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# Computing Liquid-Vapor Phase Diagrams for non-ideal binary mixtures

by
Franklin Chen
Department of Natural and Applied Science
University of Wisconsin-Green Bay
Green Bay, WI 54311
chenf@uwgb.edu
Copyright 2005 by the Division of Chemical Education, Inc., American Chemical Society. All
rights reserved. For Classroom use by teachers, one copy per student in the class may be made
free of change. Write to JCE Online, jceonline@chem.wisc.edu, for permission to place a
document, free of charge on a class intranet.

Goal
The goal of this document is to introduce the mathematical models that are used to describe
vapor-liquid equilibrium of binary mixtures. This document focuses on the solubility parameter theory
approach to calculate the activity coefficients of non-ideal mixtures.

Prerequisites
1. Experience with concepts of the 2nd Law of thermodynamics, chemical potentials,
and equilibrium constants.

Performance Objectives
At the end of this exercise you will be able to:
1.
2.
3.
4.

relate the phase rule to liquid-phase and vapor-phase compositions of binary mixtures at
equilibrium;
explain why azeotrope arises only in the non-ideal mixtures;
calculate activity coefficients using solubility parameter theory and the variation of the solubility
parameter approaches;
construct a phase diagram of a given non-ideal binary mixture.

For Instructors
Although most of the materials in this document are suitable for undergraduate physical chemistry
students, theories of non-ideal binary mixtures may be beyond the scope of introductory physical
chemistry. These theories are collected in the collapsible section embedded in the main
document. Beginning physical chemistry students are encouraged to skip this more advanced
theory section and move on to work on the algorithm for constructing the liquid vapor phase
diagram. Two flow charts were constructed to help students follow the algorithm to construct a
phase diagram. Guided by the flow charts, the algorithm can be understood more easily.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 1

## Chemical potential, activity, and activity coefficient

Chemical potential is a partial molar quantity. Raoult's Law allows us to write

1 = 10 + RT ln X 1

Eq. 

## when the mixture is an ideal mixture. For a chemical equilibrium,

aA + bB = cC + dD

Eq. 

the equilibrium constant and the standard free energy change (in the ideal case) are related as:

G 0 = RT ln K
K=

X Cc X Dd
X Aa X Bb

Eq. 

## The general expression for a chemical potential is expressed in Equation 4.

1 = 10 + RT ln a1

Eq. 

## Throughout the remainder of this document the blue color indicates an

exercise or problem for students to solve.
Exercise 1
Write the equilibrium constant for the equilibrium reaction shown in Eq. when chemical potential is
written as Eq. ?

a1 = 1 X 1

Eq. 

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 2

Exercise 3: The experimental data allowing us to calculate the activity coefficients of chlorobenzene
in equilibrium with a chlorobenzene/1-nitropropane solution at 75 o C are listed as follows:

0.119
0.289

xchlorobenzene := 0.460
0.691

19.0
41.9

pchlorobenzene := 62.4
86.4

119

units in torr

## Navy blue color text explains

i := 0 , 1 .. 4
p chlorobenzene
achlorobenzene :=
i

achlorobenzene

119

0.16
0.352

= 0.524
0.726

## There are two kinds of subscripts. For a

subscript which is part of a variable
name, we use period "." after the variable
name.
When we want an entity from a vector,
we use "[".
In Mathcad, the vector entity starts with
0. This is why we wrote i=0, 1 (;) 4 on
the left. The semicolon appears as ".."
in the document.

Now that you know the activities you should be able to write a vector for the activity coefficients for
chlorobenzene at various compositions in the mixture. At what mole fraction of chlorobenzene in the
mixture would its activity coefficient be equal to 1? Are the activity coefficients at other mixture
conditions greater than or less than zero?
Next plot real and ideal vapor pressures of chlorobenzene against mole fractions of chlorobenzenes
and explain the deviations of real vapor pressure from ideal vapor pressure.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 3

i
i

120

torr

92.5

65

37.5

10

0.25

0.5

0.75

Ideal
Real

## Phase rule, Vapor and liquid phase compositions at equilibrium

You may recall that the Gibbs phase rule states that the degree of freedom, f, is related to the
number of components, c, and the number of phases, p, by the following relation:
f=c-p+2

Eq. 

