical variables T and V :
dA = - P dV- SdT (6.9)
'
We remarked in connection with Eq. ( 16. 13) that the partition function Z is a state function
from which all thermodynamic properties may be found once it is known as a function of T
and V. Its relation to the Helmholtz energy fo llows from Eq. ( I6. 19), which may be written:
U- T S = -kT in Z
Reference to Eq. (6.2) shows that the left side of this equation is by definition the Helmholtz
energy A . Therefore,
I A= -kT tn Z I (16.2 1)
This equation provides a direct link between thermodynamics and statistical mechanics. Since
R = kNA, where NA is Avogadro's number, Eq. (16.2 1) may be expressed alternatively as:
A ln Z
- = - --
RT NA
Equations (6.37) through (6.39) for the Gibbs energy have as their counterparts analo-
gous equations for the Helmholtz energy. Derived from Eqs. (6.9) and (6.2), they are
I'*
d ( RTA) =- RTd U
P V - RT2dT ( 16.22)
_!_ = _ [ B(A JRT) ] (16.23)

RT av r
!!_ = - T[ 8(A/ RT) ] (16.24)

RT BT v
662 CHAPTER 16. Introduction to Molecular ThermodynaJ:L:5:
The remaining properties come from defining equations:

su
-=---
A H U PV
R RT RT RT = RT + RT
Note that Eq. (16.14) follows immediately from Eqs. (I 6.24) and (16.21).
Thus, when we know how A/ RT (or In Z) is related to its canonical variables. -:-
V, we can evaluate all other thermodynamic properties by simple mathematical ope~
The Helmholtz energy and therefore the partition function serve as generating fun crio"U -
the other thermodynamic properties, and implicitly represent complete property informaa
Although a powerful toolrO"r the estimation of thermodynamic properties, the appli,..._......._
of statistical mechanics require~ an enormous number of computations. Making the co--roo -
tion between the microscopic states of matter and its manifest macroscopic propertie :..: ~
accomplished by molecular simulation, carried out numerically with high-speed computez-5
Monte Carlo techniques the generation of a very large number of microscopic replicas
system containing on the order of one hundred molecules serves to create an ensemble :_
which by appropriate statistics the partition function of Eq. ( 16.13) can be deduced. :-~ -
tennolecular potential-energy function is key to the accurate prediction of the thermod~ ~...........
properties of real fluids, and this is a continuing area of research. Molecular simulari - _ -
subject unto itself, and is treated in detai l elsewhere. 13
Fluids for which the intennolecular potential energy U(r) is given by the Lennard-
equation (Sec. 16.1) are said (as a class) to be confonnal. More generally, fluids for -rlo-;:;-.
U(r) is of the same functional form comprise a conformal class. It is a property of cor::: - -
fluids that they obey the two-parameter theorem of corresponding states as stated in Sec -: ~
Thus different classes of conformal fluids, distinguished by different functional forms of:
obey different corr-esponding-states con-elations. The purpose of the acentric factor in PCr::r
type correlations (such as Lee/Kesler) is therefore to differentiate between classes o:
polar conformal fluids, primruily on the basis of molecular asymmetry. These clas~"""
obey the three-parameter theorem of corresponding states. An extended set of Lee::_
correlations 14 incorporates a fourth parameter t(\characterize classes of polar conforma:-=
--~
Thus an even larger collection of conformal classes of fluids obeys a four-parameter rt~~~
of conesponding states.
16.5 HYDROGEN BONDING AND CHARGE-TRANSFER

COMPLEXING
The intermolecular potential is dominated at small separations by repulsions, and atla...'""f:!

arations by attractions varying approximately as r - 6 (Sec. J6.1 ). These interactions are.:___
"physical," because their origins are explained on the presumption that interacting Spe'4-~
serve their identities. For some system s another class of interactions, called "quasiche-_....__.
13R. L. Rowley, SLaristical Mechanics for Thermophysical Property Calculations, PTR Prentice Hclli. E;_:---
Cliffs, NJ, 1994. Both Monre Carlo and molecular-dynamics simulations, which have a different basis. are-"----
14 R. L. Rowley, Statistical Mechanics for Tl!ermophysical Property Calculations, sec. 11.5 and app. 1= ~ ?""="
tice Hall, Englewood Cliffs, NJ, 1994
16.5. Hydrogen Bondi11g and ClJarge-Transfer Complexing 663
Table 16.4: Pauling Electronegativity X p for Some Nonmetallic Elements
Element Xp Element Xp
F 4.0 I 2.5
0 3.5 c 2.5
N 3.0 s 2.5
Cl 3.0 Se 2.4
Br 2.8 H 2.1
operates primarily at intermediate separations, i.e., at r ~ ro (Fig. 16.1). As the name suggests,
quasichemical forces are manifested as strong attractive interactions, in which participating
species combine to form new chemical entities. We descrjbe below two important classes of
quasichemical interactions: hydrogen bonding and charge-transfer complexing.
Essential to a discussion of hydrogen bonding is the concept of electronegativity. Ac-
cording to valence-bond theory, the atoms which combine to form a molecule share electrons.
If the bonded atoms are identical (e.g., the Cl atoms in a Ch molecule), the bonding electrons
are shared equally betweeltthe atoms. However, if the atoms are different (e.g., the Hand Cl
atoms of HCl), the shared electrons are generally attracted more strongly by one of the atoms
(Cl in the case of HCl), and this atom is said to be more electronegative than the other. Thus,
electronegativity is a measure of the relative ability of an atom in a molecule to attract electrons
to itself.
The notion of electronegativity was introduced in 1932 by Pauling; 15 he was the first
of several to propose a quantitative scale for its expression. Based largely on thermochemical
data, Pauling's electronegativity Xp assumes values between about 0.7 and 4.0 for those ele-
ments known to participate in compound formation. Metallic elements have values less than
about 2.0; nonmetals, values greater than about 2.0. Table 16.4 shows Pauling electronegativ-
ities for ten nonmetallic elements. Of these, fluorine is the most electronegative (Xp = 4.0),
and hydrogen, the least (Xp = 2.1).
An intermolecular hydrogen bond forms between a hydrogen-donor molecule (conven-
tionally represented as A-H) and an electron-rich acceptor site (conventionally denoted by the
letter B). Entity A is an atom (possibly attached to other atoms), which is more electronegative
than hydrogen. Hydrogen-acceptor site B may be an atom more electronegative than hydrogen;
the site may also be a double or triple bond, or it may be an aromatic hydrocarbon ring. The
hydrogen-bonded complex is conventionally represented as A-H B, where the three dots
denote the hydrogen bond. "
Examples of strong hydrogen don or~include hyQ.rogen fluoride (HF), water (HOH), hy-
drogen peroxide (HOOH), alcohols (ROH), carboxylic acids (RCOOH), ammonia CH2NH),
ptimary amines (RNH2), and secondary amines (R2NH). In each of these molecules, one or
more hydrogen atoms is attached to an atom. of a highly electronegative element (F, 0, or N;
Table 16.4). The halogen acids HCl, HBr, and HI are also hydrogen donors, as are a few
species containing the C-H bond. However, the difference in electronegativity between carbon
15 Linus Pauling ( 1901- 1994), American chemist and (twice) Nobel laureate.
664 CHAPTER 16. Introduction to Molec ular Thermodyn -
and hydrogen is not large (Table 16.4), and the ability of the HinC-H to function as a--~
hydrogen seems possible only when the carbon atom is itself attached to highl y eleclr
ative atoms or electron-rich sites. Verified examples of C-H hydrogen donors thu in . .
chloroform (Cl3CH), dichloromethan e (CbCH2), and hydrogen cyanide (NCH).
The highly electronegative elements F, 0 , and N serve as atomic hydrogen-accepto:- _
Hence HF, HOH, HQOH, ROH, RCOOH, H2NH, RzNH and NCH are hydrogen acce~_
But so are aldehydes (ROCI-1), ketones (ROCR), ethers (ROR), esters (ROCOR), and re- _
amines (R3 N), species which have no active hydrogens.
The phenomenon of hydrogen bonding is easily rationalized. The H in donor ~ ..,_
A-His electron deficient because of the higher electronegativity of A. Hence the Hi am-..:.- -
to the eJectron-rich acceptor site B . Unfo rtunately, such a simple electros tatic picture i
16 As a res:::r:...
to account quantitatively fo r some important features of the hydrogen bond.
an algebraic contribution cannot generally be ascribed to the intermolecular potential ftm...
U(r) for hydrogen-bonding interactions. Nevertheless, we can by example indicate the kin~
intermolecular pairs for which hydrogen-bondi ng i nteracti ons are important. Convenience
sugges ts division of hydrogen-bondi ng interactions into two classes: association and soh
Association is an attracti ve interaction between molecules of the same kind. In the ~ -
text of hydrogen bonding, an associating species must have both an active hydrogen .m::
hydrogen-acceptor site. Examples include water (the 0 is an acceptor site), ammonia (\ :_
the acceptor site), alcohols, primary and secondary amines, and carboxylic acids. H) d.- =
bonding by association is often refl ected drama6cally in the properties (e.g., boiling p
heats of vapotization, and viscosities) of the pure species.
Table 16.5: Hydrogen-bonding Interactions among Pairs of Species

V = nonassociating H-donor; A= nonassoci~ting H-acceptor; AV = associating spec~e--:
V( l ) A(l) AV(l)
V(2) No H-bonding V(2) ... A( I) V(2) ... AV( l )

AV(l) ... AV(l )
A(2) V( l ) ... A(2) No H-bonding AV(l) ... A(2)

AV(l) ... AV(l )
AV(2) V(l ) ... AV(2) AV(2) ... A(l) AV(l) ... AV(2)
AV(2) ... AV(2) AV(2) . . . AV(2) AV(2) ... AV(l )
A V(l) ... AV(I)
AV(2) ... AV(2)
Solva6on is an attractive interaction between unlike molecular species. With re pe....

hydrogen bondi ng, solvation occurs between a species that is a hydrogen donor and .......... -......
species that is a hydrogen acceptor. In "pure" solvation, neither species associates; an ex ~
is the acetone/chloroform system, in which chloroform is (only) a hydrogen donor and a\.~
16 See, e.g., J. E. Huheey, lnorga,ic Clzemisny, 3d ed., pp. 268-272, Harper & Row, New York, 1983.
f-.6. Behavior of Excess Proper ties
665
(e.g..
only) a hydrogen acceptor. However, solvation may occur between two associa tors
orm) .
elhanol and water), between an associat or and a hydroge n donor (e.g., ethanol and chlorof
.utd between an associa tor and a hydrog en accepto r (e.g., ethanol and acetone).
Table 16.5 suggests the types of hydroge n-bonding interactions that can occur between
(e.g ..
molecul es of various kinds. Here, 1) denotes a nonassociating hydroge n-donor species
O],
Cl3CH or Br3CH) , A is a nonasso eiati ng hydroge n acceptor [e.g., (CH3)2CO or (C2Hsh
NH].
and AV is a species that can a ociate by hydrogen bonding [e.g., CH30H or (C2Hsh
ni-
Mixtures containing two different associati ng species offer the richest variety of opportu
),
lies for hydroge n bonding. For example, in a binary mixture of ammon ia( I ) and water(2
ion:
hydroge n-bonde d dimcrs may be formed in four ways: two by solvation , two by associat
H H H
N-H O HO-H NH
H H H
H H H
N-H NH HO-H 0
H H H
Compelling experim ental evidenc e ex ists for quasichemic al interactions between certain
c
non-hyd rogen-d onor polar compounds (e.g., pyri dine, keLones , and aldehyd es) and aromati
ns,
hydroca rbons (e.g., benzene). In these cases, the polar compounds have no active hydroge
to be
and hence the interact ion cannot be hydroge n bonding. Neverth eless, a comple x appears
such
formed. Mullike n 17 gave the name electron donor-acceptor complex to these and other
tion of
entities; they are more commo nly called charge-transfer complexes. Proper explana
we
charge- transfer comple xing requires use of concept from molecular orbital theory, which
transfer
cannot develop here. Additional1y, because of the apparent near-ub iquity of charge-
to
phenom ena, and of the widely varying strength s of the interactions, it is often d ifficult
n and
predict when they wi ll make significant contributions to intermo lecular forces. Mullike
on of charge-
Person (loc. cit.) offer guidanc e, but most enginee rs would view the invocati
role is
transfer comple xing as a helpful explanatory, rather than a predictive, exercise. Its
clearest for the kinds of systems mentioned at the begin ning of this paragraph.
16.6 BEHAVIOR OF EXCESS PROPERTIES
As sugge ted by Fig. 11.4, the principal excess properties (GE, H E, and S) can exhibit
es are
a variety of com binati ons of signs. The signS" and relative magnitudes of these quantiti
which
useful for qualitative enginee ring purposes and for elucida ting the molecu lar phenomena
are the basis for observe d solution behavior. Abbott al. 18 et
have organiz ed c EI H EIs
Wilcy-lnterscience. 1 ew
17 R. S. Mullike n and W. B. Person, Molecu/(lr Cnmplexes: A Lecture and Repri11r Volume.
York. 1969.
I8 M. M . Abbot!, J.P. O' Conne ll, and Twenty Rensselae r Students, Chem. Eng. Educ.,
vol. 28, pp. 18-23 and T.
1994.
data for about 400 binary liquid mixtures in a visual scheme which permits identification of
patterns, trends, and norms , of behavior with respect to mixture type. In what follows, we
describe the basis for the scheme, and present a few important generalizations which follow
from exrunination of representative data.
Excess properties for li9..uid mixtures depend primarily on temperature and composition;
therefore comparison of data for different mixtures is best done at fixed T and x . Since many
M E data are available at nea<Fambient temperatures, Tis chosen as 298.15 K (25 C). Because
extreme values for ME often occur near equimolar composition; we fix x1 = x2 = 0.5.
Division of Eq. (1L.86) by RT puts it into dimensionless form:
HE sE
--- (16.25)
RT R
The six possible combinations of sign for the three excess properties are enumerated in Table
16.6. Each combination defines a region on the diagram of Fig. 16.4, which shows GE I RT
vs. HE I RT in skeleton form.
Table 16.6: Definition of Regions on the oE I RT vs. HE I RT Diagram
Region Sign GE Sign HE Sign s E

