Fluid Phase Equilibria 249 (2006) 165–172

Thermodynamic properties of aqueous polypropylene oxide 400 solutions

from isopiestic measurements over a range of temperatures
Rahmat Sadeghi ∗ , Fatemeh Ziamajidi
Department of Chemistry, University of Kurdistan, Sanandaj, Iran
Received 22 August 2006; received in revised form 24 September 2006; accepted 24 September 2006
Available online 30 September 2006

Abstract
The water activities of aqueous polypropylene oxide 400 solutions in the polymer mass fraction range 0.1–0.9 were measured by the isopiestic
method at 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15 K. The data obtained were used to calculate vapor pressure and osmotic coefficient
of solutions and actvity coefficient of solute and solvent at 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15 K as a function of concentration. A
comparison was made with the results for aqueous solutions of polyethylene oxide that is structurally closely related to polypropylene oxide. The
effect of temperature on the vapor–liquid equilibrium of polypropylene oxide + H2 O systems has been studied and the results have been discussed
on the basis of the effect of temperature on the hydrophobicity of the polymer. Furthermore, the segment-based local composition Wilson model
has been used for the correlation of the experimental water activity data and the obtained model parameters have been used for predicting the
excess molar enthalpy of aqueous polypropylene oxide solutions. The agreement between the prediction and the experimental data is good.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Water activity; Vapor–liquid equilibrium; Osmotic coefficient; Vapor pressure; Polypropylene oxide; Wilson

1. Introduction One of the thermodynamic properties of aqueous polymer

In recent years there has been an increasing interest in water-
soluble polymers containing propylene oxide moieties, espe-
cially copolymers between propylene oxide (PO) and ethylene
oxide (EO) monomers. These may have either a block struc-
ture as the much-studied (EO)x (PO)y (EO)x triblock copolymer
[1–9], often referred to as Pluronic polymers, or a random distri-
bution of PO and EO units, often referred to as Ucon polymers.
A typical feature of polypropylene oxide (PPO) and polyethy-
lene oxide (PEO) as well as copolymers of PO and EO is their
reduced solubility in aqueous solution with increasing temper-
ature. Much of the interest in these copolymers is rooted in the
possibility that the solubility and other solution thermodynamic
properties may be varied and optimised for various applications
by appropriate choice of the relative proportions of PO and EO
units in the chains [10].
∗ Corresponding author. Tel.: +98 871 6624133; fax: +98 871 6624133.
E-mail addresses: rahsadeghi@yahoo.com, RSadeghi@uok.ac.ir
(R. Sadeghi).
solutions is water activity which is an important and key ther-
modynamic property, because, it is closely related with the
other thermodynamic properties such as vapor pressure, osmotic
coefficient, activity coefficient, excess enthalpy, excess entropy,
excess Gibbs energy and excess volume and also in thermo-
dynamic modeling for separation methods, it is the essential
variable. It should, therefore, be useful to have information about
vapor–liquid equilibria of the PPO and PEO with water in order
to understand better and possibly predict the solution behav-
ior of these polymers. There have been a number of studies on
vapor–liquid equilibria of PEO in water [11–27], while the corre-
sponding information on PPO in water is more scarce and exist-
ing data were limitedly reported only for a very samll concentra-
tion range. Malcolm and Rowlinson [11] reported measurements
of the vapor pressures of aqueous solutions of PPO400 in the
polymer mass fraction range 0.6–0.99 at 303.15 and 323.15 K.
They only reported six experimantal data at each temperature.
Kim et al. [28] measured water activity of aqueous solutions
of PPO2000 at 303.15 K by a vacuum electro-microbalance cell.
Similar to Malcolm and Rowlinson [11], Kim et al. [28] reported
six experimental water activity data only for high PPO2000 con-
centrations (polymer mass fraction range 0.96–0.99). Recently,

