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IOSR Journal of Applied Physics (IOSR-JAP)
e-ISSN: 2278-4861.Volume 7, Issue 1 Ver. II (Jan.-Feb. 2015), PP 70-79
www.iosrjournals.org
DOI: 10.9790/4861-07127079 www.iosrjournals.org 70 | Page
Dielectric Relaxation And Molecular Interaction Studies Of PEG
With Non-Polar Solvents Using TDR Technique
D.J.S. Anand Karunakaran *1
, T.Ganesh2
, M.Maria Sylvester3
, Pravin Hudge4
,
A.C. Kumbharkhane4
1
And 3. Post graduate & research department of physics, bishop heber college, tiruchirapalli,
Tamil nadu– 620 017
2
Post graduate & research department of physics, rajah serfoji government college, thanjavur
Tamil nadu – 613 005.
4
School of physical sciences, swami ramanad teerth marthwada university, nanded, ms – 431606.
Abstract: The complex dielectric permittivity measurements of Poly Ethylene Glycol (PEG) HO[CH2-CH2-
O]n H of molecular weight 400 (n=9)g mol−1
with carbon tetra chloride(CCl4), benzene and 1,4-dioxane
mixtures has been carried out at different concentration in mol/lit at 25o
C and in the frequency range of 10 MHz
to 30 GHz using Time Domain Reflectometry (TDR). The least squares fit method has been used to obtain the
static dielectric constant, relaxation time, and Bruggeman factor for binary mixtures. The Kirkwood–Frohlich
theory is applied to compute the dielectric constant for the mixtures. It adequately reproduces the experimental
values of static dielectric constants for the binary mixtures. The excess parameters confirm that the
heteromolecular hydrogen bonding interaction between alcohol-alcohol and alcohol-CCl4, benzene and 1,4-
dioxane pairs very significantly in the mixtures. The Bruggeman model for the nonlinear case has been fitted to
the experimental dielectric data for the mixtures.
Keywords: dielectric relaxation, time domain reflectometry, ethylene glycol.
I. Introduction
The dielectric properties of a medium is measured as a function of frequency in Dielectric
spectroscopy(DS). It is based on the interaction of an external field with the electric dipole moment of the
sample, often expressed by permittivity. The Dielectric Spectroscopy is especially sensitive to interference
polarization and intermolecular interactions. The properties between individual constituents of complex
material, characteristic of bulk properties and dielectric relaxation studies of various surfactants in aqueous
solutions studied using TDR [1-3].
In low frequency, the measurement of conductive systems was strongly limited due to electrode
polarization. To determine various relaxation parameters on dielectric spectrum over a wide frequency range,
one step pulse (Time window) method is used. The successful development of Time Domain Spectroscopy
(TDS) method and [4-8]Broad Band Dielectric Spectroscopy(BDS) have radically changed the attitude towards
DS making it an effective tool for investigation of solids and liquids on the macroscopic, microscopic and
mesoscopic levels.
Dielectric relaxation studies are very useful in understanding the structure of polymers. The properties
of chemically homologous series of polymer molecule are of special interest because changes in properties are
related to chain length and temperature and very useful to study the structural properties of polymers. Poly
Ethylene Glycol (PEG) is of great significant in industry, in biomedicine, cosmetics, food additives and
plasticizer. The general chemical formula of PEG is HO(CH2CH2O)nH, where n is the number of repeat units.
The dielectric relaxation study with a variation in chain length is impartment in binary system to study the effect
of molecular dynamics and shape of the dielectric relaxation curve in the room temperature. Low molecular
weight polymers have good solubility in polar and non polar solvents. As oxygen atoms and OH groups are
present in the molecular chain and at the ends of the chain due to which these molecules have several hydrogen
bonding giving rise to several confirmations in non polar mixtures. Extensive experimental attempts [9] have
been made to study the absorption behavior of PEG molecules and their oligomers at radio waves and
microwaves to understand their dielectric behavior. Earlier, the dielectric and thermodynamic properties of
Polyethylene glycols have been studied to know the effect of chain length and the variation of temperature on
the configuration of PEG by knowing the configuration of Polyethylene oxide (PEO) chain by measurements of
NMR spectra [10-12] , IR spectra [13,14], X-ray diffraction studies [15], the dipole moments [16] , dielectric
loss [17-19] and by theoretical determination of energies [16,20] associated with rotational isomeric state about
skeletal bonds of the molecules of PEO, its oligomers and polymers.
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 71 | Page
The dielectric constant is one of important physicochemical properties of the mixed solvents, which
enhance most of the biological, pharmaceutical, chemical, physical, analytical, laboratory industrial application
[21]. The dielectric study of PEG on addition of dioxane provides information about breaking of molecular
structure in the systems. In binary mixtures of PEG with benzene and CCl4 the hydroxyl groups are present on
the terminal carbon atom and neighboring carbon atom, therefore the strong intermolecular interaction, possible
through hydrogen bonds, results in specific dynamics properties compared to PEG with 1,4- dioxane. Dielectric
characterization has great potential in studying the H-bond interactions: dipolar alignments, hydrogen bond
connectivity, and stoichiometric ratio of stable adduct formation in mixed solvents [21-23]. Crossely et al. [24]
have examined the dielectric permittivity and loss for a series of glycols. It is observed that the relaxation times
for the glycols are almost independent of alkyl chain length. The study of dielectric relaxation in glycol
mixtures, a correlation between the PEG and non-polar solvents obtained from the values of the relaxation time
and the number density of molecules. This can be interpreted as an indication that only one hydroxyl group in
the PEG is active in the main relaxation process. This implies that the other end of the PEG, the ethylene
molecule remains “anchored” to another molecule by the hydrogen bond. This reduces the flexibility at the
molecular level leading to a slower relaxation than in normal glycols.
Main purpose of this study is to understand the dielectric behavior of PEG in terms of hydrogen bond
and modification of hydrogen bonding due to presence of other non-polar molecules. In the present work
dielectric measurements of the mixtures of PEG with benzene, CCl4 and 1, 4-dioxane solvents using TDR
method are reported. The complex dielectric permittivity in the frequency range of 10 MHz to 30 GHz has been
determined. The static dielectric constant, dielectric loss, Bruggeman factor, Kirkwood correlation factors,
excess dielectric permittivity, relaxation time have been determined for this binary mixtures at 25o
C.
