Prediction of Activity Coefficient of Polymer Solution Using

Modified UNIFAC Model

A PROJECT REPORT
Submitted by
DIVIJ KISHAL
PARV KUMAR
VENKATA VIJAYAN

2013H101017P
2013H101026P
2013H101027P

Under the guidance of

Dr. Arvind Kumar Sharma
Assistant Professor, Department of Chemical Engineering

BIRLA INSTITUTE OF TECHNOLOGY & SCIENCE, PILANI

Pilani Campus, Rajasthan (India) - 333031
NOVEMBER 2013
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ACKNOWLEDGEMENT

We take this opportunity to express our gratitude to have

been instrumental in the successful completion of the project. We take
this opportunity to thank Dr. Arvind Kumar Sharma, Assistant Professor,
Department of Chemical Engineering, Birla Institute of Technology &
Science, Pilani Campus for giving us an opportunity to work in the field
of polymer solutions and their activity coefficient predictions and
guiding us for the past one semester through the course of Advanced
Chemical Engineering Thermodynamics that added valuable inputs for
the development of the project.
It gives us immense pleasure to express profound gratitude
to God Almighty for supporting us.

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ABSTRACT
UNIQUAC and UNIFAC models are used to predict the activity
coefficient of a Vapor-Liquid equilibrium of binary solution. These
models have proved to be consistent with the practical results for the
binary solution but when incorporated with a Vapor-Liquid equilibrium
of a polymer solution, these models prove to be inconsistent and
deviation is found to be significantly large. In order to get a consistent
result, UNIFAC model is further extended for a polymer solution using a
proposed relation between the volume parameter-r(n) for an n-mer
polymer and r(1) of the monomer. Unlike the UNIFAC model there is no
need for the free volume term, which proves to be advantageous in the
extended model. The extended model known as UNIFAC-FV model has
been used in this article for the prediction of activity coefficient of a
Vapor-Liquid equilibrium.

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Table of Contents
Section

Contents

Page No.

Chapter 1

Introduction

Chapter 2

UNIFAC Model

Chapter 3

UNIFAV-FV Model

12

Chapter 4

Calculation of Activity of a Polymer Solution

14

Chapter 5

Results and Discussion

20

Chapter 6

List of Symbols

21

Chapter 7

References

23

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Chapter 1
Introduction
A large part of chemical engineering design is concerned
with separation operations. Many of these are diffusional operations of
the phase-contacting type, distillation, absorption, and extraction are the
most common. For rational design of such separation processes, we
require quantitative information on phase equilibria in multi-component
mixtures. Satisfactory experimental equilibrium data are only rarely
available for the particular conditions of temperature, pressure, and
composition required in a particular design problem. It is therefore
necessary to interpolate or extrapolate existing mixture data or, when
suitable data are lacking, to estimate the desired equilibria from some
appropriate correlation. A very useful correlation for this purpose,
UNIFAC, was proposed.
The availability of solvent and polymer activity
coefficients is of great importance in the design and operation of
polymer processes. Polymerization often takes place in solvents, and it is
quite important to know how the produced polymer will distribute
between the polymer- rich and solvent-rich phases. In such cases liquidliquid equilibrium (LLE) information is necessary, i.e., both polymer and
solvent activity coefficients. On the other hand, the removal of solvents
or non-polymerized monomers from the produced polymer requires the
knowledge of vapor-liquid equilibrium (VLE), i.e., the solvent activity
coefficients. But for Polymer solutions, the result obtained for activity
coefficient by UNIFAC deviates to greater extent when compared with
the practical results. So a modified model called UNIFAC-FV model
was made which produces better results.

