CHEMICAL ENGINEERING

THERMODYNAMICS I
(chapter 3)

Chemical Engineering Program

Department of Industrial and Process Technology
 Pada Vaporization Curve
terjadi VLE

Pada Fusion Curve terjadi

SLE

Fluida Superkritis

P dan T tertinggi dimana

substansi murni berada
pada VLE

F=1 F=0 F=2

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 superkritis

triple point
subkritis

B C menunjukkan liquid jenuh (single-phase) pada T boiling

C D menunjukkan uap jenuh (single-phase) pada T condensed

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9
 𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇

Volume Expansivity Isothermal Compressibility

1 𝜕𝑉 1 𝜕𝑉
𝛽≡ 𝜅≡−
𝑉 𝜕𝑇 𝑃
𝑉 𝜕𝑃 𝑇

𝑑𝑉
= 𝛽 𝑑𝑇 − 𝜅 𝑑𝑃
𝑉

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑃𝑉 = 𝑎 + 𝑏𝑃 + 𝑐𝑃2 + ⋯
′ ′𝑃 2
𝑃𝑉 = 𝑎 1 + 𝐵 𝑃 + 𝐶 +⋯ 𝑃𝑉 ∗
= 𝑎 = 𝑓(𝑇)

∗
𝑃𝑉 = 𝑎 = 𝑅𝑇

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑃𝑉
𝑍≡
𝑅𝑇
Compressibility Factor

𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯
𝐵 𝐶 𝐷 Virial Expansions
𝑍 =1+ + 2+ 3+⋯
𝑉 𝑉 𝑉

2 3
′
𝐵 𝐶 − 𝐵 𝐷 − 3𝐵𝐶 + 2𝐵
𝐵 = 𝐶′ = 𝐷′ =
𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑍=1 𝑜𝑟 𝑃𝑉 = 𝑅𝑇

P gas pada T konstan, sehingga volume gas

Tidak ada interaksi molekuler Term B/V, C/V2, dsb = 0

Persamaan Keadaan :
𝑃𝑉 = 𝑅𝑇 (gas ideal)

Energi Dalam:
𝑈 = 𝑈(𝑇) (gas ideal)

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝐻 ≡ 𝑈 + 𝑃𝑉 = 𝑈 𝑇 + 𝑅𝑇 = 𝐻 𝑇
𝜕𝑈 𝑑𝑈 𝜕𝐻 𝑑𝐻
𝐶𝑉 ≡ = = 𝐶𝑉 𝑇 𝐶𝑃 ≡ = = 𝐶𝑃 𝑇
𝜕𝑇 𝑉 𝑑𝑇 𝜕𝑇 𝑃 𝑑𝑇

Cv
𝑑𝐻 𝑑𝑈
𝐶𝑃 = = +𝑅
𝑑𝑇 𝑑𝑇

𝐶𝑃 − 𝐶𝑉 = 𝑅
this equation does not imply that Cp and Cv are themselves constant for an ideal
gas, but only that they vary with temperature in such a way that their difference is
equal to R

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Not Constant Volume
Process

Constant Volume Process

not depend on the path of the process ∆𝑈 = 𝐶𝑉 𝑑𝑇

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑑𝑉
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑇 • Valid for Ideal Gas
𝑉 • Mechanically Reversible
𝑃 = 𝑅𝑇 𝑉 • Closed System
𝑑𝑉
𝑑𝑊 = −𝑅𝑇
𝑉
𝑑𝑃
𝑉 = 𝑅𝑇 𝑃
𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑅𝑇
𝑃
𝑑𝑃
𝑑𝑊 = −𝑅 𝑑𝑇 + 𝑅𝑇
𝑃
𝐶𝑉 𝐶𝑃
𝑑𝑄 = 𝑉 𝑑𝑃 + 𝑃 𝑑𝑉
𝑅 𝑅
𝑇 = 𝑃𝑉 𝑅
𝑑𝑊 = −𝑃 𝑑𝑉
chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9
 Isothermal Process

