European Polymer Journal 46 (2010) 587591

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Prediction of excess thermodynamic functions and activity coefcients

of some polymeric liquid mixtures using a new equation of state
Elaheh K. Goharshadi a,*, Maryam Imani b, Rayhaneh Rahimi-Zarei c, Fahimeh Razghandi a,
Maryam Abareshi a, Ali R. Berenji a
a

Dept. of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran

Chemistry & Chemical Engineering Research Institute of Iran, Tehran 14335-186, Iran
c
Dept. of Chemistry, Faculty of Basic Sciences, Tarbiat Modares University, 14115-335 Tehran, Iran
b

a r t i c l e

i n f o

Article history:
Received 25 April 2009
Received in revised form 5 November 2009
Accepted 6 November 2009
Available online 3 December 2009
Keywords:
Polymer mixture
Excess properties
Activity coefcients
GMA equation of state

a b s t r a c t
In this work, the excess thermodynamic properties, namely excess molar Gibbs energy,
excess molar enthalpy, excess molar entropy, excess molar internal energy, and excess
molar Helmholtz energy for four polymer mixtures and blends at different temperatures,
pressures, and compositions have been calculated using the GMA equation of state. We
have also calculated the activity coefcient for these polymeric mixtures using the GMA
equation of state. The values of statistical parameters between experimental and calculated
properties show the ability of this equation of state in reproducing and predicting the
excess thermodynamic functions and activity coefcients for studied polymeric mixtures.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, great interest has been focused on the
measurement, correlation, and prediction of thermodynamic properties of polymers. Thermodynamics of polymeric systems play an important role in the polymer
industry and are often a key factor in polymer production,
processing, and material development, especially for the
design of advanced polymeric materials [17].
Although equations of state (EoSs) can predict and
reproduce the thermodynamic properties of polymer systems, little systematic work has been devoted to test the
ability of current EoSs for this purpose. The literature data
are relatively scarce for the thermodynamic properties of
polymer solutions and blends, especially for multicomponent systems [8].
Excess thermodynamic properties of mixtures provide
insight into the molecular interactions between the various components and can be used for the development of
* Corresponding author. Tel.: +98 511 8797022; fax: +98 511 8796416.
E-mail address: gohari@ferdowsi.um.ac.ir (E.K. Goharshadi).
0014-3057/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2009.11.008

molecular models describing the thermodynamic behaviour of mixtures [9]. In recent years, there has been a considerable upsurge in the theoretical and experimental
investigations of the excess thermodynamic properties of
binary liquid mixtures.
The activity coefcient is a predominant factor in
liquidliquid equilibrium calculations for polymer solutions. A large number of equations of state and activity
coefcient models capable of describing phase equilibrium
in polymer solutions are available today, but only a few of
these models have been tested for several different systems [1012].
The values of excess thermodynamic functions and the
activity coefcients of polymer systems show their strong
deviations from ideal behaviour. On the other hand, these
properties can help to obtain information on the intermolecular interactions of these systems. The insufcient availability of experimental data for these properties often lead
to predict them using an equation of state.
This study was undertaken to investigate the excess
thermodynamic properties and activity coefcients of four
polymer mixtures and blends consist of poly (ethylene

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Table 1
The minimum and maximum values of square of correlation coefcient (R2) of Eq. (1) and pressure and temperature ranges of the data for studied polymeric
mixtures.
Mixtures

DT (K)

DP (MPa)

R2min  R2max

Ref.

