Chap.

10 Vapor/Liquid Equilibrium: Introduction

Phase Rule and Duhem’ss Theorem

How to determine the number of independent variables for a system at equilibrium?

Phase rule: F = 2 – π + N
where π is the number of phases and N is the number of species.
For
or example, at the boiling point liquid water is in equilibrium with saturated water vapor or
steam.

π =2
N=1

F = 2-2+1

The number of independent variable is one. Temperature and pressure are not independent of
each other. Only one of them is independent.

Duhem’s theorem:

or a closed system filled with specified amounts of species, if any two independent variables
For
are fixed at the equilibrium state the other intensive and extensive variables can be
determined. (The
The number of independent intensiveve variables are determined by the phase rule.

Ex) 5 kg of water and 5 kg of alcohol are put in a container in vapor-liquid

vapor liquid equilibrium. The
number of independent intensive variable = 2-2
2 2 +2 = 2. If temperature and pressure are given
the other variables (for
for example mass of water in vapor, mass of alcohol in alcohol, mass of
vapor mixture, etc.) can be determined.

What is the difference between phase rule and Duhem’s

Duhem theorem?

10.3 VLE: qualitative behavior for binary mixture

iagram)
(P-x-y and T-x-y diagram) (P
(P-T-x-y diagram)
(P-T diagram) (x-y diagram)

(P-x-y diagram)

(T-x-y diagram)
F=2– π +2=4- π

For two phase, F = 4 – 2 = 2

Among P, T, and mole fractions of species in two phases, if two of them (for example, P and
T, P and x1, T and y1, etc.) are specified, the others can be determined.

If P and T are specified, then x1 and y1 are determined.

If P and x1 are specified, then T and y1 are determined.

p
 x
P
 (Raoult’s law)

For ideal solutions,

where p
= partial pressure of component i in the vapor phase

x
= mole fraction of component i in the liquid phase
P
 = vapor pressure of pure component i at the given temperature

The Raoult’s applies for solutions quite similar in chemical nature or for a component whose
mole fraction in the liquid phase approaches to 1.0.

For a component whose mole fraction in the liquid phase approaches to 0, the following
Henry’s law applies.

p
 H
x

where Hi is the Henry’s law constant for component i.

y

K-value (vapor-liquid equilibrium ratio)
K

x

Dew point and bubble point calculations:

P  ∑
p
 ∑ γ
x
P

At the bubble point, the partial pressures (pi) of components add up to the system pressure (P).

(for ideal solutions, γ
 1.0)

Determine the bubble point temperature by trial and error so the above requirement could be
met.

p

At the dew point, the mole fractions in the liquid phase add up to 1.0
  1.0
γ
P


Determine the dew point temperature by trial and error so the above requirement could be
met.

Problem 9- Chemical Process Calculation, Vapor pressure data on benzene and toluene are
given as follows:
Temperature (oC) vapor pressure (mm Hg)
benzene toluene
80 760 300
92 1078 432
100 1344 559
110.4 1748 760

9.1 Determine the Antoine equation constants for benzene and toluene by nonlinear
regression using Polymath.
9.2 Construct a P-x-y diagram at 100oC
9.3 Construct a T-x-y at 1 atm.
9.4 Calculate the bubble point temperature of a 50-50 mol% benzene and toluene mixture and
determine the mole fraction of the bubble.
9.5 Calculate the dew point of a 50-50 mol% benzene and toluene vapor and determine the
mole fraction of the droplet.

Ex 10-1 (for student)

Ex 10-2 (for student)

Ex 10-3

10.6 VLE from K-value correlations

y

K-value (vapor-liquid equilibrium ratio)
K

x

y
P

For ideal solution,
K
 
x
P
At bubble point, ∑ K
x
 0
At dew point, ∑
 1



Flash calculations:

If a liquid at a pressure is suddenly depressurized, then a fraction of liquid is turned into a

vapor. The vapor and the remaining liquid are in equilibrium.

Basis of calculation: 1 mol of liquid before flashing.

