Solution Thermodynamics:

Theory
Chapter 11, 7th Edition
Chapter 10, 8th Edition

CLO3 : Able to identify, formulate and solve engineering

problems involving phase equilibria.

[email protected] 1
Learning Objectives

Student should be able to ;

❑ Define the concept of chemical potential

❑ Define and explain partial molar property concept and
able to calculate property changes of a system as a
result of mixing.
❑ Define and explain fugacity and able to calculate
fugacity and fugacity coefficient of pure components
and gas mixtures
❑ Define and explain excess properties
2
Solution thermodynamics: Theory

What is the most important property ?

➢ ……G……….
➢ For pure component;
G = G (T, P)
➢ For a homogeneous mixture e.g. containing i
components mixture;
G = G (T, P, n1, n2, …, ni)

3
Revisit Ch. 6

Total Gibbs energy of any closed system:

𝑑 𝑛𝐺 = 𝑛𝑉 𝑑𝑃 − 𝑛𝑆 𝑑𝑇 (6.6)

When the composition is constant:

𝜕(𝑛𝐺) 𝜕(𝑛𝐺)
= 𝑛𝑉 and = −𝑛S
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛

4
Fundamental property relation

• The basic relation connecting the Gibbs

energy to the temperature and pressure in
any closed system:
  (nG)    (nG) 
d (nG) =   dP +   dT = (nV )dP − (nS )dT
 P  T ,n  T  P ,n
– applied to a single-phase fluid in a closed system
wherein no chemical reactions occur.
• Consider a single-phase, open system:

  (nG)    (nG)    (nG) 

d (nG) =   dP +   dT +    dni
 P  T ,n  T  P ,n i  ni  P ,T , n
j

5
Chemical Potential
  (nG) 
Define the chemical potential: i   
 ni  P ,T , n j

The fundamental property relation for single-phase fluid systems of constant or

variable composition:

d (nG) = (nV )dP − (nS )dT +  i dni

i

When n = 1, dG = VdP − SdT +   dx

i
i i G = G ( P, T , x1 , x2 ,..., xi ,...)

 G   G 
V =  S = − 
 P T , x  T  P , x

The Gibbs energy is expressed as a

function of its canonical variables.6
Chemical Potential
➢ In thermodynamics, chemical potential, known as partial
molar free energy, is a form of potential energy that can be
absorbed or released during a chemical reaction. It may also
change during a phase transition.

➢ An extensive property

➢ Molecules move from high chemical potential to low

chemical potential

➢ Chemical potential is ZERO for stable form of element e.g .,

µH2 (gas) = 0, µC (solid) = 0
7
 Chemical potential and phase equilibria

• Consider a closed system consisting of two

phases in equilibrium:

d (nG) = (nV ) dP − (nS ) dT +  i dni d (nG)  = (nV )  dP − (nS )  dT +  i dni
i i

nM = (nM ) + (nM ) 

d (nG) = (nV )dP − (nS )dT +  i dni +  i dni

i i

Mass balance:
Multiple phases at the same T and P are in dni = −dni
equilibrium when chemical potential of
i = i
each species is the same in all phases. 8
 Now we are going to learn
about
• Partial molar properties

• Because the chemical potential is a partial molar

property

• At the end of this section think about this

– What is the chemical potential in physical terms
– What are the units of the chemical potential
– How do we use the chemical potential to solve a PE
(phase equilibrium) problem

9
Partial Properties
Problem: If we mix 59 kg ethanol with 41 kg water, both at 25
0C ,what would be the volume of the mixture ? ( Density of

water= 998.0 kg/m3 and density of ethanol = 785.0526 kg/m3 )

41 kg water 100 kg mixture

59 kg ethanol

75.15 L ethanol 41.08 L water 116.23 L mixture ?

No , measured volume is 112.51 L

10
Partial Properties
38 g of water at 15.56 0C is mixed with 80 wt% sulfuric acid , also at 15.56 0C .

38 g water at 15.56 0C 80 wt% sulfuric acid Mixture at 15.560C ??

At 15.56 0C

No , mixture temp is 65.56 0C

11
Partial properties
• Define the partial molar property of species i:
  (nM )  Solution properties, M
Mi   
 ni  P ,T ,n j
Partial properties, M i
Pure-species properties, Mi

– the chemical potential and the particle molar

Gibbs energy are identical: i  Gi
– for thermodynamic property M:
nM = M ( P, T , n1 , n2 ,..., ni ,...)

 M   M 
d (nM ) = n   dP + n   dT +  M i dni
 P  T ,n  T  P ,n i

12
  M   M 
d (nM ) = n   dP + n   dT +  M i dni
 P  T ,n  T  P ,n i

 M   M 
ndM + Mdn = n   dP + n   dT +  M i ( xi dn + ndxi )
 P  T ,n  T  P ,n i

  M   M    


dM −  
 P T ,n
dP −  
 T  P ,n
dT − 
i
M i dxi n
 
+  M − 
i
xi M i  dn = 0


 M   M  M −  xi M i = 0
dM −   dP −   dT −  M i dxi = 0 and
 P T ,n  T  P ,n i
i

dM =  xi dM i +  M i dxi
i i
nM −  ni M i = 0
i

 M   M 
  dP +   dT −  xi dM i = 0 Calculation of mixture
 P T ,n  T  P ,n i properties from partial
properties
The Gibbs/Duhem equation 13
Gibbs/Duhem equation
 M   M 
  dP-  dT =  xi d M i
 P T,x  T  P,x i

If T and P constant:

x dM
i
i i =0

14
Example 11.3
The need arises in a laboratory for 2000 cm3 of an
antifreeze solution consisting of 30 mol-% methanol in
water. What volumes of pure methanol and of pure
water at 25°C must be mixed to form the 2000 cm3 of
antifreeze at 25°C? The partial and pure molar volumes
are given.

V1 = 38.63cm3 / mol V1 = 40.73cm3 / mol methanol

V2 = 17.77cm3 / mol V2 = 18.07cm3 / mol water

15
Example 11.3 (Cont’d)

• Calculate total molar volume

• We know the total volume, calculate the number

of moles required, n

• Calculate n1 and n2

• Calculate the volume of each pure species

16
Example 11.3 (Cont’d)
Solution

V = x1V1 + x2V2 = (0.3)(38.632) + (0.7)(17.765)

V = 24.025 cm3mol −1
Vt 2000 cm3
n= = 3 −1
= 83.246 mol
V 24.025 cm mol
n1 = x1n = (0.3)(83.246 ) = 24.974 mol
n2 = x2 n = (0.7)(83.246 ) = 58.272 mol

The volume of each pure species is 𝑉𝑖𝑡 = 𝑛𝑖 𝑉𝑖 ; thus

𝑉𝑖𝑡 = 24.974 40.73 = 1017 𝑐𝑚3
𝑉2𝑡 = 58.272 18.07 = 1053 𝑐𝑚3
17
Example 11.3 (Cont’d)
Solution

Fig 11.2 18
Self Assessment
The need arises in a laboratory for 1000 cm3 of an
antifreeze solution consisting of 35 mol-% methanol in
water.
• What volumes of pure methanol and of pure water at
25°C must be mixed to form the 1000 cm3 of
antifreeze at 25°C? The partial and pure molar
volumes are given.