0378-3812/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.09.028
166 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172
isopistic measurements have also been reported for water activ-
ities of ternary solutions of PPG425 + salt + water systems at
298.15 K in the low concentrations of PPO425 [29,30]. In fact, as
far as we know there are no any water actvity data in the literature
for the PPO + H2 O system for the whole range of PPO concen-
trations and over an extended ranges of temperatures. Therefore,
in this study, the improved isopiestic method [18] has been used
to obtain activities of water for the aqueous solutions of PPO400
for the wide range of polymer concentration at 293.15, 298.15,
303.15, 308.15, 313.15 and 318.15 K. From the obtained water
activity data, the vapor pressure and osmotic coefficient of solu-
tions and actvity coefficient of solute and solvent have been
determined. The effect of temperature on the water activity of
aqueous solutions of PPO400 has been studied. Furthermore, the
segment-based local composition Wilson model has been used
for the correlation of the experimental water activity data and
the obtained model parameters have been used for predicting
the excess molar enthalpy of aqueous PPO solutions at different
temperatures.
2. Experiments
2.1. Materials
PPO with a quoted molar mass 400 was obtained from Fluka.
The manufacturer has characterized this polymer as P400 with
lot and filling code 1252304 20206282. For molar mass of PPO,
the value 400 g mol−1 was used. Sodium chloride was obtained
from Merck. All chemicals were used without further purifi-
cation. The salt was dried overnight above 377.15 K. Double
distilled, deionized water was used.
2.2. Method
In this study, the isopiestic method was used to obtain the
activity of water in aqueous PPO400 solutions. It is based on
phenomenon that different solutions, when connected through
the vapor space, approach equilibrium by transferring solvent
mass by distillation. Equilibrium has been established once the
temperature and pressure are uniform throughout the system,
provided that no concentration gradients exist in the liquid phase.
At equilibrium, the chemical potentials of the solvent in each of
the solutions in the closed system are identical. Equality of the
solvent chemical potential implies the equality of the solvent
activity. Since the solvent activity is known for one or more
standard solutions, it will be known for each solution within the
isopiestic system. The isopiestic apparatus used in this work
was similar to the one used by Ochs et al. [18]. This appa-
ratus consisted of five-leg manifold attached to round-bottom
Table 1
Density and sound velocity of pure PPO400 at different temperatures
T (K) 293.15 298.15
Density (g cm−3 ) 1.007909 1.003929
Sound velocity (m s−1 ) 1383.51 1366.70
flasks. Two flasks contained the standard pure NaCl solutions,
two flasks contained the pure PPO solutions and the central
flask was used as a water reservoir. The apparatus was held in
a constant-temperature bath at least 120 h for equilibrium. Dur-
ing the equilibration process the manifold was removed at least
once a day and the samples were agitated. After the third day
the sample were not agitated, but left in the bath to approach
their final equilibrium conditions. The temperature was con-
trolled to within ±0.01 K. After equilibrium had been reached,
the manifold assembly was removed from the bath, and each
flask was weighed with an analytical balance with a precision of
±0.0001 g. From the weight of each flask after equilibrium and
the initial weight of salt and polymer, the mass fraction of each
solution was calculated. The water activity for the standard aque-
ous NaCl solutions at different concentrations and temperatures
has been calculated from the correlation of Colin et al. [31]. It
was assumed that the equilibrium condition was reached when
the differences between the mass fractions of the duplicates were
less than 1%. In all cases, averages of the mass fractions of the
duplicates are reported as the total isopiestic mass fractions for
the reference and sample. The accuracy of the method depends
upon the standard solutions, temperature stability, and the time
allowed for the equilibrium process. The uncertainty in the mea-
surement of solvent activity was estimated to be ±0.0002.
3. Results and discussion
3.1. Experimental results
Table 1 reports the density and sound velocity data of pure
PPO400 at different temperatures. Tables 2–7 report the water
activities, a1 , of PPO400 (2) + H2 O(1) system at 293.15, 298.15,
303.15, 308.15, 313.15 and 318.15 K, respectively. In these
tables, w2 is the mass fraction of polymer. The vapor pres-
sures (p) of various aqueous solutions at each temperature were
computed from the water activity measurements by using the
following equation:
  ◦ ◦ ◦
p (B1 − V1 )(p − p1 )
ln a1 = ln ◦ + (1)
p1 RT
◦ ◦
where B1 is the second virial coefficient of water vapor, V1 the
◦
molar volume of liquid water, and p1 the vapor pressure of pure
water. The second virial coefficients of water vapor were cal-
culated using the equation provided by Rard and Platford [32].
Molar volumes of liquid water were calculated using density
of water at different temperatures [33]. The vapor pressures of
pure water were calculated using the equation of state of Saul
and Wagner [34]. The calculated values of p have also been given
in Tables 2–7.
303.15 308.15 313.15 318.15
0.999941 0.995937 0.991938 0.987900
1350.10 1333.64 1317.20 1301.26
 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172 167

Table 2 Table 4
Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ- Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ-
ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for
PPO400 (2) + H2 O(1) at 293.15 K PPO400 (2) + H2 O(1) at 303.15 K