II. Experimental
2.1. Materials
The poly(ethylene glycols) of number average molecular weight 400 g/ mol is obtained from Sigma
Aldrich India. Benzene, CCl4 and 1,4 Dioxane were obtained from Merck India Pvt. Ltd., and were used to
prepare combination of binary mixtures without further purification. The dielectric permittivity ε′ and dielectric
loss ε″of pure liquid PEG's binary mixtures at emperatures 25°C were measured using TDR employed in the
frequency region 10 MHz to 30 GHz. The detailed analysis and procedures of the TDR system are explained
below. The mole fractions of the mixture constituents were determined by using their individual volume in the
mixture, the room temperature density and the molecular weight.
2.2. Measurements and Data Analysis
The complex permittivity spectra were studied using Time Domain Reflectometry (TDR) method [25,
26]. The basic TDR setup consists of broad band sampling oscilloscope, TDR module and coaxial transmission
line. The Tektronix DSA8200 sampling oscilloscope with 30 GHz bandwidth and TDR module 80E08 with step
generator unit was used. A 200 mV step pulse with 18 ps incident pulse and 20 ps reflected pulse time and 200
KHz repetition rate passes through coaxial 50 Ω lines. All measurements are carried out in open load condition.
Sampling oscilloscope monitors changes in step pulse after reflection from sample. Reflected pulse without
sample R1 (t) and with sample RX (t) were recorded in time window of 5 ns and digitized in 2000 points.
Temperature of the sample was controlled electronically within ±1°C.
The step pulses recorded without sample R1 (t) and with sample RX (t) were subtracted and added to get
(t)]R(t)[R=p(t) x1 (1)
(t)]R+(t)[R=q(t) x1 (2)
The complex reflection coefficient ρ*(ω) over a frequency range of 10 MHz to 30 GHz were
determined as follows:
)
)
)
jwdq(ω
cp(ω
(ωρ  (3)
where p(ω) and q(ω) are Fourier transforms of p(t) and q(t) obtained using summation and Samulon methods
[27] respectively, c is the velocity of light, ω is angular frequency and d is effective pin length (0.09 mm).







 



 βα
0 ])(JωJ+[
)ε(ε
+ε=(ωε
1
0
1
) (4)
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 72 | Page
The complex permittivity spectra ε*(ω) is obtained from reflection coefficient spectra ρ*(ω) by
applying the non – linear least square fit method suggested by Cole [25, 26]. The frequency dependent complex
permittivity spectra ε*(ω) of PEG-400 with their respective binary mixtures of benzene, CCl4, and 1,4, Dioxane
for different concentrations in liquid state at temperature 25°C are shown as real part (ε') and imaginary part (ε"
). It has been found that ε0, ε', ε" and ε∞ are the linear functions of the concentration of binary mixture solute in
dilute concentrations used for analysis of dielectric relaxation data and the values are recorded in Table.1. It is
also found that the variations in relaxation time τ, gf and geff
values in binary mixtures are also calculated in
various non-polar solvents. The Kirkwood correlation factor provides useful information regarding the
orientation of dipoles. The dielectric constant can be used to calculate Kirkwoood correlation factor g defined in
general by
γz+=g cos1 (5)
where z is the average number of nearest neighbors and γ is the angle between the dipole moments of the
neighboring molecule, Kirkwood correlation factor is greater than 1 are indicative of a tendency towards parallel
alignment of dipoles, values less than 1 are obtained when anti parallel alignment is favored and a value unity is
expected when orientational ordering is absent.
III. Results And Discussion
The complex permittivity spectra (real (ε′) and imaginary (ε″)) as a function of log frequency (GHz) at
25°C for Poly (ethylene glycol) with benzene, CCl4 and 1,4,dioxane for various concentrations are shown in
Fig.(1a - 3b), and the Variation of excess permittivity (ε∞), dielectric permittivity(ε′), , static permittivity
(ε0),relaxation time (τps) and dielectric loss (ε″) verses concentration in mol/lit at 25 °C for Poly (ethylene
glycol) having molecular weight 400gmol−1
at 25 °C with beneze,CCl4, 1, 4, dioxane are shown in Fig.(4a - 4e)
respectively. Both static dielectric constant and relaxation time increases with increase in concentration. The
frequency dependence of the complex dielectric permittivity and the excess properties are reported in Table.1.
The Kirkwood correlation factor g [28] provides the information regarding the orientation of the
electric dipoles. For the pure liquid polymer, the Kirkwood correlation factor g may be obtained by the
expression





 


2
0
002
2
2ε
4ππN
9
)ε+(ε
)ε+)(ε(εkTM
=gμ (6)
where, μ is the dipole moment, ρ is density at temperature T, M is the molecular weight, k is
Boltzmann constant, N is Avogadro's number, ε0 is static permittivity and ε∞ is the dielectric permittivity at high
frequency, often represented by the square of the refractive index (ε∞=n2
D). In associating molecules, the
molecular relaxation time is affected by the intra and intermolecular hydrogen bonding. The departure of the
Kirkwood correlation factor g from unity is a measure of the extent of intermolecular hydrogen bonding. For the
molecules with parallel dipole moments g will be greater than unity, while for anti-parallel dipole alignment g
will be smaller than unity. To examine the effect of intermolecular association on the dielectric relaxation time
of these molecules, the values of Kirkwood correlation factor g have been determined.