V1 = 38.63cm / mol
3
V1 = 40.73cm / mol methanol
3

V2 = 17.77cm / mol
3
V2 = 18.07cm / mol water
3

19
 Summary

• Multiple phases at the same T and P are in equilibrium

when the chemical potential of each species is the same in
all phases.
  (nG) 
i   
 ni  P ,T , n j

• Partial properties:
  (nM ) 
Mi   
 ni  P ,T ,n j

𝑀 = ෍ 𝑥𝑖 𝑀𝑖
𝑖

20
How we can estimate partial molar properties???

❑ Graphically from molar property vs mol fraction

❑ Using equations (theoretically)

21
Partial properties for binary systems
• For binary system ( see Page 386)
M = x1M 1 + x2 M 2

dM = x1dM 1 + M 1dx1 + x2 dM 2 + M 2 dx2

Const. P and T, using Gibbs/Duhem equation

dM = M 1dx1 + M 2 dx2
x1 + x2 = 1
dM dM dM
= M1 − M 2 M 1 = M + x2 M 2 = M − x1
dx1 dx1 dx1

22
Obtain dM/dx1 from (a) 23
Example: 11.4
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is:
H = 400 x1 + 600 x2 + x1 x2 (40 x1 + 20 x2 )
Determine expressions for H1 and H 2 as functions of x1, numerical values for the
pure-species enthalpies H1 and H2, and numerical values for the partial enthalpies at
infinite dilution H1 and H 2 

H = 400 x1 + 600 x2 + x1 x2 (40 x1 + 20 x2 )

x2 = 1 − x1
x2 = 1 − x1
H = 600 − 180 x1 − 20 x 3
1 H1 = 420 − 60 x12 + 40 x13 H 2 = 600 + 40 x13
dH
H 1 = H + x2
dx1

dH
H 2 = H − x1 x1 = 0 x1 = 1
dx1
 J  J
H1 = 420 H 2 = 640
mol 24mol
22
Example: 11.4 (cont’d)

H = 600 − 180 x1 − 20 x13 H1 = 420 − 60 x12 + 40 x13 H 2 = 600 + 40 x13

x1 = 1 x1 = 0 x1 = 1 x1 = 0

J J J J
H 1 = 400 H 2 = 600 H 1 = 400 H 2 = 600
mol mol mol mol

25
Example: 11.4 x1 H 𝐇𝟏 𝐇𝟐
0 600 420 600
H = 600 − 180 x1 − 20 x 3
1 0.2 563.84 417.92 600.32
0.4 526.72 412.96 602.56
H1 = 420 − 60 x12 + 40 x13 0.6 487.68 407.04 608.64
0.8 445.76 402.08 620.48
H 2 = 600 + 40 x13 1 400 400 640

700
H2 𝐻2 𝐻2∞
600
500 H
H (J/mol)

𝐻1∞
400 H1
𝐻1
300
200
100
0
0 0.2 0.4 0.6 0.8 1
x1 26
Self Assessment Problem11.13
The molar volume (cm3/mol) of a binary liquid mixture at T and P
is given by
V= 120x1 + 70x2 + (15x1 + 8x2)x2x1
(a) Derive the expression for partial molar volumes of species 1 and 2
at T and P as function of x1
(b) Determine pure-species molar volumes
(c) Estimate numerical values for the partial molar volume
at infinite dilution

(d)Show that (dV1 / dx1 ) x1 =1 = (dV 2 / dx1 ) x1 =0 = 0

(e) Plot V vs x1 and label and show all related values

Given:
dM dM
M 1 = M + x2 M 2 = M − x1
dx1 dx1 27
Relations among partial properties

d (nG) = (nV )dP − (nS )dT +  Gi dni

i

• Maxwell relation:
 V   S   Gi    (nS )   Gi    (nV ) 
  = −    = −     =  
 T  P ,n  P T ,n  T P ,n  ni  P ,T , n j  P T ,n  ni  P ,T , n j

 Gi   Gi 
  = − Si   = Vi
 T  P ,x  P T ,x

dGi = Vi dP − Si dT

H = U + PV H i = U i + PVi
28
Problem

The molar volume of a binary liquid mixture at 300 K is given by

V = 2.7T x1x22

a) Find expressions for the partial molar volumes of species 1

and 2.
b) Label points 𝑉ത 1∞ and 𝑉ത 2∞, show their values.
c) Determine the partial molar volume at x1 = 0.5.
d) Generate a plot of the volume (V) against x1 at 300 K and show
the comparison of partial molar volume between the plotted
data and your answer in part (c).

29
Answers

𝑉 = 2.7 300 𝑥1 1 − 𝑥1 2

dM dM
M 1 = M + x2 M 2 = M − x1
dx1 dx1

𝑑𝑉
𝑉ഥ1 = 𝑉 + 𝑥2 = 810 − 3240𝑥1 + 4050𝑥12 − 1620𝑥13
𝑑𝑥1

𝑑𝑉
𝑉2 = 𝑉 − 𝑥1 = 1620𝑥12 − 1620𝑥13
𝑑𝑥1

30
𝑉ഥ1 𝑥1 = 0.5 = 810 − 3240 0.5 + 4050 0.5 2 − 1620 0.5 3 =0

𝑉2 𝑥1 = 0.5 = 1620 0.5 2 − 1620 0.5 3 = 202.5

x1 x2 V
𝑉ത2
0 1 0 200
0.1 0.9 65.61 180

0.2 0.8 103.7 160

140
0.3 0.7 119.1
0.4 0.6 116.6 𝑉 120
100
0.5 0.5 101.3
80
0.6 0.4 77.76
60
0.7 0.3 51.03 40
0.8 0.2 25.92 20
0.9 0.1 7.29 0
1 0 0 0 0.2 0.4 0.6 0.8 1
𝑉ത1
1.2

𝑥1
31
 Summary

• Partial properties could be found by using following

formulas:
dM dM
M 1 = M + x2 M 2 = M − x1
dx1 dx1

• Relation among partial properties are shown among these

analogies:
dGi = Vi dP − Si dT

H i = U i + PVi

32
The ideal- Gas mixture model
𝑛𝑅𝑇
𝜕(𝑛𝑉 𝑖𝑔 ) 𝜕( ) 𝑅𝑇 𝜕𝑛 𝑅𝑇
𝑉𝑖
𝑖𝑔
= = 𝑃 = =
𝜕𝑛𝑖 𝑇,𝑃,𝑛𝑗
𝜕𝑛𝑖 𝑇,𝑃,𝑛𝑗
𝑃 𝜕𝑛𝑖 𝑛𝑗
𝑃

𝑖𝑔 𝑖𝑔 𝑅𝑇
𝑉ത𝑖 = 𝑉𝑖 =𝑉 𝑖𝑔
=
𝑃

𝑦𝑖 𝑅𝑇
𝑝𝑖 = 𝑖𝑔 = 𝑦𝑖 𝑃 𝑖 = 1, 2, … , 𝑁
𝑉

𝑝𝑖 is the partial pressure of species i

33
The ideal- Gas mixture model
For any partial molar property other than
volume, in an ideal gas mixture:

M (T , P) = M (T , pi )
i
ig
i
ig

H (T , P) = H (T , pi ) = H (T , P)
i
ig
i
ig
i
ig

𝑖𝑔
𝑑𝑆𝑖 = −𝑅 𝑑 𝑙𝑛𝑃 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇)
S (T , pi ) = S (T , P) − R ln yi
i
ig
i
ig