w2 a1 p (kPa) Φ γ1 γ2 w2 a1 p (kPa) Φ γ1 γ2

0.0864 0.9952 2.327 1.130 0.9994 0.8721 0.1113 0.9943 4.221 1.013 0.9999 2.1565
0.1376 0.9920 2.320 1.118 0.9991 1.2734 0.1855 0.9907 4.205 0.911 1.0009 3.0506
0.1749 0.9893 2.313 1.127 0.9987 1.6157 0.1886 0.9905 4.205 0.912 1.0009 3.0870
0.2798 0.9817 2.296 1.056 0.9989 2.6448 0.2290 0.9881 4.194 0.895 1.0013 3.5346
0.3052 0.9806 2.293 0.990 1.0000 2.8627 0.2401 0.9870 4.190 0.919 1.0010 3.6454
0.3650 0.9751 2.280 0.974 1.0003 3.2405 0.3117 0.9833 4.174 0.826 1.0034 4.1627
0.3740 0.9742 2.278 0.971 1.0004 3.2766 0.3249 0.9837 4.176 0.758 1.0050 4.2127
0.4168 0.9704 2.269 0.934 1.0016 3.3624 0.4243 0.9786 4.154 0.652 1.0111 4.0765
0.5501 0.9603 2.246 0.736 1.0132 2.7870 0.4583 0.9773 4.149 0.603 1.0145 3.8424
0.6439 0.9516 2.225 0.609 1.0291 1.9987 0.4690 0.9765 4.145 0.598 1.0153 3.7536
0.6662 0.9482 2.217 0.592 1.0334 1.8176 0.5053 0.9749 4.138 0.553 1.0197 3.4121
0.6979 0.9458 2.212 0.536 1.0442 1.5797 0.5458 0.9735 4.132 0.496 1.0262 2.9855
0.7962 0.9226 2.157 0.458 1.0849 1.0405 0.5869 0.9708 4.121 0.463 1.0329 2.5420
0.8056 0.9196 2.150 0.449 1.0912 1.0063 0.6721 0.9650 4.096 0.386 1.0541 1.7239
0.8117 0.9154 2.140 0.455 1.0931 0.9858 0.7014 0.9615 4.081 0.371 1.0632 1.4978
0.8169 0.9140 2.137 0.448 1.0977 0.9694 0.7317 0.9579 4.066 0.350 1.0756 1.2989
0.8396 0.8956 2.094 0.468 1.1067 0.9088 0.7560 0.9524 4.043 0.349 1.0853 1.1651
0.8681 0.8702 2.035 0.469 1.1281 0.8591 0.8098 0.9317 3.955 0.369 1.1104 0.9480
0.8777 0.8608 2.013 0.464 1.1390 0.8491 0.8339 0.9221 3.914 0.359 1.1306 0.8849
0.8863 0.8506 1.989 0.461 1.1492 0.8432 0.8578 0.9031 3.833 0.375 1.1485 0.8429
0.9008 0.8144 1.904 0.502 1.1475 0.8399 0.8668 0.8932 3.791 0.385 1.1550 0.8324
0.9138 0.7897 1.846 0.495 1.1667 0.8443 0.8947 0.8505 3.609 0.423 1.1760 0.8196
0.9149 0.7768 1.816 0.522 1.1529 0.8450 0.8993 0.8382 3.557 0.439 1.1753 0.8204
0.9043 0.8265 3.507 0.448 1.1782 0.8222
0.9232 0.7697 3.266 0.483 1.1864 0.8387

The osmotic coefficients (Φ) of aqueous PPO solutions were

Table 3
Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ-
calculated form the experimental water activity data using the
ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for expression:
PPO400 (2) + H2 O(1) at 298.15 K a1
Φ = −ln (2)
w2 a1 p (kPa) Φ γ1 γ2 x2 /x1
0.1080 0.9942 3.150 1.067 0.9996 1.4985
where x1 and x2 are the mole fractions of solvent and solute,
0.1761 0.9903 3.138 1.013 0.9998 2.2146
0.1823 0.9900 3.137 1.001 0.9999 2.2829 respectively. The data for the osmotic and activity coeffi-
0.2165 0.9879 3.130 0.978 1.0002 2.6572 cient (measured from the experimental water activity data,
0.2814 0.9839 3.118 0.920 1.0013 3.2903 γ 1 = a1 /x1 ) for aqueous PPO solutions are also collected in
0.2932 0.9829 3.114 0.923 1.0013 3.3847 Tables 2–7. Figs. 1–4, respectively show the measured water
0.3363 0.9803 3.106 0.872 1.0027 3.6503
activity, vapor pressure, osmotic coefficient and water activ-
0.3432 0.9800 3.105 0.858 1.0031 3.6799
0.3655 0.9781 3.099 0.854 1.0035 3.7486 ity coefficient data for binary PPO400 (2) + H2 O(1) system at
0.3788 0.9775 3.097 0.829 1.0043 3.7694 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15 K. As shown
0.4282 0.9738 3.086 0.787 1.0066 3.7146 in Fig. 1, water activity of PPO400 (2) + H2 O(1) system increases
0.4901 0.9705 3.075 0.692 1.0125 3.3825 with increasing temperature. Therefore from Eq. (1), we con-
0.5213 0.9677 3.066 0.669 1.0152 3.1327
clude that by increasing temperature, increase of vapor pressure
0.5926 0.9634 3.053 0.569 1.0265 2.4659
0.6676 0.9580 3.035 0.474 1.0447 1.7867 of PPO400 (2) + H2 O(1) solution is larger than those of pure
0.6679 0.9592 3.039 0.460 1.0461 1.7843 water. This is because the PPO becomes more hydrophobic with
0.6864 0.9543 3.024 0.474 1.0484 1.6382 increasing temperature. The solubilities of PPO in water [10],
0.7125 0.9513 3.014 0.447 1.0575 1.4513 mixing enthalpies [10] and excess molar volume [35] of PPO
0.7716 0.9372 2.969 0.426 1.0798 1.1179
in water support this interpretation. It was found that the sol-
0.7770 0.9339 2.959 0.436 1.0805 1.0938
0.7920 0.9323 2.954 0.409 1.0922 1.0323 ubility of PPO in water decreases with increasing temperature
0.8393 0.9125 2.891 0.389 1.1271 0.8914 [10]. Carlsson et al. [10] measured mixing enthalpy of PPO in
0.8569 0.8948 2.835 0.412 1.1361 0.8594 water at two temperatures and showed that the excess enthalpy of
0.8716 0.8810 2.791 0.414 1.1503 0.8414 this system is negative and decrease in magnitude as temperature
0.8901 0.8443 2.675 0.464 1.1523 0.8304
increases. Similar to the excess enthalpy, Zafarani-Moattar et al.
0.9038 0.8200 2.598 0.469 1.1670 0.8310
[35] showd that the excess volume of the PPO + water system is
168 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172

