CHEMICAL ENGINEERING

THERMODYNAMICS
PROJECT-I
(CHX-204)
TOPIC: Excess Properties and Liquid Phase Properties from VLE Data

DEPARTMENT OF CHEMICAL ENGINEERING

DR. B R AMBEDKAR NATIONAL INSTITUTE OF TECHNOLOGY,
JALANDHAR-144011, PUNJAB (INDIA)

SUBMITTED TO: SUBMITTED BY:

Dr. Shashikant Yadav Rohit Gupta
Assistant Professor (17112075)
(Chemical Engineering)
Page 1 of 11
CONTENTS COVERED:
1.1 Introduction …………………………………………………………………………………….....2
1.2 Vapour-Liquid Equilibria………………….......................………………………………………..2
1.3 Liquid Phase Properties from VLE Data ……………………………………………………….....3
1.4 Activity Coefficients from low VLE Data ……………………………………………………......5
1.5 Correlation of Liquid Phase Data.....................................................................................................6
1.6 Models for the Excess Gibbs Energy...............................................................................................6
1.7 Symmetric Equations for the Binary Mixtures................................................................................7
1.8 Excess Gibbs Energy Models...........................................................................................................7
1.9 Margule’s Equation..........................................................................................................................8
1.10 Van-Laar Equation.........................................................................................................................9
1.11 Numericals...................................................................................................................................10

INTRODUCTION

This project focuses on the vapour-liquid equilibria (VLE) problems which is depicted in the figure
shown. When any liquid vapor component, both phase each containing N chemical species co-exist
in thermodynamic equibibrium at temperature T and pressure P, the phase compositions {y 1.y2,....yN-
1} ans {x1.x2,....xN-1}remain invariant with time, and are related by a unique set of correlations. If the
correlations are known as a function of temperatue,
pressure and compositions {yi and xi} for each species, then
provided some of these variables are specified the rest can
be calculated. We will now derive such relatons for real
multi-component systems., but as in all cases of
thermodynamic modelling we take the ideal system as our
starting point. Net the VLE data of the systems at moderate
pressures are treated. Finally the correlations for VLE at
high pressures are presented.

VAPOUR – LIQUID EQUILIBRIA

In chemical engineering thermodynamics, the vapour–liquid equilibrium (VLE) describes the

distribution of a chemical species between the liquid phase and a vapour phase.

Page 2 of 11
The concentration of a vapour that is direct contact with its liquid, especially at equilibrium, is
expressed in terms of vapour pressure, which will be a partial pressure if any other gas are present
with the vapour. The equilibrium vapour pressure of a liquid is generally dependent on all
itstemperature. At vapour–liquid equilibrium, a liquid generally having individual components in
certain concentrations will have an equilibrium vapour in which the concentrations or partial
pressures of the vapour components have some values depending on all of the liquid components
concentrations and the temperature. The converse is also true: if a vapour with components at certain
concentrations or partial pressures is in vapour–liquid equilibrium with its liquid, then the component
concentrations in the liquid will be determined dependent on the vapour concentrations and on the
temperature. The equilibrium concentration of each and every component in the liquid phase is
generally different from its concentration (or vapour pressure) in the vapour phase, but there is a
relationship between them. The VLE concentration data can be determined experimentally or
approximated with the help of theories such as Raoult's law, Dalton's law, and Henry's law.

LIQUID PHASE PROPERTIES FROM VLE DATA

For sake of calculations we take the advantage of the facts that as P>0 the vapour phase molecular
interactions in a mixture at VLE become very weak, hence the vapor try to behaves as an ideal gas.
In thermodynamic terms this can be written as-

ϕ i ≅ 1.0

The modified form of Raoult’s law can now be used for the estimation of the activity coefficients
from experimental low P VLE.

The mixture fugacity of a component in non-ideal liquid solutions is defined as:

μiI ( T , P ) =Γ I ( T ) + RTln f ¿i I

We also define the activity coefficient as:

f ¿i I
γ i= I
xi f i

which is a measure of the extent of the departure of the component behaviour from an ideal solution.

Using the activity coefficient, equation becomes:

μiI ( T , P ) =Γ I ( T ) + RTln γ i X i f iI

Page 3 of 11
How do we calculate or measure these properties?