S (T , P) = S (T , P) − R ln yi
i
ig
i
ig

S i
ig
= S − R ln yi
i
ig 34
The ideal- Gas mixture model

Gi ig = H iig − TSiig = H iig − TS iig + RT ln yi

Chemical potential of
iig = Gi ig = Giig + RT ln yi component i in an
ideal gas mixture
*******************************************************************************
𝑖𝑔
𝐻 𝑖𝑔 = σ𝑖 𝑦𝑖 𝐻𝑖 (11.25)
𝑖𝑔
𝑆 𝑖𝑔 = 𝑖 𝑦𝑖 𝑆𝑖 − 𝑅 σ𝑖 𝑦𝑖 𝑙𝑛𝑦𝑖
σ (11.26)
𝑖𝑔
𝐺 𝑖𝑔 = σ𝑖 𝑦𝑖 𝐺𝑖 + 𝑅𝑇 σ𝑖 𝑦𝑖 𝑙𝑛𝑦𝑖 (11.27)
𝑖𝑔
𝐻 𝑖𝑔 − σ𝑖 𝑦𝑖 𝐻𝑖 = 0
35
The ideal- Gas mixture model

𝑖𝑔 1
𝑆 𝑖𝑔 − ෍ 𝑦𝑖 𝑆𝑖 = 𝑅 ෍ 𝑦𝑖 𝑙𝑛
𝑦𝑖
𝑖 𝑖

RT
dG = Vi dP =
i
ig
dP = RTd ln P at constant T
ig

P
integrating between P = 1atm and P
i = i (T ) + RT ln P
G ig This is  for a pure component !!!

iig = i (T ) + RT ln P + RT ln yi = i (T ) + RT ln yi P

𝐺 𝑖𝑔 = ෍ 𝑦𝑖 Γ𝑖 𝑇 + 𝑅𝑇 ෍ 𝑦𝑖 ln(𝑦𝑖 𝑃)
𝑖 𝑖 36
Now we introduce a new concept:
fugacity
• For “real” systems, the expression for the
chemical potential that is used for ideal
systems is no longer valid
• Fugacity of component i in a mixture plays
an analogous role to the partial pressure
of the same component i in an ideal
mixture
• At low pressure, fugacity of component i
in the mixture tends to be partial pressure
of component i 37
Fugacity: Pure species

G = i (T ) + RT ln P
i
ig
Pure component i, ideal gas

i = i (T ) + RT ln( yi P)
ig
Component i in a mixture
of ideal gases

Let’s define:

Gi = i (T ) + RT ln f i For a real fluid, we define

Fugacity of pure species i

38
Unit of fugacity?????
Fugacity and fugacity coefficient: Pure species
Residual Gibbs free energy

fi
G = Gi − G = RT ln
i
R
i
ig Valid for species i
P in any phase and
any condition

GiR = RT ln i Fugacity coefficient

Combine with equation 6.49, we get,

R
G P dP
i
= ln i =  ( Z i − 1)
RT 0 P
39
Zi from an EOS, Virial, van der Waals, etc
 Chemical Engineering Thermodynamics (CDB 2033) Sept 2018

Fugacity and fugacity coefficient: Pure species

Zi from EOS
Bii P Bii P
• From Virial EOS: ln i = Zi −1 =
RT RT
• Cubic equation of state:
ln i = Z i − 1 − ln(Z i −  i ) − qi I i

• From van der Waals EOS

 bi P  ai P
ln i = Z i − 1 − ln  Z i − − 2 2
 RT  R T Z i

40
Example 6.4
Find value for the fugacity coefficient, 𝜙 for n-butane gas at 500 K and
50 bar as given by the Redlich/Kwong equation.
Solution
For n-butane at the given conditions,
𝑇𝐶 = 425.1 K, 𝑃𝐶 = 37.96 bar
500 50
𝑇𝑟 = = 1.176 ; 𝑃𝑟 = = 1.317
425.1 37.96
Using the value for Ω, Ψ and 𝛼(𝑇𝑟 ) for Redlich/Kwong equation of state,
𝑃𝑟 (0.08664)(1.317)
𝛽=Ω = = 0.09703
𝑇𝑟 1.176
Ψ𝛼(𝑇𝑟 ) 0.42748
𝑞= = = 3.8689
Ω𝑇𝑟 (0.08664)(1.176)1.5
We now need to find the vapor-like root of the equation of state for Z.
Recall that the form of Redlich/Kwong equation suitable for iteration is:
𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
Example 6.4
Find value for the fugacity coefficient, 𝜙 for n-butane gas at 500 K and
50 bar as given by the Redlich/Kwong equation.
Solution
Substituting the values of 𝛽, 𝑞, ϵ = 0, and 𝜎 = 1,
𝑍 − 0.09703
𝑍 = 1 + 0.09703 − (3.8689)(0.09703)
𝑍 𝑍 + 0.09703
Solution of this equation by iteration leads to 𝑍 = 0.6850.
Recall that for the case where 𝜖 ≠ 𝜎
1 𝑍 + 𝜎𝛽 𝑍+𝛽
𝐼= ln = ln = 0.13247
𝜎−𝜖 𝑍 + 𝜖𝛽 𝑍
𝑙𝑛𝜙 = 0.6850 − 1 − ln 0.6850 − 0.09703 − 3.8689 0.13247
𝜙 = 0.743

Bii P
Compare your answer by using virial coefficient. ln i =
RT
Generalized Correlations for the Fugacity Coefficient
P = Pc Pr
dP = Pc dPr
Pr
dPr
ln i =  ( Z i − 1) (11.65)
0
Pr
Pr r P
dPr 1 dPr
ln  =  ( Z − 1)
0
+  Z
0
Pr 0
Pr
ln  = ln  0 +  ln  1 (11.66)
Pr
dPr
where ln  =  ( Z − 1)
0 0

0
Pr
Pr
dPr
ln  1 =  Z 1
0
Pr

Eq. 11.66 can be written,

 = ( 0 )( 1 ) (11.67) 43
Generalized Correlations for the Fugacity Coefficient
Example 11.8

Estimate from Eq. (11.67) a value for the fugacity of 1-butene

vapor at 200°C (473.15 K) and 70 bar.
Combination Eq. 3.61 and 3.63 gives,

Z −1 =
Pr 0
Tr
(
B + B1 )
from eq 11.65,

ln  =
Tr
(
Pr 0
B + B1 )
or
 Pr 0 1 
(
 = exp  B + B  ) (11.68)
 Tr  44
Generalized Correlations for the Fugacity Coefficient

Class exercise: For SO2 gas at 600 K and 300 bar,

determine good estimates of the fugacity, Fugacity
coefficient and GR/RT.
Solution:

Find Tc, Pc, and acentric factor, ω in Table B1, Appendix B

Calculate reduced properties: Tr, Pr
Tr=1.393 and Pr=3.805

45
Generalized Correlations for the Fugacity Coefficient
Class exercise: (Cont’d)
• From tables E.15/D.15 and E.16/D.16 find 𝜙0 and
𝜙1 (interpolation)

• 𝜙0 = 0.672; 𝜙1 = 1.354

• 𝜙 = 𝜙0 𝜙1𝜔 = 0.724

• 𝑓= 𝜙 𝑃 = 0.724 x 300 bar = 217.14 bar

• GR/RT = ln 𝜙 = −0.323
46
 Fugacities of a 2-phase system

G = i (T ) + RT ln f i
i
v v

G = i (T ) + RT ln f i
i
l l

One component, two phases:

saturated liquid and saturated vapor at Pisat and Tisat
v
f
Gi − Gi = RT ln i l
v l

fi
At equilibrium : f i = f i = f i
v l sat
(11.39)

How we can calculate the fugacity of water/steam?