I + + +
II + +
III +
IV \
v +
VI + +
Along the diagonal line on Fig. 16.4, s = 0. In regions to the right of the diagonal (V.
VI, and 1), s is positive; for regions to the left of the diagonal (II, Ill, and IV), sEis negative.
Lines of constant nonzero s are parallel to the diagonal.
Convenience in modeling and rationalizing the behavior of GE suggests a focus on
enthalpic (energetic) and entropic contributions, a separation suggested by Eqs. (11.86) and
(16.25). According to these equations, cE can be positive or negative if a and sE ha\e
the same sign. If HE and sE are positive and jf cE is also positive, then H > T sE and
"enthalpy dominates"~ If HE and sE are positive and G is negative, then T s > H E and
~'entropy dominates". Similar reasoning applies when both HE and s are negative, leading
to the identification of Regions I and IV on Fig. 16.4 as regions of enthalpy domination, and
of Regions III and VI as regions of entmpy domination. The notions of enthalpy and entropy
domination can be helpful for explaining the molecular origins of observed mixture-prope~
behavior.
Abbott et al. classify binary organic and aqueous/organic mixtures by a simple scheme
based on hydrogen-bonding concepts (Sec. 16.5). A pure species is categorized as nonpolar-
("NP": e.g., benzene, carbon tetrachlmide, or n-heptane); polar but nonassociating ("NA:
e.g., acetone, chloroform, or cliethylether); or polar and associating ("AS": e.g., acetic acid.
ethanol, or water). With these categories for pure species, there are then six binary mixture
16.6. Behavior of Excess Properties 667
types: NP/NP (e.g., benzene/n- heptane); NA/NP [e.g., chloroform/n.-heptane, Fig. 11.4(a)];
AS/NP [e.g., ethanol/n-h eptane, Fig. 11.4(d)]; NA/NA [e.g., acetone/ch loroform, Fig. 11 .4(c)];
AS/NA [e.g., ethanol/chloroform, Fig. 11.4(e)]; and AS/AS [e.g., ethanol/wa ter, Fig. 1 1.4({)].
Figure 16.5 is ac I RT vs. H EI RT plot of data fo r 135 different binary mixtures at
298 K, with systems distinguished according to the NP/NA/AS classification scheme. For
clarity, we mainly omit data for which the three principal excess properties are very small. The
fig ure appears chaotic at first glance, but on inspection important patterns emerge. We list here
a few; statistics, where given, apply to the full data set analyzed by Abbott et al.
About 85% of all mixtures exhibit positive GE or positive H E (Regions I, II, III, and
VI); about 70% have positive G E and positive H E (Regions I and II). Thus positive G E
and positive H E are the "norms".
About 60% of all mixtures fal l in Regions I and IV, with only about 15% in Regions
III and VI. Thu s the enthalpy is more likely to dominate solu tion behavior than is the
entropy.
NP/NP mixtures (the open circles on Fig. 16.5) tend to concentrate in Regions I and VI:
for such mixtures, HE and s are normally positive. When G E is positive {enthal py
domination), cE I RT rarely exceeds about 0.2. If cE is negative (entropy dominatio n),
aE I RT is rarely less than -0.2.
NA/NP mixtures (the filled circles) usually fall in Region I, with occasional significan t
excursjons into Region It Thus, c
and H E are positive, as is (normally) s.
B oth G 6
and H E can be large.
se
-= 0
II R
Ill
Entropy
Dominates
Entha lpy
Dominates
Figure 16.4: Diagram of
H E cE f RT vs. H E / RT in
IV RT skeleton form.
Enthalpy
Dom inates
VV"
Entropy
Dommates ..,
v
668 CHAPTER 16. Introduction to Molecular Thermodynam. ~
c"
RT II
D.
0.6 4,D.
Ill ~
D.~
~ ~
D.D.D.
D. D. D.D. b.
D.

~~
D.
.......
nD.D.
... ... ...
... ~
~
;'
...... D. D.
A
...
~
A
\.
~
~ 0.6 HE
- 0.6 0 -
A ... ~ RT
0 0 0 0
0
0 ocP 0
0 0 0 0
0
IV
VI
v - 0.6
Figure 16.5: Equimolar excess properties for 135 binary mixtures at 298. 15 K.
Legend: 0 NP/NP mixtures; e
NA/NP mixtures; 6 AS/N P mixtures; AS/NA and AS .
mixtures; D solvati ng NA/NA mixtures.
AS/NP mixtures (the open triangles) invaliably occupy Region I or Il, with Regic:-
behavior (negative s ) favored when the polar species is a very strong associator. _
as an alcohol or a carboxylic acid. In the latter case, GE can be extremely large O\ - =
to the reinforcing effects of positive H E and negati ve sE [Eq. (11.86)].
Mixtures containing two polar species exhibit a diversity of behaviors. Perhaps the ez.-
iest class to categorize involves pure solvation, in which one species is a nonassocia - =
hydrogen donor and the other a nonassociaUng hydrogen acceptor. Here, un less one
the species bas exlremely high effective polarity (e.g., acetonitrile), Region IV beha
obtains: c E, H E, and s are all negative (enthalpy dominates). Examples are re~
sented by the open squares on Fig. 16.5. For AS/NA and AS/AS mi xtures (the ar.....
triangles on Fig. 16.5), a va riety of hydrogen-bonding possibilities is available (see-:-_
blc 16.5), and it is impossible to make easy generalizations. We note however Lhar the ....
are the mixture types with significant representation in Region Ill; here, both H E
SE are negative, but entropy dominates.
16. 7. Molecular Basis for Mixture Behavior 669
16.7 MOLECULAR BASIS FOR MIXTURE BEHAVIOR
The relations between excess propertie..<; and property changes of mixing (Sec. 12.3) facilitate
discussion of the molecular phenomena which give ri se to observed excess-property behavior.
An essential connection is provided by Eq. ( 12.33), which asserts the identity of HE and b. H.
Thus we focus on the mix ing process (and hence on 6H) for explaining the behavior of H E.
The sign and magnitude of 6H roughly reflect differences ill the strengths of intermolec-
ular attractions between pairs of unlike species on the one hand, and pairs of like species on
the other. In the standard mixing process (Fig. 12. 10) interactions beLween I ike species are
disrupted, and interactions between unlike species are promoted. lf the unlike attractions are
weaker than the average of those between species of the same kind, then in the mixi ng process
more energy is requ ired to break like anractions than is made available by formation of un li ke
attractions. In this case t:.H (= HE ) is positive, i.e., the mixing process is endothermic. If the
unlike attractions are stronger, then t:.H is negative, and the mixing process is exothermic.
In Sees. 16.1 and 16.5 we identify intermolecular attractive interactions of four kinds:
dispersion, induction, direct electrostatic, and quasichemical. A summary list of important
points follows:
Of the four attractive interactions, the dispersion force is always present. It dominates
when interacting molecules are nonpol ar or sl ightly polar. (See Table 16.2 and the ac-
companying discussion.)
The induction force requi res that at least one of the interacting species be polar. It is
normally the weakest of the "physical" intermolecular attractive forces (Table 16.2).
For neutral molecules, the simplest and normally the strongest direct electrostatic force
is that operating between two permanent dipoles. This force can dominate "physical"
attractive interactions if the molecules have high effective polarity, i.e. , if they are small
and have large permanent dipoles.
Quasichemical forces, when present, can be the strongest of the four attractive inter-
actions. However, their existence requires special chemical make-up of the interacting
molecules. Hydrogen bonding is the most impo11ant interaction of th is type, although
charge-transfer complexing can play a major role in some kinds of systems.
Excess Enthalpy
With these notions in mind, we offer some rationalizations of the observed s igns and magni-
tudes of HE ( = b. H) for binary liquid mixtures of the kinds discu ssed in Sec. 16.6.
HE ofNP/NP Mixtures
Here, dispersion forces are usually the only significant attractive intermolecular forces. Thus
HE reflects energetic effects associated with disruption of di persian inleractions between like
species, and simultaneous promotion of dispersion interaction between unlike species. Molec-
ular theory 19 suggests that dispersion forces between unlike species are weaker than the aver-
19 Sec, e.g., J. M. Prausnit7.. R.N. Lichtenlhuler,

and E. G. de Azevedo. Molecular Thermodyntunics of Fluid-Phase
Equilibria, 2d ed., sec. 4.4. Prentice Hall, Englewood Cliffs, NJ, 1986.
age of dispersion forces between like species. (This is the molecular basis of the "like prefers
like" rule of elementary chemistry.) Here, then, one expects HE to be positive. This is what is
usually observed for NP/NP mixtures (Fig. 16.5).
HE ofNAINP Mixtures
For this class of mixtures, interpctions between molecules of like species are different in kind
for the two species. In particular, two molecules of the polar species experience a direct-
electrostatic interaction and a (usuaJly weak) induction interaction, in addition to the usual
dispersion interaction; here, the attractive forces are stronger than would be observed for a
nonpolar species of similar size and geometry. Interaction between unlike species, on the other
hand, involves only the dispersion and (weak) induction forces. One therefore expects H E to
be positive, only more so than for otherwise similar NP/NP mixtures. Experiment bears this
out, on average (Fig. 16.5).
HE of ASINP Mixtures
As for NP/NP and NAINP mixtures, one expects positive H E; this is what Fig. 16.5 shows.
However, HE is often observed to be only modest in magnitude, frequently less than H E for
otherwise similar NA/NP mixtures. The reason for this is the unusua l strength of the like in-
teractions for the associating polar species. Here, hydrogen-bonded complexes for the poJar
species can persist in soJution up to rather high dilution, thus mitigating the otherwise very
large positive values of HE expected from simple djsruption/promotion arguments.
H E of Solvating NAINA Mixtures

These mixtures are the major occupants of Region IV in Fig. 16.5. Since neither species asso-
ciates by hydrogen bonding, attractions between like species result from dispersion, induction.
and dipole/dipole interactions. The same kinds of interaction obtain for unlike molecules, but
in addition there is superposed a strong attraction owing to the formation of a hydrogen-bonded
solvation complex. The net effect is a negative value for HE; the system is exothermic.
J
H of AS/NA and AS/AS Mixtures