∆𝑈 = ∆𝐻 = 0

𝑉2 𝑃2
𝑄 = −𝑊 = 𝑅𝑇 ln = −𝑅𝑇 ln (𝑐𝑜𝑛𝑠𝑡. 𝑇)
𝑉1 𝑃1

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Isobaric Process

∆𝑈 = 𝐶𝑉 𝑑𝑇 and ∆𝐻 = 𝐶𝑃 𝑑𝑇

𝑊 = −𝑅 𝑇2 − 𝑇1

and

𝑄 = ∆𝐻 = 𝐶𝑃 𝑑𝑇 (𝑐𝑜𝑛𝑠𝑡. 𝑃)

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Isochoric Process

∆𝑈 = 𝐶𝑉 𝑑𝑇 and ∆𝐻 = 𝐶𝑃 𝑑𝑇

𝑊=0

and

𝑄 = ∆𝑈 = 𝐶𝑉 𝑑𝑇 (𝑐𝑜𝑛𝑠𝑡. 𝑉)

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Adiabatic Process : Constant Heat Capacities
𝑅 𝑅 𝐶𝑃
𝑇2 𝑉1 𝐶𝑉 𝑇2 𝑃1 𝐶𝑃 𝑃2 𝑉1 𝐶𝑉
𝑑𝑄 = 0 =
𝑇1
=
𝑃2
=
𝑇1 𝑉2 𝑃1 𝑉2

𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐶𝑃
𝑇𝑃 1−𝛾 /𝛾
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝛾≡
𝐶𝑉
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝛾−1 /𝛾 𝛾−1 /𝛾
𝑃1 𝑉1 𝑃2 𝑅𝑇1 𝑃2
𝑊= −1 = −1
𝛾−1 𝑃1 𝛾−1 𝑃1

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Polytropic Process
𝑇𝑉 𝛿−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝑃 1−𝛿 /𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝑉 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝛿−1 /𝛿
𝛿 − 𝛾 𝑅𝑇1 𝑃2
𝑄= −1
(𝛿 − 1) 𝛾 − 1 𝑃1

𝛿−1 /𝛿
𝑅𝑇1 𝑃2
𝑊= −1
𝛿−1 𝑃1

Isobaric process, δ = 0 Adiabatic process, δ = γ

Isothermal process, δ = 1 Isochoric process, δ = ~
chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9
 𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯

𝜕𝑍
= 𝐵′ + 2𝐶 ′ 𝑃 + 3𝐷 ′ 𝑃2 + ⋯
𝜕𝑃 𝑇

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Persamaan keadaan kubik pertama kali dikemukakan oleh J. D. van der Waals pada
tahun 1873, yakni sebagai berikut :

𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

• a dan b, konstanta
• a, b = 0; gas ideal
• V>b

no
significance

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑅𝑇 𝜃 𝑉−𝜂
𝑃= −
𝑉−𝑏 𝑉 − 𝑏 𝑉 2 + 𝜅𝑉 + 𝜆

vdW EoS 𝜂 = 𝑏, 𝜃 = 𝑎, 𝑑𝑎𝑛 𝜅 = 𝜆 = 0

𝜂 = 𝑏, 𝜃 = 𝑎 𝑇 , 𝜅 = 𝜖 + 𝜎 𝑏, 𝑑𝑎𝑛 𝜆 = 𝜖𝜎𝑏 2

𝑅𝑇 𝑎(𝑇)
𝑃= −
𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏

bergantung pada substansi

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 horizontal inflection

𝜕𝑃 𝜕2 𝑃
= =0
𝜕𝑉 𝑇𝑐𝑟 𝜕𝑉 2 𝑇𝑐𝑟

𝜓 Ω

3 𝑅𝑇𝑐 27 𝑅 2 𝑇𝑐2 1 𝑅𝑇𝑐

vdW EoS 𝑉𝑐 = 𝑎= 𝑏=
8 𝑃𝑐 64 𝑃𝑐 8 𝑃𝑐

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Pada tahun 1949, Otto Redlich dan J. N. S. Kwong mengemukakan persamaan
keadaan kubik sebagai berikut :

𝑅𝑇 𝑎 𝑇
𝑃= −
𝑉−𝑏 𝑉 𝑉+𝑏
dimana,
𝛼 𝑇𝑟 𝑅 2 𝑇𝑐2 𝑅𝑇𝑐
𝑎 𝑇 =𝜓 𝑏=Ω
𝑃𝑐 𝑃𝑐

−1/2
𝛼 𝑇𝑟 = 𝑇𝑟

𝑇 𝑃
𝑇𝑟 ≡ 𝑃𝑟 ≡
𝑇𝑐 𝑃𝑐
reduced temperature reduced pressure

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑇 𝑃
𝑇𝑟 ≡ 𝑃𝑟 ≡
𝑇𝑐 𝑃𝑐
reduced temperature reduced pressure

