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DIELECTRIC SPECTROSCOPIC STUDIES ON CYCLOHEXANONE AND 1,4–DIOXANE
*
B.Thapa,
†
P. Bhattarai and B. Pokhrel
*
Central Department of Physics, University Campus, Tribhuvan University, Kirtipur, Kathmandu, Nepal
†
Department of Physics, Padmakanya Campus, Bagbazar, Kathmandu, Nepal
Department of Physics, Institute of Engineering, Pulchowk, Lalitpur, Nepal
Key Words: Condensed Matter/Organic Liquids/Dielectric Property
The variation of dielectric constant of cyclohexanone (C6H10O) with the frequency from 42 Hz to 2 MHz and that of 1,4–
dioxane (C4H8O2) from 42 Hz to 0.5 MHz were studied at a constant temperature of 250
C (298 K) by using HIOKI –
HiTESTER (3532-50). The dependency of dielectric constant of binary mixture of these liquids with the concentration of
cyclohexanone was also observed. The experimental data and literature data were used to test the theories of mixture
of dielectric constant proposed by Lichtenecker – Rother, L. Landau and E. Lifshitz, Beer and Looyenga.
INTRODUCTION
The study of dielectric properties of liquid
dielectrics provides the information about the
structure, rotation and orientation of the
molecules of liquids [1-2]. Several
investigations have been made on dielectric
studies for liquid dielectrics. Prasai et al. [3]
and Yoshizaki et al. [4] studied the dielectric
properties for polymer/solvent binary
systems. The static dielectric constant (ε) for
cyclohexanone and triethylamine mixture was
investigated by Ratkovics and Parragi [5].
Likewise, Sudo et al. [6] examined the
dielectric properties of ethyleneglycol–1,4-
dioxane mixtures in the frequency range from
100 MHz to 30 GHz at 250
C using time domain
reflectometry (TDR) mathod. The same
method was implemented by Kumbharkhane
and Shinde [7] to study the structural
behavior of alcohol–1,4-dioxane through
dielectric properties in the frequency range 10

2. 2
MHz to 20 GHz. Similarly, various researches
were made on the dielectric studies for liquid
dielectrics [8-10].
Previously, Sharma et al. [11] reported the
dependencies of static dielectric constant on
temperature for liquid dielectrics using
Schering Bridge. Kattel [12] also used the
same methodology to study the similar
properties for polystyrene-dichloromethane
binary system. At present, we are interested
to study the dielectric properties of liquid
dielectrics at high frequencies rather than the
static using HIOKI-HiTESTER (3532-50) (HH).
Besides, there has been a pervasive curiosity
to bring out the use of HH for the study on
liquid dielectrics which was previously used
for the study only on solid dielectrics, i.e.
ceramics [13-16]. For this fulfillment, the
major challenge was the construction of a
parallel plate capacitor as a
*, †
To whom correspondence should be addressed.
E-mail:
bibech.thapa@gmail.com,
bhattaraipradeep@hotmail.com;
Phone: + 977-9841649286.
◙ Presented on INTERNATIONAL CONFERENCE
ON FRONTIERS OF PHYSICS 2009, Kathmandu,
Nepal. And it is still to be reviewed.
sample holder for liquid dielectric. So we
devised a glass-sealed parallel plate capacitor
as a sample holder intending to have
advantage over the dielectric cell used in
Schering Bridge since this sample holder
requires relatively lesser amount of dielectric
than the dielectric cell. On over, the
accessibility of the gang condenser, essential
for the dielectric cell, has been rare in the
market in Kathmandu. In addition to the study
on high frequency dependencies of ε, the
present work also basically focuses on to find
out the plausibility of HH for the study on
liquid dielectrics using this sample holder.
So we have made the first attempt to use HH
for the study on liquid dielectrics. In this work,
we have opted cyclohexanone as a polar and
1,4-dioxane as a non-polar liquid dielectrics.
