Thermal and Rheological Studies

of Aqueous Solutions of PEG 400 and PEG

1500 Having Pharmaceutical Applications

R. Padmanaban, K. Venkatramanan, S. Girivel, K. Kasthuri,

A. Usharani and Roy Vellaichamy

Abstract Polyethylene glycol is formed by the interaction of ethylene oxide with

water, ethylene glycol or ethylene glycol oligomers. Acidic or basic catalysts are
used as catalysts in this reaction. Ethylene glycol and its oligomers are preferable as
a starting material instead of water because it allows the creation of polymers with a
low polydispersity. Polyethylene glycol has many desirable applications like an
anti-dusting agent in agricultural formations, dye carrier in paints and ink and mold
release agent, etc. Molecular interaction studies of PEG in various solvents are
reported by many researchers. It is proposed to determine the activation energy and
the molecular interaction properties of Polyethylene Glycol (PEG 400 and PEG
1500) in water for various concentrations ranging from 1 to 5 % at different tem-
peratures from 303 to 318 K in steps of 5 K from the knowledge of relative
viscosity which can be determined using a suitable viscometer.

1 Introduction

The material taken for the present analysis is Polyethylene glycol which has a lot of
applications in pharmaceutical preparations, cosmetics, medical devices and in the
metal casting process [1]. Thermodynamic properties of polymer solutions have
shown that ultrasonic velocity and its derived parameters provide much information
on molecular interactions, which are of utmost importance for processes involving
polymer production and their uses. Many reports [1–3] are there in the literature on

R. Padmanaban (&)
K. Venkatramanan
S. Girivel
K. Kasthuri
A. Usharani

Department of Physics, SCSVMV University, Kanchipuram 631561, India
e-mail: padhu.mphil@gmail.com
R. Vellaichamy
Department of Physics and Materials Science, City University of Hong Kong,
Kowloon, Hong Kong

© Springer International Publishing Switzerland 2017 723

J. Ebenezar (ed.), Recent Trends in Materials Science and Applications,
Springer Proceedings in Physics 189, DOI 10.1007/978-3-319-44890-9_58
724 R. Padmanaban et al.

ultrasonic studies of solutions of PEG in binary aqueous + non-aqueous solvent

systems. Activation energy is a term used to describe the minimum energy that
must be available for initiating a chemical process. For analyzing the properties and
interactions taking place in polymer-polymer systems, knowledge of rheological
properties is essential and viscometry is one of the efficient techniques for studying
the properties. A positive and attractive interaction enhances the viscosity of the
systems taken for this analysis. The effect of temperature in determining the vis-
cosity of polymers was reported by many researchers over a period of time [4–6]. In
the present proposal, it is planned to apply Arrhenius equation to dilute polymer
solutions. It has been reported by many researchers [7–9] that the concentration,
molecular weight, chain stiffness and coil expansion of polymers play a vital role
for the activation energy of flow. The pre-exponential term also depends on these
parameters. It is also observed that the variation between the activation energy of
the solution and the solvent is very much greater than that of the flexible chains.
Guadalupe Olayo et al. [10] have studied the electrical conductivity, activation
energy, and morphology of polythiophene synthesized by radio frequency resistive
plasmas. In the present proposal, aims to determine the activation energy and the
molecular interaction properties of Polyethylene Glycol (PEG 400 and PEG 1500)
in water for various concentrations ranging from 1 to 5 % at different temperatures
from 303 to 318 K in steps of 5 K from the knowledge of relative viscosity.
Various molecular interaction parameters such as free volume, intermolecular free
length, internal pressure and adiabatic compressibility are calculated and the results
are interpreted.