PEG-200 + PPG-400
PPG-425 + PEGME-350
PEGME-350 + PEG-200
PEGME-350 + PEG-600

298.15328.15
298.15348.15
298.15338.15
298.15338.15

0.140
0.150
0.130
0.130

0.999470.99999
0.999520.99999
0.999140.99994
0.998270.99995

[6]
[22]
[23]
[23]

glycol methyl ether)-350 (PEGME-350) + poly (ethylene

glycol)-200 (PEG-200), poly(propylene glycol)-425 (PPG425) + PEGME-350(2), PEGME-350 + PEG-600, and PEG200 + PPG-400 using the GMA EoS [13].

liquid mixtures [1720]. The equation of state is based

on the average potential energy and is given as:

2Z  1V 3m AT; x BT; xq

where Z, Vm, and q are compressibility factor, molar volume, and molar density, respectively.
The intercept and slope of this equation depend on temperature via the equations:

2. The GMA EoS and derived properties

A new equation of state has been derived for liquids by
Goharshadi et al. [13], (GoharshadiMorsaliAbbaspour,
GMA EoS). It has been used to calculate the different
thermodynamic and volumetric properties for a wide
range of uids including polar, nonpolar, and hydrogenbonded uids [7,1316]. The GMA EoS has been also
applied for calculating the thermodynamic properties of

2A1 2A2 ln T

R
RT
2B1 2B2 ln T

BT; x B0 
R
RT
AT; x A0 

2
3

where A0A2 and B0B2 are constants. To use the EoS for a
liquid, the A and B parameters must be known. To nd

Table 2
The statistical parameters for the excess thermodynamic functions for studied polymeric mixtures and blends.
x1

DGEm

DHEm
a

AAD
(J mol1)

a
b

Bias
(J mol1)

AAD
(J mol1)

DSEm
Bias
(J mol1)

DU Em

DAEm

AAD
(J mol1K1)

Bias
(J mol1K1)

AAD
(J mol1)

Bias
(J mol1)

AAD
(J mol1)

Bias
(J mol1)

PEGME-350(1) + PEG-200(2)
0.10
0.668
0.668
0.20
0.270
0.270
0.30
0.283
0.283
0.58
0.445
0.432
0.70
0.204
0.157
0.80
0.434
0.156
0.90
0.755
0.682

4.716
3.646
16.187
7.511
3.040
14.396
12.581

3.906
0.453
8.587
0.718
3.040
0.070
2.843

0.015
0.011
0.050
0.023
0.015
0.044
0.039

0.014
0.000
0.028
0.001
0.010
0.000
0.010

4.398
3.162
14.068
28.181
4.111
12.577
10.936

3.892
0.219
7.713
28.181
2.490
0.018
3.098

0.346
0.177
0.218
28.426
0.269
0.370
0.386

0.028
0.062
0.110
28.426
0.251
0.175
0.077

PPG-425(1) + PEGME-350(2)
0.1
2.480
2.480
0.2
0.372
0.254
0.3
0.462
0.443
0.4
0.503
0.499
0.5
0.577
0.502
0.6
0.966
0.856
0.7
0.218
0.094
0.8
0.258
0.140
0.9
0.216
0.051

2.448
4.788
3.469
8.833
3.466
4.590
3.256
2.692
3.336

2.439
4.788
1.851
0.130
2.237
0.062
1.721
2.482
2.479

0.016
0.015
0.012
0.028
0.011
0.015
0.010
0.008
0.011

0.016
0.009
0.007
0.001
0.006
0.004
0.010
0.007
0.008

4.493
4.719
3.538
8.757
3.236
4.826
3.439
2.736
3.528

4.493
3.260
2.055
0.184
1.621
0.993
1.765
2.235
2.529

0.968
0.570
0.522
0.489
0.532
0.659
0.349
0.539
0.476

0.426
0.378
0.239
0.185
0.114
0.075
0.138
0.108
0.014

PEGME-350(1) + PEG-600(2)
0.034
0.109
0.1
0.3
0.103
0.057
0.6
0.175
0.017
0.9
0.257
0.177

3.699
1.047
6.391
6.723

1.671
0.080
2.601
6.354

0.011
0.003
0.020
0.021

0.005
0.000
0.007
0.020

4.439
1.439
6.490
6.024

1.599
0.848
2.183
5.537

1.439
1.092
1.571
1.768

0.037
0.870
0.401
0.640

PEG-200(1) + PPG-400(2)
0.1348 0.446
0.334
0.2839 0.535
0.514
0.3960 0.739
0.734
0.6072 0.480
0.003
0.8038 0.277
0.273
0.8845 0.265
0.109