47
Fugacities of a 2-phase system
• For a pure species coexisting liquid and
vapor phases are in equilibrium when
they have the same temperature,
pressure, and fugacity.
sat
fi
i
sat
= sat (11.40)
Pi
i =  = 
f
i
v
i
sat
(11.41)
48
Fugacity of a pure liquid at P and T
v sat l sat l
f i ( Pi ) f i ( Pi ) f i ( P) sat
f i ( P) =
l
sat v sat l sat
Pi
Pi f i ( Pi ) f i ( Pi )

(A) (B) (C)

𝑃𝑖𝑠𝑎𝑡
Ratio (A) is 𝜙𝑖𝑠𝑎𝑡 𝑑𝑃
ln 𝜙𝑖𝑠𝑎𝑡 =න 𝑍𝑖𝑣 −1 (𝑐𝑜𝑛𝑠𝑡 𝑇)
0 𝑃
Ratio (B) is unity

Ratio (C) 𝑃
𝐺𝑖 − 𝐺𝑖𝑠𝑎𝑡 = ‫𝑙𝑖𝑉 𝑡𝑎𝑠𝑃׬‬ 𝑑𝑃 (const T)
𝑖

49
Fugacity of a pure liquid at P and T
𝑓𝑖
𝐺𝑖 − 𝐺𝑖𝑠𝑎𝑡 = 𝑅𝑇 𝑙𝑛
𝑓𝑖𝑠𝑎𝑡

The two expressions for 𝑓𝑖 1 𝑃 𝑙

𝑙𝑛 = න 𝑉𝑖 𝑑𝑃
𝐺𝑖 − 𝐺𝑖𝑠𝑎𝑡 are set equal: 𝑓𝑖𝑠𝑎𝑡 𝑅𝑇 𝑃𝑠𝑎𝑡
𝑖

𝑓𝑖𝑙 (𝑃) 1 𝑃 𝑙
Ratio (C) is then 𝑙 𝑠𝑎𝑡 = 𝑒𝑥𝑝 𝑅𝑇 න 𝑠𝑎𝑡 𝑉𝑖 𝑑𝑃
𝑓𝑖 (𝑃𝑖 ) 𝑃𝑖

Substituting for the three ratios in the initial equation yields

𝑃
1
𝑓𝑖 = 𝜙𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 𝑒𝑥𝑝 න 𝑉𝑖𝑙 𝑑𝑃
𝑅𝑇 𝑃𝑠𝑎𝑡
𝑖
50
Fugacity of a pure liquid at P and T
𝑙 𝑠𝑎𝑡
𝑠𝑎𝑡 𝑠𝑎𝑡 𝑉𝑖 (𝑃 − 𝑃𝑖 )
𝑓𝑖 = 𝜙𝑖 𝑃𝑖 𝑒𝑥𝑝
𝑅𝑇

The exponential is known as a Poynting factor. Data required for

application of this equation:

• Values of 𝑍𝑖𝑣 for calculation of 𝜙𝑖𝑠𝑎𝑡 . This may come from an

equation of state, from experiment, or from a generalized
correlation.
• The liquid-phase molar volume 𝑉𝑖𝑙 , usually the value for
saturated liquid.
• A value for 𝑃𝑖𝑠𝑎𝑡 .

51
Fugacity of a pure liquid at P and T
By using the virial equation:
𝐵𝑖𝑖 𝑃 𝐵𝑖𝑖 𝑃
𝑍𝑖𝑣 −1= and 𝜙𝑖𝑠𝑎𝑡 = 𝑒𝑥𝑝
𝑅𝑇 𝑅𝑇

𝑠𝑎𝑡 𝑙 𝑠𝑎𝑡
𝑠𝑎𝑡 𝐵 𝑃
𝑖𝑖 𝑖 + 𝑉𝑖 (𝑃 − 𝑃𝑖 )
𝑓𝑖 = 𝑃𝑖 𝑒𝑥𝑝
𝑅𝑇

52
Book Example 11.5
For water at 300oC and for P up to 10,000 kPa (100 bar)
calculate values of fi and i from data in the steam tables and
plot them vs. P
𝐺𝑖 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖 𝐺𝑖∗ = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖∗

fi 1 1  H i − H i* * 
ln * = (Gi − Gi ) =  − ( Si − Si )  (A)
*

fi RT R T 

A low-pressure reference state is denoted by *

At low P, steam is an ideal gas => fi* =P*

Get Hi* and Si* from the steam tables at 300oC and the lowest P, 1 kPa

𝐽
𝐻𝑖∗ = 3076.8 𝐽/𝑔 𝑆𝑖∗ = 10.345
𝑔.𝐾

53
fi of a compressed liquid is calculated in 2 steps:

• fi of saturated liquid and vapor

• Compress liquid from Psat to P

54
Then get values of Hi and Si at 300oC and at other pressure P and calculate fi
(P)
𝐽
𝐻𝑖 = 2962.0 𝐽/𝑔 𝑆𝑖 = 6.3642
𝑔. 𝐾
Values of H and S must be multiplied by the molar mass of water for
substitution into eq. (A)

𝑓𝑖 18.015 2962.0 − 3076.8

ln ∗ = − 6.3642 − 10.3450 = 8.1917
𝑓 8.314 573.15
𝑓𝑖
ൗ𝑓 ∗ = 3611.0
Whence,
𝑓𝑖 = 3611.0 𝑓 ∗ = 3611.0 1 𝑘𝑃𝑎 = 3611.0 𝑘𝑃𝑎

Thus the fugacity coefficient at 4000 kPa is,

𝑓𝑖 3611.0
𝜙𝑖 = = = 0.9028
𝑃 4000

At pressures up to the saturation pressure 𝑃𝑖𝑠𝑎𝑡 = 8592.7 𝑘𝑃𝑎,

𝜙𝑖𝑠𝑎𝑡 = 0.7843 and 𝑓𝑖𝑠𝑎𝑡 = 6738.9 𝑘𝑃𝑎

55
Values of 𝑓𝑖 and ∅𝑖 for liquid water at higher pressure: (with 𝑉𝑖𝑙 equal
to the molar volume of saturated liquid water at 300°C)