We have assumed that the mixture can be represented by one correlation factor geff
as follows:
=
)ε+)(ε(ε ii
0i
0i0i
9ε
2ε 
  eff
gX
M
ρμ
+X
M
ρμ
kT 







 1
2
2
22
1
1
1
12
1
9
4ππ
(7)
where 1 and 2 stand for PEG and non-polar solvent, XAis the volume fraction of PEG. The value of geff
> 1 indicates average parallel orientation of electric dipole in a molecule. It can be seen that as PEG is added in
non-polar solvents at regular steps in the mixture the value of geff
increases is shown in Fig.6. We also assume
that correlation factors of PEG and non-polar solvent molecules are affected by the same amount gf in the
mixture [29]. The Kirkwood–Frohlich equation for the mixture can be written as
=
)ε+)(ε(ε ii
0i
0i0i
9ε
2ε 
  gfX
M
ρμg
+X
M
ρμg
kT 







 1
2
2
22
2
1
1
1
12
1
1
9
4ππ
(8)
The Kirkwood correlation factors g1, g2 for individual species are modified by assuming for PEG –
non-polar solvents mixture that two kinds of intermolecular hydrogenbonds exist. One is the hydrogen bond
between the PEG - PEG molecules; another is the hydrogen bond between the PEG – non-polar solvent
molecules. These new correlations (g1and g2) are described by the relation as follows [30]:
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 73 | Page
1
2
121211111 coscos1
μ
μ
γZ+γZ+=g (9)
2
1
21212 cos1
μ
μ
γZ+=g (10)
where Z11, Z12 and Z21 are the average number of particles forming the hydrogen bond with PEG–PEG, PEG–
non- polar solvents, and non-polar solvents–PEG pairs, respectively. γ11 and γ21 are the angles between the
neighbouring dipoles of PEG and non-polar solvents molecules. The values of g1 and g2 depend on the
concentration of non-polar solvents in binary mixtures. The values of geff
and gf for PEG– non-polar solvents
mixture are reported in Table 2. The observation shows that the g values are greater than unity in all these binary
systems, which leads to the conclusion that the molecules associate to form multimers with parallel dipole
moments. Dielectric measurements in the megahertz to gigahertz range are very important for investigating
molecular dynamics of polymers, especially in solution state. One empirical relation, the Kohlrausch- Williams-
Watt (KWW) function, has considerable use not only for the dielectric relaxation behavior of liquid polymers
but also for the other polymer relaxation phenomena including volume and enthalpy relaxations, NMR and
dynamical relaxations, Quasi elastic light scattering, small angled relaxation scattering, transient optical
relaxation and time dependent fluorescence depolarization. Dielectric behavior of polymer at a frequency region
higher than 100 MHz has not been examined satisfactorily. In case of liquid polymers the dielectric
measurements in the higher frequency studies are very scarce. In general, polar polymers in dilute solutions of
non-polar solvent show an absorption peak at a frequency between 100 MHz and 2 GHz, if they have dipolar
component perpendicular to their chain contour [31]. Frequency obtained from TDR measurements peak does
not depend on the molecular weight of the polymer chains [32]. Poly ethylene glycol shows the dielectric
relaxation process in polar and non-polar solutions in the gigahertz region [33, 34]. The static permittivity of
mixture with volume fraction of solute is given by Bruggeman mixture formula [35]
3/1
0m
01
0201
020m








ε
ε
εε
εε
=fB (11)
It can seen from Fig.(5a - 5c) that fB is not a linear function of PEG volume fraction as predicted by Bruggeman
equation. The Bruggeman equation may be modified for binary liquid [36] as follows;
3/1
0m
01
0201
020m








ε
ε
εε
εε
=fB (12)
  AA X)X(aa= 11  (13)
where fB is the Bruggeman dielectric factor. The εom, ε01, and ε02 are the static dielectric constant
corresponding to mixtures, PEG with benzene, CCl4 and 1,4-dioxane respectively, XA is the volume fraction of
PEG. From the above equation, a linear relation is expected from a plot of fB versus XA . In this equation, volume
fraction XA is changed by a factor a−(a−1)XA of the mixture; for a = 1 it corresponds to Bruggeman equation.
The value of a can be determined by least squares fit method and is found to be 1.29, 1.16 and 1.65 for the
binary systems respectively, its deviation from unity indicates the molecular interaction in the mixture.
IV. Conclusion
The dielectric relaxation parameter for PEG-400 with their respective binary mixtures of benzene,
CCl4, and 1,4, dioxane for different concentrations in liquid state has been measured using TDR method in the
frequency range 10 MHz to 30 GHz at 25o
C. The dielectric constant for the mixtures can be explained using
hydrogen-bonded model by assuming the formation of hydrogen bonds between solute-solute and solute-solvent
pairs. The orientation correlations between neighbouring molecules due to hydrogen bonding interaction are
determined in terms of Kirkwood factors. A modification in the Bruggeman equation provides a better
description of dielectric behavior in the mixtures. The study shows the influence of varying chain length on the
molecular size, shape, dielectric relaxation and structural properties of the binary system. At the relaxation
frequency the oscillation of the applied field becomes very fast for the molecules to have time to fully rotate. As
compared to relaxation time of pure liquid, the relaxation time of binary mixtures is higher which suggest that
the formation of complexes or presence of association in unlike molecules, which gives an idea about the
behavior of dielectric constant and relaxation time with respect to mixture compositions. The gf and geff
values
are found to be greater than unity shows the molecules are with parallel dipole moment and confirm that in these
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 74 | Page
binary systems the dipolar orientation has an activated state and more ordered. It also suggests that there is more
hindrance to the rotation of the molecule clusters in binary mixture in comparison with the rotation of their
homogeneous clusters. This also supports the conclusion drawn from the positive values of relaxation time. The
proper choices of reference liquids for calibration are very useful to keep the errors in the values of these
dielectric parameters within the desired limit.
References
[1]. Ganesh, T, Sabesan, R, Krishnan, S, J. Mol. Liq., 128 (2006) 77.
[2]. Ganesh, T, Balamurugan, D, Sabesan, R, Krishnan, S, J. Mol. Liq., 123 (2006) 80.
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Chem, 79(1975)1459.
[5]. Cole, R. H. , Evaluation of dielectric behavior by Time Domain Spectroscopy-II complex permittivity, J. phys.Chem., 79(1975)
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[6]. Cole, R. H., Berberian, J. G, Mashimo, S, Unryssik, G, Brnins, A and Tombari, E Time Domain reflection methods for dielectric
measurements to GHz. J. Appl. Phys, 66(1989) 793.
[7]. Feldman, Y. D and Levinin, V. V, obtaining the dipole correctional function from TDS data directly in the time domain,
Chem.Phys.letters 85(1982)528.
[8]. Kumbharkhane, A. C, Shinde, M. N, Mehrotra, S. C, Oshiki, N, Shinyashiki, N, Yagihara, S and Sudo, N, J. Phys. Chem. A 113,
(2009) 10196–10201.