6.838
12.757
10.000
5.052
6.641
7.872

3.852
12.570
9.914
2.524
1.526
1.510

0.023
0.040
0.035
0.017
0.021
0.025

0.012
0.039
0.035
0.008
0.001
0.005

6.722
12.846
9.804
5.079
6.606
7.950

4.116
12.730
9.655
3.149
1.746
1.623

3.183
0.695
0.994
0.666
0.130
0.272

0.598
0.674
0.994
0.628
0.053
0.223

P
AAD 1=N ni1 jY Ecalc  Y Eexp j; Y E : excess molar thermodynamic property.
P
Bias 1=N ni1 Y Ecalc  Y Eexp .

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E.K. Goharshadi et al. / European Polymer Journal 46 (2010) 587591

these parameters, we may plot 2Z  1V 3m against q for

different isotherms. The slope and intercept of the straight
lines can be tted with Eqs. (2) and (3) from which A0A2
and B0B2 can be found.
The density of the GMA EoS at different temperatures,
pressures, and compositions can be calculated by the following equation:

BT; xq5 AT; xq4 q 

2P
0
RT

The excess volume, VE, excess Gibbs energy, DGE, excess

enthalpy, DHE, excess entropy, DSE, excess internal energy,
DUE, and excess Helmholtz energy, DAE, can be calculated
using Eqs. (5)(10), respectively [21].

VE V 

DGE

xi V i

V E dp

P0

DH E

VE  T

P0

@V E
@T

!!
dP

DH E  DG E
T
DU E DHE  PV E
DSE
E

DA DU  T DS

8
9
E

10

The volumes of pure components and mixtures at the same

temperature and pressure are needed for calculating the
excess volume (Eq. (5)).
The activity coefcient, ci, of a component in a binary
mixture can be calculated by the following equation:

1
ln ci
RT

@GEm
@xi

!
11
T;P

3. Results and discussion

We have used the experimental PVT data of some liquid
polymeric mixtures at various temperatures and compositions to examine the linearity of 2Z  1V 3m versus q (Eq.
(1)), namely the GMA EoS. Table 1 represents the minimum and maximum values of the square of correlation
coefcient (R2) of Eq. (1) and pressure and temperature
ranges of the data for studied polymeric mixtures. As the
values of the square of correlation coefcient of this table
show the linearity of 2Z  1V 3m versus q holds very well
for these mixtures.
The experimental values of excess thermodynamic
properties have been calculated using the above equations.
For example, the values of excess Gibbs energy are calculated by integration from the experimental values of excess
volumes. The statistical parameters of excess thermodynamic functions, namely excess Gibbs energy DGE, excess
enthalpy, DHE, excess entropy, DSE, excess internal energy,
DUE, and excess Helmholtz energy, DAE, for the four polymer mixtures and blends have been given in Table 2. It can
be claimed that the GMA EoS can reproduce the experimental values of the excess thermodynamic functions with
a good accuracy.
Typical graphs for excess molar enthalpy, excess molar
entropy, and excess molar Gibbs energy for mixture of
PPG-425 + PEGME-350 at 298.15 K and different pressures
have been given in Figs. 13, respectively. Since PPG has
specic interaction with PEGME due to the hydrogen bond,
the values of excess molar enthalpy and excess molar entropy are negative at different pressures. The excess molar
Gibbs energy was found to vary from negative to positive
as increasing the mole fraction of PPG-425. The sign of excess molar Gibbs energy depends on the magnitude of excess molar enthalpy and excess molar entropy. In fact,

20
0

E
m

(J mol-1)

-20
-40
-60
-80
-100
-120
-140
-160
-180
0.0

P= 0.1 M Pa
10
15
20
25
30
35
40

0.2

0.4

0.6

0.8

1.0

x1
Fig. 1. Experimental (symbols) and calculated (solid lines) excess molar enthalpy for the PPG (1) + PEGME (2) versus mole fraction at 298.15 K for different
pressures.