𝑉𝑖𝑙 = 1.403 18.015 = 25.28 𝑐𝑚3 𝑚𝑜𝑙 −1

At 10,000 kPa (for example),

(25.28)(10000 − 8592.7)
𝑓𝑖 = 0.7843 8592.7 𝑒𝑥𝑝 = 6789.8 𝑘𝑃𝑎
(8314)(573.15)

The fugacity coefficient of liquid water at this condition:

𝑓
𝜙𝑖 = 𝑖ൗ𝑃 = 6789.8ൗ10000 = 0.6790

56
57
Fugacity and Fugacity Coefficient: Species in solution

• The ideal solution (analogous to the ideal gas)

i = i (T ) + RT ln fˆi (11.42)

•At equilibrium:

ˆ
fi
 ˆ  ˆ
= f i = ..... f i

(11.47)

• For the specific case multiple component vapor/liquid

equilibrium

ˆf v = fˆ l (i = 1, 2, ..., N) (11.48)
i i 58
Fugacity and Fugacity Coefficient: Species in solution

𝑛𝑀𝑅 = 𝑛𝑀 − 𝑛𝑀𝑖𝑔

Differentiation with respect to ni at constant T, P, and nj gives

𝜕(𝑛𝑀𝑅 ) 𝜕(𝑛𝑀) 𝜕(𝑛𝑀𝑖𝑔 )

= −
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗

ഥ𝑖𝑅 = 𝑀
𝑀 ഥ 𝑖𝑔
ഥ𝑖 − 𝑀
𝑖

ҧ 𝑅 ҧ ҧ 𝑖𝑔
𝐺𝑖 = 𝐺𝑖 − 𝐺𝑖

59
Fugacity and Fugacity Coefficient: Species in solution

Subtracting Eq. (11.29) from Eq. (11.46), both written for the
same T and P, yields

𝑖𝑔 𝑓መ𝑖
𝜇𝑖 − 𝜇𝑖 = 𝑅𝑇 𝑙𝑛 , 𝜇𝑖 ≡ 𝐺ҧ𝑖
𝑦𝑖 𝑃

𝐺ҧ𝑖𝑅 = 𝑅𝑇 𝑙𝑛𝜙෠ 𝑖

𝑓መ𝑖
Where, 𝜙෠ 𝑖 ≡
𝑦𝑖 𝑃

መ 𝑖𝑔 ෠ 𝑖𝑔
For ideal gas: 𝑓𝑖 = 𝑦𝑖 𝑃, 𝜙𝑖 = 1, and 𝐺ҧ𝑖𝑅 = 0

60
 The Fundamental Residual-Property Relation
𝑛𝐺 1 𝑛𝐺
𝑑 ≡ 𝑑 𝑛𝐺 − 2
𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇

d(nG) is eliminated by Eq. (11.2) and G is replaced by its definition, H-TS.

𝑛𝐺 𝑛𝑉 𝑛𝐻 𝐺ҧ𝑖
𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖

𝑖𝑔
𝑛𝐺 𝑖𝑔 𝑛𝑉 𝑖𝑔 𝑛𝐻 𝑖𝑔 𝐺𝑖ҧ
𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ 𝑑𝑛𝑖 Ideal gas
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖

𝑛𝐺 𝑅 𝑛𝑉 𝑅 𝑛𝐻 𝑅 𝐺ҧ𝑖𝑅
Residual 𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖
61
 The Fundamental Residual-Property Relation

𝑛𝐺 𝑅 𝑛𝑉 𝑅 𝑛𝐻 𝑅
𝑑 = 𝑑𝑃 − 𝑑𝑇 + ෍ 𝑙𝑛 ෠ 𝑖 𝑑𝑛𝑖
𝜙
𝑅𝑇 𝑅𝑇 𝑅𝑇 2
𝑖

𝑅 𝑅
𝐺 𝐺
𝑉𝑅 𝜕( ) 𝐻𝑅 𝜕( )
= 𝑅𝑇 𝑅𝑇
=
𝑅𝑇 𝜕𝑃 𝑇,𝑥 𝑅𝑇 𝜕𝑇 𝑃,𝑥

𝐺𝑅
𝜕( )
𝑙𝑛𝜙෠ 𝑖 = 𝑅𝑇
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗

𝐺𝑅
𝑙𝑛𝜙෠ 𝑖 is a partial property with respect to .
𝑅𝑇
62
Fugacity Coefficient from the Virial EOS
𝐵𝑃
𝑍 =1+
𝑅𝑇
For mixture
B =  yi y j Bij (11.61)
i j
e.g. binary mixture, i=1,2 and j=1,2;

B = y1y1B11 + y1y2B12 + y2y1B21+ y2y2B22

B = y12B11 + 2y1y2B12 + y22B22 (11.62)

Where, B11 & B22 are pure species viral coefficient

B12 = B21 is a cross coefficient, characterize a biomolecular
interaction between molecule 1 &2
63
Fugacity Coefficient from the Virial EOS

B = y1B11 + y2B22 + y1y2δ12 Where, δ12 = 2B12 – B11 − B22

We can derive, (see page 405 and 406 for details)

ˆ
ln 1 =
P
RT
( )
B11 + y2212 (11.63a)

ˆ
ln 2 =
P
RT
( )
B22 + y1212 (11.63b)

P  1 
ˆ
ln k =  Bkk +  yi y j (2 ik −  ij )  (11.64)
RT  2 i j 

𝑤ℎ𝑒𝑟𝑒, 𝛿𝑖𝑘 ≡ 2𝐵𝑖𝑘 − 𝐵𝑖𝑖 − 𝐵𝑘𝑘 𝛿𝑖𝑗 ≡ 2𝐵𝑖𝑗 − 𝐵𝑖𝑖 − 𝐵𝑗𝑗
64
 Fugacity Coefficient from the Virial EOS
Book example 11.7:

Determine the fugacity coefficients for nitrogen (1) and

methane (2) mixture at 200 K and 30 bar if the mixture
contains 40 % mole nitrogen. Experimental viral coefficient
Data are given as: B11 = -35.2; B22 = -105.0 and
B12 = -59.8 cm3/mol. Equations are given below:

12 = 2 B12 − B11 − B22

ˆ
ln 1 =
P
RT
( B11 + y2212 )

ˆ
ln 2 =
P
RT
(B22 + y1212 )

65
Example 11.7:

Solution
𝛿12 = 2 −59.8 + 35.2 + 105.0 = 20.6 cm3 mol−1

30
ln 𝜙෠1 = −35.2 + 0.6 2 (20.6) = −0.0501
(83.14)(200)
30
෠
ln 𝜙2 = −105.0 + 0.4 2 (20.6) = −0.1835
(83.14)(200)

𝜙෠1 = 0.9511

𝜙෠ 2 = 0.8324

66
Fugacity Coefficient from Generalized correlation
Example 11.8

Estimate a value for the fugacity of 1-butene vapor at 200°C (473.15 K)

and 70 bar using generalized correlation.

