IJ4-CHEM-A1 Process lfala nces and Chemical Th ermodynamics

May 2016

04-CHEM-Al, PROCESS BALANCES and CHEMICAL THERMODYNAMICS

MAY 2016

Three Hours Duration

NOTES:

1) If doubt exists as to the interpretation of any question, you are urged to submit a clear
statement of any assumptions made along with the answer paper.

2) Prope1ty data required to solve a given problem are provided in the problem statement or are
available in the recommended texts. If you are unable to locate the required data, do not let
this prevent you from solving the rest of the problem. Even in the absence of property data,
you still have the opportunity to provide a solution methodology.

3) This is an open-book exam.

4) Any non-communicating calculator is permitted.

5) The examination is in two parts - Part A (Questions 1 to 3): Process Balances

Part B (Questions 4 and 6): Chemical Thermodynamics

6) Answer TWO questions from Part A and TWO questions from Part B.

7) FOUR questions constitute a complete paper.

8) Each question is of equal value.

1of6
 04-C:ttEM-A 1 Procus Balauc~s anrl Chemical Therm(ldynamics
May 2016

PART A: PROCESS MASS an d ENERGY BALA NCES

1) Consider an iron bl.ast furnace charged with iron ore, limestone (CaC03) and coke. The
weight analyses of the charge is as follows:

Fc20 :i Si02 MnO AhOJ FhO c CaC01

Ore 80% 12% 1% 3% 4%
Limestone 4% 1% 95%
Coke 10% 90%

The ultimate weight analysis of the pig iron gives 93.8% Fe, 4% C, 1.2% Si and I % Mn.
For every ton of pig iron produced, 1750 kg of iron ore and 500 kg of limestone are used
and 4200 m 3 of flue gas is produced. The rational analysis of Hue gases gives 5 8% N 2, 26%
CO, 12% C02 , and 4% H20. The reactions occurri ng in the blast furnace are:

Fe20 3 + 3CO H 2Fe + 3C02

CaC03 H CaO + C02
C + Y2 0 2 H CO
Si02 + 2C H Si+ 2CO
J\fuO + C B Mn + C02
C02 + C H 2CO

Determine the following:

a) Quantity of coke used per ton of pig iron.

b) Consumption of air per ton of pig iron
c) Composition of the slag

2 of6
 04-CHEi'Vl-A I Proct.<s Balances and Cht>mical Thf'.rn1odynamir.s
May 20Hi

2) Consider the oxidation of toluene given by the follo\Ning reaction

Calculate the standard heat of reaction for oxidation of toluene.

DATA:
Gross heat of combustion of liquid benzaldchydc at 18 C = - 841.3 kcal/gmol
Normal boiling point of benzaldehyde = 179 C
Heat of vaporization of benzaldehyde at l 79 C = 86.48 cal/g
Specific heat capacity of liquid benzaldchyde = 0.428 cal/g C
Specific heat capacity of benzaldehyde vapor = 3 l cal/gmol C
Average molar heat capacity ofliquid H 20 = 18 cal/gmol C
Average molar heat capacity of C02 = 8.87 cal/gmol C
Average molar heat capacity of 0 2 = 7.0 cal/gmol C
Standard heat of formation of H20 vapor= - 57.8 kcal/gmol
Standard heat of formation of toluene vapor= 1 l.95 kcal/gmol

3) 1000 kg/lu of a liquid solution of 60 wt% naphthalene (CroHs) and 40 wt% benzene (C6H6)
at 80 C is cooled to 10 C. The resulting solid and liquid phases are separated in a rotary
drnm filter. The process operates at steady state. Your job is to determine how well the
drum filter is performing. You determine that the filtrate liquid flow rate is 505 kg/hr.

(a) How much entrainment (kg entrained/kg solids) does the filter leave?
(b) By how much docs any entrainment change the recovery of naphthalene in the filter
cake product or the purity of the products?