Exercise 4 Consider the vapor-phase equilibrium of a binary mixture, how would you assign c and
p ? What is the degree of freedom when both phases are present at constant temperature and
pressure?
The text with maroon color indicates sections that
instructors can delete for copies of this template given
to students.

For a binary mixture, we have c=2. When both liquid and vapor are present, p=2. At constant p
and T, and when both vapor and liquid phases are present , f=0.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 4

We are now ready to construct vapor-liquid diagrams in which the y-axis is the boiling point of the
mixture while the x-axis is either mole fraction of the component in the liquid phase , or the mole
fraction of the component in the vapor phase.
Exercise 5 What is the definition of a boiling point? What is the total vapor pressure when the
mixture is at the boiling point?
Boiling point of a liquid is the temperature at which the total vapor pressure of the liquid is equal to
the external pressure.
Since boiling points vary with the compositions of mixtures, and the total vapor pressures of the
mixture are also functions of temperature, we need to construct vapor pressure versus temperature
data. Some data at selected temperatures are available in the CRC Chemistry Handbook. We
still, however, need to construct regression equations to interpolate between published points. For
this we will use the Clausius-Clapeyron equation, which you learned in General Chemistry.

p2
vap H 1
1

=
ln

R T2 T1
p1

Eq. 

where p1 and T1 are the reference point vapor pressure and temperature, vapH is heat of
vaporization of the liquid, and R is the gas constant. Data on vapH and boiling points are available
in CRC Handbook.

Exercise 6: What are the assumptions used when Eq is used to calculate p2 at T2 ?
There are 2 assumptions: 1) Molar volume of a liquid is insignificant when compared to that of a
gas. 2) Heat of vaporization is a constant from T1 to T2.
We now will set up vapor pressure data for both toluene and benzene
from 350 K to 420 K at 0.7 K interval
R := 8.314 joule K

mole

5
bar := 10 Pa

3
kJ := 10 joule

The following reference gives the triple point and normal boiling point data for toluene
(http://www.nist.gov/srd/PDFfiles/JPCRD3711.pdf) Goodwin R.D., J. Phy. Chem. Ref. Data, 18,
1565-1636.
Toluene, triple point: 178.15K, 4.362*10 -7 bar. boiling point: 383.764K, 1.01325 bar.
Heat of vaporization at 388 K is 33.11 kJ/mol.
Benzene, the reference is http://www.nist.gov/srd/PDFfiles/JPCRD350.pdf, Goodwin,R.D., J Phy.
Chem. Ref. Data, 17, 1541 (1988)
Benzene, triple point: 278.65K, 0.04785 bar. boiling point: 353.24K, 1.01325 bar.
Heat of vaporization at 300K is 33.737 kJ/mol

## Author: Franklin Chen

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Exercise 7: We choose our reference points for toluene and benzene as their normal boiling
points. Explain why these fixed points are chosen as reference points?

T1tolu := 383.76 K

T1benz := 353.24 K
p1benz := 1.013 bar

## p1tolu := 1.013 bar

H vaptolu := 33.11 kJ mole

## H vapbenz := 33.737 kJ mole

j := 0 , 1 .. 100
Tj := ( 350 + j 0.7) K

Hvaptolu 1

R
T1tolu

j

Tj

Hvapbenz 1

T1benz

## p2benz := p1benz exp

j

Tj

Ideal Case:
Exercise 8: Let us assume benzene and toluene form an ideal solution. Is this a good
assumption? Why or why not?