Table 5 Table 6
Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ- Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ-
ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for
PPO400 (2) + H2 O(1) at 308.15 K PPO400 (2) + H2 O(1) at 313.15 K
w2 a1 p (kPa) Φ γ1 γ2 w2 a1 p (kPa) Φ γ1 γ2

0.1113 0.9945 5.595 0.978 1.0001 2.9586 0.1297 0.9943 7.339 0.852 1.0010 4.2270
0.1180 0.9942 5.594 0.965 1.0002 3.0493 0.1381 0.9941 7.337 0.820 1.0013 4.3448
0.1712 0.9917 5.580 0.896 1.0009 3.7492 0.1439 0.9935 7.333 0.861 1.0010 4.4244
0.1944 0.9906 5.573 0.869 1.0014 4.0269 0.1478 0.9933 7.332 0.861 1.0011 4.4770
0.2023 0.9905 5.573 0.836 1.0018 4.1154 0.1765 0.9923 7.324 0.801 1.0019 4.8377
0.2075 0.9904 5.572 0.818 1.0021 4.1716 0.2648 0.9893 7.302 0.663 1.0053 5.5249
0.2132 0.9900 5.570 0.824 1.0021 4.2314 0.3242 0.9876 7.289 0.578 1.0089 5.5230
0.2302 0.9898 5.569 0.761 1.0031 4.3965 0.5402 0.9836 7.260 0.313 1.0356 3.1512
0.2519 0.9886 5.562 0.756 1.0036 4.5753 0.5443 0.9825 7.252 0.328 1.0354 3.0956
0.2761 0.9875 5.556 0.732 1.0045 4.7267 0.6556 0.9793 7.228 0.244 1.0633 1.8056
0.3361 0.9848 5.541 0.672 1.0073 4.8551 0.6883 0.9743 7.191 0.262 1.0712 1.5286
0.3887 0.9839 5.535 0.567 1.0121 4.6707 0.6960 0.9743 7.191 0.253 1.0748 1.4706
0.4996 0.9790 5.508 0.472 1.0230 3.6036 0.7201 0.9705 7.163 0.258 1.0830 1.3061
0.5208 0.9790 5.508 0.434 1.0269 3.3460 0.7319 0.9702 7.161 0.246 1.0895 1.2349
0.5257 0.9786 5.506 0.433 1.0274 3.2859 0.7421 0.9696 7.156 0.238 1.0953 1.1781
0.6334 0.9743 5.481 0.335 1.0501 2.0492 0.7524 0.9688 7.150 0.232 1.1014 1.1251
0.7194 0.9678 5.445 0.283 1.0795 1.3434 0.7819 0.9624 7.103 0.237 1.1178 0.9966
0.7205 0.9661 5.435 0.297 1.0783 1.3364 0.7967 0.9586 7.075 0.240 1.1278 0.9447
0.7660 0.9571 5.384 0.297 1.0982 1.0891 0.8690 0.9057 6.683 0.332 1.1763 0.8043
0.7935 0.9497 5.343 0.298 1.1141 0.9787 0.8748 0.8971 6.620 0.345 1.1794 0.8012
0.7996 0.9479 5.333 0.298 1.1182 0.9580 0.8797 0.8901 6.568 0.353 1.1832 0.7996
0.8017 0.9446 5.314 0.313 1.1166 0.9512 0.8911 0.8659 6.389 0.391 1.1850 0.7992
0.8343 0.9251 5.204 0.343 1.1349 0.8660 0.9050 0.8426 6.217 0.399 1.2041 0.8057
0.8447 0.9217 5.185 0.333 1.1475 0.8468 0.9224 0.7920 5.843 0.436 1.2160 0.8250
0.8549 0.9169 5.158 0.327 1.1602 0.8318
0.8788 0.8803 4.952 0.390 1.1678 0.8113
0.8906 0.8556 4.812 0.425 1.1693 0.8092
0.9064 0.8272 4.652 0.435 1.1880 0.8149
ative values of both excess volume and excess enthalpies are
obtained. In other words the PPO becomes more hydrophobic
with increasing temperature.
negative and decrease in magnitude as temperature increases. In Fig. 5, comparisons of the experimental water activity data
Strong hydrogen bond interactions between PPO and water measured in this work with those taken from the Refs. [11,29]
at low temperatures are consistent with the obtained negative
excess enthalpies and excess volumes. At higher temperatures,
hydrogen bond interactions are weakened and hence less neg-
Table 7
Activity of water (a1 ), vapor pressure (p), osmotic coefficient (Φ), activ-
ity coefficient of water (γ 1 ) and activity coefficient of polymer (γ 2 ) for
PPO400 (2) + H2 O(1) at 318.15 K
w2 a1 p (kPa) Φ γ1 γ2