We have observed the frequency
dependencies of ε at constant temperature of
250
C (298 K) for each dielectric. In addition, we
have also studied the dependency of ε on
concentration of cyclohexanone (f1) for the
binary system [(f1) cyclohexanone + (1- f1) 1,4–
dioxane] at the constant frequency of 100 Hz
and temperature of 250
C (298 K). The
experimental data and literature data [17] are
used to test the theories of mixture of
dielectric constant.
EXPERIMENTAL SECTION
Materials. The chemical substances
employed were purchased from Glaxo India
Limited (Mumbai, India), manufactured by
Qualigens Fine Chemicals. The molecular
weights and densities of the corresponding
chemicals are listed in Table 1.
Table 1. Characteristics of ‡
cyclohexanone
and 1,4-dioxane.
(N: product number)
‡
N N ‡
Mw Mw
‡
ρ ρ
18265 18365 98.15 88.11 0.946 1.030
In the dielectric measurements of binary
system, the concentration of cyclohexanone
was gradually increased from 0 – 20%, 20 –
30%, and so on and finally to 100%.
Theory of Mixture of Dielectric
Constant. The theories of mixture of
dielectric constant [1] under investigation are
given by the relationships as:
Landau-LifshitzLL
: εm
1/3
= f1 ε1
1/3
+ (1- f1)
ε2
1/3
,
BeerB
: εm
1/2
= f1 ε1
1/2
+ (1- f1)
ε2
1/2
,
Lichtenecker-RotherLR
: logεm= f1logε1+ (1- f1)
logε2 and
LooyengaL
: εm= [(ε2
1/3
- ε1
1/3
) (1-
f1) + ε1
1/3
]3
Where, ε1: ε for cyclohexanone and ε2: ε for
1,4-dioxane.
Apparatus and Procedure. Dielectric
measurements were carried out in the
frequency range from 42 Hz to 2 MHz at
constant temperature of 250
C (298 K) with LCR
HIOKI-HiTESTER (3532-50) (www.hioki.co.jp).
The sample holder used with HH was
especially designed for the measurements on
liquid dielectrics. It is a glass-sealed parallel
plate capacitor consisting two conical shaped
parallel plate brass electrodes of diameter 1.8
cm each and thickness 3.3 cm as shown in
Figure 1.
Figure 1. Experimetal Arrangement

3. 3
The sample holder consists of a small aperture
at the top of its middle part through which the
desired amount of dielectric sample can be
poured in it. A thermocouple, which is
insulated, is dipped inside the sample to
record its temperature. A DUAL CHANNEL
THERMOMETER having standard type K (NiCr -
NiAl) probe is used to measure the
temperature at which the sample is kept. The
two ends of the Brass electrodes are
connected to HH impedance analyzer through
coaxial cables of length 0.5 m. The HH is an
impedance meter having a touch panel as the
user interface that enables extremely easy
operation. The test frequency can be set from
42 Hz to 5 MHz at high resolution of accuracy
of ±0.008 %. The determination of dielectric
constant of dielectrics involves measuring the
capacitances of the capacitor with and without
dielectrics. The straight line (■), y=
-0.503x+17.482, clearly indicates the decrease
in
RESULTS AND DISCUSSION
Dependency of dielectric constant of
cyclohexanone and 1,4-dioxane with
frequency.
Table 2 presents the experimental data
showing the frequency (f) dependence of
dielectric constant () for cyclohexanone and
1,4-dioxane and Figure 2 represents the
corresponding plot.
Table 2. Capacitances measured at different
frequencies.
cyclohexanone
f/ Hz C/ pF ε
42 569.88 16.523
1x102
560.15 16.241
5x102
551.15 15.98
1x103
538.73 15.62
5x103
519.01 15.048
1x104
524.25 15.2
5x104
499.17 14.473
1x105
478.17 13.864
5x105
422.67 12.255
1x106
413.85 11.999
2x106
410.53 11.903
1,4-dioxane
42 72.532 2.102
1x102
72.774 2.11
5x102
72.946 2.114
1x103
73.112 2.119
5x103
72.725 2.108
1x104
71.833 2.082
5x104
72.590 2.104
1x105
70.172 2.034
5x105
70.106 2.032
Figure 2. Plot of dielectric
constant versus frequency. The
scale on X-axis is logarithmic.