[9]. Stockmeyer W.H., Pure. Appl. Chem. 15(1967)539.
[10]. Harmann, G. Weill, G, Macromolecules 8 (1975) 171.
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[13]. Kuroda, Y, Kubo, M, Journal of Polymer Science 26 (1957) 323.
[14]. Panov, V. P, Ovsepyan, A. M, Kobyakov, V. V,Zhbankov, R. GJournal of Applied Spectroscopy 29 (1978) 803.
[15]. Takahashi, Y, Tadokoro, H Macromolecules 6 (1973) 672.
[16]. Rossi, C, Magnasco, V, Journal of Polymer Science 58 (1962) 977.
[17]. McCrum, N. G, Read, B. E, Williams, G, Anelastic and Dielectric Effects in Polymeric Solids, John Wiely and Sons, New York,
1967.
[18]. Porter, C. H, Boyd, R. H, Macromolecules 4 (1971) 589.
[19]. Arisawa, K, Tsuge, K, Wada, Y, Japanese Journal of Applied Physics 4(1965) 138.
[20]. Mark, J. E, Flory, P. J, Journal of the American Chemical Society 88 (1966) 3702.
[21]. Sudo, S. Shinyashiki, N and Ygihara, S. J. Mol. Liq.90, (2001) 113–120.
[22]. Moumouzias, G, Panopoulos, D. K, and Ritzoulis, G, J. Chem. Eng. Data 36(1), (1991) 20–23.
[23]. Papanastasiou, G. E and Zlogas, I. I, J. Chem. Eng. Data3 7, (1992) 167–172.
[24]. Crossely, J, Can. J. Chem. 56, (1978) 352–354.
[25]. Cole, R. H, Berbarian, J. G, Mashimo, S, Chrysikos, G, Burns, A, Tombari, E, Journal of Applied Physics 66 (1989) 793.
[26]. Kumbharkhane, A. C, Puranik, S. M, Mehrotra, S,.C, Journal of Chemical Society Faraday Transactions 87 (1991) 1569.
[27]. Hager N. E, III, The Review of Scientific Instruments 65 (1994) 887.
[28]. Oster, G, Kirkwood, J, G. Journal of Chemical Physics 11 (1943) 175.
[29]. Kumbharkhane, A. C, Puranik, S. M, and Mehrotra, S. C, J. Mol. Liq. 51(3–4), (1992) 261–277.
[30]. Luzar, A and Stefan, J, J. Mol. Liq. 46, (1990) 221–238.
[31]. Stogermorger, W.H., pure. Appl. Chem 15 (1967), 539.
[32]. Mashimo. S, Macromolecules 9 (1967), 91.
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[34]. Joshi, Y. S,. Kumbharkhane, A. C Journal of Molecular Liquids 161 (2011) 120–124
[35]. Bruggeman, D. A. G, Ann. Phys. (Leipzig) 24, (1935) 636–664.
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Table.1 Dielectric parameter of PEG binary system of various concentration at T=250
C
mol/lit    ps 
0.1 2.01 2.13 2.12 14.84 0.008
PEG - 0.3 2.05 2.28 2.34 16.31 0.009
BENZENE 0.5 2.08 2.41 2.54 18.78 0.183
0.7 2.18 2.48 2.70 21.21 0.216
0.9 2.19 2.57 2.86 22.45 0.278
0.1 1.96 2.21 2.23 14.55 0.043
PEG - CCl4 0.3 2.03 2.29 2.50 15.1 0.065
0.5 2.05 2.37 2.53 17.65 0.154
0.7 2.12 2.45 2.67 19.12 0.191
0.9 2.14 2.53 2.90 21.2 0.262
0.1 2.01 2.29 2.31 10.34 0.203
PEG - 0.3 2.11 2.44 2.49 10.72 0.290
DIOXANE 0.5 2.28 2.57 2.65 10.82 0.350
0.7 2.37 2.66 2.78 11.31 0.433
0.9 2.44 2.76 2.88 11.97 0.528
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 75 | Page
Table.2 Effective correlation factor and correlation factor of PEG with various volume fractions
vol. fr. solute geff
gf
0.038 1.67 1.00
PEG-BENZENE 0.099 2.36 1.22
0.153 3.33 2.14
0.200 3.94 2.72
0.242 4.24 3.19
0.038 1.39 1.00
PEG - CCl4 0.099 3.01 2.48
0.153 4.36 2.64
0.200 5.09 3.36
0.242 5.84 3.92
0.038 1.19 1.00
PEG - 0.099 1.38 1.07
DIOXANE 0.153 1.52 1.13
0.200 1.67 1.18
0.242 1.74 1.21
Fig.1a
Fig. 1b
Fig. 1a and 1b. Variation of of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency
in (GHz) at 25 °C for Poly (ethylene glycol) with benzene for various concentrations.
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 76 | Page
Fig.2a
Fig.2b
Fig. 2a and 2b. Variation of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency in
(GHz) at 25 °C for Poly (ethylene glycol) with, CCl4 for various concentrations.
Fig.3a
Fig.3b
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 77 | Page
Fig. 3a and 3b. Variation of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency in
(GHz) at 25 °C for Poly (ethylene glycol) with 1, 4, dioxane for various concentrations.