After flashing,
First check if it is a mixture of vapor and liquid by calculating the dew point and bubble point
pressures. The system pressure lies in between the dew and bubble point pressures, it is a
mixture of vapor and liquid.

The next step is to determine the amount of each component in liquid and vapor, respectively.
Unknowns: xi, yi, L, V (2N +2) where N is the number of components.
Independent equations: 2 N + 2

xiL + yiV = 1 (N equations)

yiP = xiPi* (N equations)
 x
 1

 y
 1

Ex. 10-5

Ex. 10-6

Chapter 11 Solution Thermodynamics: Theory

For a closed system of single phase wherein no chemical reaction occurs,

G=G(T,P)
dG = VdP – SdT

In general, G = G(T,P, x1, x2, x3, …).

The Gibbs energy of a mixture depends upon not only temperature and pressure but also
composition.

∂G
dG  VdP  SdT    dx
∂x
,
,

where  ,
,    ,
,  µ
(chemical potential)
 

Chemical potential is the amount of change in the Gibbs energy of a system when one mole
of component i is added into the system with temperature, pressure, and the amounts of the
other components kept constant.

For a closed system consisting of two phases, α and β in equilibrium,

µ
 µ



11.3 Partial Properties

∂nM
M
   
∂n

,,
M
 : partial properties of component i
M: V, U, H, S, G

M   x
M

For example, V
 is partial molar volume of component i and G
 is partial molar Gibbs
energy of component i or chemical potential component i.

For a mixture of water-ethanol solution, V


is different from V

, and the partial
molar volume of water or ethanol is composition dependant.

∂M ∂M
In general for M = M (P, T, x1, x2, x3, …),
dM   
,   ,   M
 dx

∂T ∂P
At constant temperature and pressure, dM  ∑ M
 dx
.
From
M   x
M


dM   x
dM
   M
 dx

0  ∑ x
dM
 (Gibbs-Duhem equation)

The partial property of a component is not independent of the others.

For a binary mixture,

0  x dM
  x dM

dM  dx M  x M   x dM  M dx  x dM  M dx  M dx  M dx

dx  dx
dM  M dx  M dx

dM
 M  M
dx

dM
M  x M  1  x M  x M  M   M  x  M
dx
dM
M  M  x
dx

dM
Likewise,
M  M  x
dx

Thus for binary systems, the partial properties can be readily calculated from the slopes of the
curve of the total property M, as shown in Fig. 11.1.

Ex. 11-2
Ex. 11-3
Ex. 11-4

In analogous to dG  VdP  SDT,  

  V, and 
 S
 

dG
  V
 dP  S
 dT,  

  V
 , and  

 S

   
11.4 The ideal-gas mixture

nRT
∂#
V
,
 
∂!nV
 "
,
,   P % RT ∂n RT
,
,   ,
,   V

∂n
∂n
P ∂n
P


The partial volume of component I in an ideal gas is equal to the molar volume of the gas
mixture.

Gibbs’s Theorem:
A partial molar property (other than volume) of a constituent species in an ideal-gas mixture
is equal to the corresponding molar property of the species as a pure ideal gas at the mixture
temperature but at a pressure equal to its partial pressure in the mixture.

By the Gibbs’s theorem, H
,


T, P  H
,
 T, p
.
For ideal gas, enthalpy is independent of pressure. Therefore, H
,
 
T, P  H
,
 T, p
 
H
,
 T, P. In other words, the partial molar enthalpy of component i in an ideal gas mixture
is the same as the enthalpy of pure i at the given system pressure and temperature.