All four types of attractive interaction occur between unlike species, and for at least one of the
pure species. Thus the sign and magnitude of H reflect a balance between competing effect
of dipole/dipole interactions, association, and solvation. Qualitative prediction of enthalpic be-
havior is difficult, except by analogy. Figure 16.5 suggests the diversity of behavior observed
for such mixtures.
Excess Entropy
The excess entropy is related to t:J.S through Eqs. (12.38) and (12.35). Thus,
(16.26)
where (12.35)
An ideal solution is one comprising molecules of identical size and shape, and for which in-
16.7. Molecular Basis for Mixture Beha vior 671
termolecular forces are the same for all molecular pairs, whether like or unlike. For such a
hypothetical solution, tfle entropy change of mixing, given by Eq. (12.35), is always positive.
In a real mixture, molecules of different species have different sizes and/or shapes, and
the intrinsic strengths of molecular interactions are different for different molecular pairs. As
a result, ~S for a real mixture may be greater or less than ~Sid, and by Eq. (16.26), s
may be positive or negative. The behavior of sE is most conveniently rationalized by separate
consideration of size/shape effects on the one hand and structural effects on the other. (The
word "structure" refers to the order brought about at the molecular level by intermolecular
forces.)
Pure size/shape effects result in a !1S greater than ~Sid, and hence provide a positive
contribution to sE. Prausnitz et al.20 discuss the relative roles of size and shape, and give
references to the relevant literature. If size effects alone are considered, an approximate upper
bound to this contribution to s is given by the Flory-Huggins equation:
E ~ <P; X; V;
S = -R LJ x; ln - where <P;=
; X;
LJ xV
~ ) J
j
Here, <P; is the apparent volume frac tion, and V; is molar volume of the pure species.
Structural contributions to !1S (hence to sE) reflect primarily the relative strengths of
competing intermolecular attractions. Consider the mixing of a nonassociating polar species
(e.g., acetone) with a nonpolar species (e.g., n-hexane). Energetically, the ne t result of the mix-
ing process is determined primarily by the energy associated with disruption of dipole/dipole
interactions, as discussed earlier with respect to H E for NAINP mixtures. With respect to en-
tropy, this is a structure-breaking process wherein molecu lar aggregates promoted by a strong
dipole/dipole interaction are broken up by mixing.
Consider instead the mixing of two nonassociating polar species, one a hydrogen donor
and the other a hydrogen acceptor [e.g., chloroform/acetone, Fig. 11.4(c)]. Energetically, the
net result of the mixing process is determined primarily by the energy associated with forma-
tion of a solvation complex, as discussed earlier regarding H for solvating NA/NA mixtures.
This is a structure-making process, wherein molecular aggregates promoted by a strong quasi-
chemical interaction are formed on mixing.
Structure breaking implies a positive contribution to sE (~S > ~Sid), and structure
making a negative contribution to sE (!1S < b. Sid). When used in conjunction with size/shape
arguments, these simple notions help to explain observed signs for s. By way of example,
we consider again binary liquid mixtures of the kinds discussed in Sec. 16.6.
s of NP/NP Mixtures
In the absence of significant size/shape effect , S is usually positive, owing to the relative
weakness of unl ike vs. li ke intermolecular attractions. Thus structure breaking on mixing
is a stronger effect than structure making. However, the enthalpy contribution to G E often
dominates, and Region I behavior obtains. For mixtures of species of signi ficantly different
size (e.g., n-hexane/n-hexadecane), positive size/shape contributi ons can reinforce structural
effects, producing values of s large enough for entropy to dominate; GE is then negative and
Region VI behavior is observed.
20 J. M. Prausnitz, R.N. Lichtenthaler, and E. G. de Azevedo, op. cit., sec. 7.4.

672 CHAPTER 16. Introduction to Molecular Thermod_-
s of NA/NP Mixtures
As already noted, the mixing process here primarily involves structure breaking (po ic ~ _
tributions to s ). Size/shape effects can have an augmenting influence to produce su """-..._...-.....
positive SE. However, H E often is also large, and enthalpy usually dominates (RegioG I
sE of ASINP Mixtures
Mixing nornina11 y promote~a structure-breaking di sruption of hydrogen -bonded comp.~
the associating species. However, the persistence of these complexes in solution up t
high diluti on Can greatly reduce thiS pOSitive COntribUtiOn tO s, leading tO negatiYe \ d i -
s over much of the composition range. This effect is observed for mixtures of srron; _
ciators (e.g., alcohols and carboxylic acids) with hydrocarbon s. An example is the eth.-=.
heptane system of Fig 1 J.4(cl), which shows Region II behavior.
s of Solvating NA!NA Mixtures

As noted in earlier discussion, this is predominate ly a structure-making situation. an~ _
negative. However, H is also negative (and large), whence enthalpy usuall y dominate--_
ing G negative (Region IV).
sEof ASINA and AS/AS Mixtures

The complexities discussed with respect to H E also apply to s; struc ture-breakw ;
structure-ma king effects compete to provide a variety of sign combinations and a :--~=
magnitudes for SE.
16.8 VLE BY MOLECULAR SIMULATION
In Sees. 16.2, 16.3, and 16.4 we describe how macroscopic thermodynam ic properrie-.
as internal energy, e ntropy, and the Helmholtz energy are connected to properties of in'"'
molecules and their assemblies. These connections are explo ited quantitati vely throu;11 _
puter simulation of collections of molecules.21 This approach has also been applied ....__
to VLE, primarily to pure species and to binary and simple ternary mi xtures. Descrip..
assumptions, methods, and calculational procedures are given by Panagiotopoulos1:? anc
extended review by Gubbins.23 Their extensive bibliographies are a guide to relevam li~..........-
The method requires suitable intermolecular potential energy functions U(r ) and
of the equations of statistical mechanics for the assemblies of molecules. As menri
Sec. 16.1, potential energy functions are as yet primarily empirical. Except for the .:.
21 M. P. Allen and D.
J. Tildesley, CompuTer Simulation of Liquids, Clarendon Press, Oxford, 1989: D.
F.
B. Srnit, Understanding Molecular Simulations: From Algorithms to ApplicaTions, Academic Press, San Dr :
22 A. Z. Panaglotopoulos, Molecular Simulation , vol. 9,

pp. 1- 23, 1992.
23 K. E. Gubbins, "Applications of Molecular Theory
to Phase Equilibrium Predictions" in Models for *"-__..
nomic and Phase Equilibrium Calculations, S. I. Sandler, eel., pp. 507-600, Marcel Dekker, Inc., Ne\\ YorL
16.8. VLE by Molecular Simulation
24
molecules, U (r) cannot be predicted by ab initio calculations, because of still-inadequate
computer speed. Therefore, semi-empirical functions based on quantum-mechanical theory
and expetimental data are employed.
Two procedures are used for the very large number of computer calculations required
to treat molecular assemblies. The first, proposed by PanagiotopouJos,25 is called the direct
Gibbs-ensemble Monte Carlo method. One considers two separate phases, each represented
by a finite number of molecules contained in a simulation box. Both are a t the same specified
temperature but are of different initial densities and compositions. The idea is to implement
a sequence of perturbations which gradually bring these two phases into equilibrium. This
ultimately insures internal equilibrium for each phase separately, equality of pressures between
the two phases, and equality of the chemical potentials for each species in the two phases. The
perturbations ("moves") designed to bring about these conditions of equilibrium are therefore:
1. Random displacement of molecules within each box. These are the usual moves of
Monte Carlo simulation, insuring internal equilibrium and generating the ensemble upon
which the partition function is based, thus leading to a set of thermodynamic properties
for the molecules of each box.
2. Random equal and opposite volume changes in the two boxes. These moves alter the
pressures in the boxes and ultimately bring about their equality. As the pressures change,
the ongoing Monte Carlo simulations in the boxes generate evolving thermodynamic
properties.
3. Random transfer of molecules between the two boxes. These moves alter compositions
and chemical potentials IJ-i of the species in the boxes, ultimately bringing about equality
of the chemical potentials for each species in the two boxes. These moves also contribute
to the evolution of the thermodynamic propetties of the molecules in the boxes.
Moves may be accepted or rejected on the basis of certain probabilities that insure progres-
sion on average to states of lower Gibbs energy for the two boxes considered together. Phase
equilibrium obtains at the state of minimum total Gibbs energy.
A limitation of the Gibbs-ensemble Monte Carlo method is that the successful transfer
of molecules between phases (item 3) becomes difficult (improbable) for dense fluids, lead-
ing to excessive calculation time. In this event, a second, more indirect, procedure can be
employed. The idea here is to calculate the chemical potentials of the s pecies in each box
for a range of states. Equilibrium compositions are then identified as those states having the
same temperature, pressure, and chemical potential for each species in the two boxes. Much
more computation is needed by this procedure than for the direct procedure, except where the
molecular-transfer step becomes difficult. For high-density fluids and for solids, the indirect
procedure is preferred.
Molecular simulation is not a routine method for VLE calculations nor does it substitute
for experimental data. At present, it is most useful for extrapolating to conditions not accessible
by other means.
24 Mcaning: from the beginning. i.e. , f rom first principles.
25 A . Z. Panagiotopoulos, Molecular Physics, vol. 61 , pp. 8 I 3-826, I 987.

The Gibbs-ensemble procedure has also been employed to estimate adsorption isotherms
for simple systems. The approach is illustrated26 by calculations for a straight cylindrical pore
where both fluid/fluid and fluid/adsorbent molecular interactions can be represented by the
Lennard-Jones potential-energy function [Eq. (16. 1)]. Simulation calculations have also been
made for isotherms of methane and ethane adsorbed on a model carbonaceous slit pore. 27 Jsos-
teric heats of adsorption have als&been calculated.28
,,
PROBLEMS
16.1. The following rectilinear potential is an augmentation of the square-well potential [See
Eq. (16.11)]:
U=oo for r <d

U=$ for d< r <k d
U= -E for kd<r<ld
U=O for l d < r
Here, quantities k, l, $, and E are positive constants, wi th k < L. Draw a sketch of

this potential , and find an algebraic expression for the second virial coefficient B (T ).
Demonstrate that B(T) for this model can exhibit a maximum with respect to T .
16.2. Table 16.2 applies for like molecular pairs. Prepare a similar table for all unlike molec-
ular pairs comprising species from the following: methane, n-heptane, chloroform.
acetone, and acetonitrile. Discuss the result. Data in addition to values that appear
in Table 16.2: For methane, J-1- = 0, & = 2.6 x 10-24 cm 3 , 1 = 2. 1 x Jo- 18 J. For
n-heptane, J-1- = 0, & = 13.6 x 10- 24 cm3 , I= 1.7 x to- 18 J.
16.3. The heat of mixing (or heat of solution) is negative for the systems represented oc
Figs. 12.14, 12. 17, and 12.19. Offer molecular explanations of why this is so.
16.4. Naive numerology suggests that there should be 23 = 8 possible combinations of sig::
forGE, H E, and s. Table 16.6 shows only six. Why?
26 A. z. Panagiotopoulos, Molecular Physics, vol. 62, pp. 701-719, 1987
27 R. F. CrackneU and David Nicholson, Adsorption, vol. 1, p. 7, 1995.
28R. F. Cracknell, D. Nicholson, and N. Quirke, Molecular Simulation , vol. 13, p. 16 1, 1994.
Problems 675
16.5. Listed below are excess-enthalpy data at 25C for two series of equimolar binary liquid
mixtures. Explain why the mixture containing benzene is the "outlier" in each series.
H11 mol- 1
Series Mixture
A CH2Ch/b enzene -18.

