Indian Journ al of Chemistry
Vol. 41 A, April 2002, pp. 751-755
Partial molal volume and partial molal
compressibility of polyethylene
glycol in water
A K Puri , N K Soni*, Amit Pandey & Ashish K Sharma
Department of Chem istry, Uni ve rsit y of Allahabad,
Allahabad 2 11 002 , India
Received 14 Jllly 2000; re vised 3 1 Jllly 200 1
Using the ex perimental data of Gerecze [ACIISlica, 38 ( 1977)
51 Ion ultrasonic ve locity, de nsity and refractive index or aqueous
polyet hylene glyco l, the va lues of partial molal vo lume (<1'),
experimental slope (S v) and partial molal compressibility (<I>KO) at
differe nt temperatures, interac ti on coefficient (Q ), mo lal volume
of Vand's eq uati on at 20C (V) and mol ar refracti on (Rill) have
been calculated. Validit y of Va nd's equati on and molar refracti on
equati on for polyet hylene glyco l is disp layed. Temperature
dependence hydrati on nature of polyethylene glyco l has also been
di scussed.
In recent years, th ere has been considerable interest in
the solute-solvent interactions of dilute solutions of
non-electrolytes. Enhanced stabilisation of water
structure around the solute molecule in the form of
clusters or cages in the ethylene-glyco l water system
has been disc ussed by Glew l . Abnormalities in many
thermodynamic behaviour including partial molal
vo lume and partial molal compressibility were
discussed by Frank and Ives 2. According to Hioland 3,
parti al molal vo lume (<Pvo) and partial molal com-
pressibility (<PKO) of polyfunctional alcohols havin g
several hydroxy l groups, are capable of hydrogen
bonding to water molecul e. Adi abatic and isothermal
apparent molal compressibilities of secondary
alcohols and ethers in water were reported by Cabini4.
Viscosity of non-electrolyte solutes in water was
anal yzed in the light of Vand 5 , Moulik 6 and Thomson7
. AI exander el a , .8- 10 propose d an equatIon
. to
equatIons.
describe the viscos ity B-coefficient for dilute so lu-
tions of non-electro lytes in water. Islam et al. 11
reported B-coefficient and apparent molal volume at
infinite dilution (<Pvo) for tetraalkyl halides in ethyl ene
gycol-water mixture. RecentlyI 2-16, ultrasoni c veloc-
ity, density and viscosity data have been used sati s-
factoril y to study vari ous types of interactions in
multicomponent systems contammg some very
important bio molecules and ions.
In the present note, we present the results of calcu-
lations of parti al molal volume (<Pvo) and parti al molal
compressibility (<PK 0), interaction coefficient (Q),
molar volume of Vand's equation (V) and molar
refraction (Rm) of aqueous polyethylene glyco l
solutions using the volumetric, ultrasonic, viscometric
and refractometric data of Gerecze l7 .
Equations used
Apparent molal vo lume, (<Pv), has been calculated
using the relation
1000 (d o - d) M
v = +- ... (I)
m.d o do
where do and d are the density of solvent and soluti on
respectively, and other sy mbol s have their usual
notation .
The apparent molal volume (<Pvo) at infinite diluti on
has been obtained using equ ation (2).
... (2)
Isentropic compressibility , (Ks) has been obtained
from sound velocity (u) and density (d) data using the
relation :
... (3)
Apparent molal compressibility, (<PK) tS computed
from the equation:
.. . (4)
where Ks and Ks.o are the isentropi c compressibility
coefficients of solution and solvent respective ly.
Apparent molal compress ibility at infinite dilution ,
(<PKO) has been obtained from ex pression,
... (5)
Refractive index data have been used for obtaining
the mol ar refraction (Rill) using th e relation
RIll=(no 2- lIn D2+ I) + Mid ... (6)
where no is the index of refracti on (sod ium D line)
and M is the molec ul ar weight of polyethylene glyco l.
752 INDIAN J CHEM , SEC A, APRIL 2002

Table I-Apparent molal volume, (<I>v), apparent molal compressibility, (<I>K), and isentropic compressibility, (f3s), of
polyethylene glycol in water at 20, 25 and 30C
Molec ular Conc. <l>v x 10
3
<l>K X IO
J
f3s X 10- 12
(mol kg- I) (011 mo)'l) 3
(cm mol-I bar- I) Cll1 2 dyne- I
Weight

At 20C
20,000 0.0032 16.45 -7 .720 43. 07
0.0020 16.63 - 12.170 43.88
0.0016 17.03 4.940 44.45
0.0007 19.79 98 .900 45 .64

