Académique Documents
Professionnel Documents
Culture Documents
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
588
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]
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:
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 .
589
2P
0
RT
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
1
ln ci
RT
@GEm
@xi
!
11
T;P
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.
590
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
591
[3] Brannock GR, Sanchez IC. Off-lattice van der Waals equations of state
for polymer liquids. Macromolecules 1993;26:49702.
[4] Bogdanic G, Fredenslund A. Revision of the group-contribution Flory
equation of state for phase equilibria calculations in mixtures with
polymers. 1. Prediction of vaporliquid equilibria for polymer
solutions. Ind Eng Chem Res 1994;33:133140.
[5] Gupta RB, Prausnitz JM. Vaporliquid equilibria for copolymer/
solvent systems: effect of intramolecular repulsion. Fluid Phase
Equilibr 1996;117:7783.
[6] Colin AC, Rubio RG, Compostizo A. Equation of state of a blend of
water-soluble polymers: poly(propylene glycol) 1 poly(ethylene
glycol). Polymer 2000;41:740714.
[7] Berenji AR, Goharshadi EK. Prediction of thermodynamic properties
of polymeric liquids using a new equation of state. Polymer
2006;47:472633.
[8] Lee MJ, Hsu TS, Tuan YC, Lin HM. Pressurevolumetemperature
properties for 1-octanol + acetophenone, poly(propylene glycol) + 1octanol + acetophenone, and poly(ethylene glycol) + poly(ethylene
glycol methyl ether) + anisole. J Chem Eng Data 2004;49:10528.
[9] Koyuncu M, Demirtas A, Ogul R. Excess properties of liquid mixtures
from the perturbation theory of BarkerHenderson. Fluid Phase
Equilibr 2002;193:8795.
[10] Bogdanic G, Vidal J. A segmental interaction model for liquidliquid
equilibrium calculations for polymer solutions. Fluid Phase Equilibr
2000;173:24152.
[11] Kontogeorgis GM, Saraiva A, Fredenslund A, Tassios DP. Prediction of
liquidliquid equilibrium for binary polymer solutions with simple
activity coefcient models. Ind Eng Chem Res 1995;34:182334.
[12] Pedrosa N, Gao J, Marrucho IM, Coutinho JAP. Correlation of solvent
activities in polymer solutions: a comparison of models. Fluid Phase
Equilibr 2004;219:12938.
[13] Goharshadi EK, Morsali A, Abbaspour M. New regularities and an
equation of state for liquids. Fluid Phase Equilibr 2005;230:1705.
[14] Goharshadi EK, Berenji AR. A new equation of state for predicting the
thermodynamic properties of liquid alkali metals. J Nucl Mater
2006;348:404.
[15] Moosavi F. Prediction of the volumetric and thermodynamic
properties of some refrigerants using GMA equation of state. Int J
Refrig 2007;30:37783.
[16] Goharshadi EK, Moosavi M. Thermodynamic properties of some
ionic liquids using a simple equation of state. J Mol Liq 2008;
42:414.
[17] Goharshadi EK, Moosavi M. Extension of a new equation of state to
the liquid mixtures. Ind Eng Chem Res 2005;44:697380.
[18] Goharshadi EK, Moosavi M. Application of a new equation of state to
liquid refrigerant mixtures. Thermochim Acta 2006;447:648.
[19] Goharshadi EK, Moosavi M, Abareshi M. Calculation of
thermodynamic properties of lubricant + refrigerant mixtures using
GMA equation of state. Int J Therm Sci 2007;46:94452.
[20] Goharshadi EK, Abareshi M. Prediction of volumetric and
thermodynamic properties of two aromatic-alcohol mixtures using
GMA equation of state. Fluid Phase Equilibr 2008;268:617.
[21] Barreiros SF, Galado JCG, Clancy P, da Ponte MN, Streett WB.
Thermodynamic properties of liquid mixtures of argon + krypton. J
Phys Chem 1982;86:17226.
[22] Lee MJ, Tuan YC, Lin HM. Pressurevolumetemperature properties
for binary and ternary polymer solutions of poly(ethylene glycol),
poly(propylene glycol), and poly(ethylene glycol methyl ether) with
anisole. Polymer 2003;44:3891900.
[23] Lee MJ, Lo CK, Lin HM. PVT measurements for mixtures of
poly(ethylene glycol methyl ether) with poly(ethylene glycol) from
298 K to 338 K and pressures up to 30 MPa. J Chem Eng Data
1998;43:107681.