S
,


T, P  S
,
 T, p


C
R
Even for ideal gas, entropy changes with pressure, according to
dS  dT  dP
T P
p
y
P
∆S  S
,
 T, p
  S
,
 T, P  Rln  Rln  Rlny

P P
S
,


T, P  S
,
 T, p
  S
,
 T, P  Rlny

G
,


T, P  H
,


T, P  TS
,


T, P  H
,
 T, P  TS
,
 T, P  RTlny

 G
,
  RTlny

Total property of ideal mixture:

H
   y
H
,


T, P   y
H
,
 T, P

S
   y
S
,


T, P   y
!S
,
 T, P  Rlny
"

G
   y
G
,


T, P   y
!G
,
 T, P  RTlny
"

Changes in entropy and Gibbs energy associated with mixing,

S
 T, P   y
S
,
 T, P  R  y
lny

G
 T, P   y
G
,
 T, P  RT  y
lny

By mixing, the entropy increased and the Gibbs’s energy decreased. In other words, the
chemical potential decreased with mixing.
11. 5 Fugacity and Fugacity Coefficient: Pure Species

Gilbert Lewis, American chemist, introduced fugacity for the first time to represent the
tendency to escape of a molecule for interfacial transfer and chemical reaction. At low
pressures at which intermolecular forces are negligible, fugacity equals pressure. At a high
pressure where the intermolecular force is serious, fugacity deviates from pressure.

For a real fluid, Gibbs’s energy is defined as a function of fugacity as follows:

G
 Γ
T  RTlnf
where Gi is the Gibbs’s energy of the real fluid, T is the temperature,
and fi is the fugacity of pure species i.

For ideal gases, Gi = Gi,ig and fi = P.

Then, the residual Gibbs’s energy, G
 can be represented by

f

G
  G
 G
,
  RTln
P

f

The ratio fi/P is defined as fugacity coefficient denoted by symbol Фi:

Ф 

P

G dP
By using eq. (6.49) of
 + Z  1

RT  P

dP
lnФ  + Z  1

 P

For Z  Z  ωZ
Ф = (Ф0)(Ф1)ω (Appendix Table E13 thru E16)

Fugacity coefficients for pure gases can be calculated by this equation from PVT data.

Vapor/Liquid Equilibrium for Pure Species

At equilibrium, chemical potential or molar Gibbs’s energy for pure species should be equal
between vapor and liquid:

G
  Γ
T  RTlnf
  G
  Γ
T  RTlnf


Thus, f
  f


Fugacity of a Pure Liquid:

V
 P  P
 
f
  Ф P
exp


RT



where,

 , P
 is the vapor pressure, V
 is the molar liquid volume, P is the system




Ф





pressure, and T is the temperature.

Ex. 11-5

11.6 Fugacity and Fugacity Coefficient in Solution

The fugacity of each constituent species, i should be the same in vapor and liquid phases:

f
,

 f
,

G
,  G
  G
,
  Γ
T  RTlnf
   Γ
T  RTlny
P  RTln 

 RTlnФ

  

nG nV  nH G
, nV  nH

d. / dP  dT   dn  dP  dT   lnФ dn

 

RT RT RT  RT
RT RT 

By inspection,

G
V ∂RT
 
RT ∂P ,

G
H ∂RT
 T 
RT ∂T
,

nG
∂ RT 
lnФ   
,,


∂n

nG dP
 + nZ  n

RT P
∂nZ  n dP ∂nZ dP dP


lnФ  +  
,,  +  
,,  1  + Z
  1


∂n
P ∂n
P P
Usually, it is complicated to determine Z
.

  


For a gas mixture whose compressibility factor, Z  1   where B is a function of



temperature and composition: B  ∑ ∑ y
y B
,

P 1
lnФ  B!!    y
y δ
! 


! RT 2

δ
!  2B
!  B

 B!! , δ
 2B
 B

 B

δ

 0, δ!!  0, etc. δ!
 δ
! , etc.

Values of the pure-species virial coefficients Bkk, Bii, etc., are found from
 B   ωB , where



B  0.083 

 .#
,
B  0.139 
 .

.$
.