/cyclohex ane 1,188.
In-hexane I ,311.
B acetone/benzene 144.
/cyclohex ane 1,574.
In-hexane 1,555.
16.6. What signs would you expect to observe forGE, HE , and s for equimolar liquid
solutions of the following pairs of species at 298 K? Explain your answers.
(a) Acetone/c yclohexan e

(b) Acetoneldichlorome thane
(c) Aniline/cyclohexane
(d) Benzene/c arbon disulfide
(e) Benzene/n -hexane
if) Chlorofor m/ I ,4-dioxane
(g) Chloroforrnln-hexane
(h) EthanoUn-nonane
=
16.7. The quantity 8ij 2Bij - Bii- Bjj plays a role in the thermodynamics of gas mixtures
at low pressures: see, e.g., Eq. (14.4) for;. This quantity can be positive or negative,
depending on the chemical nature of species i and j. For what kinds of molecular
pairs would one expect 8ij to be
(a) Positive; (b) Negative; (c) Essentiall y zero?
16.8. Table 10.1 includes Henry's constants for three C2 hydrocarbon gases dissolved in
water at 25C. Explain the observed trend, viz.,
1tethane > 1tethylene > 1tacetylene
16.9. Interpreting entropy as a qualitative. .measure of the "structure" or "order" of a phase,

suggest why the latent heats 6 H sf, 6H tv, an~..~~H su are positive.
16.10. Determin e from Eq. (16.20) numerical values of the absolute entropies in the ideal-gas
state at l bar and 298.15 K for Argon, Krypton, and Xenon. Compare with values from
the NIST Chemistry WebBook.
Js 34
Reminder: h (Planck's constant) = 6.626x 10-
1
k (Boltzman n's constant= 1.381 x Io- 23 J K-
23 1
N A (Avogadro 's number= 6.023 x 10 mol-
676 CHAPTER 16. Introduction to M ol ecular Thermody namic.
16.11. The heat of vaporization at the normal boiling point is an approximate measure of the
strength of intermolecular forces in the liquid phase. Why? The compounds methane
and water have similar molar masses and si milar values of T,.11 Yet for methane
~H,~v = 8. 17 kJ mol- 1, and fo r water ~H,~" = 40.66 kJ mol- 1 Explain the large
difference.
16.12. The molar heat capacity of a liquid is normally greater than its vapor-phase heat ca-
pacity at modest pressure and the same temperature. Why?
16.13. Use classical arguments to estimate the average separation (in m) between idea l -g~
particles at 300 K and 1 bar. Discuss.
'
Appen dix A
Conve rsion Factors and Values

of the Gas Const ant
Because standard reference books contain data in diverse uniLc;, we include Tables A. J and
,.. A.2 to aid the conversion of val ues from one set of units to another. Those unite; having no
connection with the SI system arc enclosed in parentheses. The following definitions are noted:
(ft) = U.S. defined foot= 3.048 x 10- 1 m

o-
(in) = U.S. defined inch .._ 2.54 X 1 2 m
(gal)= U.S. liquid gallon= 23 1(i n)3
(Ibm)= U.S. defined pound mass (avoirdupois)
= 4.5359237 x I o- 1 kg
(lbr) = force to accelerate 1(Ibm ) by 32. J 740(ft) s-2
(atm) =standard atmospheric pressure= 101,325 Pa
(psi a) = pounds force per square inch absolute pressure
(torr) = pressure exerled by I mm mercury at 0C and standard gravity
(cal)= thermochemical calorie
(Btu) = international steam table British thermal unit
(lb mole)= mass in pounds mass with numeri cal value equal to the molar mass
(R) = absolute temperature in Rankines
The conversion factors of Table A. I are refened to a single basic or derived unit of lhe
SI system. Conversions between other pairs of units for a given quantity are made as in the
following example:
J bar = 0.986923(alm) = 750.061 (torr)
thus
750.061
1(atm) = = 760.00(J.orr)
0.986923
677
678 APPENDIX A. Conversion Factors and Values of the Gas Constant
Table A.l: Conversion Factors

Quantity Conversion
Length 1 rn = 100 em
= 3.28084(ft) = 39.3701(in)
~
Mass l kg= 103 g
= 2.20462(lbm)
Force l N = 1 kg m s-2
= 105 (dyne)
= 0.224809(Jbr)
Pressure 1 bar= 105 ko0 m- 1 s-2 = 105 N m- 2

= 105 Pa = 102 kPa
= I06 (dyne) cm- 2
= 0.986923(atm)
= 14.5038(psia)
= 750.061 (torr)
Volume 1m3= 106 cm3 = 103 liters

= 35.3147(ft) 3
= 264.172(gal)
Density 1 g cm- 3 = 103 kg rn- 3

= 62.4218(lbm)(ft)-3
Energy J 1 = l ko0 m2 s-2 = 1 N m

= 1 m3 Pa = 10- 5 rn 3 bar= 10 cm3 bar
= 9.86923 cm3(atrn)
= 107 (dyne) em = 107 (erg)
= 0.239006(cal)
= 5.12197 X l0-3 (ft)3 (psia) = 0.737562(ft)(lbr)
= 9.47831 x 10-4 (Btu) = 2.77778 x 10- 7 kWhr
Power 1 kW = 103 W = J0 3 kg m2 s- 3 = 10 3 J s- 1
= 239.006(cal) s- 1
= 737.562(ft)(lbr) s- 1
= 0.94783J(Btu) s-1
= 1.34102(hp) .\
Table A.2: Values of the Universal Gas Constant

R = 8.3 14 J mol- l K- 1 = 8.3 14 m3 Pa mot- I K- 1
=83.14cm 3 barmol- 1 K- 1 =8,314cm3 kPamol- 1 K- 1
= 82.06 cm3(atm) mol- 1 K- 1 = 62,356 cm3(torr) moc 1 K- 1
= 1.987(cal) mol- 1 K- 1 = 1.986(Btu)(lb mole)- 1(R)- 1
= 0.7302(ft)3(atm)(lb mol)- 1(R)- 1 = I0.73(ft)3(psia)(lb mol)- 1(R)- 1
= 1,545(ft)(Jbr)(lb mol)- 1(R)- 1
Appendix B
Properties of Pure Species
.. Table B.l Characteristic Properties of Pure Species

Listed here for various chemical species are values for the molar mass (molecular weight),
acentric factor w, cri tical temperature Tc, critical pressure Pc, critical compressibility factor ~
critical molar volume Vc, and nbrmal boiling poin t T,. Abstracted from Project 801, DIPPR,
Design Institute for Physical Property Data of the American Institute of Chemical Engineers,
they are reproduced with permission. The full data compilation is published by T. E. Daubert,
R. P. Danner, H . M. Sibul, and C. C. Stebbins, Physical and Thermodynamic Properties of Pure
Chemicals: Data Compilation, Taylor & Francis, Bristol, PA, 1,405 chemicals, extant 1995.
Included are values for 26 physical constants and regressed values of parameters in equations
for the temperature dependence of 13 thermodynamic and transport properties.
Electronic versions by the same authors include:
DJPPR Dala Compilation of Pure Compound Properties, ASCII Piles,

National Institute of Science and Technology, Standard Reference Data,
Gaithersburg, MD, 1,458 chemicals, extant 1995.
DIPPR Data Compilation, Student DIPPR Database, PC-DOS Version, National In-
stitute of Science and Technology, Standard Reference Data,
Gaithersburg, MD, 100 common chemicals for teaching purposes, 1995.
Table 8.2 Constants for the Antoine Equation for Vapor Pressures of Pure Species
679
APPENDIX B. Properties of Pure Species
680
Table B.l: Characteris tic Properties of Pure Species
Molar Vc
mass (J) TcfK Pclbar Zc cm3 mol- 1 T,,IK
0.012 190.6 45.99 0.286 98.6 I l J.4

Methane
Ethane ,.,
16.043
30.070 0.100 305.3 48.72 0.279
0.276
145.5
200.0
184.6
23 1.1
Propane 44.097 0.152 369.8 42.48
58.123 0 .200 425.1 37.96 0.274 255. 272.7
n-Butane
72.150 0.252 469.7 33.70 0.270 3 13. 309.2
n-Pentane
86.177 0.301 507.6 30.25 0.266 37 1. 34 1.9
n-Hexane
0.350 540.2 27.40 0.261 428. 37 1.6
n-Heptane 100.204
0.400 568.7 24.90 0.256 486. 398.8
n-Octane 114.231
0.444 594.6 22.90 0.252 544. 424.0
n-Nonane 128.258
0.492 617.7 21.10 0.247 600. 447.3
n-Decane 142.285
58. 123 0.181 408.1 36.48 0.282 262.7 26 1.4
Isobutane
0.302 544.0 25.68 0.266 468. 372.4
Isooctane 114.231
70.134 0.196 511.8 45.02 0.273 258. 322.4
Cyclopentane
84.161 0.210 553.6 40.73 0.273 308. 353.9
Cyclohexane
0.230 532.8 37.85 0.272 319. 345.0
Methy lcyclopentane 84. 16 1
0.235 572.2 34.71 0.269 368. 374.1
Merhylcycloh exane 98.188
28.054 0.087 282.3 50.40 0.281 131. 159.4
Ethylene
0.140 365.6 46.65 0.289 188.4 225.5
Propylene 42.081
56.108 0. 191 420.0 40.43 0.277 239.3 266.9
!-Butene
56.108 0.205 435.6 42.43 0.273 233.8 276.9
cis-2-Butene
56.108 0.218 428.6 41.00 0.275 237.7 274.0
trans-2-Butene
84.161 0.280 504.0 31.40 0.265 354. 336.3
1-Hexe ne
56.1 08 0.194 417.9 40.00 0.275 238.9 266.3
Isobury lene
54.092 0.190 425.2 42.77 0.267 220.4 268.7
I ,3-Butadiene
82.145 0.212 560.4 43.50 0.272 291. 356.1
Cyclohexene
0.187 308.3 6 1.39 0.271 113. ' 189.-+
Acetylene 26.038
0.210 562.2 48.98 0.271 259. 353.2
Benzene 78.114
92. 141 0.262 591.8 41.06 0.264 316. 383.8
Toluene
0.303 617.2 36.06 0.263 374. 409.-+
Eth y lbellLene 106.167
0.326 631 .1 32.09 0.261 427 . 425.6
Cumene 120.194
0.310 630.3 37.34 0.263 369. 417.6
o Xylene 106.167
106.167 0.326 6 17.1 35.36 0.259 376. 412.3
m-Xyl ene
0.322 616.2 35.11 0.260 379. 411.:
p-Xylcnc 106.167
0.297 636.0 38.40 0.256 352. 418.3
Sty rene 104.152
0.302 748.4 40.5 1 0.269 413. 491.2
Naphthalene 128.174
0.365 789.3 38.50 0.295 502. 528.2
Biphenyl 154.21 L
0.282 408.0 65.90 0.223 115. 254.1
Formaldehyde 30.026
44.053 0.291 466.0 55.50 0.221 154. 294.0
Acetaldehyde
74.079 0.331 506.6 47.50 0.257 228. 330.1
Methyl acetate
523.3 38.80 0.255 286. 350.~
Ethy I acetate 88.106 0.366
58.080 0.307 508.2 47.01 0.233 209. 329.-1
Acetone
72.107 0.323 535.5 41.50 0.249 267. 352.
Methyl ethyl ketone
74.123 0.281 466.7 36.40 0.263 280. 307.6
Diethy l ether
497.1 34.30 0.273 329. 328.~
Methy lt-butyl ether 88.150 0.266
681
Table B.l (Co ntin ued)
Molar
Vc
mass (JJ Tc!K Pclb ar cm3 mol -l
Zc ~,IK
Meth anol 32.042 0.56 4 5 12.6 80.9 7 0.22 4 118. 337. 9
Ethanol 46.0 69 0.64 5 5 13.9 61.4 8 0.24 0 167. 351. 4
1-Pro pano l 60.0 96 0.62 2 536. 8 51.75 0.25 4 219. 370. 4
1-Butanol 74.1 23 0.59 4 563.1 44.2 3 0.26 0 275. 390. 8
1-Hexanol 102.177 0.57 9 61l. 4 35.1 0 0.26 3 381. 430. 6
2-Pr opan ol 60.0 96 0.66 8 508. 3 47.6 2 0.24 8 220. 355. 4
Phen ol 94.113 0.44 4 694.3 61.3 0 0.24 3 229. 455. 0
Ethy lene glycol 62.0 68 0.48 7 7 19.7 77.00 0.24 6 191. 0 470. 5
Acetic acid 60.053 0.46 7 592.0 57.8 6 0.211 179. 7 391.1
n-Bu tyric acid 88.1 06 0.681 615. 7 40.6 4 0.23 2 29 1.7 436. 4
Benz oic acid 122. 123 0.60 3 75 L.O 44.7 0 0.24 6 344. 522. 4
Acetonitrile 4l.0 53 0.33 8 545.
... 5 48.3 0 0.18 4 173. 354. 8
Meth ylam ine 31.0 57 0.28 1 430.1 74.6 0 0.321 154. 266. 8
Ethyl amin e 45.0 84 0.28 5 456. 2 56.2 0 0.30 7 207. 289. 7
Nitro meth ane 61.0 40 0.34 8 588. 2 63.1 0 0.22 3 .173 . 374. 4
Carb on tetra chlo ride 153. 822 0.19 3 556. 4 45.6 0 0.27 2 276. 349.8
Ch lorof orm 119.377 0.22 2 536. 4 54.7 2 0.29 3 239. 334. 3
Dich lorom etha ne 84.932 0.19 9 510. 0 60.8 0 0.26 5 185. 312. 9
Meth yl chlo ride 50.4 88 0.15 3 4 16.3 66.8 0 0.27 6 143. 249.1
Ethyl chlo ride 64.5 14 0.19 0 460. 4 52.7 0 0.27 5 200. 285. 4
Chlo robe nzen e 112.558 0.25 0 632. 4 45.2 0 0.26 5 308. 404. 9
Tetr an uoro etha ne 102. 030 0.327 374. 2 40.6 0 0.25 8 198. 0 247.1
Argo n 39.9 48 0.00 0 150.9 48.9 8 0.29 1 74.6 87.3
Kryp ton 83.8 00 0.00 0 209. 4 55.0 2 0.28 8 91.2 119.8
Xen on 131.30 0.00 0 289. 7 58.4 0 0.28 6 118.0 165.0
Heli um 4 4.00 3 -0.3 90 5.2 2.28 0.30 2 57.3 4.2
Hyd roge n 2.01 6 -0.2 16 33.1 9 13.13 0.30 5 64. 1 20.4
Oxy gen 3l.9 99 0.02 2 154.6 50.4 3 0.28 8 73.4 90.2
Nitr ogen 28.0 14 0.03 8 126. 2 34.0 0 0.28 9 89.2 77.3
Airt 28.851 0.035 132. 2 37.4 5 0.28 9 84.8
Chlo rine 70.9 05 0.06 9 417. 2 77.1 0 0.26 5 124. 239.1
Carb on mon oxid e 28.0 10 0.04 8 132.9 Jtr.99 0.29 9 93.4 8 1.7
Carb on diox ide 44.0 10 0.22 4 304. 2 73.8
.... 3 0.27 4 94.0
Carb on disu lfide 76.1 43 0.111 552. 0 79.0 0 0.27 5 160. 3 19.4
Hyd roge n sulfide 34.0 82 0.09 4 373. 5 89.6 3 0.28 4 98.5 2 12.8
S ulfur diox ide 64.065 0.245 430. 8 78.8 4 0.26 9 122. 263.1
Sulf ur triox ide 80.0 64 0.42 4 490.9 82. 10 0.25 5 127. 317. 9
Nitric oxid e(NO ) 30.0 06 0.58 3 180. 2 64.8 0 0.251 58.0 121. 4
Nitro us oxid e (N2 0) 44.0 13 0.141 309. 6 72.4 5 0.27 4 97.4 184.7
Hyd roge n chlo ride 36.461 0.1 32 324. 7 83.1 0 0.24 9 8 1. 188. 2
Hydrogen cyan ide 27.0 26 0.41 0 456. 7 53.9 0 0.197 139. 298. 9
Wat er 18.015 0.345 647.1 220.55 0.22 9 55.9 373. 2
Amm onia 17.031 0.25 3 405. 7 112.80 0.24 2 72.5 239. 7
Nitri c acid 63.013 0.71 4 520. 0 68.9 0 0.23 1 145. 356. 2
Sulfuric acid 98.0 80 924. 0 64.0 0 0.14 7 177. 610. 0
'i' Pseu dopa rameters for YN = 0.79 and Yo =
2 2
0.21. See Eqs. (6.97 )-(6. 99).
682 APPENDIX B. Properties of Pure Species
Table B.2: Constants for the Antoine Equation for Vapor Pressures of Pure Species
' In P sat /kPa = A - B