Fig.4a
Fig.4b
Fig.4c
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 78 | Page
Fig.4d
Fig.4e
Fig. 4a , 4b, 4c, 4d and 4e.Variation of permittivity at infinite frequency (εinfinity), dielectric permittivity(ε „
), ,
static permittivity (ε0),relaxation time (τps) and dielectric loss (ε “
) verses concentration in mol/lit at 25 °C
Fig.5a
Fig,5b
Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents…
DOI: 10.9790/4861-07127079 www.iosrjournals.org 79 | Page
Fig.5c
Fig.5a, 5b and 5c variation of Bruggeman dielectric factor with volume % of PEG with benzene, CCl4 and 1,4
dioxane
Fig.6
Fig.6 variation of Kirkwood effective correlation factor with volume fraction of PEG with benzene, CCl4 and
1,4 dioxane

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Dielectric Relaxation And Molecular Interaction Studies Of PEG With Non-Polar Solvents Using TDR Technique

  • 1. IOSR Journal of Applied Physics (IOSR-JAP) e-ISSN: 2278-4861.Volume 7, Issue 1 Ver. II (Jan.-Feb. 2015), PP 70-79 www.iosrjournals.org DOI: 10.9790/4861-07127079 www.iosrjournals.org 70 | Page Dielectric Relaxation And Molecular Interaction Studies Of PEG With Non-Polar Solvents Using TDR Technique D.J.S. Anand Karunakaran *1 , T.Ganesh2 , M.Maria Sylvester3 , Pravin Hudge4 , A.C. Kumbharkhane4 1 And 3. Post graduate & research department of physics, bishop heber college, tiruchirapalli, Tamil nadu– 620 017 2 Post graduate & research department of physics, rajah serfoji government college, thanjavur Tamil nadu – 613 005. 4 School of physical sciences, swami ramanad teerth marthwada university, nanded, ms – 431606. Abstract: The complex dielectric permittivity measurements of Poly Ethylene Glycol (PEG) HO[CH2-CH2- O]n H of molecular weight 400 (n=9)g mol−1 with carbon tetra chloride(CCl4), benzene and 1,4-dioxane mixtures has been carried out at different concentration in mol/lit at 25o C and in the frequency range of 10 MHz to 30 GHz using Time Domain Reflectometry (TDR). The least squares fit method has been used to obtain the static dielectric constant, relaxation time, and Bruggeman factor for binary mixtures. The Kirkwood–Frohlich theory is applied to compute the dielectric constant for the mixtures. It adequately reproduces the experimental values of static dielectric constants for the binary mixtures. The excess parameters confirm that the heteromolecular hydrogen bonding interaction between alcohol-alcohol and alcohol-CCl4, benzene and 1,4- dioxane pairs very significantly in the mixtures. The Bruggeman model for the nonlinear case has been fitted to the experimental dielectric data for the mixtures. Keywords: dielectric relaxation, time domain reflectometry, ethylene glycol. I. Introduction The dielectric properties of a medium is measured as a function of frequency in Dielectric spectroscopy(DS). It is based on the interaction of an external field with the electric dipole moment of the sample, often expressed by permittivity. The Dielectric Spectroscopy is especially sensitive to interference polarization and intermolecular interactions. The properties between individual constituents of complex material, characteristic of bulk properties and dielectric relaxation studies of various surfactants in aqueous solutions studied using TDR [1-3]. In low frequency, the measurement of conductive systems was strongly limited due to electrode polarization. To determine various relaxation parameters on dielectric spectrum over a wide frequency range, one step pulse (Time window) method is used. The successful development of Time Domain Spectroscopy (TDS) method and [4-8]Broad Band Dielectric Spectroscopy(BDS) have radically changed the attitude towards DS making it an effective tool for investigation of solids and liquids on the macroscopic, microscopic and mesoscopic levels. Dielectric relaxation studies are very useful in understanding the structure of polymers. The properties of chemically homologous series of polymer molecule are of special interest because changes in properties are related to chain length and temperature and very useful to study the structural properties of polymers. Poly Ethylene Glycol (PEG) is of great significant in industry, in biomedicine, cosmetics, food additives and plasticizer. The general chemical formula of PEG is HO(CH2CH2O)nH, where n is the number of repeat units. The dielectric relaxation study with a variation in chain length is impartment in binary system to study the effect of molecular dynamics and shape of the dielectric relaxation curve in the room temperature. Low molecular weight polymers have good solubility in polar and non polar solvents. As oxygen atoms and OH groups are present in the molecular chain and at the ends of the chain due to which these molecules have several hydrogen bonding giving rise to several confirmations in non polar mixtures. Extensive experimental attempts [9] have been made to study the absorption behavior of PEG molecules and their oligomers at radio waves and microwaves to understand their dielectric behavior. Earlier, the dielectric and thermodynamic properties of Polyethylene glycols have been studied to know the effect of chain length and the variation of temperature on the configuration of PEG by knowing the configuration of Polyethylene oxide (PEO) chain by measurements of NMR spectra [10-12] , IR spectra [13,14], X-ray diffraction studies [15], the dipole moments [16] , dielectric loss [17-19] and by theoretical determination of energies [16,20] associated with rotational isomeric state about skeletal bonds of the molecules of PEO, its oligomers and polymers.