Suppose we conduct the VLE experiments on our system of interest.

 At a given temperature, we can easily vary the system pressure by changing the cell volume.
 Wait until equilibrium is established.
 Measure the compositions of the liquid and vapour.

Our understanding of molecular dynamics does not allow us to predict non-ideal solution fugacities,
fil . We must calculate them by experiment, often by knowledge of vapour-liquid equilibria.

Assume we need the liquid solution fugacity data for a binary mixture of A+B at P,T. At
equilibrium,

f ¿i I =f ¿V
i

The vapour mixture fugacity for component i is given by,

¿V
f ¿V
i =ϕi y i P

If we conduct our VLE experiments at low pressure, but at the required temperature, we can also
use-

f ¿V
i = yi P

by assuming that, ϕ ¿V
i =1

Since our experimental measurements are taken at equilibrium,

f ¿i I =f ¿V
i

Page 4 of 11
¿ yi P

What we need now is VLE data at various pressures (all relatively low)

ACTIVITY CO-EFFICIENTS FROM LOW VLE DATA

With a knowledge of the liquid solution fugacity, we can derive activity coefficients.
I

f ¿i ( Actual Fugacity)
γ i=
x i f Ii ( Ideal Solution Fugacity)

Our low pressure vapour fugacity simplifies f Ii to give:

yi P
γ i=
x i f Ii

and if P is close to Psat

i

V iI ( P−Psat
i )
I sat
f =ϕ P exp
i i
sat
i ( RT )
≈ Psat
i

Leaving us with

Page 5 of 11
 yi P
γ i=
x i Psat
i

Our low pressure VLE data can now be processed to yield experimental activity coefficient data:

yi P
γ i=
x i Psat
i

CORRELATION OF LIQUID PHASE DATA

The random number of molecular interactions in non-ideal systems makes prediction of liquid phase
properties very difficult.

 Experiments on the system of interest at the conditions (P,T,composition) of interest

is needed.
 Earlier, we noticed the use of low-pressure VLE data for the calculation of liquid
phase activity coefficients.

As practicing engineers, you will rarely have the time to conduct your own experiments.

 You must depend on correlations of data developed by other researchers.

 These correlations are empirical models (with limited fundamental basis) that
reduce experimental data to a mathematical equation.

MODELS FOR THE EXCESS GIBBS ENERGY

Models which represent the excess Gibbs energy have several purposes:

Page 6 of 11
  They cut down experimental data down to a few cetain parameters.
 They encourage computerized calculation of liquid phase properties by providing
equations from tabular data.
 In some cases, we can use binary data (A-B, A-C, B-C) to calculate the properties of multi-
component mixtures (A,B,C)

A series of these GE equations is derived from the Redlich/Kister expansion:

GE 2
=B+C ( x 1 −x2 ) + D ( x 1−x 2 ) (Constant T )
RT x 1 x2

Equations of this kind fist excess Gibbs energy data very well. However, they are empirical
and cannot be generalized for multi-component (3) mixtures or temperature.

SYMMETRIC EQUATIONS FOR BINARY MIXTURES

The simplest Redlich/Kister expansion results from C=D=...=0

GE
=B
RT x 1 x2

To calculate activity coefficients, we express GE in terms of moles n1 and n2.

n GE Bn n
= ¿¿1¿ 2
RT x 1 x2

and through differentiation

nG E
ln γ i=∂( )/∂ n1
RT

We find,

ln γ 1=B x 22∧ln γ 2=B x 21

EXCESS GIBBS ENERGY MODELS

Research engineers figures most of the liquid-phase information needed for equilibrium calculations

in the form of excess Gibbs Energy models. These models are:

 reduce diverse quantities of experimental readings into a few empirical parameters.

 provide data an equation format that might be used in thermodynamic simulation packages .

Page 7 of 11
“Simple” Empirical Models

 Symmetric, Margules, van Laar

 No fundamental basis but very easy to use
 Parameters applied to a given temperature, and the models generally cannot be extended after
binary systems.

Local Composition Models

 Wilsons, NRTL, Uniquac

 Some fundamental basis
 Parameters are generally temperature dependent, and multi-component behaviour can easily
be predicted from binary data.