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E.K. Goharshadi et al. / European Polymer Journal 46 (2010) 587591

0.0
-0.1
E
-1
S m(J mol )

-0.2
-0.3
P=0.1 MPa
10
15
20
25
30
35
40

-0.4
-0.5
-0.6
-0.7
0.0

0.2

0.4

0.6

0.8

1.0

x1
Fig. 2. Same as Fig. 1. for excess molar entropy.

120
P=0.1 MPa
10
15
20
25
30
35
40

100
80

GEm (J mol-1)

60
40
20
0
-20
-40
-60
-80

0.0

0.2

0.4

0.6

0.8

1.0

x1
Fig. 3. Same as Fig. 1. for excess molar Gibbs energy.

Table 3
The statistical parameters for the activity coefcients for studied polymeric mixtures and blends.
PEGME-350(1) + PEG-200(2)

a
b

x1

AADa

0.10
0.20
0.30
0.40
0.50
0.58
0.70
0.80
0.90

0.004
0.001
0.002
0.001
0.002
0.001
0.001
0.002
0.003

Biasb

PPG-425(1) + PEGME-350(2)

PEG-200(1) + PPG-400(2)

PEGME-350(1) + PEG-600(2)

x1

Bias

x1

AAD

Bias

x1

AAD

Bias

0.009
0.004
0.000
0.002
0.001
0.001
0.001
0.000
0.001

0.135
0.284
0.396
0.607
0.804
0.885

0.001
0.001
0.000
0.000
0.000
0.002

0.000
0.001
0.000
0.000
0.000
0.001

0.10
0.30
0.60
0.90

0.4797
0.5158
0.4423
1.0571

0.4588
0.1626
0.3905
0.6475

AAD

0.004
0.10
0.010
0.001
0.20
0.004
0.001
0.30
0.001
0.001
0.40
0.002
0.001
0.50
0.001
0.001
0.60
0.001
0.001
0.70
0.001
0.002
0.80
0.015
0.003
0.90
0.001


PN
Y exp Y calc 
1
AAD N i1 100 Y exp ; Y : activity coefficient:


P
Y exp Y calc
.
Bias N1 N
i1 100
Y exp

E.K. Goharshadi et al. / European Polymer Journal 46 (2010) 587591

liquidliquid phase separation in polymer blend systems

occurs through a competition between the enthalpy and
the entropy of mixing. Fig. 3 shows that the enthalpic effects arising from attractive forces are more important
than the entropic ones in PPG-rich blend.
Increasing pressure leads to a decrease in excess molar
enthalpy or entropy through the whole concentration
range. In contrast, after the mid-concentration range, i.e.
in PPG-rich blend, increasing the pressure decreases the
excess molar Gibbs energy thus making the mixing process
more favorable.
Table 3 shows the statistical parameters for the activity
coefcient for the four polymer mixtures. By referring to
this table, it is plausible to say that the GMA EoS can predict and reproduce the activity coefcients of these polymeric mixtures.
4. Conclusions
The results of the present paper show that the GMA EoS
can predict the excess thermodynamic functions and activity coefcients for studied polymeric mixtures and blends
with a high precision.
It seems to us that this work contains the following
conclusions:
(1) The form of the GMA EoS is generalized and very
simple.
(2) It can predict the thermodynamic properties of the
polymeric mixtures at any temperature, pressure,
and composition.
(3) The values of statistical parameters between experimental and calculated properties conrm the ability
of this equation of state in reproducing and calculating of different volumetric properties of the polymeric mixtures.
Acknowledgement
The authors gratefully acknowledge the support of the
Research Committee of Ferdowsi University of Mashhad.
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