6,000 0.022 4.85 1.800 41.55

0.013 4.94 -7 .350 42 .68
0.010 4.98 -1.140 43 .27
0.0053 5.14 -2 .000 44.27

2,000 0.100 1.61 -0.090 39.19

0.075 1.63 0.880 41.21
0.050 1.66 2.010 43 .02
0.025 1.68 -0.560 43 .61

1,000 0.340 0.81 0.033 35.83

0.250 0.80 -0.301 37.32
0.170 0.82 0.366 39.50
0.062 0.83 0.216 43.48

Al 25C
20,000 0.0032 16.31 -10.82 42.34
0.0020 17.02 -18.01 43.04
0.0016 17.07 -8.86 43.55
0.0007 19.57 63 . 10 44.69

6,000 0.0220 4.91 -3.02 39.90

0.130 4.97 -5.87 41.43
0.0100 5.05 -7.22 41.97
0.0053 5.15 -14.60 42.92

2,000 0. 1000 1.63 -0.55 38. 11

0.0750 1.01 -1.82 40.44
0.0500 1.66 -0.35 41.27
0.0250 1.68 1.47 43.4 !

1000 0.340 0.8! -0.27 34.43

0.250 0.84 -0.42 36. 19
0.170 0.82 -0.15 39.16
0.062 0.85 0.46 42.65

Al 30C
20,000 0.0032 16.34 -30.39 40.95
0.0020 16.75 -47.13 41.72
0.0016 17.10 -31.72 42 .39
0.0007 18.77 48.43 43 .78

(Comd)
 NOTES 753

Table I-Apparent molal volume, (<!>v), apparent molal compressibility, (<!>K), and isentropic compressibili ty, (~s), 01"
polyethylene glycol in water at 20,25 and 30C-Contd
~sX 10-
12
Molecular Conc. <!>vx 10) <!>K X 10.1
Weight (mol r l) (mlmorl) (cm) mol - I bar- I) cm 2 dyne- 1

At 30C

6,000 0.022 4.89 -7.32 38.34

0.013 5.00 -10.38 40.11
0.010 5.05 -15.64 40.39
0.0053 5.12 -23.75 41 .67

2,000 0.100 1.64 -0.75 37.22

0.075 1.66 0.76 39.70
0.050 1.66 -2 .22 39.65
0.Q25 1.69 -2.35 41.71

1,000 0.34 0.82 -0.28 33.71

0.25 0.81 0. 17 35.02
0. 17 0.82 -2. 17 35.45
0.62 8.84 0.20 42.00

Table 2:-Apparent molal volume at infinite dilution, (<!>vo) and Table 3-Apparent molal compressibility at infinite diluti on,
experimental slope, Sv of polyethylene glycol at different (<!>KO) of polyethylene glycol at differe nt temperatures and
temperatures and concentrations co ncentrati ons
Molecular T Conc. <!>VOx 102 Sv Molecular T Concentration <!>KOX 10)
weight (mol kg- I) (ml mor l) weight (0C) range (cm' mol bar- I)

20,000 20 0.0007 17.86 0.71 20,000 20 0.0007m III

25 to 17.96 0.90 25 to 78
30 0.0032 19.25 1.80 30 0.0032m -56

6000 20 0.OO53m -3 .5
6000 20 0.0053 5.28 0. 16
25 to -I I
25 to 5.27 0.33
30 0.022m -25
30 0.022 5.45 0.35

2000 20 0.Q25 1.68 0.10 2000 20 0.025m -3 .0

25 to 1.98 0.50 25 to 4.3
30 0.1 2.07 0.55 30 O.lm 4.8

1000 20 0.062 0.241 1.20 1000 20 0.062m 0.80

25 to 0.303 1.25 25 to 1.60
30 0.34 0.313 1.37 30 0.34m 2.15

Results and discussion
In Table 1, values of apparent molal volume (<Pv),
apparent molal compressibility (<PK) along with the
values of isentropic compressibility (~s) have been
recorded for polyethylene glycol in water at 20, 25
and 30C. The values of partial molal volume (<Pvo)
for the systems under present investigation are
presented in Table 2 along with the experimental
slope, Sv. The values of partial molar compressibility
(<PKO) are recorded in Table 3. The values estimated
for interaction coefficient, Q, molar vo lume of Yand's
e
euqation (V), at 20 0 are recorded in Table 4.
It is obvious from Table 2, that the values of appar-
ent molal volume at infinite dilution (<Pvo) are gradu-
ally decreasing with increase in concentration . It is
concluded that, polyethylene glycol is more hydrated
754 INDIAN J CHEM, SEC A, APRIL 2002