2 Materials and Methods

The polymers used for the present study (PEG 400 and PEG 1500, SPECTRA
Grade) are supplied by SOUTHERN INDIA SCIENTIFIC, Trichy. The polymers
PEG 400 and PEG 1500 are dissolved in double distilled water and the polymer
solutions are prepared for various concentrations (1, 2, 3, 4 and 5 %). A REMI
make magnetic stirrer operating at a rate of 1000 rpm is used for preparing the
polymer solutions. Ubbelohde Viscometer is used to determine the relative vis-
cosity of the prepared polymer solutions at different concentrations at 303, 308, 313
and 318 K. A RACER make digital stopwatch is used to measure the timings
(±0.01 s). The viscometer was kept in an electronically controlled thermostat
having a thermal stability of ±0.05 K for taking measurements at different tem-
peratures. Pycnometric method is employed to determine the density of the solu-
tions. A K-ROY electronic balance having an accuracy of ±0.001 g is used to
measure the mass of the liquid. A digital ultrasonic velocity meter (VCT-70A
model, VI MICROSYSTEMS) is used to measure the ultrasonic velocity.
Thermal and Rheological Studies of Aqueous Solutions … 725

The measurements were taken at a frequency of 2 MHz (accuracy ±0.1 m/s). The
ultrasound velocity measurements are taken at 303 K by circulating water from a
thermostat having a thermal stability of ±0.05 K.

3 Results and Discussion

3.1 Determination of Activation Energy

Viscosity measurements are taken for Polyethylene glycol (PEG 400 and PEG
1500) in aqueous solution in the concentration range from 1 to 5 % at different
temperatures from 303 to 318 K in steps of 5 K. Table 1 shows the variation of
relative viscosity against concentration for PEG 400 and PEG 1500 in water at
temperatures from 303 to 318 K. The results show that the relative viscosity
increases as concentration increases and the relative viscosity decreases with rising
temperature. The reason for this behavior may be due to the development of large
frictional force between the layers of the solution.
The Arrhenius expression which is valid for pure solvents and also for dilute
polymer solutions is give by Moore et al. [11] as mentioned below

g ¼ AeQ=RT ð1Þ

where A is the pre-exponential term with an activation entropy significance and Q is

the apparent activation energy of flow. The logarithm of this equation leads to a
straight-line type. Activation energy is obtained by plotting a graph between log-
arithm of relative viscosity and inverse of temperature for PEG (400, 1500).

Table 1 Relative viscosity and activation energy values of aqueous PEG

Compound Concentration Relative viscosity (10−3 Nsm−2) Activation
(w/v) (%) 303 K 308 K 313 K 318 K energy
(KJ mol−1)
PEG 400 1 1.0583 1.0512 1.0210 1.0132 2.4854
2 1.0731 1.0623 1.0321 1.0210 2.7790
3 1.0812 1.0731 1.0432 1.0306 2.6746
4 1.0934 1.0802 1.0614 1.0556 1.9284
5 1.1121 1.1050 1.0733 1.0690 2.2998
PEG 1500 1 1.0731 1.0593 1.0330 1.0296 2.3165
2 1.0851 1.0731 1.0451 1.0399 2.3871
3 1.0923 1.0851 1.0552 1.0431 2.5767
4 1.1256 1.1091 1.0762 1.0656 3.0106
5 1.1531 1.1321 1.0913 1.0876 3.2920
726 R. Padmanaban et al.

Fig. 1 Variation of activation energy against concentration of aqueous solutions of PEG

The variation of activation energy (Q) against concentration (C) of aqueous

solution of PEG 400 in water is shown in Fig. 1. In this system, it is observed that
the activation energy suddenly decreases for 2 % concentration. It is understood
that as polymer concentration increases the activation energy for the viscous flow of
polymer solution also increases and this is not observed in critical mixtures [12].
The reason for sudden decrease is that the activation energy for the viscous flow of
polymer solutions in poor solvent decreases with polymer concentration at high
dilution and this is ascribed to the temperature dependence of the limiting viscosity
number [13]. Figure 1 depicts the change in activation energy of aqueous solution
of PEG 1500 against concentration (C). It is observed that as concentration
increases the activation energy also increases, which reveals that more amount of
energy is required to move the molecules into the structure [10].

3.2 Density and Ultrasonic Velocity Studies

Figure 2 shows that the density of the polymer solutions taken for the study
increases with concentration. The reason for this increase is because of the addition
of more number of polymer chains with increase in the concentration of polymer
solutions. The molecular weight of the polymers is comparatively higher than that
of the solvents. This characteristic feature may also contribute to the increase in the
density of the solution.
Thermal and Rheological Studies of Aqueous Solutions … 727

Fig. 2 Variation of density against concentration of aqueous solutions of PEG

The variation of ultrasonic velocity (Fig. 3) against concentration indicates the

presence of strong solute-solvent interaction. As density increases, number of
particles in the given region also increases, which leads to quick transfer of sound
velocity and hence ultrasonic velocity increases with concentration.