For the ideal case, the strategy of calculation is to set Tj as the boiling temperature. We will then use
both Raoult's law and Dalton's law to find both Xj (liquid mole fraction for component j) and Yj (vapor
mole fraction for component j) such that p benzj + ptoulj =pext=1.013 bar
pext := 1.013 bar
pext p 2benz
Xj :=

p2tolu p 2benz
j
j

## Author: Franklin Chen

p2tolu Xj
Yj :=

p ext

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Block #1

Page 6

## Liquid Vapor Equilibrium of Benzene Toluene Mixture

390

377.5

365

352.5

340

0.25

0.5

0.75

Liquid
Vapor

b.p. (K)
Mole Fraction of Toluene

Exercise 9: This diagram correctly predicts the b.p. of pure benzene which is at 353 K,and
b.p. of toluene which is at 383.76K. Practice yourself using the triple point of the toluene as
the reference point. What do you see?
Now, in the ideal case plot 1-Y i vs (1-Xj) (benzene vapor phase composition against benzene
liquid phase composition), what do you see? Would this plot convince you that there will be
no azeotrope when (1-Y i) >(1-Xi) whether 1-X-->0 or 1-X-->1?
1

1 Y j

0.5

0.5

1 X j

## Author: Franklin Chen

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Nonideal Solutions
In this document, van Laar's theory is used to calculate activity coefficient of each
component in a binary mixture: Activity coefficients ( 1 and 2 ) are calculated based on
differences in solubility parameters.

This collapsible section covers theory for the non ideal case.

Non-ideal Case comes from enthalpy and entropy changes induced by interactions taking
place when solutions form. The effects of the interactions is treated in terms of a contact free
energy change, Gcontactm .

10

10

ideal

Eq. [C1]

= RT ln X 1

Excess

Eq [C2]

= RT ln 1

Different models propose different expressions for the excess chemical potential.
parameters.

H mcontact = Vm1 2 ( 1 2 )

= [( vap H RT ) /V ]1 / 2

Eq.[C3]
Eq [C4]

where Vm is the molar volume of the mixture, d1 and d2 are the solubility parameters of
components 1, and 2 respectively, V is the molar volume. f 1 and f 2 are the component
volume fractions of components 1 and 2.
Exercise C1: Why do we subtract RT from vapH in Eq. [C4]? (This Exercise is the same
as Exercise 10 in the main document).

= (U /V )1 / 2
Author: Franklin Chen

## U and H are related as U=H-RT

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Exercise C2: Calculate the solubility parameters for toluene and benzene
using the following parameters.
Toluene: vapH=38 kJ/mol; V=106.275 mL/mole
Benzene: vapH=33.737 kJ/mol; V=89.786 mL/mole

38 kJ mole 1 R 300 K
toluene :=

1
106.275 mL mole

0.5
3
0.5 1.5
toluene = 18.278 10 joule m

## 33.737 kJ mole 1 R 300 K

benzene :=

1
89.786 mL mole

0.5
3
0.5 1.5
benzene = 18.654 10 joule m

Two solubility parameter numbers are really close. The enthalpy of interaction between
toluene and benzene is approximately zero. The mixture is close to being an ideal
mixture.

## Van Laar Theory

Rewriting Eq.[C3] yields:

H mcontact = V m 1 2 ( 1 2 ) = ( X 1 V1 + X 2 V 2 )1 2 ( 1 2 )
2

Eq.[C4]
_

V 1 and V 2

are partial

## molar volumes for components 1 and 2.

Taking partial differentiation of Eq. against n 1 , the number of moles of component 1,we have

RT ln 1 = V 1 2 ( 1 2 )
2

Eq [C5]

## The left hand side of Eq [C5] is derived from:

10

Excess

= RT ln 1 =

nonideal
G ideal
contact H
m
m G
= m
n1
n1

Similarly, we have

## Author: Franklin Chen

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Page 9

RT ln 2 = V 2 1 ( 1 2 )
2

Eq [C6]

V1
( 1 2 )2
A12 =
RT
Eq.[C7]