0.1450 0.9941 9.533 0.775 1.0017 5.6538

0.2110 0.9916 9.509 0.700 1.0035 6.2900
0.2737 0.9906 9.499 0.556 1.0074 6.4303
0.3571 0.9893 9.487 0.430 1.0140 5.8851
0.5170 0.9865 9.460 0.282 1.0341 3.5281
0.6647 0.9806 9.403 0.219 1.0682 1.6872
0.7498 0.9766 9.365 0.175 1.1084 1.1085
0.7548 0.9755 9.354 0.179 1.1107 1.0845
0.7940 0.9637 9.241 0.213 1.1310 0.9306
0.8090 0.9594 9.199 0.217 1.1424 0.8869
0.8229 0.9559 9.165 0.216 1.1559 0.8536
0.8345 0.9502 9.111 0.225 1.1660 0.8311
0.8461 0.9397 9.010 0.251 1.1724 0.8132
0.8624 0.9180 8.801 0.303 1.1771 0.7961
0.8810 0.8944 8.574 0.335 1.1926 0.7884
0.8857 0.8835 8.469 0.355 1.1918 0.7884
0.8937 0.8700 8.339 0.368 1.1994 0.7905
Fig. 1. Plot of water activity data, a1 , against mass fraction of PPO, w2 , 0.9136 0.8307 7.962 0.390 1.2263 0.8067
for PPO400 (2) + H2 O(1) solutions at different temperatures: , 293.15 K; , 0.9246 0.7975 7.643 0.410 1.2379 0.8226
298.15 K; ×, 303.15 K; , 308.15 K; ♦, 313.15 K; 䊉, 318.15 K.
 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172
Fig. 2. Plot of vapor pressure data, p (kPa), against mass fraction of PPO, w2 ,
for PPO400 (2) + H2 O(1) solutions at different temperatures: , 293.15 K; ,
298.15 K; ×, 303.15 K; , 308.15 K; ♦, 313.15 K; 䊉, 318.15 K.
have been made for PPO(2) + H2 O(1) system. Fig. 5 shows that
there is a good agreement between our data and those taken
from the Ref. [29]. But measured data in this work do not agree
well with those taken from the Ref. [11], especially for low PPO
concentration. In fact, two samples of the same polymer, e.g.,
equal in weight average molecular weight may, exhibit different
physicochemical properties if they differ in their molecular-
weight distribution.
Fig. 6 shows a comparison between the vapor pressure
depression of PPO400 (2) + H2 O(1) and PEO400 (2) + H2 O(1)
[27] as a function of polymers mass fractions at 303.15 K. As
can be seen from this figure, for a given polymer mass frac-
tion vapor pressure depression for PEO400 (2) + H2 O(1) system
is larger than those for PPO400 (2) + H2 O(1) system. This would
follow both from the fact that the PPO contains a greater pro-
Fig. 3. Plot of osmotic coefficient data, Φ, against molality of PPO, m,
for PPO400 (2) + H2 O(1) solutions at different temperatures: , 293.15 K; ,
298.15 K; ×, 303.15 K; , 308.15 K; ♦, 313.15 K; 䊉, 318.15 K.
169
Fig. 4. Plot of water activity coefficient data, γ 1 , against mass fraction of PPO,
w2 , for PPO400 (2) + H2 O(1) solutions at different temperatures: , 293.15 K;
, 298.15 K; ×, 303.15 K; , 308.15 K; ♦, 313.15 K; 䊉, 318.15 K.
portion of hydrocarbon in its molecule and also from the steric
effect of the side chain methyl groups in PPO which probably
hinder hydrogen bonding between water molecules and the ether
oxygen atoms. The calorimetric measurements [36] of heat of
mixing of PPO and PEO in water support this interpretation.
Gunninghame and Malcolm [36] showed that the heat of mix-
ing with water per mole of glycol is more negative for PEO
than for PPO. Also, the plot for PPO shows markedly larger
negative slope of the vapor pressure depression against polymer
mass fraction above mass faction 0.8, implies that the interaction
between the water and PPO molecules at high mass fractions of
PPO must be of a very satble nature. In fact, larger negative
slopes of the p − p◦ against w2 at high mass fraction of PPO is
attributed to extensive hydrogen bonding of water molecules to
the PPO. On the other hand, smaller negative slopes of the p − p◦
Fig. 5. Plot of water activity data, a1 , against mass fraction of PPO, w2 , for
PPO(2) + H2 O(1) solutions: , this work at 298.15 K; ×, Ref. [29] at 298.15 K;
, Ref. [11] at 303.15 K.
170 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172

tions decreases while that in aqueous PEO400 solutions increases

as a function of polymer molality. From Fig. 7 it is observed
that the deviation from ideality is more pronounced in aque-
ous PEO400 solutions than that in aqueous PPO400 solutions
indicating that the water–PEO400 interactions are stronger than
water–PPO400 interactions.