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Vapor-Liquid Equilibria:
It is a condition where a liquid and its vapor are in
equilibrium with each other so the rate of evaporation equals the rate of
condensation on a molecular level such that there is no net vapor-liquid
inter-conversion. In theory equilibrium takes a very long time to reach
and is practically reached in a closed location if the liquid and its vapor
are allowed to stand in contact with each other without any interference
from outside.
Activity Coefficient:
Modified Raoults law results when an activity coefficient,
is inserted into Raoults law on account of deviations from solution
ideality in Liquid phase:
P yi

sat

Pi x i

Where

is the activity coefficient, P is the total

pressure and Pisat is the saturation pressure of component i and xi is the

mole fraction of component i.
Bubble point and dew point calculations made with this
equation are only a bit more complex than the same calculations made
with Raoults law. Activity coefficients are functions of temperature and
Liquid-phase composition, and ultimately are based on experiment.
Activity coefficients may be measured experimentally or calculated
theoretically, using the Debye Huckel equation or extensions such as
Davies equation. Alternatively correlative methods such as UNIQUAC,
NRTL or UNIFAC may be employed, provided fitted componentspecific or model parameters are available.

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Chapter 2
Prediction of Activity using UNIFAC Model
UNIFAC Model:
The UNIFAC method (UNIQUAC Functional-group
Activity Coefficients) is a semi-empirical system for the prediction of
non-electrolyte activity in non-ideal mixtures. UNIFAC uses the
functional groups present on the molecules that make up the liquid
mixture to calculate activity coefficients. By using interactions for each
of the functional groups present on the molecules, as well as some
binary interaction coefficients, the activity of each of the solutions can
be calculated. This information can be used to obtain information on
liquid equilibria, which is useful in many thermodynamic calculations,
such as chemical reactor design, and distillation calculations.
The UNIFAC model was first published in 1975 by
Fredenslund, Jones and Prausnitz, a group of chemical engineering
researchers from the University of California. Subsequently they and
other authors have published a wide range of UNIFAC papers, extending
the capabilities of the model. The model is also called lattice model and
has been derived from a first order approximation of interacting
molecule surfaces in statistical thermodynamics. The model is however
not fully thermodynamically consistent due to its two liquid mixture
approach. In this approach the local concentration around one central
molecule is assumed to be independent from the local composition
around another type of molecule.

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Correlation:
The method used is called group contribution method
which uses the principal that the simple structures of chemical
components are always the same in many different molecules. The
smallest common constituents are the atoms and the bonds. All organic
components for example are built of carbon, hydrogen, oxygen,
nitrogen, halogens, and maybe sulphur. Together with a single, a double,
and a triple bond there are only ten atom types and three bond types to
build thousands, of components. The next slightly more complex
building blocks of components are functional groups which are
themselves built of few atoms and bonds. The advantage of a group
contribution method is that it enables systematic interpolation and
extrapolation of vapor-liquid equilibrium data simultaneously for many
chemically related mixtures. Most important, it provides a reasonable
method for predicting properties of mixtures where no mixture data at all
are available. The UNIFAC correlation attempts to break down the
problem of predicting interactions between molecules by describing
molecular interactions based upon the functional groups attached to the
molecule. This is done in order to reduce the sheer number of binary
interactions that would be needed to be measured to predict the state of
the system.
Group Interaction Parameters:
Group interactions are approximated in this method
because any group within a molecule is not completely independent of
the other. Increasing the distinction of groups also increases the number
of group interactions that has to be characterized. So if there are
increased numbers of interaction parameters, the advantage of group
contribution will be lost. So one has to define the functional group by

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experience and judgment to achieve a compromise between accuracy

and simplicity of calculation.

The Model:
In order to use the model, no experimental data are
required for the particular mixture of interest. One needs to know the
temperature and composition of the system and the molecular structure
of every component in the mixture and the necessary group parameters
must be known.
Equations giving the activity coefficients as functions of
composition and temperature are here stated. The UNIFAC model has a
combinatorial contribution to the activity coefficients, essentially due to
differences in size and shape of the molecules, and a residual
contribution, essentially due to energetic interactions.
ln i=ln iC +ln iR

Combinatorial

Residual

Combinatorial Part:
The combinatorial contribution is
ln iC =ln

li

r iqi
z

i =

i z

+ q i ln i + li i x j l j
xi 2
i
xi j

qi xi

xj qj
j

r i1 ; z=10

)(

; i=

ri xi

xj r j
j

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Pure-component parameters ri and qi are respectively measures of

molecular van der Waals volumes and molecular surface areas. They are
calculated as the sum of the group volume and group-area parameters,
Rk and Qk.
r i= v k (1) Rk ; qi = v k (1) Q k
k