Solution
Using Lee/Kesler correlation

𝑇𝑟 = 1.127
𝑃𝑟 = 1.731
By interpolation in Tables E.15/D.15 and E.16/D.16 at these conditions,
𝜙 0 = 0.627 𝜙 = 0.627 1.096 0.191 = 0.638
𝜙1 = 1.096 𝑓 = 𝜙𝑃 = 0.638 70 = 44.7 bar
67
Fugacity Coefficient from Generalized correlation
Example 11.8 Cont’d

Solution
Using 2nd virial coefficient (Pitzer 2nd)

𝑃𝑟 0 0.422
𝑍−1= 𝐵 + 𝜔𝐵1 𝐵0 = 0.083 − = −0.2655
𝑇𝑟 1.1271.6
𝑃𝑟 0
ln 𝜙 = 𝐵 + 𝜔𝐵1 0.172
𝑇𝑟 𝐵1 = 0.139 − = 0.0349
1.1274.2

1.731
𝜙 = exp −0.2655 + (0.191)(0.0349 = 0.672
1.127

𝑓 = 0.672 70 = 47 bar

68
Generalized Correlations for the Fugacity
Coefficient: Gas mixtures
0.422
𝐵0 = 0.083 − − 3.65
𝐵෠𝑖𝑗 = 𝐵0 + 𝜔𝑖𝑗 𝐵1 𝑇𝑟 1.6
0.172
𝐵1 = 0.139 − − 3.66
𝑇𝑟 4.2

𝐵𝑖𝑗 𝑃𝑐𝑖𝑗
𝐵෠𝑖𝑗 ≡ 𝜔𝑖 + 𝜔𝑗
𝑅𝑇𝑐𝑖𝑗 𝜔𝑖𝑗 =
2

𝑍𝑐𝑖𝑗 𝑅𝑇𝑐𝑖𝑗 1/2

𝑃𝑐𝑖𝑗 = 𝑇𝑐𝑖𝑗 = 𝑇𝑐𝑖 𝑇𝑐𝑗 1 − 𝑘𝑖𝑗
𝑉𝑐𝑖𝑗
1/3 1/3 3
𝑍𝑐𝑖 + 𝑍𝑐𝑗 𝑉𝑐𝑖 + 𝑉𝑐𝑗
𝑍𝑐𝑖𝑗 = 𝑉𝑐𝑖𝑗 =
2 2
69
 Find Fugacity Coefficient in Gas mixtures
Book Example 11.9
Estimate f1 and f2 for an equimolar mixture of methyl ethyl ketone (1) and
toluene (2) at 50°C and 25 Kpa. Given ( R=8.314 J.K/mol).Set all kij = 0

Solution: from Table B.1

ij Tcij [K] Pcij [bar] Vcij Zcij ωij

[cc/mol]
11 535.5 41.5 267 0.249 0.323
22 591.8 41.06 316 0.264 0.262
12 563.0 41.3 291 0.256 0.293

Eqn. 11.71 Eqn. 11.72 Eqn. 11.74 Eqn. 11.73 Eqn. 11.70

70
Book Example 11.9 (Cont’d)
ij Trij B° B1 Bij

11 0.603 -0.865 -1.300 -1387

22 0.546 -1.028 -2.045 -1860

12 0.574 -0.943 -1.632 -1611

Eqn. 3.65 Eqn. 3.69 Eqn. 11.69

𝐵𝑖𝑗 𝑃𝑐𝑖𝑗
𝐵෠𝑖𝑗 ≡
𝑅𝑇𝑐𝑖𝑗

𝐵෠𝑖𝑗 𝑅𝑇𝑐𝑖𝑗
𝐵𝑖𝑗 =
𝑃𝑐𝑖𝑗

−0.865 + (0.323 (−1.3))(83.14)(535.5)

𝐵11 = = −1387 cm3 /mol
41.5
71
Book Example 11.9 (Cont’d)
−1.028 + (0.262 (−2.045))(83.14)(591.8)
𝐵22 = = −1860 cm3 /mol
41.1
−0.943 + (0.293 (−1.632))(83.14)(563.0)
𝐵12 = = −1611 cm3 /mol
41.3

𝛿12 = 2𝐵12 − 𝐵11 − 𝐵22 = 25 cm3 mol−1

𝑃
෠
ln 𝜙1 = 𝐵11 + 𝑦22 𝛿12 = −0.0128
𝑅𝑇
𝑃
෠
ln 𝜙2 = 𝐵22 + 𝑦12 𝛿12 = −0.0172
𝑅𝑇

𝜙෠1 = 0.987 𝑓1 =y1 𝜙෠1 P = 12.30 kPa

𝜙෠ 2 = 0.983 𝑓2 =y2 𝜙෠ 2 P = 12.28 kPa

72
Self-assessment
Determine the fugacity and fugacity coefficient of a mixture
of 20 mol% ethane(1) in propane(2) at a pressure of 50 bar
and temperature of 25 oC.

73
Self-assessment
• Estimate the fugacity of isobutylene as a gas at 280°C (553.15 K)
and 20 bar. (Problem 11.18 Smith)

• Determine a good estimate of fugacity for liquid water at 150°C

(423.15 K) and 150 bar. (Problem 11.21 Smith)

• Calculate 𝑓 𝑎𝑛𝑑 𝜙 by the Redlich/Kwong equation of state for

carbon dioxide at 350 K and 35 bar and compare the results with
the values taken from a suitable generalized correlation.
(Problem 11.38-d Smith)

• For the system ethylene (1)/propylene (2) as a gas, estimate

1 , 𝑓2 , 𝜙1 , 𝜙2 at T = 150°C (423.15 K), P = 30 bar, and y1 = 0.35.
෢
𝑓 ෢ ෢ ෢
(Problem 11.25 Smith)
74
Checklist:
• Fugacity,
• Fugacity coefficient,
• Fugacity coefficient from the virial equation,
• Fugacity from the generic cubic EOS,
• Generalized correlations for the fugacity coefficient,
• Fugacity of pure liquid,
• Fugacity and fugacity coefficient: species in solution,
• Fugacity coefficients from the Virial Equation of State,
• Extension to mixtures.

75
The Ideal-Solution Model

❑The chemical potential as given by the ideal-gas mixture

model:
𝒊𝒈 𝒊𝒈 𝒊𝒈
𝝁𝒊 ≡ 𝑮𝒊 = 𝑮𝒊 𝑻, 𝑷 + 𝑹𝑻 𝒍𝒏 𝒚𝒊
Then , for ideal solution:

𝝁𝒊𝒅
𝒊 ≡ 𝑮𝒊𝒅
𝒊 = 𝑮𝒊 𝑻, 𝑷 + 𝑹𝑻 𝒍𝒏 𝒙𝒊

The partial volume of ideal solution:

𝜕𝐺𝑖𝑖𝑑 𝜕𝐺𝑖
𝑉𝑖𝑖𝑑 = = = 𝑉𝑖
𝜕𝑃 𝑇,𝑥 𝜕𝑃 𝑇 76
The Ideal-Solution Model

77
The Ideal-Solution Model

78
The Lewis/Randall Rule

❑The composition dependence of the fugacity of a species in

ideal solution:
𝜇𝑖 ≡ Γ𝑖 𝑇 + 𝑅𝑇𝑙𝑛 𝑓෡𝑖 (11.46)
𝐺𝑖 ≡ Γ𝑖 𝑇 + 𝑅𝑇𝑙𝑛 𝑓𝑖 (11.31)
Subtraction yields the general equation:
𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇𝑙𝑛 (𝑓෡𝑖 /𝑓𝑖 )
For the special case of an ideal solution,

𝑓෢𝑖𝑑
𝜇𝑖𝑖𝑑 ≡ 𝐺𝑖𝑖𝑑 = 𝐺𝑖 + 𝑅𝑇 ln( 𝑖 )
𝑓𝑖
79
The Lewis/Randall Rule

𝑓෢𝑖𝑑
𝑖 = 𝑥𝑖 𝑓𝑖

❑This equation is known as Lewis/Randall rule, applies to

each species in an ideal solution at all conditions of
temperature, pressure, and composition.