V2
( 1 2 )2
A21 =
RT

## Equation [C7] is the same as Eq. in the main document.

Then, we can show that

g=

H mcontact
A12 A21 X 1 X 2
=
( X 1 A12 + X 2 A21 )
RT

A12
g
=
2
X 1
A12 X 1
1 +

A21 X 2
A21
g
ln 2 =
=
X 2 A X 2
21
2
1 +

A
X
12
1

Eq [C8]

ln 1 =

This is because:

Eq [C9]

contact
H
m
= RT ln 1
n1

## Equation [C9] is the same as Eq. in the main document.

Although Van Laar theory is not different from the solubility parameter theory in principle, it
does provide an algorithm to calculate the activity coefficients for a non-ideal mixture if
azeotrope data of the mixtures are available.
The tasks are to determine A12 and A 21 , two Van Laar coefficients. Once these
two coefficients are found, Eq.[C9] allows us to calculate g1 and g2 at any compositions.
Looking at Eq.[C7], A12 and A 21 can be calculated from solubility parameters and partial
molar volumes of the components. Solubility parameters can be calculated from heat of
vaporization, and molar volume. Partial molar volume can be calculated from
density-composition data. In principle, they can be calculated, although the calculations
may be quite tedious.
If we know the azeotrope point at one known external pressure, then Eq.[C8] and Eq[C9]
allow us to calculate g1 and g2 at any compositions. These data, in turn, allow us to
calculate azeotrope points at any other external pressures. We shall use water-propanol
binary system as the example.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 10

Before we discuss the calculations of g1 and g2 at the azeotrope conditions, we shall simplify the
expressions in the brackets of Eq[C9]
Exercise C3: Show that

x 2 ln 2
A x
= 12 1
x1 ln 1
A21 x 2

Eq [C10]

Before we proceed to prove Eq[C10], we shall see the utility of Eq[C10]. This relation
suggests that A 12 and A 21 can be obtained from Eq[C9] using the relation of Eq[C10].

ln ( 2 ) x 2
A x
A12 = ln( 1 ) 1 + 12 1 = ln( 1 ) 1 +

A21 x 2
ln ( 1 ) x1
2

A x
ln ( 1 ) x1
A21 = ln( 2 ) 1 + 21 2 = ln( 2 ) 1 +

A12 x1

ln ( 2 ) x 2
2

Eq [C11]

Eq[C11] is the same as Eq. in the main document. Eq.[C13] indicates that A 12 and A 12
can be calculated for a given x1 , x2 , g1 , and g2. Once A 12 and A 21 are determined, Eq can
the be used to determine g1 and g2 at any compositions
We now shall proceed to prove Eq [C10]

In Eq[C9], multiplying Eq[C9 b] with x 2 and Eq[C9 a] with x1 and take the ratio for these 2
expressions. We have:
2

2
2

## A21 x 2 + 2 A12 A21 x1 x 2 + A122 x12

A12 x1

A
x
+
1
21
2

2
2
A21 x 2
x 2 ln 2
A21 x 2
A21 x 2

=
2
2
2
x1 ln 1
A12 x1
A21 x 2 + 2 A12 A21 x1 x 2 + A122 x12
A21 x 2

A
x
12
1
2
1 +

A12 x12
A12 x1

A x
= 12 1
A21 x 2

You can go back to the original document to continue for constructing a vapor-liquid
diagram (VLE) for water-propanol binary system.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 11

Here we are just going to use several essential equations to allow students compute vapor-liquid
equilibrium in the non-ideal case.

## The solubility parameter, , is defined as follows:

= [( vap H RT ) /V ]1 / 2

Eq 

where 1 and 2 are the solubility parameters of components 1, and 2 respectively, V is the molar
volume of the volatile liquid. 1 and 2 are the component volume fractions of components 1 and
2.
Exercise 10: Why do we subtract RT from vapH in Eq. ?
The definition of the solubility parameter is actually:

= (U /V )1 / 2

## U and H are related as U=H-RT

When two solubility parameter numbers are really close, the mixture is close to an ideal
mixture. The enthalpy of interaction between toluene and benzene is approximately zero. The
mixture is close to ideal. This is shown in exercise C2 in the collapsed section.
Van Laar Theory
Van Laar theory allows us to compute 1 and 2 using the differences in the solubility
parameters.