The cross coefficients Bik, Bij, etc. are found from

 B   ω
B , where


,


ω
 ω
,


ω
 T%,
 T%,
T%,  1  k
, where kij =0 for

2 i=j, but kij is a small positive number

Z%,
RT%,

otherwise.
P%,
 Z%,
 , V%,
  *
V%,

/ /
&,
'&, (,
' (,
 

P
For binary mixtures,
lnФ  B  y δ 


 RT 
P
lnФ  B  y δ 


 RT 

Ex. 11-9

11.8 The Ideal Solution Model

Analogous to the representation of the total property of ideal gas mixture, total property of
ideal liquid mixture can be represented as follows:

H
+   y
H
,
+

T, P   x
H
,
+ T, P

S
+   y
S
,
+

T, P   x
!S
,
+ T, P  Rlnx
"

G
+   y
G
,
+

T, P   x
!G
,
+ T, P  RTlnx
"

The Lewis/Randall Rule:

 is proportional to its mole fraction: the proportionality constant is the fugacity

This rule applies to each species in an ideal solution. The fugacity of each species in an ideal


of pure species f
.

solution (f
,
+

f
,
+

 x
f

In other form,
f
,
+ x
f

Ф  Ф
 

x
P
,
+ x
P

Activity coefficient:

f

γ

x
f

11.9 Excess properties

In order to calculate the fugacity coefficients in a liquid mixture, introduced are excess
properties that are similar to residual properties used for the calculation of fugacity
coefficients in gas mixtures.

M ,  M  M
+ for G, H, and S.
f

G
,,  G
  Γ
T 
G
,
 RTlnf
 
 Γ
T  RTlnx
f
  RTln  RTlnγ

x
f

 

G
,  G
  G

+  G
  G
 RTlnx
  RTlnγ

Therefore, G
  µ
 G
 RTlnγ
x
where Gi is the molar Gibbs’s energy of pure liquid
species i.

nG nV  nH  nG, nV , nH ,
vapor liquid

d. / dP  dT d. / dP  dT
RT RT RT  RT RT RT 
  lnФ dn
  lnγ
dn



G G,

V  ∂ V ∂ 
  RT ,   RT ,
 ,

RT ∂P RT ∂P

G G,
H ∂RT H ∂RT
 T   T 
 ,

RT ∂T
, RT ∂T
,

lnФ   
,, , lnγ
  
,, ,
  
- . - .
 




lnФ  : Z
  1
, fugacity coefficient of Activity coefficient, γi is determined from


+

component i in a gas mixture can be vapor-liquid equilibrium data or estimated by
calculated a equation of state empirical model.

∑ x
dlnγ
 0 (Gibbs-Duhem equation)

Chapter 12 Solution Thermodynamics: Applications

Vapor-Liquid Equilibrium Experimental Data for Binary Mixture:

P-x-y or T-x-y data

f x P γ f x P γ

P-x-y data: Table 12.1

f f
P/kPa x1 y1
 
x P x P
12.30 0.0000 0.0000 0.000 0.000 12.300 12.300 1.000
15.51 0.0895 0.2716 4.212 3.230 1.304 11.298 11.199 1.008
18.61 0.1981 0.4565 8.496 7.149 1.188 10.114 9.863 1.025
21.63 0.3193 0.5934 12.835 11.524 1.114 8.795 8.372 1.051
24.01 0.4232 0.6815 16.363 15.273 1.071 7.697 7.095 1.085
25.92 0.5119 0.7440 19.284 18.474 1.044 6.636 6.003 1.105
27.96 0.6096 0.8050 22.508 22.000 1.023 5.542 4.802 1.154
30.12 0.7135 0.8639 26.021 25.750 1.011 4.099 3.524 1.163
31.75 0.7934 0.9048 28.727 28.634 1.003 3.023 2.541 1.190
34.15 0.9102 0.9590 32.750 32.849 0.997 1.400 1.105 1.267
36.09 1.0000 1.0000 36.090 36.090 1.000 0.000 0.000

f
  Ф y
P , for low pressures Ф ; 1

 

f


γ

x
f

f
  Ф P
 exp , for low pressure f
 ; P


(
-
/


.



f
  y
P
For low pressures,
γ

x
P


Excess Gibbs Energy:

G,
 x lnγ  x lnγ
RT
G,
lim  0lnγ1  1 ln1  0
 0 RT
G,
lim  1ln 1  0 ln γ1
 0
 0 RT

 0, but not zero inbetween.


