New Physics: Sae Mulli, DOI: 10.3938/NPSM.64.

692
Vol. 64, No. 7, July 2014, pp. 692∼695

Complex Dielectric Properties of Crude Oils in the Wide Frequency Range

10−2 Hz ∼ 109 Hz

Jong-Ho Park∗
Department of Science Education, Chinju National University of Education, Jinju 660-756, Korea

(Received 2 April 2014 : revised 9 May 2014 : accepted 9 May 2014)

A cylindrical-type sample cell has been designed and produced to investigate the complex dielec-
tric properties of crude oils in the frequency range from 10−2 Hz to 109 Hz by using an impedance
analyzer. The characteristics of the measurement cell are optimized to give high sensitivity. High-
sensitivity, complex dielectric constant measurements are obtained by using calibrations with several
known fluids. From the complex dielectric spectra, we observed a dielectric behavior consisting of
two regions for the measurement frequencies the low-frequency region may be due to diffusion charge
transport caused by impurities while the dielectric relaxation mechanism for the high-frequency
region seems to be a non-interacting Debye-type mechanism. In the high-frequency region, the
relaxation time has been observed to be related to the viscosities of the crude oils.

PACS numbers: 77.22.-d, 77.22.Gm, 77.84.Nh

Keywords: Dielectric relaxation, Heterogeneous system, Crude oil

I. INTRODUCTION complex dielectric constant of materials (solid, liquid,

gas, etc). According to kinds of materials, the sample
Dielectric spectroscopy has proved to be a powerful cell was parallel-type in case of solid and cylinder-type
technique in analyzing heterogeneous systems [1–8]. In in case of liquids. This means that geometrical form of
these studies the time dependence of processes occurring electric field supplied on electrode of sample cell is very
in the systems will determine the frequencies of imme- important [1,4,5]. This geometrical factor engenders er-
diate interest to the user. Low frequency equipment has ror in the dielectric constant value.
advantages when applied to aqueous solid suspensions, Dielectric measurements can be used in the oil indus-
emulsions or heterogeneous polymer blend system. Espe- try to determine the amount of oil, water and gas in a
cially in the first mentioned systems relaxation processes multiphase flow. The components of crude oil have differ-
in the electrical double layer of the changed particles or ent natures [6–8]. Among these components are dipolar
droplets can be studied. For the reversed problem with fractions that exist due to different heteroatoms. The
electrically conducting cavities (aqueous domain) in non- concentration of heteroatom are highest in heavy frac-
polar environments, the frequency dependence is highly tions, resins and asphalts, and play an important role in
dependent on the properties of the aqueous domains. the forming of permanent dipoles in heavy petroleum
Several methods for the measurement of dielectric fractions [9, 10]. Resins and asphalts are polar, and
properties have been developed, including both time and conducting asphalts, which are defined as n-heptance-
frequency domain methods [1, 2]. Automatic measure- insolubles, are large polar molecules that are reported to
ment systems have made frequency-domain methods the from aggregates or inverse micelles structures. It is rea-
most economical. However, sample cell is more impor- sonable to believe that these polar compounds are the
tant than measurement instrument in obtaining exact source of the dielectric dispersions measured in asphalts.
However, dielectric spectroscopy implies the measure-
∗ E-mail: parkkdp@cue.ac.kr ment of the complex dielectric constant as function of
692

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License
(http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any
medium, provided the original work is properly cited.
Complex Dielectric Properties of Crude Oils in the Wide Frequency Range 10−2 Hz ∼ 109 Hz – Jong-Ho Park 693