3 of 6
 04-CUEM-Al Process BR111ncr.s imd Chemical ThennodyClami<:~
tlfay 20)(i

80

70 Liquid solu li uri

(benzene + naphthalene)
60

50
Liquid solution
40 +solid naphthalene Liquid solution + __
-u 30
u
solid benzene

<h
20

10

0
Solid naphthalene + sol id benzene
- 10
a 0.5 1.0
. {Naphthalene) Mole frac t ion benzene (B~ruene)
(A) (Bl

Figure: Liquid-Solid Phase Equilibrium Diagram for Benzene-Naphthalene Mixtures

(taken from "Phase Equilibria in Chemical Engineering" by Stanley M.
Wala!'!, Butterworth Publishers, 1985)

4 of 6
 04-CHEM-A l I'rocr..ss Balau<:.cs and Clt~mic 11I ThcnuO<fynamics
May 2016

PART B: CHEMICAL THERMODYNAMICS

4) The calcination of sodium bicarbonate takes place according lo the follow ing equa6on:

When this reaction was run in the laboratory by placing sodium bicarbonate in an initially
evacuated cylinder, it was observed that the equilibrium total pressure was 0.826 kPa at 30
C and 166. 97 kPa at 110 C. The heat of reaction for the calcination can be assumed to be
independent of temperature.

(a) What is the heat of reaction for this reaction?

(b) Develop an equation for the equilibrium constant as a fLmction of temperature.
(c) At what lempcrature will the partial pressure of carbon dioxide in the reaction vessel
be 1 bar?

5) At 45 C and 40.25 k.Pa total pressure, a vapor phase containing 43.4 mol% ethanol and
56.6 mo!% benzene is in equilibrium with a liquid phase containing 61..1 mol% benzene.
The system forms an azeotrope at 45 C. Assmning that few molecular iotcractions exist,
detem1ine the composition of the azeotrope and the total pressure of the azcotropic sys Lem.

Vapor. pressure of pure ethanol at 45 C = 22.9 kPa

Vapor pressure of pure ethanol at 45 C = 29.6 kPa

5 of 6
 04-CEIEM-Al Process Hahrnces anti C:hemical Thermody1rnmic.~
r.fHy 201 6

6) A chemical species A is known to decompose according to the following equation:

A (g) ~ B (g) + C (g)

A rigid container is filled with pure gaseous A at 300 Kand 760 mmHg, and then heated.
The pressure was observed to he 1114 mmHg at 400 K and 1584 mmllg at 500 K.
Assuming ideal gas behavior and chemical equilibrium, estimate the pressw:e for a
temperature of 600 K.

6 of 6
 The Periodic Table of the Elements
13
~

~ -~
llYGf,.,ll

1 Element name- f.-7 Mercury 2

Aliatit:e eanh metal:s
H Trse.nsition metals
80 <E- Atomic# He
1.01 2 Other metals 13 14 1S 16 17 4.00

,,.,;~

3
... 8'o1yl!0..1t1
4
M.l!'t.allotds (s:~tnl-mct31}
Nonmetals
Ht:loge.11s
Symbol -
---7 Hg "'~
5
,...,.
6
Nb'f"'
7 - 8
,..,_f.n
9
~"'
10
Li Be Noble gaHS 200.59 ~ ..__ Avg. Mass B c N 0 F Ne
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18

........
11
l\1agi'li.nl
12
111.~r''""
13
Sl>Po:a
14
P~1n
1S
~Jf..
16
c..........
17
....,....
18
Na Mg Al Si p s Cl Ar
22.99 24.31 26.98 26.09 30.97 32.07 35.45 39.95
l 4 s 6 7 8 9 10 11 12
;.,... c ..,.
F\t1enlu""
19 """"'
%0
~1141..f!\
21
TttltrilO!t
22
Vtnt6'.m
23
C!INotnium
24
'OllltfllfH