at hi gher temperatures than at lower temperatures. Table 5-Molecular refraction of polyethylenc glyco l- Col/ld
Thus, both temperature and concentration are respon-
Molecular Conc.
sible for the solute-solvent interaction with respect to " Rill
weight (mol kg-I)
molecular weight of solute. On the other hand, Sv
values considerably increase with temperature but the
20,000 20 0.0007 41 42.84 64.36
trend is not the same in the entire range of concentra-
25 41 4 1.11 64.35
tion .
30 41 38.53 64.33
It IS evident from the recorded values, Sv are
hi gher at hi gh temperatures, suggesting strong solute- 6,000 20 0.022 1267.33 35.59
solute interaction . rt is evident from Table 3, that 25 1269.02 35.62
va lues of <PK 0 increase with temperature and decrease 30 1268 .61 35.6 1

Table 4- The coefficicnt Q and molar vo lume V of Vand's 6,000 20 0.0130 1257.16 35.45
viscosity equati on at 20C 25 1257.67 35.46
30 1286.31 35.86
Molecular Conc. Q V
we ight (mol kg l ) 6,000 20 0.0102 1251.54 35 .38
20,000 0.0032 0.559 125.38 25 1252. 58 35.39
0.0020 137.49 30 1251.65 35 .37
0.0016 141.72
152.0 1 6,000 20 0.0053 1245.29 35.28
0.0007
25 1245.02 35.28
6,000 0.022 0.5996 31.76 30 124 1.91 35 .24
0.013 38.07 2,000 20 0.1000 427.40 20.67
0.010 40.58 25 427.70 20.68
0.0053 46.29 30 427.70 20.68
h
J

2,000 0.100 0.61 4.38 2,000 20 0.0750 42 3.80 20.58

0.075 4.59 25 424.20 20.59
0.050 5.06 30 424.30 20.59
0.025 5.48
2,000 20 0.0500 419.90 20.49
1000 0.34 1.23 1.20
25 419.90 20.49
0.25 1.40
30 419.70 20.48
0.17 1.67
0.062 2.19 2,000 20 0.0250 4 16. 10 20.39
25 4 15.90 20.39
Table 5-Molecular refraction of polyethylene glycol 30 4 15.90 20.39
Molecular T Conc.
1,000 20 0.340 220.25 14.84
weight (0C) (mol kg- I)
25 220.10 14.83
20,000 20 0.0032 4174.20 64.60 30 220.20 14.84
25 4169.26 64.56
30 4169.22 64.57 1,000 20 0.2500 2 16.00 14.69
25 2 16.00 14.69
20,000 20 0.0020 4142.29 64.36 30 2 15.70 14.68
25 4 155.95 64.46
30 3814.35 61.76 1,000 20 0.17 2 12.90 14.59
25 2 12.80 14.59
20,000 20 0.0016 4168.67 64.56 30 2 12.80 14.58
25 4148.94 64.40
30 4149.17 64.41 1,000 20 0.0620 208.46 14.43
25 208 .61 14.44
(Con/d) 30 208.55 14.44
 NOTES
sharply with increase in concentration. The values of
<PKO are highly influenced by the molecular size of
solute. In the present investigation , negative values
for <PK 0 can be associated wi th structure promoti ng
ability of solvent, i.e., loss of structure compressibility
of water on account of increase in population of four
bonded water molecule. Critical evaluation of
physico-chemical data leads to the conclusion that
there must be reinforcement of water structure in the
neighbourhood of alcohol molecule in dilute so lution .
It is seen from Table 4 that viscosity interaction
coefficient, Q, is constant for all ranges of concentra-
tion with respect to molecular size of solute molecule.
It is concluded, therefore, that hydrophobic interac-
tions are mainly dependent on size of polyethylene
glycol. The stability of solvent water increase with
decrease in molecular size of polyethylene glycol. On
the other hand, molar volume, (V) decreases with
increase in polyethylene glycol concentration and can
be ascribed to the decrease in hydrophobic interaction
between water dipole and ion of polyethylene glycol
with respect to molecular size.
It is evident from Table 5 that the molar refraction,
Rnll values increase with increase in the molecular
weight of polyethylene glycol but is almost constant
between the temperature range 10C and 30C.
755
Acknowledgement
The authors are thankful to Prof. J. D. Pandey
(Former Head) and Dr Ranjan Dey, Department of
Chemistry, University of Allahabad, for valuabl e
suggestion s.
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