[(■) cyclohexanone, (▲) 1,4-
dioxane]
ε with the increase in f for the polar dielectric:
cyclohexanone. This is due to the fact that the
increase in frequency causes the rapid
orientation of the permanent dipoles along the
direction of the applied electric field forcing
them to overcome the viscosity of the
dielectric. Consequentlythis results the
thermal agitation disturbing

4. 4
Table 3. e
Experimental and l
Literature data of dielectric constant for the binary system.
Figure 3. Plot to demonstrate the
relation between experimental and
literature results calculated from
theories of mixture of dielectric
constant.
[(♦)e
εm,(*) l
εm
B
, (○) e
εm
B
, (●) l
εm
LL
, (□)
l
εm
L
, (■) e
εm
LL
, (∆) e
εm
L
, (○) L
εm
LR
, (+)
e
εm
LR
]
the orienting tendency of the electronic and
orientational polarization in the polar
dielectric, thereby decreasing the
capacitance of the capacitor [2]. Similar
result has been mentioned for polar
polymer – polyvinylacetate – by Tareev [1].
Unlike the polar dielectrics, in case of non-
polar dielectrics, electric moment is
produced due to an external applied electric
field by the displacement of an elastically
bound charge. The contribution of this
induced moment to the polarization and
hence to the dielectric does not significantly
change over the broad frequency. The
straight line (▲), y= -0.0094x+2.1365, in
Figure 2 shows the independency of ε on
frequency for non-polar dielectric like 1,4-
dioxane. This result is in favor of Tareev [1]
who illustrated the variation of ε of solid
non-polar dielectrics:
polytetrafluoroethylene, polystyrene and
polydichlorostyrene within the frequency
range of 10 Hz to 1 GHz showing the
independency of ε on frequency. He
also presented the ε versus wavelength for
liquid non-polar dielectrics: transformer oil
and transformer oil with
20% of strongly polarized liquid,
nitrobenzene (C6H5NO2), over 400 m. He has
suggested the dipole polarization in the
polar dielectric causes ε to remain invariable
with the increase in ac voltage. Besides,
Table 3 provides the experimental and
literature data for the dependency of ε on f1
for binary system [(f1) cyclohexanone + (1-
f1) 1,4–dioxane]. Figure 3 gives the
comparison of experimental data of ε for the
binary system [(f1) cyclohexanone + (1- f1)
1,4–dioxane] with that experimental and
literature data calculated from the relations
given by the theories of mixture. It is found
that our present experimental result favors
the Beer’s theory of mixture while the data
for Landau-Lifshitz, Lichtenecker-Rother and
Looyenga have marginal deviation from it.
Conclusions. It has been found the
dependency of dielectric constant of
cyclohexanone on the frequency that goes
on diminishing as the frequency advances to
higher values indicating the gradual loss of
the tendency of electronic and orientational
polarization which is one of the major
characteristics of a polar dielectric. On the
other hand, 1,4-dioxane has shown the
independent behavior with the frequency
variation confirming its non-polar
characteristic. On the basis of the test of
theories of mixture of dielectric constant for
f1
e
εm
l
εm
LL e
εm
LL l
εm
B e
εm
B l
εm
LR e
εm
LR l
εm
L e
εm
L
0 2.11 2.219 2.11 2.2189 2.11 2.219 2.11 2.2189 2.1100
0.2 4.008 3.713 3.5996 3.9767 3.8733 3.292 3.1736 3.7128 3.5997
0.3 5.301 4.662 4.5541 5.0466 4.9542 4.021 3.8921 4.6620 4.5541
0.4 6.989 5.761 5.6639 6.2437 6.1680 4.904 4.7732 5.7605 5.6639
0.5 7.991 7.019 6.9408 7.5682 7.5147 5.978 5.8539 7.0194 6.9408
0.6 9.775 8.449 8.3964 9.0199 8.9942 7.287 7.1793 8.4494 8.3964
0.7 10.732 10.062 10.043 10.599 10.607 8.842 8.8047 10.062 10.043
0.8 12.477 11.867 11.891 12.305 12.352 10.85 10.799 11.867 11.891
0.9 14.014 13.876 13.953 14.139 14.230 13.26 13.243 13.876 13.953
0.95 15.01 14.960 15.068 15.103 15.219 14.51 14.666 14.960 15.068
1 16.241 16.100 16.241 16.1 16.241 16.1 16.241 16.1 16.241

5. 5
the binary system, it is concluded that our
observation is in favor of Beer’s theory.