RT ln 1 = V 1 2 ( 1 2 )

RT ln 2 = V 2 1 ( 1 2 )
2

Eq 

Eq 

V1
( 1 2 )2
A12 =
RT

V2
( 1 2 )2
A21 =
RT

Eq.

## Author: Franklin Chen

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Page 12

ln 1 =

ln 2 =

A12

A12 X 1
1 +

A21 X 2
A21

A21 X 2
1 +

A12 X 1

Eq 

ln ( 2 ) x 2
A x
A12 = ln( 1 ) 1 + 12 1 = ln( 1 ) 1 +

A21 x 2
ln ( 1 ) x1
2

A x
ln ( 1 ) x1
A21 = ln( 2 ) 1 + 21 2 = ln( 2 ) 1 +

A12 x1

ln ( 2 ) x 2
2

Eq 

Eq indicates that A 12 and A 12 can be calculated for a given x1 , x2 , 1 , and 2. Once A 12
and A21 are determined, Eq can they be used to determine 1 and 2 at any other
compositions.
Exercise 11 In a binary mixture, x1 /x2 are liquid compositions and y 1 /y2 are vapor compositions of
component 1 and 2. At azeotropic composition, which one of the following is correct?
(a) x1 =x2 ; y1 =y2 ; (b) x1 =y1 , x2 =y2

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 13

The following flow chart illustrates the strategy to calculate activity coefficients 1
and 2 at any composition.

## Example : Water-propanol mixture

Azeotrope data for water-propanol
For the n-propanol/water binary system, x propanol=ypropanol=0.42 for p ext=1.013
bar;
Water, Tb =373.15K,

## vapH=44.016 kJ/mol at 298 K

Propanol, T b =370.3 K

vapH=47.5 kJ/mol

Eq 

## Molar volume for water is 18mL/mole

Molar volume for n-propanol is 74.84 mL/mole
References: Majer,V., and Svoboda,V.,  Lee and Shen

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 14

Exercise 12: Given the data in Eq, calculate solubility parameters for water and propanol.

## 44.016 kJ mole 1 R 298 K

water :=

1
18 mL mole

0.5

0.5 1.5 3
water = 48.038 joule m
10

Eq 

## 47.5 kJ mole 1 R 298 K

propanol :=

1
74.84 mL mole

0.5
0.5 1.5 3
propanol = 24.527 joule m
10

The difference is big enough to treat the case with nonlinear approach. That means we need to
calculate activity coefficients for water and propanol at many compositions.
Propanol Mole Fraction at the azeotrope (assertive) point
Taz := 360.95

X1az := 0.42

pext := 1 bar

T1propanol := 370.3 K

## H vappropanol := 47.5 kJ mole

H vapwater := 44.016 kJ mole

T1water := 373.15 K

## p1propanol := 1.013 bar

p1water := 1.013 bar

Taz := 360.95 K

Hvapwater 1

T1water

Hvappropanol
1

T1propanol

Taz

Taz

Eq 

## p2wateraz + p 2propanolaz = 1.306 bar

Exercise 13: Why the sum of the partial pressures of propanol and water are greater the
total external pressure which is 1.013 bar?
These are the partial pressures that the pure substances would have at the azeotrope if
they acted as ideal gases. The activity coefficients at the azeotrope can be calculated as
follows:

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 15

## Activity coefficients at azeotrope for water-propanol

p10az := p2propanolaz

p20az := p2wateraz

## Recall that a=(pextyaz)/p*=(pextxaz )/p*;

pext

1 az :=

2 az :=

p10az

=a/xaz; =pext/p*=pext/paz

Eq 

pext
p20az

Eq 
1 az = 1.472

2 az = 1.595

## Van Laar constants at azeotrope for water-propanol

Using the van Laar equation (Eq), one can calculate the van Laar constants for this system.