Our objectives are to judge how to fit Excess Gibbs Energy models into experimental data, and
to implement how to use these models to calculate activity coefficients.

MARGULE’S EQUATION

We know that the simplest Redlich/Kister-type expansion is the Symmetric Equation, whereas a
more accurate model is the Margules expression:

GE
= A21 x1 + A12 x2
RT x 1 x2

Note that as x1 goes to zero,

GE
= A12
RT x 1 x2

Now,

A12=ln γ 1∞

Page 8 of 11
And similarly,

A21=ln γ 2∞

If you have Margules parameters, the activity coefficients can then be easily derived from the
excess Gibbs energy expression:

GE
= A21 x1 + A12 x2
RT x 1 x2

to yield,

ln γ 1=x 22 [ A 12+2 ( A 21− A 12) x 1 ]

2
ln γ 2=x 1 [ A 21+ 2 ( A 12− A 21) x 2 ]

These empirical equations are mostly used to describe binary solutions. A knowledge of A12 and A21
at the given T is all will require to calculate activity coefficients for a given solution composition.

VAN-LAAR EQUATIONS

Another multi-parameter excess Gibbs energy model is developed from an expansion of

(RTx1x2)/GE instead of using GE/RTx1x2. The end results can now be written as -

GE A '12 A'21
=
RT x 1 x2 A '21 x 1 + A '12 x 2

For the excess Gibbs Energy and:

'A '12 x 1 −2
ln γ 1= A (1+ '
12 )
A 21 x 2

A '21 x 2 −2
ln γ 2= A '21(1+ '
)
A 12 x 1

For the activity coefficients.

Note that as x1 tends to zero,

ln γ 1∞= A '12

And similarly,

Page 9 of 11
 ln γ 2∞= A '21

NUMERICALS

Ques1. For the acetone /methanol system a vapour mixture for which z1=0.75 and z2=0.25 is cooled
to temperature T in the multi-phase region an flows into a separation chamber at pressure of 1 bar. If
the composition of the liquid product is to be x1=0.275, what is the required value of T, and what is
the value of y1? Give liquid mixtures of this system to a good approximation:

ln γ 1=0. 3 4 x 22∧ln γ 2=0.3 4 x 21

Ques2. A double phase system of species 1 and 2 consists of vapor and liquid phases in equilibrium
at temperature T, for which

 ln γ 1=1. 2 x 22∧ln γ 2 =1.2 x 21

 Psat ¯ sat
1 =0.89 ¿ P2 =1.24 b ar

Assume the validity of the equation,

a) For what values of the mole fraction z1 can this two-phase system exist with a liquid mole
fraction x1=0.35?
b) What is the pressure P and vapour mole fraction y1 within this range?
c) What are the pressure and composition of the azeotrope at this temperature T?

Ques3. For the system ethyl ethanoate/n-heptane at 343.15K

 ln γ 1=0.95 x 22∧ln γ 2=0.95 x 21

Psat sat
 1 =79.80 kPa∧P 2 =40.50 kPa

Assume the validity of the equation,

a) Make a BUBL P calculation for T=343.15 K, x1=0.05

b) Make a DEW P calculation for T=343.15 K, y1=0.05
c) What is the final azeotrope composition and final pressure at T =343.15 K ?
Page 10 of 11
Ques4. A process stream contains light species 1 and heavy species 2. A comparetively pure liquid
stream containing mostly 2 is desired, obtained by a single stage liquid/vapor separation.
Specifications on the equilibrium composition are x1=0.002 and y1=0.950. Make the use of data
given downwards to determine T(K) and P(bar) for the separator. Assume that Equation applies, the
calculated P should validate this assumption. Data:

For liquid phase, ln γ 1=0. 93 x 22∧ln γ 2=0. 93 x 21

ln Psat
i
B
¯¿= Ai − i ¿
T/K

A1=10.08 B1=2572.0 , A2=11.63 B2 =6254.0

Ques5. If a system exhibits vapour-liquid equilibrium, at least one of the K-Values must be greater
than 1.0 and at least one must be less than 1.0 . Offer a proof of this observations .

Page 11 of 11