Finally, we have successfully carried out this
investigation concluding the plausibility of
HH for the study on liquid dielectrics.
Acknowledgement. Appreciation is
expressed to Professor D. R. Mishra for his
constructive suggestions and department
head of Central Department of Physics,
Professor L. N. Jha, for his profound support.
B. T. and P. B. wish to thank Institute of
Engineering (IOE) for granting the
opportunity to work in its laboratory
providing HH. B. T. wishes to thank Mr.
Nandalal Maharjan for his valuable
contribution for the construction of sample
holder.
REFERENCES
[1] B. Tareev, 1975, PHYSICS OF DIELECTRIC
MATERIALS, Mir Publishers, Moscow, Russia.
[2] C. P. Smyth, 1955, DIELECTRIC BEHAVOIR
AND STRUCTURE, McGRAW-HILL BOOK
COMPANY, INC., New York, US.
[3] B. K. Prasai, P. Bhattarai and D. R. Mishra,
Different Disordered-Systems, First Edition,
October 2001, pp. 78 – 81.
[4] Kazuyuki Yoshizaki, Osamu Urakawa and
Keiichiro Adachi, Dielectric Study of
Concentration Fluctuation in Solutions of
Polystyrene, Macromolecules, 2003, 36,
2349 – 2354.
[5] Ferenc Ratkovics and Maria Laszlo-Parragi,
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[6] Seiichi Sudo, Noriaki Oshiki, Naoki
Shinyashiki and Shin Yagihara, J. Phys.
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[7] Ashok C. Kumbharkhane and M. N. Shinde,
J. Phys. Chem. A, 2009, 113(38), pp. 10196 –
10201.
[8] Ramana Ch. V.V and Malakondaiah K.,
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[9] V. Satheesh, M. Jeyaraj and J. Sobhanadri,
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[10] Gudrun Ahn-Ercan, Hartmut Krienke and
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[11] S. Sharma, M. Ojha and P. Bhattarai, The
Physics of Disordered Materials, Edited by
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Bhandari, 1997, pp. 396 – 400.
[12] S. P. Kattel, 2005, An Experimental Study of
Dielectric Constants of Polystyrene-
Dichloromethane Binary Solution, M.Sc.
Thesis, Central Department of Physics,
Tribhuvan University, Kathmandu, Nepal.
[13] Nunu Lal Sahu, An Experimental Study on
Phase Transition Behavior of the PbZrO3
Ceramics, M.Sc. Thesis, Central Department
of Physics, Tribhuvan University,
Kathmandu, Nepal.
[14] Mitra Mani Subedi, An Experimental Study
on Electrical Behavior of (Pb1-XSnx) TiO3 (X =
0.10, 0.20, 0.30) Ceramics, M. Sc. Thesis,
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University, Kathmandu, Nepal.
[15] Nabin Chauhan, An Experimental Study on
Electrical Behavior of [Pb1-x(Snx)] TiO3 (X=
0.05, 0.10, 0.15) Ceramics, M. Sc. Thesis,
Central Department of Physics, Tribhuvan
University, Kathmandu, Nepal.
[16] Medani Prasad Sangroula, An Experimental
Study on Phase Transition Behavior of the
[Pb1-x(Snx)] TiO3 (X= 0.02, 0.04, 0.06)
Ceramics, M. Sc. Thesis, Central Department
of Physics, Tribhuvan University,
Kathmandu, Nepal.
[17] D. R. LIDE, 1995-1996, CRC HANDBOOK OF
CHEMISTRY AND PHYSICS, 76th
Edition, CRC
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