tf C +.. C
Latent heat of vaporization at the normal boiUng point (AH11 ), and normal boiling point (t17 )
Parameters for Antoine Eqn. Temp. Range 6.Hn tn

Name Form ul ~ At B c oc kJ/mol oc
Acetone C3H60 14.3145 2756.22 228.060 -26-77 29.10 56.2
Acetic acid C2H402 15.0717 3580.80 224.650 24- 142 23.70 I 17.9
Acetonitrile* C2H3N 14.8950 3413.10 250.523 -27-81 30.19 81.6
Benzene C6H6 13.7819 2726.81 217.572 6-104 30.72 80.0
iso-Butane C4H10 13.8254 2181.79 248.870 -83-7 21.30 -11.9
n-Butane C4 H 10 13.6608 2154.70 238.789 -73-19 22.44 -0.5
!-Butanol C4H100 15.3144 3212.43 182.739 37-138 43.29 117.6
2-Butanol* C4H 100 15.1989 3026.03 186.500 25-120 40.75 99.5
iso-Butano1 C4H100 14.6047 2740.95 166.670 30-128 41.82 107.8
rert-Butanol C4H 100 14.8445 2658.29 177.650 10- 101 39.07 82.3
Carbon tetrachloride CC4 14.0572 2914.23 232.148 - 14-101 29.82 76.6
Chlorobenzene C6H5 CI 13.8635 3174.78 211.700 29-159 35.19 131.7
1-Chlorobutane C4H9CJ 13.7965 2723.73 218.265 - 17-79 30.39 78.5
Chloroform CHCI3 13.7324 2548.74 218.552 -23-84 29.24 61.1
Cyclohexane C6H1 2 13.6568 2723.44 220.618 9-105 29.97 80.7
Cyclopentane CsHw 13.9727 2653.90 234.510 -35-71 27.30 49.2
n-Decane C10H22 13.9748 3442.76 193.858 65-203 38.75 174.1
Dichloromethane CH2Cl2 13.9891 2463.93 223.240 -38-60 28.06 39.7
Diethyl ether C4H100 14.0735 2511.29 231.200 -43-55 26.52 34.4
I ,4-Dioxane C4Hg02 15.0967 3579.78 240.337 20-105 34.16 101.3
n-Eicosane C2oH42 14.4575 ..
4680.46 132.100 208-379 57.49 343.6
Ethanol C2H60 16.8958 3795.17 230.918 3 - 96 38.56 78.2
Ethyl benzene CgHIO 13.9726 3259.93 212.300 33- 163 35.57 136.2
Ethylene glycol* C2H602 15.7567 4187.46 178.650 J00-222 50.73 197.3
n-Heptane C7H16 13.8622 2910.26 216.432 4 - 123 31.77 98.4
n-Hexane C6H t4 13.8193 2696.04 224.3 17 -19-92 28.85 68.7
<.l
Methanol CH40 16.5785 3638.27 239.500 - 11-83 35.21 64.7
Methyl acetate C3H602 14.2456 2662.78 2 19.690 - 23-78 30.32 56.9
Methyl ethyl ketone C4HsO 14. 1334 2838.24 218.690 - 8 - 103 31.30 79.6
Nilromelhane* CH3N0 2 14.7513 3331.70 227.600 56-146 33.99 101.2
n-Nonane C9H20 13.9854 33 1J.l9 202.694 46-178 36.91 150.8
iso-Octane CsHts 13.6703 2896.31 220.767 2-125 30.79 99.2
n-Octane Csl-It s 13.9346 3123.13 209.635 26-152 34.41 125.6
n-Pentane CsH12 13.7667 2451.88 232.0 14 -45-58 25.79 36.0
Phenol C6H60 14.4387 3507.80 175.400 80-208 46.18 181.8
!-Propanol C3H80 16.1154 3483.67 205.807 20 - 116 41.44 97.2
2-Propano1 C3H80 16.6796 3640.20 219.610 8-100 39.85 82.2
Toluene C7Hs 13.9320 3056.96 217.625 13-136 33.18 I 10.6
Water H20 16.3872 3885.70 230.170 0 - 200 40.66 100.0
o-Xylene CgH1o 14.0415 3358.79 212.041 40 - 172 36.24 144.4
m-Xylene C8H 10 14.1387 3381.81 2 16.120 35-166 35.66 139.1
p-Xylene CsHto 14.0579 3331.45 214.627 35 - 166 35.67 138.3
Based primarily on data presented by B. E. Poling, J. M. Prausnitz, and J. P. O'Connell ,

The Properties o.fGases and Liquids, 5th ed., App. A, McGraw-Hill, New York, 2001.
*Antoine parameters adapted from Gmehling et al . See footnole 2, p. 791.
; Antoine parameters A are adjusted to reproduce the listed values of t11
Appendix C
Heat Capacities and Property

Changes of Formation
Table C.l Heat Capacities of Gases in the Ideal-Gas State

Table C.2 Heat Capacities of Solids
Table C.3 Heat Capacities of Liquids
Table C.4 Standard Enthalpies and Gibbs Energies of Formation at 298.15 K
..
683
684 APPENDTX C. Heal Capacities :wd Property Changes of Formation
Table C.l: Heat Capacities of Gases in the Ideal-Gas State t

Constants in equation C ~g I R =A + BT + CT2 + or- 2 T (kelvins) from 298 to Tmax
cig fR J03 B 10 6 c 10- 5 D

Chemical species
Paraflins:
7;nax P?9S
"
Me thane CH4 !),00 4.217 1.702 9.081 - 2. 164
Ethane C2H6 1500 6.369 1. 13 1 19.225 -5.561
Propane C3Hs 1500 9.01 I 1.213 28.785 -8.824
n-Butane C4 H10 1500 I 1.928 1.935 36.915 -I 1.402
iso-Butane C-1H10 1500 11.90 1 1.677 37.853 -I 1.945
n-Pentanc Cs H12 1500 14.73 1 2.464 45.35 1 - 14. 11 1
n-l lcxanc C6H t4 1500 17.550 3.025 53.722 - 16.79 1
n-Heptane C7 H16 1500 20.361 3.570 62.127 - 19.486
fi-Octane CsHts 1500 23.174 4.108 70.567 -22.208
1-Aikenes:
Ethylene C2H.J 1500 5.325 1.424 14.394 -4.392
Propylene C3H6 1500 7.792 1.637 22.706 -6.9 15
1-Rutene C4Hs 1500 10.520 1.967 31 .630 -9.873
1-Pentene Cs H to 1500 13.437 2.691 39.753 -12.447
1-Hexene C6H12 1500 16.240 3.220 48. 189 - 15. 157
1-Heptene C7 H14 1500 19.053 3.768 56.588 - 17.847
1-0 ctene CI!Ilt6 1500 2 1.868 4.324 64.960 -20.52 1
Miscellaneous organics:
Acetaldehyde c2~o 1000 6.506 1.693 17.978 -6. 158
Acetylene C2H2 1500 5.253 6. 132 1.952 - 1.299
Ben:~-ene C6H6 1500 10.259 -0.206 39.064 - 13.301
I ,3-Butadiene C4H6 1500 10.720 2.734 26.786 -8.882
Cyclohexane ~ H 12 1500 13.121 -3.876 63.249 -20.928
Ethanol C2Ht;O 1500 8.948 3.518 20.00 1 -6.002
Ethylbenzene Cs H to 1500 15.993 ' 1. 124 55.380 - 18.476
Ethylene oxide C2H40 1000 5.784 - 0.385 23.463 - 9.296
Fo rmaldehyde CH20 1500 4.191 2.264 7.022 - 1.877
Methanol CH40 1500 5.547 2.2 1I 12.2 16 -3.450
Styrene Cgi-Ig 1500 15.534 2.050 50. 192 -16.662
To luene C7Hs 1500 12.922 0.290 47.052 -15.7 16
Miscellaneous inorganics:
A ir 2000 3.509 3.355 0.575 - 0.016
Ammonia HJ 1800 4.269 3.578 3.020 -0.1 86
B romi ne Br2 3000 4.337 4.493 0.056 -0.1 54
Carbon monoxide co 2500 3.507 3.376 0.557 -0.03 1
Ca1 bon dioxide C02 2000 4.467 5.457 1.045 -1.157
Carbon disulfide cs2 1800 5.532 6.31 I 0.805 -0.906
Ch lorine Cl2 3000 4.082 4.442 0.089 -0.344
Hydrogen H2 3000 3.468 3.249 0.422 0 .083
Hydrogen sulfide H2S 2300 4.114 3.931 1.490 - 0.232
Hydrogen chloride I-ICl 2000 3.5 12 3. 156 0.623 0. 15 1
Hydrogen cyanide HCN 2500 4.326 4.736 1.359 - 0.725
Nilrogcn N2 2000 3.502 3.280 0.593 0.040
Nitrous oxide N20 2000 4.646 5.328 1.214 - 0.928
Nitric oxide NO 2000 3.590 3.387 0.629 0.0 14
Nitrogen dioxide N02 2000 4.447 4.982 1.195 -0.792
Dinitrogen tetroxide N20 -1 2000 9.1 98 I 1.660 2.257 -2.787
Oxygen 02 2000 3.535 3.639 0.506 -0.227
Sulfur dioxide so2 2000 4.796 5.699 0.80 1 - 1.0 15
Su lfur trioxide so3 2000 6.094 8.060 1.056 - 2.028
Water H20 2000 4 .038 3.470 1.450 0.12 1
tselected !Tom H. M. Spencer, Ind. Eng. Chem., voL 40, pp. 2 152-2154. 1948; K. K. Kelley,
U.S. Bur. Mines Bull. 5M, 1960; L. B. Pankratz, U.S. Bur. Mines Bull. 672. 1982.
685
Table C.2: Heat Capacities of Solidsi