Where vk(l), always an integer, is the number of groups of type k in

molecule i. Group parameters Rk and Qk are obtained from van der
Waals group volumes and surface area Vk and Ak.
Rk= Vk/15.17
Qk= Ak/ (2.5*10^9)
Residual part:
The contribution from group interactions, the residual part, is
assumed to be the sum of the individual contributions of each solute
group in the solution less the sum of the individual contributions in the
pure component environment.
ln iR = v k(1) [ln k ln k (1 )]
k

All groups
k is the group residual activity coefficient, and k(i) is the
residual activity coefficient of group k in a reference solution containing
only molecules of type i. The individual group contributions in any
environment containing groups of kinds 1,2 ...N are assumed to be only
a function of group concentrations and temperature.

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 m mk
m nm

m km /

1ln
ln k Qk
v m(1) x j

Qm X m
i
m =
; X m=
Qn X n
v k(1) x j
n

Xm is the fraction of group m in the mixture.

mk

= exp [-(anm/T)]

Parameter anm characterizes the interaction between groups n

and m. For each group interaction, there are two parameters: amn anm.
No ternary (or higher) parameters are needed to describe multicomponent equilibria.

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Chapter 3
Prediction of Activity by UNIFAC-FV Model
UNIFAC-FV MODEL
A new model has been proposed by Oishi and Praunsnitz for the
estimation of solvent activities in polymer solutions. The approach is
based on a group contribution method(UNIFAC) with a free volume
correction.
Due to the limitations seen in the UNIFAC model, one cannot use it in
the case of polymer solutions as it will give greater deviation. According
to UNIFAC-FV model, solvent activities are calculated as contributions
from three sources which are:
Combinatorial
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 Residual
Free Volume term (Flory EOS)
So here it includes an extra term called free volume. The combinatorial
and residual term can be calculated by Van der Berg method. That is
using the relation:
a
( 1)R , C =ln 1 + 2' r 1 /r 2 +ln x 1
ln

Where r1 and r2 are the molar volume parameters, and

2' =
x1

x1

is given by

P x2 r 2
x 1 r 1+ P x 2 r 2

w1 M 2
w1 M 2 + w2 M 1

Here w1 and w2 are the weight fractions of the solvent and polymer and
P is the degree of polymerization. The value of ln1 is calculated using
the equations of Fredenslund.
For calculation of combinatorial and residual part, the
correlations from UNIFAC model are also applicable and those
correlations will be used for the calculation in this article.
Free Volume parameter:
For the free volume parameter, ln(a 1)fv is calculated from
florys equation-state theory of polymer solutions.

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a
ln ( 1)FV

V 13

=3

V1
1
VM

[ ]
1
3

V 1 1
1
3

C 1

V M 1

C 1 ln

Where 3c1 is the reduced number of external degrees of freedom per

molecule, V1 is the reduced volume of the solvent, given by
V 1'
V 1=
15.17 b r 1'

And Vm is the reduced volume of the mixture, given by

V 1 ' w 2+ V 2' w 2
VM=
15.17 b (r 1' w1+ r 2' w 2)

V 1 and V2 are the specific volumes of the solvent and the

polymer, r1 and r2 are the volume parameters (per unit mass) as
calculated by UNIFAC, and b is a proportionality factor of order unity.
Oishi and Prausnitz found that the agreement between experimental and
calculated values is the best when b equals 1.28. The equation is
temperature dependent implicitly, through the variation of the specific
volumes with the temperature.
Combining all the contributions, the correlation for the
model is stated as:
ln a1 = ln a1C + ln a1r + ln a1fv
where ln a 1C is the combinatorial term, ln a1r I the residual
term and ln a1fv is the free volume term.

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Chapter 4
Prediction of Activity of Benzene in Polyisobutylene

at 25 C when the weight fraction of benzene is 0.1.