𝜙෢
𝑖𝑑
𝑖 = 𝜙𝑖

Thus the fugacity coefficient of species i in an ideal solution is

equal to the fugacity coefficient of pure species i in the same
physical state as the solution and at the same T and P.
80
Excess Properties

𝑀𝐸 ≡ 𝑀 − 𝑀𝑖𝑑

❑Excess property is defined as the difference between the

actual property value of solution and the value it would have
as an ideal solution at the same temperature, pressure, and
composition.
𝑀𝐸 − 𝑀𝑅 = −(𝑀𝑖𝑑 − 𝑀𝑖𝑔 )

𝑖𝑔
𝑀 𝑖𝑑
−𝑀 𝑖𝑔
= ෍ 𝑥𝑖 𝑀𝑖 − ෍ 𝑥𝑖 𝑀𝑖 = ෍ 𝑥𝑖 𝑀𝑖𝑅
𝑖 𝑖 𝑖

81
Excess Properties

𝑀𝑖𝐸 = 𝑀𝑖 − 𝑀𝑖𝑖𝑑

Where 𝑀𝑖𝐸 is a partial excess property.

The fundamental excess-property relation is written as:

𝑛𝐺 𝐸 𝑛𝑉 𝐸 𝑛𝐻 𝐸 𝐺𝑖𝐸
𝑑 = 𝑑𝑃 − 𝑑𝑇 + σ𝑖 𝑑𝑛𝑖 (11.89)
𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇

82
83
❑Example 11.10
a) If 𝐶𝑃𝐸 is a constant, independent of T, find expressions for
GE, SE, and HE as functions of T.

b) From the equations developed in Part (a), find values for

GE, SE, and HE for an equimolar solution of benzene(1)/n-
hexane(2) at 50°C (323.15 K), given the following excess-
property values for an equimolar solution at 25°C (298.15 K):
𝐶𝑃𝐸 = -2.86 Jmol-1K-1
HE = 897.9 Jmol-1
GE = 384.5 Jmol-1
84
❑ Example 11.10 cont’d
Solution
(a) Let 𝐶𝑃𝐸 = 𝑎, where 𝑎 is a constant. From the last column of Table 11.1

𝜕 2𝐺 𝐸
𝐶𝑃𝐸 = −𝑇
𝜕𝑇 2 𝑃.𝑥
Integration yields:

𝜕𝐺 𝐸
= −𝑎 ln 𝑇 + 𝑏
𝜕𝑇 𝑃,𝑥
Where b is a constant of integration. Second integration gives

𝐺 𝐸 = −𝑎(𝑇 ln 𝑇 − 𝑇) + 𝑏𝑇 + 𝑐 (A)
𝜕𝐺 𝐸
Where c is another integration constant. With 𝑆𝐸 =− (Table 11.1),
𝜕𝑇 𝑃,𝑥

𝑆 𝐸 = 𝑎 ln 𝑇 − 𝑏 (B)

85
❑ Example 11.10 cont’d
Solution
Because 𝐻 𝐸 = 𝐺 𝐸 − 𝑇𝑆 𝐸 , combination of eq. (A) and (B) yields
𝐻𝐸 = 𝑎𝑇 + 𝑐 (C)

(b) Let 𝐶𝑃𝐸0 , 𝐻0𝐸 , and 𝐺0𝐸 represent the given values at T0 = 298.15 K. But 𝐶𝑃𝐸 is

constant, and therefore 𝑎 = 𝐶𝑃𝐸0 = −2.86.

By Eq. (A) 𝑐 = 𝐻0𝐸 − 𝑎𝑇0 = 897.9 − −2.86 298.15 = 1750.6

By Eq. (C) 𝐺0𝐸 + 𝑎(𝑇0 ln 𝑇0 − 𝑇0 ) − 𝑐

𝑏=
𝑇0
384.5 + (−2.86)(298.15 × ln 298.15 − 298.15) − 1750.6
=
298.15
= −18.017

Substitution of known values into Eqs. (A), (B), and (C) for T = 323.15 K yields

𝐺 𝐸 = 344.4 J/mol 𝑆 𝐸 = 1.492 J/mol.K 𝐻 𝐸 = 826.4 J/mol

86
The Excess Gibbs Energy and the Activity Coefficient

𝐺ഥ𝑖 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓෡𝑖 𝐺𝑖𝑖𝑑 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑥𝑖 𝑓𝑖

𝑓෡𝑖
𝐺ഥ𝑖 − 𝐺𝑖𝑖𝑑 = 𝑅𝑇 ln
𝑥𝑖 𝑓𝑖

𝑓෡𝑖
𝛾𝑖 ≡
𝑥𝑖 𝑓𝑖

𝐺𝑖𝐸 = 𝑅𝑇 ln 𝛾𝑖
For an ideal solution, 𝐺𝑖𝐸 =0, and therefore 𝛾𝑖 =1.

87
The Excess Gibbs Energy and the Activity Coefficient

A further relation of interest written for the excess Gibbs energy:

𝑅𝑇 ln 𝛾𝑖 = 𝐺ഥ𝑖 − 𝐺𝑖𝑖𝑑
𝐺ഥ𝑖 ≡ 𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇 ln 𝛾𝑖 𝑥𝑖

𝑖𝑔 𝑖𝑔
𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇 ln 𝛾𝑖

𝜇𝑖𝑖𝑑 = 𝐺𝑖 + 𝑅𝑇 ln 𝑥𝑖
𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇 ln 𝛾𝑖 𝑥𝑖

88
Excess-Property Relations

An alternative form of Eq. (11.89):

𝑛𝐺 𝐸 𝑛𝑉 𝐸 𝑛𝐻 𝐸
𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ ln 𝛾𝑖 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖

𝑉𝐸 𝜕 𝐺 𝐸 /𝑅𝑇 𝐻𝐸 𝜕 𝑛𝐺 𝐸 /𝑅𝑇
= = −𝑇
𝑅𝑇 𝜕𝑃 𝑇,𝑥
𝑅𝑇 𝜕𝑇 𝑃,𝑥

𝜕 𝑛𝐺 𝐸 /𝑅𝑇
ln 𝛾𝑖 =
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗

ln ɣi is a partial property with respect to GE/RT.