3.2. Correlation

In this work, for the correlation of solvent activity for the

investigated system the segment-based local composition Wil-
son model was considered. This model uses a combination of
the truncated Freed correction [39] to Flory–Huggins expres-
sion as first correction for the configurational entropy of mixing
molecules of different sizes and the modified Wilson equa-
tion [40] for weak local physical interactions between solvents
and segments of polymer chains (enthalpic contribution). The
Wilson equation for the excess molar Gibbs energy of multi-
Fig. 6. Plot of vapor pressure depression, p − p◦ (kPa), against mass fraction
of polymer, w2, at 303.15 K: , PPO400 (2) + H2 O(1); , PEO400 (2) + H2 O(1)
component polymer solutions has the following form:
[27].    
gE,Wilson φI
= xI ln + 0.5 βIJ rI xI φJ
RT xI
against w2 at low mass fraction of PPO suggests that hydropho- I I J
⎛ ⎞
bic hydration of the polymer is an important factor in its dilute  
solution behavior, which has maximum effect at around this −C xI ri,I ln ⎝ Xj Hji ⎠ (3)
mass fraction. Crowther and Eagland [37,38] by density, calori- I i j
metric and rheological measurements of PPO-water solutions,  2
showed that in dilute solutions of the polymer in water, interac- 1 1 1
βIJ = − (4)
tions between the polymer and water are very similar to those C rI rJ
seen with corresponding concentrations of short chain alcohols rI xI
in water and also suggest that specific interactions between the φI = (5)
J rJ x J
polymer and water accur in dilute solutions of water in the poly- 
mer. These results are in agreement with our results obtained rI = ri,I (6)
from vapor pressure depression measurements. i 
Comparison between osmotic coefficients of aqueous PPO400 xI ri,I
and PEO400 solutions at 303.15 K are shown in Fig. 7. As can be I
seen from Fig. 7, the osmotic coefficient in aqueous PPO400 solu- Xi =  (7)
xJ rj,J
J j
 
−Eji
Hji = exp (8)
CRT
Eji = hji − hii (9)
where ri,I is the number of the segment i in the component I, C
is a parameter, which represents the effective coordination num-
ber in the system, which was fixed at 10, and hij is enthalpies of
short-range interaction between i–j species. In the above rela-
tions the species I and J can be solvent or polymer molecules and
species i, j and k can be solvent molecules or segments. The first
term on the right hand side of Eq. (3) accounts for the contribu-
tion for the excess entropy associated with random mixing, and
is the same as the expression in Flory–Huggins theory. The sec-
ond term is the correction to the Flory–Huggins theory, and may
be understood as the local composition effect from the chained
segments in a polymer. In fact, the first and second terms on the
right hand side of Eq. (3) is the Freed Flory–Huggins combinato-
Fig. 7. Plot of osmotic coefficient data, Φ, against molality of polymer, m, at rial term [39]. The third term is the modified Wilson equation for
303.15 K: , PPO400 (2) + H2 O(1); , PEO400 (2) + H2 O(1) [27]. weak local physical interactions between solvents and segments
 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172 171

of polymer chains (enthalpic contribution). From differentiation

of the Eq. (3), one obtains the following expression for the activ-
ity of component I in the polymer solutions:
φI
ln aIWilson = ln φI + 1 −
xI
⎡ ⎤
 
+rI ⎣ βJI φJ (1 − φI ) − 0.5 βJK φJ φK ⎦
J J=I K=I
⎡ ⎛ ⎞
 
−C ri,I ⎣ln ⎝ Xj Hji ⎠
i j
⎤
 
 Hij − X H
k k kj ⎦
+ Xj (10)
k X k Hkj
j

This equation was used for the correlation of the experimental

Fig. 8. Plot of excess molar enthalpy, HE /kJ mol−1 , against mass fraction of
water activity data. The model parameters (E) were estimated polymer, w2, at different temperatures: , experimental data at 298.15 K [10];
by minimizing the following objective function: 䊉, experimental data at 321.15 K [10]; —, calcuated from Eq. (12) at 298.15,
308.15, 318.15 and 328.15 K, respectively from botttom to top.