  • 2. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 71 | Page The dielectric constant is one of important physicochemical properties of the mixed solvents, which enhance most of the biological, pharmaceutical, chemical, physical, analytical, laboratory industrial application [21]. The dielectric study of PEG on addition of dioxane provides information about breaking of molecular structure in the systems. In binary mixtures of PEG with benzene and CCl4 the hydroxyl groups are present on the terminal carbon atom and neighboring carbon atom, therefore the strong intermolecular interaction, possible through hydrogen bonds, results in specific dynamics properties compared to PEG with 1,4- dioxane. Dielectric characterization has great potential in studying the H-bond interactions: dipolar alignments, hydrogen bond connectivity, and stoichiometric ratio of stable adduct formation in mixed solvents [21-23]. Crossely et al. [24] have examined the dielectric permittivity and loss for a series of glycols. It is observed that the relaxation times for the glycols are almost independent of alkyl chain length. The study of dielectric relaxation in glycol mixtures, a correlation between the PEG and non-polar solvents obtained from the values of the relaxation time and the number density of molecules. This can be interpreted as an indication that only one hydroxyl group in the PEG is active in the main relaxation process. This implies that the other end of the PEG, the ethylene molecule remains “anchored” to another molecule by the hydrogen bond. This reduces the flexibility at the molecular level leading to a slower relaxation than in normal glycols. Main purpose of this study is to understand the dielectric behavior of PEG in terms of hydrogen bond and modification of hydrogen bonding due to presence of other non-polar molecules. In the present work dielectric measurements of the mixtures of PEG with benzene, CCl4 and 1, 4-dioxane solvents using TDR method are reported. The complex dielectric permittivity in the frequency range of 10 MHz to 30 GHz has been determined. The static dielectric constant, dielectric loss, Bruggeman factor, Kirkwood correlation factors, excess dielectric permittivity, relaxation time have been determined for this binary mixtures at 25o C. II. Experimental 2.1. Materials The poly(ethylene glycols) of number average molecular weight 400 g/ mol is obtained from Sigma Aldrich India. Benzene, CCl4 and 1,4 Dioxane were obtained from Merck India Pvt. Ltd., and were used to prepare combination of binary mixtures without further purification. The dielectric permittivity ε′ and dielectric loss ε″of pure liquid PEG's binary mixtures at emperatures 25°C were measured using TDR employed in the frequency region 10 MHz to 30 GHz. The detailed analysis and procedures of the TDR system are explained below. The mole fractions of the mixture constituents were determined by using their individual volume in the mixture, the room temperature density and the molecular weight. 2.2. Measurements and Data Analysis The complex permittivity spectra were studied using Time Domain Reflectometry (TDR) method [25, 26]. The basic TDR setup consists of broad band sampling oscilloscope, TDR module and coaxial transmission line. The Tektronix DSA8200 sampling oscilloscope with 30 GHz bandwidth and TDR module 80E08 with step generator unit was used. A 200 mV step pulse with 18 ps incident pulse and 20 ps reflected pulse time and 200 KHz repetition rate passes through coaxial 50 Ω lines. All measurements are carried out in open load condition. Sampling oscilloscope monitors changes in step pulse after reflection from sample. Reflected pulse without sample R1 (t) and with sample RX (t) were recorded in time window of 5 ns and digitized in 2000 points. Temperature of the sample was controlled electronically within ±1°C. The step pulses recorded without sample R1 (t) and with sample RX (t) were subtracted and added to get (t)]R(t)[R=p(t) x1 (1) (t)]R+(t)[R=q(t) x1 (2) The complex reflection coefficient ρ*(ω) over a frequency range of 10 MHz to 30 GHz were determined as follows: ) ) ) jwdq(ω cp(ω (ωρ  (3) where p(ω) and q(ω) are Fourier transforms of p(t) and q(t) obtained using summation and Samulon methods [27] respectively, c is the velocity of light, ω is angular frequency and d is effective pin length (0.09 mm).              βα 0 ])(JωJ+[ )ε(ε +ε=(ωε 1 0 1 ) (4)
  • 3. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 72 | Page The complex permittivity spectra ε*(ω) is obtained from reflection coefficient spectra ρ*(ω) by applying the non – linear least square fit method suggested by Cole [25, 26]. The frequency dependent complex permittivity spectra ε*(ω) of PEG-400 with their respective binary mixtures of benzene, CCl4, and 1,4, Dioxane for different concentrations in liquid state at temperature 25°C are shown as real part (ε') and imaginary part (ε" ). It has been found that ε0, ε', ε" and ε∞ are the linear functions of the concentration of binary mixture solute in dilute concentrations used for analysis of dielectric relaxation data and the values are recorded in Table.1. It is also found that the variations in relaxation time τ, gf and geff values in binary mixtures are also calculated in various non-polar solvents. The Kirkwood correlation factor provides useful information regarding the orientation of dipoles. The dielectric constant can be used to calculate Kirkwoood correlation factor g defined in general by γz+=g cos1 (5) where z is the average number of nearest neighbors and γ is the angle between the dipole moments of the neighboring molecule, Kirkwood correlation factor is greater than 1 are indicative of a tendency towards parallel alignment of dipoles, values less than 1 are obtained when anti parallel alignment is favored and a value unity is expected when orientational ordering is absent. III. Results And Discussion The complex permittivity spectra (real (ε′) and imaginary (ε″)) as a function of log frequency (GHz) at 25°C for Poly (ethylene glycol) with benzene, CCl4 and 1,4,dioxane for various concentrations are shown in Fig.(1a - 3b), and the Variation of excess permittivity (ε∞), dielectric permittivity(ε′), , static permittivity (ε0),relaxation time (τps) and dielectric loss (ε″) verses concentration in mol/lit at 25 °C for Poly (ethylene glycol) having molecular weight 400gmol−1 at 25 °C with beneze,CCl4, 1, 4, dioxane are shown in Fig.