Constants for the equation C pI R =
A + BT + or- 2
T (kelvins) from 298 K to T.11nx
Chemical species Tmnx Cp298/ R A 103 B 10- 5 0
CaO 2000 5.058 6.104 0.443 - 1.047

CaC03 1200 9.848 12.572 2.637 -3.120
Ca(OHh 700 11.217 9.597 5.435
CaC2 720 7.508 8.254 1.429 - 1.042
CaCl2 1055 8.762 8.646 1.530 - 0.302
C (graphite) 2000 1.026 1.77 1 0.77 1 -0.867
Cu 1357 2.959 2.677 0.8 15 0.035
CuO 1400 5.087 5.780 0.973 - 0.874
Fc(a) 1043 3.005 -0. 11 1 6. 111 1.150
Fe203 960 12.480 11.8l2 9.697 - 1.976
Fe304 850 18.138 9.594 27. 11 2 0.409
FcS 41 1 6.573 2.612 13.286
12 386.8 6.929 6.48 1 1.502
LiCI 800 5.778 5.257 2.476 -0. 193
NH4CI 458 10.741 5.939 16.105
Na 37 1 3.386 1.988 4.688
NaCI 1073 6.1 11 5.526 1.963
NaOH ~
566 7.177 0.121 16.3 16 1.948
NaHC03 400 10.539 5. 128 18.148
S(rhombic) 368.3 3.748 4. 11 4 -1.728 -0.783
Si02 (quartz) 847 5.345 4.871 5.365 -1.001
tselected from K. K. Kelley, U.S. Bw: Mines Bull. 584, 1960;

L. B. Pankratz. U.S. Ow: Mines Bull. 672, 1982.
Table C.3: Heat Capacities of Liquidst

Constants for the equation C pI R = A + BT + CT 2
T from 273.15 to 373. 15 K
Chemical species C P29sl R A 103 B 106 c

Ammonia 9.7 18 22.626 -100.75 192.71
Aniline 23.070 15.81 9 29.03 - 15.80
Benzene 16.1 57 -0.747 67.96 -37.78
1.3-Butadienc 14.779 22.7 11 -87.96 205.79
Carbon tetrach Iori de 15.75 1 21.155 -48.28 101.14
Chlorobenzenc 18.240 11.278 32.86 -3 1.90
Chlorofom1 13.806 19.215 - 42.89 83.01
Cyclohexane 18.737 .-=:9.048 141.38 - 161.62
Ethanol 13.444 33.866 - 172.60 349. 17
Ethylene oxide 10.590 "2 1.039 -"86.41 172.28
Methanol 9.798 13.431 -5 l.28 13 1.1 3
n-Propanol 16.92 1 41.653 -2 10.32 427.20
Sulfur trioxide 30.408 -2.930 137.08 -84.73
Toluene 18.611 15.133 6.79 16.35
Water 9.069 8.712 1.25 - 0. 18
: Based on correlations presented by J. W. Miller, Jr.. G. R. Schorr, and

C. L. Yaws, Chem. Eng .. vol. 83(23). p. 129, 1976.
686 APPENDIX C. Heat Capacities and Property Changes of Formation
Table C.4: Standard Enthalpies and G_ibbs Energies of Formation

at 298.15 K 1
Joules per mole of the substance formed
State D.Ho b. Go
Chemical species
, (Note 2)
!298
(Note 1)
/298
(Note l)
"
Paraffins:
Methane C}4 a (g) -74,520 -50,460
Ethane C2H6 (g) -83,820 -3 1,855
Propane C3H8 (g) - 104,680 -24,290
n-Butane C4H1o (g) - 125,790 - 16,570
n-Pentane CsH12 (g) -146,760 -8,650
n-Hexane C6H14 (g) -166,920 150
n-Heptane C7H16 (g) -187,780 8,260
n-Octane CgH1s (g) -208,750 16,260
1-AJkenes:
Ethylene C2H4 (g) 52,510 68,460
Propylene C3H6 (g) 19,7 10 62,205
1-Butene C4H8 (g) -540 70,340
1-Pentene CsHIO (g) -21,280 78,410
1-Hexene C6H12 (g) -41,950 86,830
1-Heptene C7H1 4 (g) -62,760
Miscellaneous organics: '

Acetaldehyde C2H40 (g) -1 66,190 - 128,860
Acetic acid C2H402 (l) -484,500 -389,900
Acetylene C2H2 (g) 227,480 209,970
Benzene C6H6 (g) 82,930 129,665
Benzene C6H6 (l) 49,080 124,520
J ,3-Butadiene C4H6 (g) 109,240 149,795
Cyclohexane C6H12 (g) - 123,140 3 1,920
Cyclohexane C6H12 (I) -156,230 26,850
I,2-Ethanediol C2H602 (I) -454,800 -323,080
Ethanol C2H60 (g) -235,100 - 168,490
Ethanol C2H60 (l) -277,690 -174,780
Ethylbenzene CgH10 (g) 29,920 130,890
Ethylene oxide C2H40 (g) -52,630 - 13,010
Formaldehyde CH20 (g) -108,570 - 102,530
Methanol c~o (g) -200,660 - 161,960
Methanol CH40 (l) -238,660 -166,270
Methylcyclohexane C7HI4 (g) - 154,770 27,480
MethylcycJohexane C7H14 (l) -190,160 20,560
Styrene CsHs (g) 147,360 213,900
Toluene C7H8 (g) 50,170 122,050
Toluene C7H8 (l) 12,180 113,630
Subject Index
,.. Acentric factor, 95-96 , 409 Carn ot cycle, 161- 162, 164- 165, 292
table of values, 680- 681 for powe r plants, 292
Activity coefficient , 358-359, 417- 418, for refrigeration, 317 318
432- 433 (See also Heat engine; Heat pump)
analytical representation of, 438, 446
Carn ot's equations, 166
449 Carn ot's theor em, 162- 163
and data reduction, 437- 445
Char ge-tr ansfer complex, 665
effect of T and P on, 418
Chemical poten tial, 379
and the excess Gibbs energy, 417-
equality of, as equilibrium criterion,
419
from experimental data, 430- 445 380- 381
and fugacity, 401- 402
infinite-dilution value of, 436- 437
by the UNIFAC meth od, 791- 797 for ideal gas, 393- 394
Adiabatic process, 77- 78, 173- 174 for ideal soluti on, 413
Adsorption equilibrium, 606-621 Chemical reaction:
Adsorption isotherm, 608- 612 equilibrium const ant for, 490 501
Analysis of processes, 635- 644 equilibrium conversion of, 502- 514
Antoine equation, 223 heat effect of, 135- 150
table of coefficients , 682 reaction coordinate for, 48~488
Association, 664 reversible, 33- 34
Azeotrope , 346-347,362- 363,5 81,59 0- standard prope rty change for, 135-
591 139, 491- 495
stoichiometry, 484-488
Barke r 's method, 444-445 Chemical-reaction equilibrium, 488- 514,
Benedict/W ebb/ Rubi n equation, 89 518- 528
Bino dalcu rvc, 582-583 calcu lation of constant for, 496- 497
Boyle temp eratu re, 655 criter ia for, 488- 489, 577
Bubble point , 342, 345- 347, 351- 356, effect of press ure, 498- 499
590 effect of t emperature, 492- 495, 499
Bubble-point calculation , 351- 356, 360- in heterogeneous system, 510- 514
362, 367, 547- 551 , 553- 554,556, for multiple reactions , 518- 528
566- 568 set of independent react ions, 515-
517
Calorimeter, flow, 52- 54, 135 Clapeyron equat ion, 133, 221- 222
Canonical variable, 207, 379 Claus ius/Clapey ron equation, 222
807
808 SUBJEC T INDEX
Cgefficient of performance, 318- 321 Dipole moment, 650- 651

Combining rule, 409-410, 561 Duhem's theorem, 340, 517- 518
Combustion, standard heat of, 139
Compressibility, isothermal, 68- 69,.203- Efficiency:
206 Carnot-enginc, 161- 163, 292
Compressibility factor, 72, 87- 88,100- compressor, 274
104, 609 of heat engine, 161- 162
generalized correlations, 100- 107, of internal-combustion engine, 303-
696-699 310
for mixture, 238- 240 of irreversible process, 79
Compression, in flow process, 273- 277 of power plant, 294- 302
Conservation of energy, 11- 15, 47 thermal, 161, 166, 292
(See also First law of thermody- thermody namic, 182, 641, 644
namics) turbine, 268- 269
Consistency of VLE data, 441- 445 Ejector, 279- 280
Consolute temperat ure, 582- 588 Electrolytic cell, 34, 529
Continuity equation, 46 Electronegativity, 663- 664
Control surface, 45- 46 Energy, 10- 15
Control volume, 45-46 balance, 23-25, 47- 52 254- 256
Conversion factors, table of, 677- 678 conservation of, 11- 15, 47
Corresponding states: (See also First law of thermody-
correlations, 99- 111, 223- 224, 230- namics)
240, 407- 411 , 695-711 external, 22
theorem of, 95- 96 ' internal (see Internal energy)
Critical point, 64- 68, 91- 93, 225, 342- kinetic, 10- 11, 25, 47- 48, 51- 52,
344 260, 268
Critical properties, table of values, 680- potential:
681 gravitatio nal, 11- 12, 25, 47- 48,
290 ~
Critical-solution temperat ure, 582- 588
Cubic equation of state, 90- 94, 217- 220 intermolecular, 648- 649
generic, 92- 93 Engine:
residual properties from, 217- 220 Carnot, 161- 163
vapor pressure from, 557- 559 Diesel, 304- 306
VLE from, 556- 575 gas-turbine, 306- 310
heat, 161- 163
Density, 3 internal-combustion, 302- 310
generalized correlation, liquids, 109- jet, 310- 311
111 Otto~ 303- 304
Dew point, 342, 346- 347, 351- 356, 590 rocket, 310- 312
Dew-point calculation, 351- 356, 360- Enhancement factor for SVE, 602- 603
362, 367, 547- 551, 553 Enthalpy, 38- 39
Diesel cycle, 304- 306 calculation of, 212- 215, 233- 238
Differential, exact, 201 differential expression for, 200- 201 ,
Diffuser, 261, 280 202- 203
Dimensions and units, 2- 11, 15 effect of T and P on, 202- 203
table of conversion factors, 677- 678 excess (see Excess property)
SUBJEC T INDEX 809
Enthalpy : Equation of State:

experime ntal determin ation of, 52- generic cubic, 92- 93
54 ideal-gas, 73, 104
ideal-gas~ 203, 212-213, 234-235~ mixing rule for paramete rs 405 , 561 ,
393 568- 569
ideal-solu tion, 412 Peng/Robinson , 97- 98, 558
residual, 209, 216- 217, 219- 220, 230- Redlich/K wong, 94, 97~98. 219- 220
240 residual propertie s from, 215- 220
generaliz ed correlatio ns for~ 230 Soave/Re dlich/Kw ong, 97- 98, 558
240, 700- 703 van der Waals, 91, 93- 94, 97- 98
(See also Excess property; Heat of virial, 70, 72, 87-90, 101- 104, 216-
reaction; Property relations; Resid- 217, 405-407
ual enthalpy) VLE from, 556- 575
Enthalpy /concent ration diagram, 463- Equation s of balance, 255-256
469 Equilibrium, 29, 338- 339, 380-381, 401 ,
for sodium hydroxid e/water, 465 430-431, 575- 577
for sulfuric acid/wate r, 462 criteria for, 380-381, 397,401, 488-
Enthalpy /entropy (Mollier) diagram, 226- 489, 575-577
227 phase (see Phase equilibriu m)
for steam (see b~k endpaper s) reaction (see Chemical -reaction equi-
Entropy, 167- 175, 188- 190 librium)
absolute, 188 Equilibri um constant for chemical reac-
balance, 176-180 tion, 490- 501
calculatio n of, 212-215, 233-238 graph for selected reactions , 493
effect ofT and P on, 202-203 Eutectic, 601- 602
excess (see Excess property) Exact differenti al expression, 201
generatio n, 176- 178, 185- 186 Excess Gibbs energy:
ideal-gas, 170- 173, 203, 212- 213, and the activity coefficien t, 417-
234-235, 393-394 419, 435-449
ideal-solution, 412 empirical expresion for:
and irreversibility, 173- 175 Margllies, 437-438, 446-447
microscopic viewpoin t, 188-190 NRTL, 448-449
residual, 209- 210, 215-217, 219- 220, Redlich/ Kister, 446
23Q-240 UNIQUA C, 791- 792 "'
generalized correlatio ns for, 230 van Laar, 447
240, 704-707 \iVilson, 448- 449
and second law, 173- 177 Excess property, 413- 417
(See also Residual entropy) " observed behavior, 419- 420, 665-
Equation of state, 68, 70, 72, 87-.94, 668
405- 406 explanati on for, 669- 672
for adsorbate , 610 partial, 414, 417-419, 452-454
Benedict /Webb/R ubin, 89 and property change of m ixing, 449
cubic, 90- 94, 217- 220 452
fugacity coefficient from, 396, 405- relations among, 418- 419
407, 556- 565 Expansion, in flow process, 268- 273
SUBJECT IN DEX
810
, 203- 206 Fugacity:

Expansivity, volume, 68 1- 402
of species in sol ut ion, 40
Extensive property, 24 430- 432
effect of compositio n on ,
an d stability, 579-580
1
ics: <1
Fi rst law of the rm od yn am FUgacit y coefficient , 394-
40 1, 402, 404-

for closed sy ste m, 21- 25 409
as ap plied to ide al gas,
73-8 6
calcu lat ion of, 396- 40 1
for flow process, 47- 55 from cubic eq ua tion of sta
te, 396,
retical, 1t13
Fl am e tem pera tur e, theo 558- 566
0, 55 1-5 54
Fl as h calculation, 367- 37 L from gene ralized correlat
ions, 407-
280
Flow process, 44~55, 254- 411, 708- 711
46
continuity eq ua tio n for , in ide al solut ion , 413
, 47 - 52, 254--
energy eq ua tions for fro m th~ virial eq ua tio n
of sta te,
256 405- 407
180
en py balance for , 176-
tro an d th e residu al Gibbs en
ergy, 395,
mass balance for, 45- 47 402
8- 261
ma ximum velocity in , 25 erty relation,
, 254- 255 Fu nd am en tal excess-prop
mome ntu m principle for 414
in nozzle, 26Q-263 ations, 201, 207-
F\ md amen tal pr op ert y rel
in pip e, 258- 259 208, 378- 380, 403
of, 635-
t he rm od yn am ic an alysis Fu nd am en tal residual-pr
operty rel ati on ,
644 209, 403- 404
pa ns ion;
(Se also Compression; Ex
e
Fusion, lat en t he at of, 13
3, 188, 599
Th ro ttl in g process)
rmodynamics ,
Fl uid mechanics and t he Gas cOnstant, 71
254 table of values, 678
Fo rm ati rea cti on , 137
on Gas liquefaction, 327- 33
2
change of,
stand ar d Gibbs-energy Gas-t ur bi ne ,- en-gine, 306- 310
496 Gases: 1
687
ta ble of values for , 686- critic ~orlstants for, 68
al 0- 681
sta ndar d he at of, 136-13
9 99- 108, 230-
687 generalized co rre lat ions,
table of values for, 686- 240, 407- 411! 695- 711
Freundlich equa tio n, 612 he at-capacity da ta for, 68
4
FUel cell, 529- 532 ide al, 73-86, 391- 394
calculat ions for , 531- 532 PV T relations for 1 64- 73
, 87- 108
Fugacity, 394-402 Generalized correlations:
calculation of, 396- 401 0- 107, 696-
401 compressibili ty fac tor, 10
an d chemical po ten tia l, 699
uil ibrium, 490, 411, 708-
in chemical-rea ction eq ~ fug aci ty coeffici en t, 407-
498 501 711
criterion,
eq ua lity of, as eq uilibr ium Le e/K es ler , 100- 101, 231-
232, 408,
401 695- 711
8
an d Gi bb s energy, 394-39 liq ui d density, 109- 111
ideal-gas, 395, 402 tro py, 230
3 residu al enLhalpy an d en
in ide al solution , 412-41 240, 700- 707
6- 397, 401
an d ph ase equilibrium , 39
SUBJE CT INDEX 811
Generalized correlations: Heat capacity :

vapor pressure, 223- 224 ideal-gas, 127- 129, 684
virial coefficients, 101- 104,409-410 mean:
"' - Gibbs adsorption isotherm, 608 for enthalpy calculations, 130
-r Gibbs/D uhem equation , 384-387, 418, for entropy calculations, 171- 172
433- 434, 437, 441- 442, 579- ratio, 77
580 of solids and liquids: 129, 685
for an adsorbate, 608 standar d change of reaction , 141
Gibbs energy, 200, 415 Heat effects, 125- 150
for change of phase, 221 of chemical reaction , 135- 150
differential expression for, 200- 201, at constan t P or V, 40- 41
207- 208, 379, 390- 391 , 403 latent, 133- 136, 220- 222
and equilibrium, 221 , 488- 489, 576- of mixing, 456-469
577 Heat engine, 161- 163
and fugacity, 395- 399 Heat pump, 326- 327
as generating function, 207- 208, 415 Heat transfer:
for ideal gas, 393-394 irreversible, 170, 173- 174
for ideal solution, 411- 412 reversible, 33, 162, 173- 174, 177
summar y of eqmttions for, 415 Helmholtz energy, 200
(See also Excess Gibbs energy; Resid- differential expression for , 200- 201
ual Gibbs energy) and the partitio n function, 661- 662
Gibbs's theorem, 392 Henry's constan t:
for adsorption, 609- 610, 612- 614
Heat, 15, 21 24, 26, 159- 162 and standar d state, 500- 501
of adsorption, 616- 617 for VLE, 357- 358, 433- 434, 554-
of combustion, 139 556
and entropy, 167- 170 Henry's law:
of formation, 136- 139 for adsorption, 609- 610
table of values for, 686- 687 and Lewis/Randall rule, 432- 434
of fusion, 133, 188, 599 for VLE, 357- 358, 554- 556
latent, 133- 136, 220- 222 HRB , 234, 685
of mixing, 451- 452, 456-469 Hydrogen bond, 662- 665
of react ion, 135- 150 '\ .
reservoir, 161, 166, 169 ICPH , 132, 212
reversible transfer of, 33, 162, 173- ICPS, 171, 212.
174, 177 IDCPH, 142, 494
sign convention for, 23 IDCPS , 495
of solution, 456- 461 !deal gas, 68,73- 86, 391- 394
for HCl and LiCl in water, 459 Carnot cycle for, 164-166
specific (see Heat capacity) equation of state for, 73, 104
of transitio n, 133, 188 Ideal gas:
Heat capacity, 40- 44 enthalpy change for, 203, 235
at constan t P or V , 40- 41 entropy change for, 170- 173, 203,
difference, 74, 77, 206- 207 235
excess, 572- 574, 585 fugacity of, 395, 402
as function ofT, 127- 132, 684-685 heat capacity of, 127- 129, 684
812 SUBJE CT INDEX
Ideal gas: Isother mal process, 76, 79

interna l energy and enthal py changes
for, 74, 76 Jet engine, 310 -311
proper ty changes of mixing, 450 .Joule/ Thoms on coefficient, 266-267
proper ty relatio ns, 2Q3, 212, 234- Joule/T homso n expansion (see Throt-
235 tling process)
reactio n equilibrium, 499 "'
and residual property, 21 2- 213 K-valu e for VLE, 363-370, 551- 554, 565-
tempe rature scale, 70-71 , 164 166 568, 570- 572
Ideal-gas mixtur e, 129, 391-39 4 Kineti c energy, 10- 11, 25, 47- 48, 51-
Ideal-gas state, 127-12 8, 203 52, 260, 268
Ideal solut ion, 411-413 -~
chemical-reaction equilibrium, 498, Langmuir isotherm, 610 616, 620~62L
500 Latent heat, 220- 222, 133- 136
and excess property, 413- 414, 417 Riedel equatio n for, 134
proper ties of, 411- 413 vVatson correlation for, 131
proper ty changes of mixing for, 450 Lewis/ Randa ll rule, 412- 413, 431-435
and Raoult 's law, 350 and Henry 's law, 433- 435
Ideal work, 181- 184, 636 and Raoult 's law, 433
In1miscible systems, 594 597 Liquefaction, 327 332
Incompressible fluid, 68, 203, 206-207 Liquid /liquid equilibrium (LLE), 581-
Intensive proper ty, 3, 24 589
Intensive state, 29- 30 Liquid /vapor equilibrium (see Vapor /liquid
Interm olecular forces, 648- 654 equilibrium)
direct electro static, 649- 650 Liquitls:
dispersion, 651 654 fugacity of, 397- 401
induct ion, 651 654.. generalized density correlation, 109-
quasichemical, 662- 665 111
Interna l-combust ion engine, 302- 310 heat capaci ty for, 129, 685
Interna l energy, 21- 22, 47 incompressible, 68, 203, 206- 207
proper ty changes of, 68- 69, 203
differential expression for, 200- 201,
205- 206
PVT behavior of, 68- 69, 91- 92, 97-
of ideal gas, 73- 77 99
standa rd state for, 136
microscopic view, 657 659
Lost work, 185- 187, 635 -644
Interna tional Tempe rature Scale, 5
Interpo lation, 712- 714
Mach numbe r, 257
Inversion curve, 267 Maple , 99, 363, 549, 689- 690
Ionization potent ial (first), 651 652 Margules equation, 437- 438, 446- 44..7
Irreversibility, 32- 33, 185, 258 Mass balance, 45 47
and entropy change, 173- 177, 185 MathcadQ9, 99, 363, 549, 689-693
Isentropic process, 169, 171 , 226- 228, Maxim um velocity in flow, 258- 263
260- 262, 268- 279 Maxwell's equations, 201
Isobari c process, 76, 79 MCPH, 131- 132, 212, 688- 689
Isother mal compressibility, 68- G9, 203- MCPS, 172, 212, 688-68 9
206 MDCP H , 142
SUBJECT INDEX 813
Mixing process: Phase equilibrium:

entropy cha.nge, 394, 450, 454-455 criteria for, 380- 381, 396- 397, 401,
Gibbs-energy change, 450, 454-455 575- 577
heat effect of, 393 394, 450- 469 (See also Adsorption equilibrium;
in ideal gas and ideal solution, 450 Liquid/liquid equilibrium; Os-
property changes, 450, 454- 455 motic equilibrium; Solid/ liquid
Mixing rule, 405, 561, 568- 569 equilibrium; Solid/vapor equi-
Molar mass, table of values for, 680- 681 librium ; Vapor / liquid equilib-
Molecular basis for mixture behavior, rium; Vapor/liquid/liquid equi-
669- 672 librium)
Molecular simulation of VLE, 672- 674 Phase rule, 29- 31, 339- 340, 514- 518
Molecular weight (see Molar mass) for adsorpt ion equilibrium, 607
Mollier diagram, 226- 227 PH IB, 409, 690
for steam (see back endpapers) Polarizability, 651
Momentum principle, 254- 255 Polytropic process, 78 79
Potential energy:
Newton's method, 523, 552, 798- 801 gravitational, 11- 12, 25, 47-48, 290
Newton's second law, 3- 4, 10- 11, 254 intermolecular, 648- 649
Nozzle, 260 263 Potentia.! function (pair) , 648- 657
Lennard-Jones, 649- 650
Open system, 23, 44- 45 2nd virial coefficient from, 654- 657
Osmotic equilibrium, 62lr624 square-well, 654- 656
Osmotic pressure, 622- 624 Power-plant cycle, 29Q-302
Otto cycle, 303- 304 Rankine , 292 296
regenerative, 296- 302
Partial pressure, 392 , 394, 402 analysis of, 636 641
Partial property, 381 391
Poynting factor:
excess, 414 for liquid-phase fugacity, 398
graphical interpretation, 387-389
for solid-phase fugacity, 602- 605
for an ideal solution, 411-412
Pressure, 6-8
rationale for, 385
critical, 64 68
~ relations among, 390- 391
effective, fo r H2 , 101
~ially miscible system, 581- 597
interaction ( Pcij), 409
Pru-tition function, 658- 662
table of values for, 680- 681
Peng/Robinson equa~ion, 97- 98, 558
partial, 392, 394, 402
Phase, 30, 64- 68
pseudocritical, 238- 239 "'
Phase change, 65- 68, 225 reduced, 95
Phase diagrams:
Pressure/composition (Pxy) diagram,
binary VLE, 341- 350, 353-355,568, 343, 348, 353, 568, 575
575 ;'
P ressure/enthalpy (PH) diagram, 226,
binary system, limited miscibility,
583, 587- 588, 590- 593, 595 .. 789- 790
Pressure/temperature (PT) diagTarn, 65,
for a pure species, 65- 67
67, 344- 345, 347
Phase equilibrium, 338- 370, 430- 445,
545- 624
814 SUBJECT INDEX
Pressure/volum e (PV) diagram, 66- 67, PVT relationships, 64- 69, 87- 111
557, 560 equation of state as, 70- 73, 87- 99
Process: for gas mixture, 561
adiabatic, 77- 78, 173- 174 generalized, 99- 111
constant-pressure, 76, 79 thermodynamic properties from, 215-
constant-volume, 76, 79 220
isentropic, 169, !71 , 226- 228, 260-
262, 268- 279 Quality, 225
isothermal, 76, 79
polytropic, 78- 79 Rackett equation, 109
thermodynamic analysis of, 635- Rankine cycle, 292- 296
644 Raoult's law, 350- 356
throttling, 85, 264- 267 modified, for low pressures, 358-
Property: 363
critical, 64- 68 Reaction coordinate, 484- 488
table of values, 680- 681 Redlich/Kister expansion, 446
from equation of state, 215- 220 Redlich/ Kwong equation of state, 94,
excess (see Excess property) 97- 98, 219- 220
extensive and intensive, 3, 24 Soave modification, 97- 98, 558
generalized correlations, 99- 111, 223- Reduced coordinate-s,-95 -..
224, 230- 240, 407- 411, 695- Refrigeration, 317~.
711 Refrigeration cycle:
of ideal-gas mixture, 129, 391- 394 absorpt ion, 323- 326
of ideal solution, 411- 413 Carnot, 317- 318
partial (see Partial property) cascade, 323-324
reduced, 95, 109, 239 vapor-compression, 318- 323
residual (see Residual property) ' Relative volatility, 362
of single-phase system, 199- 208 Reservoir, heat, 161, 166, 169
of two-phase system, 220- 222 Residual enthalpy, 209, 216- 217, 219-
(See also Thermodynamic proper- 220, 230- 240
ties) from equation of state, 215~20
Property change of mixing, 450 generalized correlation for, 230- 238,
and excess property, 450- 452 700- 703
for ideal gas and ideal solution, 450 Residual entropy, 209- 210, 215- 217, 219-
observed behavior, 454- 455 220, 230- 240
Property change of reaction, 135- 139, from equation of state, 215- 220
491- 495 generalized correlation for, 230- 238,
Property relations, 199- 206, 378- 387 704- 707
for constant-composition phase, 199- Residual Gibbs energy, 208- 211, 216-
206 220, 395, 402- 404, 562
fundamental , 201, 207- 208, 378- Residual property, 208- 220, 230- 240, 403-
380, 403- 404, 414 404
Pseudocritical property, 238- 239 Residual volume, 208- 210, 404
Retrograde condensation, 344
SU BJ EC T IND EX
Reversibility, 31- 35, 173-176, 181-

184 Sys tem , 12- 13, 22
me cha nic al, 35
Reversible che mic al rea ctio n, 33- 34 closed : 23
Riedel equ atio n, for late nt hea t of het erogeneous, 510- 511
va- open, 23, 44- 55
por iza tion , 134
Ro cke t engine, 310- 312
Tem per atu re, 5- 6, 70- 71, 163- 166
Sat ura ted liquid and vap or, 66, 221 abs olu te zero of, 5 , 166
, 225 consol ute, 582- 588
Sec ond law of the rm ody namics,
159- crit ica l, 64- 67
160 , 173- 176 , 185
effective, for H2 , 101
sta tem ent of, 160, 171
Sec ond virial coefficient: int era ctio n (Tcij), 409
tab le of values, 680- 681
gen era lized cor rela tion for, 101- 103
, crit ica l-soluti on, 582- 588
409- 410
nor ma l-b oili ng- poi nt, 134
from pot ent ial fun ctio n, 654--657
Sha ft wo rk, 48 tab le of val ues, 680 -68 2
Soa ve/ Re dlic h/K wo ng equ atio n of pse udo crit ica l, 238 - 239
sta te, red uce d, 95
97- 98, 558
Sol id/l iqu id equ ilib riu m (SL E), 597 sur rou ndi ngs, 176, 181
-60 2 Tem per atu re/ com positio n (txy ) dia
Solid/vap~e~uilibrium (SV E), gra m.
602 -60 5 343 , 349 , 355, 590, 595
Sol ubi lity 'dia~am, 583, 587- 588,
604 Tem per atu re/ ent rop y (TS ) diagra m,
Solvation, 6J4 226
Tem per atu re scale, 5-6 , 70- 71 , 163
Son ic velocity in flow, 258- 261 -166
Specific hea t (see He at cap aci ty) ide al-gas, 71
Spr ead ing pressure, 607 , 611 , 614- Intern atio nal Tem per atu re Sca le, 5
615 Ke lvin, 5-6 , 71, 166
SRB, 234, 690
Sta bil ity crit eria , 577- 581 the rm ody nam ic, 163- 166
Th erm ody nam ic ana lys is of proces
Sta nda rd Gib bs- ene rgy change: ses,
of for ma tion , tab le of values , 686 - 635- 644
Th erm ody namic consist enc y, 441 -
687 445
Th erm ody nam ic pro per ties :
of rea ctio n, 490- 491
of me tha ne, 789
effect of tem per atu re on, 491
Sta nda rd :>tate, 136 of ste am , 715- 787
Sta te fun ctio n, 26 (See also back end pap ers )
Steady-flow process, 51 of tetr afiu oro eth ane , 322, 790
Ste am : (See also Pro per ties}
Th ird law of t her mo dyn am ics , 188
Mollier dia gra m for (see back end -
Th ird vir ial coefficient:
pap ers )
generalized cor rela qtio n for , 103-
tab les , 715- 787
Ste am pow er pla nt, 291 - 302 104
Ste am tur bin e, 269- 270 Th rot tlin g process, 85, 264- 267
Tic line , 342 , 582
Stoich iom etri c num ber , 484
To th equ atio n, 611 -615
Sup crc ritical sep ara tio n process, 603
Tri ple poi nt, 64 66
Sup erh eat , 225
TrouLon's rule: 134
Sur rou ndi ngs , 12- 13, 22
Tur bin e, 268- 273
Lemperature of, 176 , 181
Tu rbo jet, 311
SUBJECT INDEX
816
Vapor/liquid equilibrium (VLE):
Two-phase system, 220- 225
Clapeyron equation for, 133, 221- for immiscible system, 594- 597
K -value for 1 363- 370, 551- 554, 565-
222
568, 571- 572
quality in, 225
UNIFAC method, 791- 797

UNIQUAC equation, 791- 792 ~
- K-values, light hydrocarbons, 365-
366
by molecular simulation, 672- 674
for partially miscible system, 590-
Units, 2- 11, 15
conversion factors, 677- 678 594
Universal gas constant, 71 for pure species, 220- 221, 396- 397,
table of values for, 678 557- 559
Unsteady-state flow process, 47- 51 by Raoult's law, 350- 356
reduction of experimental data, 437-
van der \IVaab equation, 91, 93- 94, 97- 441
98 for solute/solvent systems, 554- 556
van Laar equation, 447/ / and thermodynamic consistency, 441-
Vapor/liquid equiLibrium (VLE): 444
and activity coefficient, 432-445 Vapor/liquid/ liquid equilibrium (VLLE),
infinite-dilution value of, 436- 437 590- 597
binary-system phase diagrams, 341- Vapor pressure, 64- 68, 95- 96, 133, 221-
350, 353- 355, 568, 575 224, 557- 559
calculations, block diagrams for, 547- empirical expressions for, 223
551 generalized correlation for , 223- 224
conditions for stability in, 579- 581 Vaporization, 64- 68, 133- 135, 220-222
correlation by excess Gibbs energy, " latent heat of, 133- 136, 220- 222
435- 441, 446-449 ~ro;~. Clapeyron equation, 133, 221
by Margules equation, 437- 438, frem' Riedel equation, 134
446- 447 from Watson correlation, 134
by NRTL equation: 448- 449 Velocity, 10, 44- 48, 258- 263
by Redlich/Kister expansion, 446 average value in pipes, 48
by UNIFAC method, 791- 797 maximum in pipes, 258
by van Laar equation, 447 profiles in pipes, 48
by Wilson equation, 448-449 sonic, 258, 260- 261
dew- and bubblepoint calculations Virial coefficients, 72, 87- 88, 101- 104,
for, 351- 356, 360- 362, 367, 547- 405, 409- 410
551, 553- 554, 556, 566- 568 generalized correlation of second,
equations, 350- 351 , 358- 359, 545- 101- 103, 409-410
547, 556- 575 generalized correlation of third, 103-
for high pressure , 556- 575 104
for ideal solution, 350 for mixture, 405, 409- 410
to moderate pressure, 358- 363 Virial equation of state, 70, 72, 87- 90,
flash calculation, 367- 370, 551- 554 101- 104, 216- 217, 405- 407
and t he Gibbs/Duhem equation, 433- Volume, 2- 3
434: 441-442 change of mixing, 450- 451
SUBJECT INDEX 81 7
Volume: Work, 8- 9, 23- 24, 159

critical, 66-68 of adiabatic compression, 77, 273-
effective, for H2, 101 279
interaction (Vcij), 409 ideal, 181- 184, 636
table of values, 680- 681 of isothermal compression, 76
excess, 450, 453- 455 lost, 185-18'7, 635- 644
residual, 208- 210, 404 for pump, 278- 279
Volume expansivity, 68, 203-206 and reversibility, 31- 33
shaft, 48
\iVagner equation, 223 sign convention for, 23
Vlatson correlation for latent beat, 134 from turbine or expander, 268- 273
\Vilson equat ion, 448- 449
yx diagram, 346, 350
(\
'
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