NP
exp 2
OF = (a1,n − a1,n
cal
) (11)
n=1 ferent polymer molecular weight and temperatures. The activity
exp coefficients of polymer, γ 2 , at each temperature and polymer
where NP is the number of experimental data points and a1,n and mass fraction were computed from the obtained parameters by
a1,n
cal are, respectively, the experimental and calculated values of
using the Eq. (10). The calculated values of γ2 have also been
the water activity. The parameters E12 and E21 were obtained given in Tables 2–7.
as −12,080 and 20,224 J mol−1 , respectively. It was found that, From differentiation of the Eq. (3), one obtains the following
the absolute relative percentage deviations of water activity are expression for the excess molar enthalpy of polymer solutions:
about 1% for each temperatures. In fact, the model parameters  
Eij are independent of temperature and one set of parameters  j Xj Eji Hji
H E,Wilson
= xI ri,I (12)
k Xk Hki
successfully has been used to correlate all experimental data
I i
measured at six temperatures. Also, since the model is segment
based, the model parameters are independent of polymer molec- Using the Eq. (12) and obtained parameters, the excess molar
ular weight. To show the prediction ability of the model, the enthalpies of aqueous solution of PPO400 at different tem-
obtained parameters have been used to predict the water activi- peratures have been predicted and shown in Fig. 8 along
ties of some PPO + H2 O systems out of the temperatures range with the experimental results for excess molar enthalpies of
and PPO molecular weight tested in this work. Table 8 summa- PPO400 − H2 O at 298.15 and 321.15 K [10]. As can be seen
rizes the corresponding deviations along with the sources of the from Fig. 8, at low mass fractions of polymer the agreement
experimental data. On the basis of the obtained deviations, given between the prediction and the experimental data is good. How-
in Table 8, we conclude that the obtained parameters can be used ever, the model cannot describe the excess enthalpies at high
to prediction of water activity data of PPO + H2 O systems at dif- polymer mass fraction. In addition, as can be seen from Fig. 8,
the calculated excess molar enthalpies are negative and decrease
Table 8 in magnitude with increasing temperature. These predictions are
Relative gap between calculated and experimental values of water activity in agreement with experimental results of Carlsson et al. [10].
data for some PPO + H2 O systems at different polymer molecular weight and
temperatures
4. Conclusion
System Polymer r2 T (K) ARD (%)a Reference
weight
fraction The isopiestic method was used to obtain activities of water
for PPO400 + H2 O system at 293.15, 298.15, 303.15, 308.15,
PPO400 + H2 O 0.59–0.99 22.05 303.15 4.27 [11]
313.15 and 318.15 K. From these measurements, values of the
PPO400 + H2 O 0.59–0.99 22.05 323.15 5.23 [11]
PPO405 + H2 O 0.18–0.43 22.29 298.15 1.00 [29] vapor pressure and osmotic coefficient of solutions and actvity
PPO2000 + H2 O 0.96–0.99 110.35 303.15 34.80 [28] coefficient of solute and solvent were determined. It was found
that, by increasing temperature, increase of vapor pressure of

NP exp
|a −acal | PPO400 + H2 O solution is larger than those of pure water, which
a ARD% = 100 1,n
exp
1,n
, where NP is the number of experimental data
NP a1,n
n=1
show that the PPO becomes more hydrophobic with increasing
points. temperature. Also, it was shown that for a given polymer mass
172 R. Sadeghi, F. Ziamajidi / Fluid Phase Equilibria 249 (2006) 165–172