(4a - 4e) respectively. Both static dielectric constant and relaxation time increases with increase in concentration. The frequency dependence of the complex dielectric permittivity and the excess properties are reported in Table.1. The Kirkwood correlation factor g [28] provides the information regarding the orientation of the electric dipoles. For the pure liquid polymer, the Kirkwood correlation factor g may be obtained by the expression          2 0 002 2 2ε 4ππN 9 )ε+(ε )ε+)(ε(εkTM =gμ (6) where, μ is the dipole moment, ρ is density at temperature T, M is the molecular weight, k is Boltzmann constant, N is Avogadro's number, ε0 is static permittivity and ε∞ is the dielectric permittivity at high frequency, often represented by the square of the refractive index (ε∞=n2 D). In associating molecules, the molecular relaxation time is affected by the intra and intermolecular hydrogen bonding. The departure of the Kirkwood correlation factor g from unity is a measure of the extent of intermolecular hydrogen bonding. For the molecules with parallel dipole moments g will be greater than unity, while for anti-parallel dipole alignment g will be smaller than unity. To examine the effect of intermolecular association on the dielectric relaxation time of these molecules, the values of Kirkwood correlation factor g have been determined. We have assumed that the mixture can be represented by one correlation factor geff as follows: = )ε+)(ε(ε ii 0i 0i0i 9ε 2ε    eff gX M ρμ +X M ρμ kT          1 2 2 22 1 1 1 12 1 9 4ππ (7) where 1 and 2 stand for PEG and non-polar solvent, XAis the volume fraction of PEG. The value of geff > 1 indicates average parallel orientation of electric dipole in a molecule. It can be seen that as PEG is added in non-polar solvents at regular steps in the mixture the value of geff increases is shown in Fig.6. We also assume that correlation factors of PEG and non-polar solvent molecules are affected by the same amount gf in the mixture [29]. The Kirkwood–Frohlich equation for the mixture can be written as = )ε+)(ε(ε ii 0i 0i0i 9ε 2ε    gfX M ρμg +X M ρμg kT          1 2 2 22 2 1 1 1 12 1 1 9 4ππ (8) The Kirkwood correlation factors g1, g2 for individual species are modified by assuming for PEG – non-polar solvents mixture that two kinds of intermolecular hydrogenbonds exist. One is the hydrogen bond between the PEG - PEG molecules; another is the hydrogen bond between the PEG – non-polar solvent molecules. These new correlations (g1and g2) are described by the relation as follows [30]:
  • 4. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 73 | Page 1 2 121211111 coscos1 μ μ γZ+γZ+=g (9) 2 1 21212 cos1 μ μ γZ+=g (10) where Z11, Z12 and Z21 are the average number of particles forming the hydrogen bond with PEG–PEG, PEG– non- polar solvents, and non-polar solvents–PEG pairs, respectively. γ11 and γ21 are the angles between the neighbouring dipoles of PEG and non-polar solvents molecules. The values of g1 and g2 depend on the concentration of non-polar solvents in binary mixtures. The values of geff and gf for PEG– non-polar solvents mixture are reported in Table 2. The observation shows that the g values are greater than unity in all these binary systems, which leads to the conclusion that the molecules associate to form multimers with parallel dipole moments. Dielectric measurements in the megahertz to gigahertz range are very important for investigating molecular dynamics of polymers, especially in solution state. One empirical relation, the Kohlrausch- Williams- Watt (KWW) function, has considerable use not only for the dielectric relaxation behavior of liquid polymers but also for the other polymer relaxation phenomena including volume and enthalpy relaxations, NMR and dynamical relaxations, Quasi elastic light scattering, small angled relaxation scattering, transient optical relaxation and time dependent fluorescence depolarization. Dielectric behavior of polymer at a frequency region higher than 100 MHz has not been examined satisfactorily. In case of liquid polymers the dielectric measurements in the higher frequency studies are very scarce. In general, polar polymers in dilute solutions of non-polar solvent show an absorption peak at a frequency between 100 MHz and 2 GHz, if they have dipolar component perpendicular to their chain contour [31]. Frequency obtained from TDR measurements peak does not depend on the molecular weight of the polymer chains [32]. Poly ethylene glycol shows the dielectric relaxation process in polar and non-polar solutions in the gigahertz region [33, 34]. The static permittivity of mixture with volume fraction of solute is given by Bruggeman mixture formula [35] 3/1 0m 01 0201 020m         ε ε εε εε =fB (11) It can seen from Fig.(5a - 5c) that fB is not a linear function of PEG volume fraction as predicted by Bruggeman equation. The Bruggeman equation may be modified for binary liquid [36] as follows; 3/1 0m 01 0201 020m         ε ε εε εε =fB (12)   AA X)X(aa= 11  (13) where fB is the Bruggeman dielectric factor. The εom, ε01, and ε02 are the static dielectric constant corresponding to mixtures, PEG with benzene, CCl4 and 1,4-dioxane respectively, XA is the volume fraction of PEG. From the above equation, a linear relation is expected from a plot of fB versus XA . In this equation, volume fraction XA is changed by a factor a−(a−1)XA of the mixture; for a = 1 it corresponds to Bruggeman equation. The value of a can be determined by least squares fit method and is found to be 1.29, 1.16 and 1.65 for the binary systems respectively, its deviation from unity indicates the molecular interaction in the mixture. IV. Conclusion The dielectric relaxation parameter for PEG-400 with their respective binary mixtures of benzene, CCl4, and 1,4, dioxane for different concentrations in liquid state has been measured using TDR method in the frequency range 10 MHz to 30 GHz at 25o C. The dielectric constant for the mixtures can be explained using hydrogen-bonded model by assuming the formation of hydrogen bonds between solute-solute and solute-solvent pairs. The orientation correlations between neighbouring molecules due to hydrogen bonding interaction are determined in terms of Kirkwood factors. A modification in the Bruggeman equation provides a better description of dielectric behavior in the mixtures. The study shows the influence of varying chain length on the molecular size, shape, dielectric relaxation and structural properties of the binary system. At the relaxation frequency the oscillation of the applied field becomes very fast for the molecules to have time to fully rotate. As compared to relaxation time of pure liquid, the relaxation time of binary mixtures is higher which suggest that the formation of complexes or presence of association in unlike molecules, which gives an idea about the behavior of dielectric constant and relaxation time with respect to mixture compositions. The gf and geff values are found to be greater than unity shows the molecules are with parallel dipole moment and confirm that in these