𝜕 ln 𝛾𝑖 𝑉𝑖𝐸 𝜕 ln 𝛾𝑖 𝐻𝑖𝐸
= =− 2
𝜕𝑃 𝑇,𝑥
𝑅𝑇 𝜕𝑇 𝑃,𝑥
𝑅𝑇 89
Excess-Property Relations
An equimolar mixture of benzene and cyclohexane at 25°C
(298.15K) and 1 bar has an excess volume of about 0.65 cm3mol-1
and an excess enthalpy of about 800 Jmol-1. Thus at this condition:

𝜕 𝐺 𝐸 /𝑅𝑇 0.65
= = 2.62 × 10−5 𝑏𝑎𝑟 −1
𝜕𝑃 𝑇,𝑥
(83.14)(298.15)

𝜕 𝑛𝐺 𝐸 /𝑅𝑇 −800 −3 𝐾 −1
= = −1.08 × 10
𝜕𝑇 𝑃,𝑥
(8.314)(298.15)2

𝐺𝐸
= ෍ 𝑥𝑖 ln 𝛾𝑖 , ෍ 𝑥𝑖 𝑑 ln 𝛾𝑖 = 0 , 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇, 𝑃
𝑅𝑇
𝑖 𝑖

90
Example 10.1
A binary system of methanol (1) and water (2) forms a phase equilibrium system at
60°C. table below shows the vapor/liquid equilibrium (VLE data) for the binary system.
VLE data for methanol (1) and water (2) system at 60 °C
P (kPa) x1 y1
39.223 0.1686 0.5714
48.852 0.3039 0.6943
56.652 0.4461 0.7742
60.614 0.5282 0.8085
67.924 0.6804 0.8733
72.832 0.7776 0.9141
The Antoine equations for methanol (1) and water (2) are given below:
𝑠𝑎𝑡 3638.27
ln 𝑃1 = 16.5785 −
𝑇 − 33.65
𝑠𝑎𝑡 3885.7
ln 𝑃2 = 16.3782 −
𝑇 − 42.98

Generate a plot of the activity coefficient (for both components) against the composition
of methanol (1) assuming ideal gas condition is valid. 91
32
Answer
The calculation of Psat by Antoine equation will result in:
P1sat = 83.989 kPa
P2sat = 19.83 kPa

GE/RT=
P (kPa) x1 y1 ɣ1 x2 y2 ɣ2 σ𝑖 𝑥𝑖 ln 𝛾𝑖

39.223 0.169 0.571 1.583 0.831 0.429 1.02 0.094

48.852 0.304 0.694 1.329 0.696 0.306 1.082 0.141

56.652 0.446 0.774 1.171 0.554 0.226 1.165 0.155

60.614 0.528 0.808 1.105 0.472 0.192 1.241 0.154

67.924 0.68 0.873 1.038 0.32 0.127 1.358 0.123

72.832 0.778 0.914 1.019 0.222 0.086 1.419 0.093

92
Example Excess Gibbs
The excess Gibbs energy of a binary liquid at T and P is given by
GE / RT = (-2.6x1 – 1.8x2)x1x2

a) Find expressions for ln𝛾1 and ln𝛾2 at T and P.

b) Show that when these expressions are combined in accord with Eq.
𝐺𝐸
(11.99) = σ𝑖 𝑥𝑖 ln 𝛾𝑖 the given equation for GE/RT is recovered.
𝑅𝑇

c) Show that these expressions satisfy eq. (11.100), the Gibbs/Duhem

equation σ𝑖 𝑥𝑖 𝑑 ln 𝛾𝑖 = 0.
d) Show that d((ln γ1)/dx1)x1=1 = d((ln γ2)/dx1)x1=0 = 0.
e) Plot GE/RT, (ln γ1), and (ln γ2) as calculated by the given equation for
GE/RT and by the equation developed in (a) vs. x1. Label point’s lnγ1∞
and lnγ2∞ and show their values.

93
Example Excess Gibbs cont’d
Solution
𝐺𝐸
= −2.6𝑥1 − 1.8 1 − 𝑥1 𝑥1 1 − 𝑥1 = 0.8𝑥13 + 𝑥12 − 1.8𝑥1
𝑅𝑇

𝐺 𝐸ൗ
𝑅𝑇 = 2.4𝑥 2 + 2𝑥 − 1.8
1 1
𝑑𝑥1

(a) 𝐸 𝐺 ൗ
𝐺1ҧ 𝐸 𝐺 𝐸 𝑅𝑇 = −1.6𝑥 3 + 1.4𝑥 2 + 2𝑥 − 1.8
ln 𝛾1 = = + 𝑥2 1 1 1
𝑅𝑇 𝑅𝑇 𝑑𝑥1
~
ln 𝛾1,𝑥1 =0
= −1.8

𝐸
𝐺ҧ2𝐸 𝐺 𝐸 𝐺 ൗ
ln 𝛾2 = = − 𝑥1 𝑅𝑇 = −1.6𝑥 3 − 𝑥 2
1 1
𝑅𝑇 𝑅𝑇 𝑑𝑥1
~
ln 𝛾1,𝑥1 =1
= −2.6

94
Example Excess Gibbs cont’d
Solution
𝐺𝐸
(b) = ෍ 𝑥𝑖 ln 𝛾𝑖 = 𝑥1 ln 𝛾1 + 𝑥2 ln 𝛾2 = 0.8𝑥13 + 𝑥12 − 1.8𝑥1
𝑅𝑇
𝑖

𝑑 ln 𝛾1
(d) = −4.8 𝑥12 + 2.8𝑥1 + 2
𝑑 𝑥1
𝑑 ln 𝛾1
at 𝑥1 = 1 = 0
𝑑 𝑥1

𝑑 ln 𝛾2
= −4.8 𝑥12 − 2𝑥1
𝑑 𝑥1
𝑑 ln 𝛾2
at 𝑥1 = 0 = 0
𝑑 𝑥1

(c) 𝑥1 𝑑 ln 𝛾1 + 𝑥2 𝑑 ln 𝛾2
= 𝑥1 −4.8 𝑥12 + 2.8𝑥1 + 2 + 1 − 𝑥1 −4.8 𝑥12 − 2𝑥1 = 0

95
 (e)
x1 ln ɣ1 ln ɣ2 GE/RT
0.00 -1.80 0.00 0.00
0.10 -1.59 -0.01 -0.17 0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20
0.20 -1.36 -0.05 -0.31
0.30 -1.12 -0.13 -0.43 -0.50

0.40 -0.88 -0.26 -0.51 GE/RT

0.50 -0.65 -0.45 -0.55
-1.00
0.60 -0.44 -0.71 -0.55 ln ɣ1
0.70 -0.26 -1.04 -0.50 ln ɣ1
0.80 -0.12 -1.46 -0.39 ln ɣ2 -1.50
0.90 -0.03 -1.98 -0.23 GE/RT
1.00 0.00 -2.60 0.00 -2.00 ln ɣ1~ ln ɣ2

-2.50

ln ɣ2~
-3.00

x1 96
The Nature of Excess Properties

𝐻 𝐸 − 𝐺𝐸
𝑆𝐸 =
𝑇

Excess properties are often strong functions of temperature, but at normal

temperatures not strongly influenced by pressure.

1. All excess properties become zero as either species approaches purity.

2. Although GE vs x1 is approximately parabolic in shape, both HE and TSE

exhibit individualistic composition dependencies.

1. When an excess property ME has a single sign (as does GE in all six
cases), the extreme value of ME (maximum or minimum) often occurs
near the equimolar composition.

97
The Nature of Excess Properties

98
Checklist

✓ The Ideal solution Model

✓ Excess Property

99