fraction vapor pressure depression for PEO400 + H2 O system is [2] D. Bedrov, C. Ayyagari, G.D. Smith, J. Chem. Theory Comput. 2 (2006)
larger than those for PPO400 + H2 O system. Furthermore, the 598–606.
slopes of the vapor pressure depression against polymer mass [3] C.D. Grant, K.E. Steege, M.R. Bunagan E.W.Jr., Castner, J. Phys. Chem.
B. 109 (2005) 22273–22284.
fraction show that, below weight fraction 0.8 of PPO, the solu- [4] Q. Wang, L. Li, S. Jiang, Langmuir 21 (2005) 9068–9075.
tion behavior is dominated by the hydrophobic hydration of the [5] J.S. Lettow, T.M. Lancaster, C.J. Glinka, J.Y. Ying, Langmuir 21 (2005)
PPO molecule, and above weight fraction 0.8 hydrogen bonding 5738–5746.
of water to the polymer is the dominant feature of solution behav- [6] O.V. Elisseeva, N.A.M. Besseling, L.K. Koopal, M.A. Cohen Stuart, Lang-
ior. Finally, the segment-based local composition Wilson model muir 21 (2005) 4954–4963.
[7] J. Jansson, K. Schillen, M. Nilsson, O. Soderman, G. Fritz, A. Bergmann,
was to correlate the experimental water activity data and the O. Glatter, J. Phys. Chem. B. 109 (2005) 7073–7083.
obtained model parameters were used for predicting the excess [8] J. Jansson, K. Schillen, G. Olofsson, R. Cardoso da Silva, W. Loh, J. Phys.
molar enthalpy of aqueous polypropylene oxide solutions. Chem. B 108 (2004) 82–92.
[9] R. Cardoso da Silva, G. Olofsson, K. Schillen, W. Loh, J. Phys. Chem. B
List of symbols 106 (2002) 1239–1246.
[10] M. Carlsson, D. Hallen, P. Linse, J. Chem. Soc. Faraday Trans. 91 (1995)
a activity 2081–2085.
B second virial coefficient [11] G.N. Malcolm, J.S. Rowlinson, Trans. Faraday Soc. 53 (1957) 921–
C coordination number 931.
E binary parameter in the wilson model [12] H. Vink, Eur. Polym. J. 7 (1971) 14111–14419.
gE excess molar gibbs energy [13] Z. Adamcova, Sci. Pap. Prague Inst. Chem. Technol. N2 (1976) 63–71.
[14] M. Herskowitz, M. Gottlleb, J. Chem. Eng. Data 29 (1984) 173–175.
H Binary parameter in the Wilson model [15] M. Herskowitz, M. Gottlleb, J. Chem. Eng. Data 29 (1984) 450–452.
HE excess molar enthalpy [16] M. Herskowitz, M. Gottlleb, J. Chem. Eng. Data 30 (1985) 233–234.
h enthalpy of interaction [17] C.A. Haynes, R.A. Beynon, R.S. King, H.W. Blanch, J.M. Prausnitz, J.
NP number of experimental data Phys. Chem. 93 (1989) 5612–5617.
OF objective function [18] L.R. Ochs, M. Kabiri Badr, H. Cabezas, AIChE J. 36 (1990) 1908–
1912.
p vapor pressure [19] J. Gaube, A. Pfennig, M. Stumpf, J. Chem. Eng. Data 38 (1993) 163–
r segment number 166.
R gas constant [20] H. Hasse, H.P. Kany, R. Tintinger, G. Maurer, Macromolecules 28 (1995)
T temperature 3540–3552.
V molar volume [21] C. Grobman, R. Tintinger, J. Zhu, G. Maurer, Fluid Phase Equilib. 106
(1995) 111–138.
w mass fraction [22] D.Q. Lin, Z.Q. Zhu, L.H. Mei, L.R. Yang, J. Chem. Eng. Data 41 (1996)
x mole fraction 1040–1042.
X effective mole fraction [23] D.Q. Lin, L.H. Mei, Z.Q. Zhu, Z.X. Han, Fluid Phase Equilib. 118 (1996)
241–248.
Greek letters [24] A. Eliassi, H. Modarress, G.A. Mansoori, J. Chem. Eng. Data 44 (1999)
52–55.
β dummy parameter [25] L. Ninni, M.S. Camargo, A.J.A. Meirelles, Thermochem. Acta 328 (1999)
γ activity coefficient 169–176.
φ segment fraction [26] D.Q. Lin, Y.T. Wu, Z.Q. Zhu, L.H. Mei, S.J. Yao, Fluid Phase Equilib. 162
Φ osmotic coefficients (1999) 159–170.
[27] R. Sadeghi, F. Ziamajidi, J. Chem. Thermodyn. 38 (2006) 1335–1343.
[28] J. Kim, E. Choi, K.P. Yoo, C.S. Lee, Fluid Phase Equilib. 161 (1999)
Subscripts 283–293.
I, J any species, polymer and water [29] M.T. Zafarani-Moattar, A. Salabat, J. Solution Chem. 27 (1998) 663–
i, j and k any species, segment and water 673.
n experimental points [30] A. Salabat, H. Dashti, K. Nasirzadeh, J. Chem. Eng. Data 49 (2004)
1 water 980–982.
[31] E. Colin, W. Clarke, D.N. Glew, J. Phys. Chem. Ref. Data 14 (1985)
2 polymer 489–610.
[32] J.A. Rard, R.F. Platford, in: K.S. Pitzer (Ed.), Activity Coefficients in Elec-
Superscript trolyte Solutions, CRC Press, Boca Raton, 1991, pp. 209–277.
cal Calculated value [33] G.S. Kell, J. Chem. Eng. Data 20 (1975) 97–105.
exp experimental value [34] A. Saul, W.J. Wagner, J. Phys. Chem. Ref. Data 16 (1987) 893–901.
[35] M.T. Zafarani-Moattar, F. Samadi, R. Sadeghi, J. Chem. Thermodyn. 36
E excess (2004) 871–875.
Wilson wilaon model [36] R.G. Gunninghame, G.N. Malcolm, J. Phys. Chem. 65 (1961) 1454–1456.
◦ pure water [37] N.J. Crowther, D. Eagland, J. Chem. Soc., Chem. Commun. 7 (1994)
839–840.
[38] N.J. Crowther, D. Eagland, J. Chem. Soc., Faraday Trans. 92 (1996)
References 1859–1862.
[39] J. Dudowicz, K.F. Freed, W.G. Madden, Macromolecules 23 (1990)
[1] R. Ganguly, V.K. Aswal, P.A. Hassan, I.K. Gopalakrishnan, S.K. Kul- 4803–4819.
shreshtha, J. Phys. Chem. B. 110 (2006) 9843–9849. [40] R. Sadeghi, J. Chem. Thermodyn. 37 (2005) 55–60.