Eq 

X2az := 1 X1az

A12 := ln 1 az 1 +

( )
X1az ln( 1 az )

X2az ln 2 az

A21 := ln( 2 az ) 1 +

( ) 2
X2az ln( 2 az )

X1az ln 1 az

Eq 

A12 = 2.749
A21 = 1.195

i := 0 .. 30

XNi :=

30

1 j := exp

j := 0 .. 29

1 +

2
XN j A12

( 1 XNj ) A21

## Author: Franklin Chen

A12

j +1

:= exp

1 +

VapLiqEquilMC11.mcd

2
1 XN
A21
j +1

XNj + 1 A12
A21

Page 16

30

:= 1

2 := 1
0

Block #2

The algorithm of Block #2 is straightforward, except you need to pay attention the indices i and j
because you don't want XNj=1 in calculating 1j, and XNj+1 =0 in calculating 2j+1.
To complete the phase diagram, we must find the temperatures at which a solution
of mole fraction X 1 will boil.
This calculation is performed by using the temperature-dependent values of the
partial pressures from the Clausius Clapeyron equation and the activity coefficients from the
van Laar equation.

## Phase diagram Construction: Water-Propanol

The following diagram illustrates the algorithm strategy of constructing water-propanol phase diagram:

## MATHCAD uses a function in which an initial guess is made, and a Leavenberg-Marquardt

algorithm modifies the guess, minimizing the difference on either side of the = sign. You should
refer to Mathcad Resource Center " Solving a Nonlinear System Equations for help.
As an initial guess, try 350K., which is slightly below the boiling points of either
of the two species.

## Author: Franklin Chen

VapLiqEquilMC11.mcd

Page 17

## Let us simplify the notation as follows:

p1p := p 1propanol

H 1p := H vappropanol

p1w := p 1water

T1p := T1propanol

H 1w := H vapwater

T1w := T1water

Eq 

Tn := 350 K

Given

H1p 1

R T1p

p1p exp

H1w 1

XN 1 + p1w exp
Tn
R T1w
1

( 1 XN) 2 = pext

Tn

Eq 

## Note here we use Ctr= for the

equal sign on the equation
above. XN, 1, and 2 are
vectors.

## End of the solve block #3.

Exercise 14: What is the physical meaning of Eq. ?

Tn := Temp ( XN , 1 , 2 )

## This is a vector of the temperatures corresponding to

the liquid mole fraction vector XN. Type Tn= in the space
to the right to see all of the components of the vector.

## YN is a vector containing the vapor-phase mole fractions. It is found directly

from Dalton Law of Partial Pressures.

H1p 1

R T1p

1i XNi p 1p exp
YNi :=

H1p 1

R T1p

1i XNi p 1p exp

Tni

H1w 1

Tni

R T1w
1

Tni

Eq 

## Author: Franklin Chen

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Page 18

Exercise 14: Explain the physical meanings of the numerator and the denominator of Eq.

Exercise 15: Plot the non-ideal liquid-vapor phase diagram for water-propanol system.

380

375

370

Tn
Tn

365
i

360

Temp
355

350

0.2

0.4

0.6

0.8

XN , YN
i
i

liquid
vapor

## Author: Franklin Chen

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Page 19

## Now plot activity coefficients as a function of mole fraction.

Activity Coefficients
20

15

1
2

10
i

0.2

0.4

0.6
XN

0.8

References
Gentilcore,M., and Healthcare, T., (2004) Apply Solubility Theory for Process Improvement,
www. cepmagzine.org; 38-41
Lee,L.S., and Shen, H.C., Ind. Eng. Chem. Res; 42, 5905-5914(2003)
Majer,V., and Svoboda,V., Enthalpies of vaporization of organic compounds: a critical review and
data compilation.International Union of Pure and Applied Chemistry Chemical Data Series, 1985,
N 32, 300 pp
Young,S., (1996) Computing a Liquid-Vapor Phase Diagram; Symbolic Mathematics Document

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