Fig. 3 Variation of ultrasonic velocity against concentration of aqueous solutions of PEG

728 R. Padmanaban et al.

3.3 Molecular Interaction Analysis

It is observed that as concentration increases the adiabatic compressibility decrea-

ses. This indicates that the molecules may be closely packed and less ionic
repulsion exists between the molecules. This also reveals that the bond strength is
enhanced at higher concentration. The inverse behavior of adiabatic compressibility
with ultrasonic velocity is clearly observed. This reveals the existence of the sig-
nificant interaction between solute and solvent molecules. This indicates the for-
mation of complexes among the molecules. Table 2 shows that there is a decrease
in the intermolecular free length with increase in concentration. Due to dominant
repulsive force a weak molecular interaction is exhibited by the molecules at lower
concentration. Significant interaction exists at higher concentration. In view of
greater forces of interaction between solute and solvent molecules forming
hydrogen bonding, there will be a decrease in free length in the mixture. Free
volume is defined as the average volume in which the central molecule can move
inside the hypothetical cell freely without getting affected by the repulsion of
surrounding molecules. A reverse trend of viscosity with free volume is observed in
the present case. So it is understood that ultrasound velocity may be responsible for
the free volume of the polymer solutions taken for analysis than the viscosity of the
systems. Since the viscosity of the polymer is varied due to molecular interaction or
polymer salvation, same parameters may influence the free volume also. It is
observed that the free volume decreases with increase in internal pressure. The
molecular interaction of the liquid is understood from the knowledge of the internal
pressure of the liquid. As the concentration of polyethylene glycol increases the
internal pressure of the system also increases. This increase in the internal pressure
of the polymer may be due the presence of strong attractive force between the
polymer and solvent molecules.

Table 2 Various molecular interaction parameters of aqueous PEG

Compound Concentration Adiabatic Free length Free volume Internal
(w/v) (%) compressibility (10−11 m) (10−8 m3 mol−1) pressure
(10−10 m2 N−1) (109 atm)
PEG 400 1 4.0784 4.1905 1.4778 2.8072
2 4.0381 4.1697 1.4777 2.7916
3 4.0024 4.1512 1.4900 2.7692
4 3.9339 4.1156 1.5027 2.7480
5 3.8824 4.0885 1.4978 2.7376
PEG 1500 1 4.1020 4.2026 1.4416 2.8300
2 4.0522 4.1770 1.4493 2.8110
3 4.0204 4.1606 1.4631 2.7868
4 3.9706 4.1347 1.4292 2.7958
5 3.8971 4.0963 1.4114 2.8011
Thermal and Rheological Studies of Aqueous Solutions … 729

4 Conclusion

Different concentrations of aqueous solutions of polyethylene glycol (PEG 400 and

PEG 1500) are prepared. The relative viscosity is determined for various temper-
atures (303, 308, 313, and 318 K) for these samples. From these values, activation
energy is calculated. From Fig. 1, it is noted that there is a decrease in the activation
energy of the system taken for the study. From this, it is concluded that the acti-
vation energy for the viscous flow of polymer solution in a poor solvent decreases
with polymer concentration at high dilution and this is due to the temperature
dependence of the limiting viscosity number. But for PEG 1500, the activation
energy varies linearly. This reveals that as concentration increases more amount of
energy is required to move the molecules into the structure. From these systems, it
may be concluded that water is a poor solvent for PEG 400 and acts as a good
solvent for PEG 1500. Density and ultrasonic studies are done at 303 K. It is found
that the activation energy increases with increase in concentration for all the sys-
tems. Density and ultrasonic velocity are found to increase with an increase in
concentration. The presence of strong interaction between polymer and solvent at
higher concentrations is observed by analyzing the variation of molecular interac-
tion parameters with increase in concentration. This helps to analyse the effect of
concentration on the system taken for study.

Acknowledgements The authors acknowledge the financial support of SCSVMV University,

Enathur, Kanchipuram for carrying out this research work.

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