At the two extremes, 

Equations to estimate activity coefficients:

(1) Margules equation

 
was assumed to be a straight line. (Figure 12.6)
lnγ  x A  2A  A x 
  

A  lnγ1
at x1 = 0,

lnγ  x A  2A  A x 

A  lnγ1
at x2 = 0,


Thermodynamic Consistency:

Experimentally obtained activity coefficients should be consistent with the Gibbs –

Duhem equation:

x  x  0 const T and P γ and γ

+2 +2
where are experimentally
+ +
obtained activity coefficients of component 1 and 2, respectively. Assuming that
experimental data meet the Gibbs-Duhem equation, #ln  ln  % is an indicator
2 2
2 2
used to represent how much a model is consistent with the Gibbs-Duhem equation,
where γ1 and γ2 are the activity coefficients predicted by the model. Absolute values
of #ln  ln  % smaller than 0.1 are probably acceptable.
2 2
2 2

Ex. 12-1

(2) Van Laar equation

A x /
lnγ  A 1
  
A x
A x /
lnγ  A 1   
A x
at x1=0, γ1  A
at x2=0, γ1  A


Λ Λ 
(3) Wilson equation
lnγ   lnx  x Λ   x   
x  x Λ x  x Λ 
Λ Λ 
lnγ   lnx  x Λ    x   
x  x Λ x  x Λ 
at x1=0, lnγ1  lnΛ  1  Λ 
at x2=0, ln2  lnΛ   1  Λ

For multi-component system,

 x! Λ 53
lnγ
 1  ln C x Λ 34 D  
∑ x Λ 54
where Λ 34  1 for i=j and Λ 34 E Λ43 .
!

Λ 34  exp
( /

(


where, Vj and Vi are the molar volumes at temperature T of pure liquids j and i, and
aij is a constant independent of composition and temperature.

(4) NRTL (Non-Random-Two-Liquid) model

G G τ

lnγ  x τ   
x  x G x  x G 
G G τ
lnγ  x τ   
x  x G x  x G 

where, G  exp #ατ % and G  exp #ατ %

τ  , τ 
6 6
 
α, b12, and b21, parameters specific to a particular pairs of species, are independent of
composition and temperature.

For multi-component system,

∑7 x τ
G
x G
∑87 x8 τ8 G8
lnγ
   τ  


∑!7 x! G!
∑!7 x! G!
∑!7 x! G!

7

(5) UNIFAC method

The UNIFAC method depends on the concept that a liquid mixture may be
considered a solution of the structural units of the subgroups. For example, n-butane
is composed of two CH3 subgroups and two CH2 subgroups. Isobutane is composed
of three CH3 groups and one CH group.

lnγ
 lnγ9
 lnγ

The subscript C refers to combinatorial term to account for molecular size and shape,

J
J

and R is a residual property to account for molecular interaction.
lnγ9
 1  J
 lnJ
 5q
1   ln 
L
L

where J
 ∑  


q

L

  

∑q x
r
  ν ! R !
-
.

!
q
  ν! Q !
-
.

ν! is the number of subgroups of type k in a molecular species of k. Rk and Qk come from

!
-
.

tabulations in the literature.

β
! β
!
lnγ
 q
1  θ!  e!
ln 
s! s!
ν Q!
!

e!
 !
-
.

q

τ8!  exp    where amk come from tabulations in the literature.
/

β
!   e8
τ8!



∑
x
q
e!

θ! 
8

∑x q
s!   θ8 τ8!
8

Table H.1: UNIFAC-VLE Subgroup parameters

Table H.2: UNIFAC-VLE Interaction Parameters, amk, in kelvins.

Ex. H.1

12.3 Property Changes of Mixing

∆M  M   x
M



M is a molar solution property and Mi is a molar property of pure species i.

Ex. 12-2
Ex. 12-3
Ex. 12-4
Ex. 12-5
Ex. 12-6
Ex. 12-7