25
:r1n
26 ''"''
27
Nio;i:tl
28 29 '"''
30 31
~~t.m
32
Arnn~

33
hl...,'-'m
34
8i.;.ml'*
3S
Krn1l'I~
36
K Ca Sc Ti v Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
3!1.10 40.08 44.96 47.88 50.IM 52.00 54.94 55.85 58.93 S!l.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80

Nut.Gii.iii";
37
.. ~

38
...... -~
39
lft.-.1.1
40
N~-

41
..!Olyllcklllft

42
7tll!\.W.la
43
RUO.nlwn
44
kllodJ.f<rl
41>
Pal!1dil.wl
<IS
.,,.,,
47
c.dirlll.'nt
48 '"""'
49 ~
60
JW.llllonr
61
:01..9111111
&2
11...
63
)(N"
S4
Rb Sr y Zr Nb Mo. Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 98.91 91.22 92.91 95.94 (98) 101.07 102.91 100.42 107.87 112.4~ 114.82 118.71 121.76 127.60 126.9() 131.29

-
SS
sir.-
56
~..U"-111'1

71
HlMIUM

72
. ..'11.114.JA,
73
Tlr'll-'"
74
l'f>!<lll!lot
75
0foflll11M
76
lfl::llW!\
77
~G'lum
78
Odo
79
.......,.
80
f11~1AAM

81
......
8%
.........
II;!
Pl.In~

84
1,~:.i.i.

SS
Rttnl'
86
Cs
132.91
Ba
137.33
..
57.70
Lu
~74.97
Hf
178.49
Ta
183.8~
w Re
160.21
Os
190.23 192.22
Ir Pt
195.08
Au
196.97
Hg
200.SQ
Tl
204.38
Pb Bi Po
{209)
At
(210)
Rn
(222)
'!80.9.5 207.20 208.96

..
on...m.u..
fl"l:!Ci.1111
87
Rtd1..n1
88 8~102
l11wttl'dllll'
10l
"..-:;'"'~"'
104 '""''
105. .
CN.bOl.!>i..m
106
Ooh!Mii
107
"f.,,,i11m
108
M,llt>ttiUll'
109
,,..~dlium

110
f\oenl21lu11t
111
Cop1m~ium

112
l,ki,,.fri_
113
Ur.unqvHlum
114
lkl1111~).fl"I

115
~Ul'll'ltdum

116 117
Ufl"""'.11'
118
Fr Ra Lr Rf Db Sg Bh Hs Mt Os Rg Cn Uut Uuq Uup Uuh Uus Uuo
(223) (7.7.6) (?.67.) (267.) (2S9) (271) (272; (?.70) (7.76) {~31) {280) {2a&) (284) (289) (288) (293) (294?) (294)

c";...,_
~1r011n1."'ll
$7 58
~,..~~'l!ll'llln
59
Ne.$0'.)1'!:!-
60
l'fOAl.Ollllum
61
~m1tri11m

62
ivo.oiJm
63
Gt~oli11rJm

64
'llt>LIM
6$
~OIOS.'Jm

66
'-W.lum
67
El'tlllll\
&8
'1'J.fh1111
69 """'70Wll
"Ian than ides La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Vb
138.91 140.12 140.91 144.24 (145) 150.30 i51.97 157.25 1S8.93 162.50 164.93 167.26 ~66.93 113.04

-actinides
14:1Jt.'.,.,.

Ac
89
"!'h.:fO..n

Th
90
Pfl:IUcll ,;_..,

Pa
91
~ ,..,.r;.,..,
92
u
f>J~r;,,,..

Np
93
P11.o...~...

94
Pu
.......;...-....
Am
95
c .........

Cm
96
"""'hliurn
97
Bk
Clfo~'"""
118
Cf
Eil!Ninl""'
99
Es
-~
100
Fm
Molv.1ilr.i
101
Md
--
102
No
(227) 232.04 231.04 238.0J (237} (244) (213) (217) (247) (251) (252} (257) (258) (259)

Page 1 of I 04-Chem-A l/May 2016