Solution

Component
Benzene
PIB

gmL

Main SubGroup Group

0.8736 78.11
0.9169

56.0
7

ACH

ACH

CH 2

CH 2

CH 2

CH 2

CH 3

Rk

Qk

No. of
Groups

0.531
3
0.219
5
0.674
4

0.40
0

0.0

0.54
0
0.84
0.9011
8

1
2

Combinatorial contribution
q1' =

1
6 ( 0.400 )=0.03073
78.11

' =

'

q2 =

1
6 ( 0.5313 )=0.04081
78.11

1
[1 ( 0 )+1 ( 0.540 ) +2 ( 0.848 ) ]=0.03987
56.07
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r 2' =

1
[ 1 ( 0.2195 )+ 1 ( 0.6744 ) +2 ( 0.9011 ) ]=0.04808
56.07

1 ' =

0.03073( 0.1)
=0.07888
0.03073 ( 0.1 )+ 0.03987(0.9)

1' =

0.04081(0.1)
=0.08618
0.04081 ( 0.1 ) +0.04808(0.9)

0.07888
0.08618
1+
0.08618
0.07888
10
( 0.08618 ) + ( 10.08618 )+ (78.11)(0.03073)
2
c
lna 1 =ln
ln

= - 1.4831
Residual Contribution:
W ACH =0.1

W CH =0.9

15.025 ( 2 )
=0.4823
56.07

W CH =0.9

14.0169
=0.2250
56.07

W C =0.9
Q' ACH =

Q' CH =
3

12.001
=0.1926
56.07

Q ACH
0.4
=
=0.03075
56.07 13.0089

QCH
0.848
=
=0.05644
15.025 15.025
3

Q' CH =
2

QCH
0.540
=
=0.03853
14.0169 14.0169
2

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Q' C=

QC
0
=
=0
12.001 12.001

' ACH =

Q' ACH W ACH

Q' ACH W ACH +Q 'CH W CH +Q 'CH W CH +Q' C W C
3

0.003075
=0.07892
0.03897
Q' CH W CH

'

CH =
3

'

Q ACH W ACH + Q

'
CH 3

CH =
2

W CH + Q
3

Q' CH W CH

'

'

Q ACH W ACH + Q

'
CH 3

'
CH 2

0.02722
0.6986
0.03897

'

0.008669
0.2225
0.03897

'

=0

W CH +Q C W C
2

W CH +Q
3

'

'
CH 2

W CH +Q C W C
2

'

Q CW C

'

CH =
2

'

'

'

Q ACH W ACH + Q CH W CH +Q CH W CH +Q C W C
3

Note that interaction parameters are only between main

groups, and in this case there are only two main groups ACH
CH 2

(benzene) and

C , CH 2

and

CH 3

subgroups) in PIB. This greatly

reduces the number of calculations for the residual contribution to the

activity of benzene as follows:
ACH , CH

ACH

ln

= exp

'

CH CH
3

a ACH ,CH
T

M ACH Q' ACH

'

, ACH

+ CH CH
2

) = exp(

[1-ln(

11.12
298

' ACH ACH , ACH

) = 1.0380 =

+ C C , ACH

+
' ACH ACH , ACH

'

2, ACH

ACH ,CH = ACH ,C

'

'

'

'

ACH ACH , ACH + CH CH , ACH + CH CH , ACH + C C , ACH

3

'

C AC H ,C
'

'

'

'

ACH ACH ,C + CH CH , C + CH CH , C + C C ,C
3

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'

ACH ACH , C

 0.400[1ln ( 0+ ( 0.22250.8145 )+ ( 0.69860.8145 )+ 0.07892 )

ln

(1 )ACH

ln a1 R

0.07892 ( 1 )
0.07892 (1 ) +0.6986 ( 0.8145 )+ 0.2225 ( 0.8145 )+

=0

= 6 (0.05036 0) = 0.3022

Free volume contribution:

v 1=

1.145
=1.445
15.17 ( 1.28 )0.048081

0.04081 ( 0.1 ) +0.04808( 0.9)

15.17 ( 1.28 )
1.1447 ( 0.1 )+ 1.0906 ( 0.9 )
v M=

lna1 FV =3 ( 1.1 ) ln

1.445 3 1
1
3

1.1920 1

] [(
1.1

1.4450
1 1
1.1920

)(

1.445

)]
1

1
1
3

=0.528

Total activity of benzene:

lna1 =1.483+ 0.302+ 0.528=0.653 ; a1=0.520

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1.2
1
0.8
Activity coefficient