(two-parameter theorem of corresponding states) All fluids, when compared

at the same reduced temperature and reduced pressure, have approximately
the same compressibility factor, and all deviate from ideal-gas behavior to
about the same degree

Simple Fluids (Argon, Krypton, Xenon)

𝑎𝑐𝑒𝑛𝑡𝑟𝑖𝑐 𝑓𝑎𝑐𝑡𝑜𝑟 (𝜔) introduced by K. S. Pitzer

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 𝑑 log 𝑃𝑟𝑠𝑎𝑡
=𝑆
𝑑 1/𝑇𝑟

All fluids having the same

value of ω, when
compared at the same Tr
and Pr, have about the
same value of Z, and all
deviate from ideal-gas
behavior to about the
same degree

𝜔 ≡ −1.0 − log 𝑃𝑟𝑠𝑎𝑡 𝑇𝑟 =0,7

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

  The generic cubic equation of state can be
rearranged to solve for the largest root:
vapor or vapor-like volume:

RT a(T ) V b
V b
P P V  b V  b 

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

  The following parameters can be
substituted into the previous equation and
V=ZRT/P and solved for Z:
bP a(T )
 q
RT bRT

Z 
Z  1    q
Z   Z   
chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9
  Parameters β and q can be solved for using the
following equations:
Pr  (Tr )
  q
Tr Tr
Z 
Z  1    q
Z   Z   
 Calculating Z is accomplished by iterating starting with the ideal
Z=1
 Once Z converges, solve for V using V=ZRT/P

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

  When iterating with V=b on the right side of the
equation a liquid or liquid-like root results when it
converges

 RT  bP  VP 
V  b  (V  b)(V  b)  
 a (T ) 

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

  Parameters β and q can be solved for using the
following equations:
Pr  (Tr )
  q
Tr Tr

1   Z 
Z    ( Z   )( Z   ) 
 q 
 Calculating Z is accomplished by iterating starting with Z=β
 Once Z converges, solve for V using V=ZRT/P

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Eq of State α(Tr) σ ε Ω ψ Zc
vdW (1873) 1 0 0 1/8 27/64 3/8
RK (1949) Tr-1/2 1 0 0,08664 0,42748 1/3
SRK (1972) αSRK (Tr ;ω) 1 0 0,08664 0,42478 1/3
PR (1976) αPR (Tr ;ω) 1+√2 1-√2 0,07779 0,45724 0,3074

1/2 2
2
𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 = 1 + 0,48 + 1,574𝜔 − 0,176𝜔 1 − 𝑇𝑟

1/2 2
2
𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 = 1 + 0,37464 + 1,54226𝜔 − 0,26992𝜔 1− 𝑇𝑟

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Pitzer Correlations for the Compressibility Factor

𝑍 = 𝑍 0 + 𝜔𝑍1

The Lee/Kesler correlation provides

reliable results for gases which are
nonpolar or only slightly polar; for
these, errors of no more than 2 or 3
percent are indicated

See Appendix E !!!!!

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 For quantum gases, ex : hydrogen, helium, and neon. Temperature-dependent
effective critical parameters was proposed by Prausnitz :

T is absolute temperature in K

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Pitzer Correlations for the Second Virial Coefficient

𝑃
0 𝑟
𝑃
1 𝑟 0,422 0,172
𝑍 =1+𝐵 + 𝜔𝐵 𝐵0 = 0,083 − 𝐵1 = 0,139 −
𝑇𝑟 𝑇𝑟 𝑇𝑟1,6 𝑇𝑟4,2

The simplest form of the virial equation has

validity only at low to moderate pressures
where Z is linear in pressure

most accurate for nonpolar species

and least accurate for highly polar
and associating molecules

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Rackett equation (Rackett, J. Chem. Eng. Data, 15 (1970) 514-517 :
estimation of molar volume of saturated liquids)

secara umum akurasinya 1-2% (error)

Lyderson, Greenkorn, and Hougen : estimation of liquid molar volume

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9

 Generalized density correlation for liquids

chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 chapter 7 chapter 8 chapter 9