  • 5. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 74 | Page binary systems the dipolar orientation has an activated state and more ordered. It also suggests that there is more hindrance to the rotation of the molecule clusters in binary mixture in comparison with the rotation of their homogeneous clusters. This also supports the conclusion drawn from the positive values of relaxation time. The proper choices of reference liquids for calibration are very useful to keep the errors in the values of these dielectric parameters within the desired limit. References [1]. Ganesh, T, Sabesan, R, Krishnan, S, J. Mol. Liq., 128 (2006) 77. [2]. Ganesh, T, Balamurugan, D, Sabesan, R, Krishnan, S, J. Mol. Liq., 123 (2006) 80. [3]. Ganesh, T, Sabesan, R, Krishnan, S, J. Mol. Liq., 137 (2008) 31. [4]. Cole, R.H. , Evaluation of dielectric behavior by Time Domain Spectroscopy. – Dielectric responds by real time analysis, J. Phys. Chem, 79(1975)1459. [5]. Cole, R. H. , Evaluation of dielectric behavior by Time Domain Spectroscopy-II complex permittivity, J. phys.Chem., 79(1975) 1469. [6]. Cole, R. H., Berberian, J. G, Mashimo, S, Unryssik, G, Brnins, A and Tombari, E Time Domain reflection methods for dielectric measurements to GHz. J. Appl. Phys, 66(1989) 793. [7]. Feldman, Y. D and Levinin, V. V, obtaining the dipole correctional function from TDS data directly in the time domain, Chem.Phys.letters 85(1982)528. [8]. Kumbharkhane, A. C, Shinde, M. N, Mehrotra, S. C, Oshiki, N, Shinyashiki, N, Yagihara, S and Sudo, N, J. Phys. Chem. A 113, (2009) 10196–10201. [9]. Stockmeyer W.H., Pure. Appl. Chem. 15(1967)539. [10]. Harmann, G. Weill, G, Macromolecules 8 (1975) 171. [11]. Bailey, R. T, North, A. M, Pethrick, R. A, Molecular Motion in High Polymers, Oxford Uinversity Press, 1981. [12]. Heatley, F, Walton, I, Polymer 17 (1976) 1019. [13]. Kuroda, Y, Kubo, M, Journal of Polymer Science 26 (1957) 323. [14]. Panov, V. P, Ovsepyan, A. M, Kobyakov, V. V,Zhbankov, R. GJournal of Applied Spectroscopy 29 (1978) 803. [15]. Takahashi, Y, Tadokoro, H Macromolecules 6 (1973) 672. [16]. Rossi, C, Magnasco, V, Journal of Polymer Science 58 (1962) 977. [17]. McCrum, N. G, Read, B. E, Williams, G, Anelastic and Dielectric Effects in Polymeric Solids, John Wiely and Sons, New York, 1967. [18]. Porter, C. H, Boyd, R. H, Macromolecules 4 (1971) 589. [19]. Arisawa, K, Tsuge, K, Wada, Y, Japanese Journal of Applied Physics 4(1965) 138. [20]. Mark, J. E, Flory, P. J, Journal of the American Chemical Society 88 (1966) 3702. [21]. Sudo, S. Shinyashiki, N and Ygihara, S. J. Mol. Liq.90, (2001) 113–120. [22]. Moumouzias, G, Panopoulos, D. K, and Ritzoulis, G, J. Chem. Eng. Data 36(1), (1991) 20–23. [23]. Papanastasiou, G. E and Zlogas, I. I, J. Chem. Eng. Data3 7, (1992) 167–172. [24]. Crossely, J, Can. J. Chem. 56, (1978) 352–354. [25]. Cole, R. H, Berbarian, J. G, Mashimo, S, Chrysikos, G, Burns, A, Tombari, E, Journal of Applied Physics 66 (1989) 793. [26]. Kumbharkhane, A. C, Puranik, S. M, Mehrotra, S,.C, Journal of Chemical Society Faraday Transactions 87 (1991) 1569. [27]. Hager N. E, III, The Review of Scientific Instruments 65 (1994) 887. [28]. Oster, G, Kirkwood, J, G. Journal of Chemical Physics 11 (1943) 175. [29]. Kumbharkhane, A. C, Puranik, S. M, and Mehrotra, S. C, J. Mol. Liq. 51(3–4), (1992) 261–277. [30]. Luzar, A and Stefan, J, J. Mol. Liq. 46, (1990) 221–238. [31]. Stogermorger, W.H., pure. Appl. Chem 15 (1967), 539. [32]. Mashimo. S, Macromolecules 9 (1967), 91. [33]. Shinyashiki, N, Asoka, N, Mashimo, S, Yagihana, , J.Chem. Phys 93 (1990), 760. [34]. Joshi, Y. S,. Kumbharkhane, A. C Journal of Molecular Liquids 161 (2011) 120–124 [35]. Bruggeman, D. A. G, Ann. Phys. (Leipzig) 24, (1935) 636–664. [36]. Puranik, S. M, Kumbharkhane, A. C, and Mehrotra, S. C, J. Mol. Liq. 59(2–3), (1994) 173–177. Table.1 Dielectric parameter of PEG binary system of various concentration at T=250 C mol/lit    ps  0.1 2.01 2.13 2.12 14.84 0.008 PEG - 0.3 2.05 2.28 2.34 16.31 0.009 BENZENE 0.5 2.08 2.41 2.54 18.78 0.183 0.7 2.18 2.48 2.70 21.21 0.216 0.9 2.19 2.57 2.86 22.45 0.278 0.1 1.96 2.21 2.23 14.55 0.043 PEG - CCl4 0.3 2.03 2.29 2.50 15.1 0.065 0.5 2.05 2.37 2.53 17.65 0.154 0.7 2.12 2.45 2.67 19.12 0.191 0.9 2.14 2.53 2.90 21.2 0.262 0.1 2.01 2.29 2.31 10.34 0.203 PEG - 0.3 2.11 2.44 2.49 10.72 0.290 DIOXANE 0.5 2.28 2.57 2.65 10.82 0.350 0.7 2.37 2.66 2.78 11.31 0.433 0.9 2.44 2.76 2.88 11.97 0.528
  • 6. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 75 | Page Table.2 Effective correlation factor and correlation factor of PEG with various volume fractions vol. fr. solute geff gf 0.038 1.67 1.00 PEG-BENZENE 0.099 2.36 1.22 0.153 3.33 2.14 0.200 3.94 2.72 0.242 4.24 3.19 0.038 1.39 1.00 PEG - CCl4 0.099 3.01 2.48 0.153 4.36 2.64 0.200 5.09 3.36 0.242 5.84 3.92 0.038 1.19 1.00 PEG - 0.099 1.38 1.07 DIOXANE 0.153 1.52 1.13 0.200 1.67 1.18 0.242 1.74 1.21 Fig.1a Fig. 1b Fig. 1a and 1b. Variation of of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency in (GHz) at 25 °C for Poly (ethylene glycol) with benzene for various concentrations.
  • 7. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 76 | Page Fig.2a Fig.2b Fig. 2a and 2b. Variation of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency in (GHz) at 25 °C for Poly (ethylene glycol) with, CCl4 for various concentrations. Fig.3a Fig.3b
  • 8. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 77 | Page Fig. 3a and 3b. Variation of dielectric permittivity (ε′) and dielectric loss (ε″) as a function of log frequency in (GHz) at 25 °C for Poly (ethylene glycol) with 1, 4, dioxane for various concentrations. Fig.4a Fig.4b Fig.4c
  • 9. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 78 | Page Fig.4d Fig.4e Fig. 4a , 4b, 4c, 4d and 4e.Variation of permittivity at infinite frequency (εinfinity), dielectric permittivity(ε „ ), , static permittivity (ε0),relaxation time (τps) and dielectric loss (ε “ ) verses concentration in mol/lit at 25 °C Fig.5a Fig,5b
  • 10. Dielectric Relaxation And Molecular Interaction Studies Of Peg With Non-Polar Solvents… DOI: 10.9790/4861-07127079 www.iosrjournals.org 79 | Page Fig.5c Fig.5a, 5b and 5c variation of Bruggeman dielectric factor with volume % of PEG with benzene, CCl4 and 1,4 dioxane Fig.6 Fig.6 variation of Kirkwood effective correlation factor with volume fraction of PEG with benzene, CCl4 and 1,4 dioxane