0.6
0.4
0.2
0
0

0.2

0.4

0.6

0.8

1.2

Activity coefficient of Polymer in the solution

Similarly, value of activity coefficient has been calculated for 3 points at
x = 0.1, 0.3 and 0.5 and the above result is then extrapolated for all the
values and plotted.
Comparison of the predictive accuracy of the UNIFAC model and
the UNIFAC-FV model:
No. of
AAD / %
Temperature
System
data
range / K
UNIFAC
UNIFAC-FV
points
PIB(4 X 104) +
298.2
11
32.7
3
benzene
PIB(4 X 104)+
298.2
8
24.1
5
cyclohexane
PIB(5 X 104)
298.3
10
33.4
10.2
+ toluene
Simulation of 3 polymer solution in the Vapor- liquid equilibrium
is done in Aspen software and the deviation of activity coefficient when

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calculated by UNIFAC model and UNIFAC-FV model respectively,

from the actual value has been shown above.
So from the above table, it is inferred that the deviation of the
polymer solution under consideration (PIB + benzene) from the
experimental result, is 32.7% in case of UNIFAC model and 3% in case
of UNIFAC-FV model and hence UNIFAC-FV model provides a better
estimate for the activity coefficient in polymer solution.

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Chapter 5
Results and Conclusions
RESULTS
We have taken 4 polymer solution systems used to test the
proposed model, which is compared with the original UNIFAC and "the
UNIFAC-FV. It should be pointed out that in our calculation the
parameters b and c~ in the UNIFAC-FV are set equal to 1.28 and 1.1,
respectively, though they should be somewhat dependent on the system .
The group volume and surface area parameters as well as the group
interaction parameters for the three models were taken from a number of
references. The average absolute deviations (AADs) for the activities
of solvents in polymer solutions are shown in Table. For most systems,
the UNIFAC-FV shows great improvement over the original UNIFAC.
The total AAD was 18.7% for the original UNIFAC and 7.4% for the
UNIFAC-FV. However, for several systems the improvement is not so
large. The reason is that the original UNIFAC model underestimates the
solvent activities in polymer solutions; our modification applies some
correction to this.
CONCLUSIONS
The UNIFAC-FV model proposed in this work provides
accurate prediction of polymer- solvent VLE and requires no additional
information over the original UNIFAC model. The predictive accuracy is
much better than the original UNIFAC model. It can be used for polymer
systems as long as the group parameters needed for the original
UNIFAC model exist. Also we have that average absolute deviations
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(AADs) for the activities of solvents in the observed polymer solutions

shows more improvement in the UNIFAC-FV Model.
Chapter 6
List of symbols
a

Activity

Monomer number in a chain molecule

Number of experimental data points

Parameter in Eq. (2), 0 < p < 1

Surface area parameter

Volume parameter

Volume

Mole fraction

Coordination number in Eq. (3), set equal to 10

Greek letters

Volume fraction

Surface area fraction

Constant

Hard-sphere diameter

Subscripts
1

Solvent

Excluded property

Component

Superscripts
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Hard-core value

Combinatorial term

calc. Calculated value

exp.

Experimental value

FV

Free volume term

Residual term

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Chapter 7
References
Fluid Phase Equilibria 123 (2005) -106, Chongli Zhong a,
Yoshiyuki Sato a, Hirokatsu Masuoka a, Xiaoning Chen, Elsevier.
Aa. Fredenslund, J. Gmehling and P. Rasmussen, 1977. VaporLiquid Equilibria Using UNIFAC, Elsevier.
T. Oishi and J.M. Prausnitz, 1978. Estimation of solvent activities
in polymer solutions using a group-contribution method. Ind. Eng.
Chem. Process Des. Dev., 17: 333-339.
C. Antunes and D. Tassios, 1983. Modified UNIFAC model for the
prediction of Henry's constants. Ind. Eng. Chem.
Joel R. Fried, Polymer Science and Technology, Second Edition,
Prentice Hall of India Private limited, New Delhi.

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