Table 1. Asphalts concentration and viscosity in the Table 2. ε0s of the standard samples at 20 ◦ C.
crude oils each samples.
Medium ε0s Ref’s
Samples Asphalts (wt%) Viscosity (arb. unit) at 100 ◦ C Air 1.0005 ± 0.0002 11
S1 11.30 2368 n-Heptane 1.924 ± 0.01 11,13,14
S2 12.30 2404 Carbon tetrachloride 2.238 ± 0.002 11
S3 12.40 2639 Chloroform 4.82 ± 0.02 13
S4 12.55 2980 Monochlorobenzene 5.699 ± 0.008 11,13
S5 12.70 3195 1,2-Dichloroethane 10.65 ± 0.05 11, 14

frequency. Static and high frequency dielectric constant, C 0 corresponding to the ordinary capacitance, while the
relaxation time distribution parameter, and conductivity imaginary component (C 00 ) represents the dielectric loss
are calculated from the spectra. These dielectric param- component. C0 the geometric capacitance given by
eters depend on the permanent dipole moments, polar-
2πε0 le
isability, dynamics and density of the molecules, ion and C0 =
ln(b/a)
free electrons [7,8].
In this paper, we designed cylindrical-type sample cell where le is the electrical length of the measurement cell.
and calibrated the dielectric measurement of the sample b is the inner radius of the outer conductor and a is
cell. We investigated the dielectric relaxation behavior of the radius of the inner conductor. Owing to existing
the refined heavy oil from crude oil and the relationship stray capacitances at the end of the cell, the electrical
between viscosity and electrical parameter of heavy oils length, le , is not equal to the mechanical length, lm . The
using the impedance analyzer. measurement cell is designed to maximize the geometric
capacitance so that it can be sensitive to small change in
the complex dielectric constant.
II. EXPERIMENT Since it is difficult to develop an exact analytical model
for the measurement cell, this system was based on a nu-
We divided the heavy oils samples into 5 classes. The merical calibration of the relationship between the mea-
properties of heavy oils are shown in Table 1. Dielec- sured capacitance (Cmeas. ) and the static dielectric con-
tric constant of standard samples (Air; Carbon tetrachlo- stant (ε0s ) of the fluid. The numerical expression is gen-
ride; Chloroform; n-Heptane; Monochlorobenezene; 1,2- erally presented as
Dichloroethane) and the heavy oils were measured in the
frequency regions (10−2 ∼ 106 Hz) using an impedance Cmeas = Cp + C0 ε0s (2)
analyzer (Solatron, SI1260) and in the high frequency
The model parameters Cp (F) and C0 (F) are determined
regions (106 ∼ 109 Hz) using an impedance analyze
by linear regression on fluids of the known dielectric con-
(HP4191A RF). The experiments were performed at 20
stant, where Cp represents stray capacitances and C0 the
◦
C on the standard samples and 100 ◦ C on the crude oils
geometric capacitance of the measurement cell. The Cp
in free atmosphere and the temperature of the sample
includes all errors, such as instrument error, geometri-
was measured with a platinum-rhodium thermocouple.
cal error and external noise. The fluids employed in the
The temperature was controlled within ±0.1 ◦ C.
calibration procedure are listed in Table 2.
In the low and high frequency range, the capacitance
and tangent of loss angle of the cylindrical measurement
cell were measured. The complex capacitance, C*, of the III. RESULTS AND DISCUSSION
cell filled with a fluid of complex dielectric constant ε∗
is given by Figure 1 shows Cmeas as a function of ε0s at (a) 104 Hz
C0 0 and (b) 107 Hz in the standard samples. We can see a
C ∗ = C 0 − iC 00 = (ε − iε00 ) (1) good linearity between Cmeas and ε0s . This implies that
ε0
694 New Physics: Sae Mulli, Vol. 64, No. 7, July 2014

Fig. 1. The relationship between Cmeas . at (a) 104 Hz, Fig. 2. ε0 (a), ε00 (b) vs. frequency characteristics of the
(b) 107 Hz and ε0s of standard samples. Solid line fitted crude oils with various asphalt contents.
by Eq. (2). The slope of the straight line correspond to
the Co . Cp is the intercept value.
dielectric behavior of heavy oils cannot be ideally de-
scribed by the Debye expression. These two different
when Cmeas is plotted against ε0s , it should raise on a
tendencies in the frequency dependence suggest that two
straight line with the slope of C0 . Indeed, the present
dispersion mechanisms should be involved. Two di-
data show a reasonable agreement with Eq. (2) as seen
electric dispersion mechanisms are possible in our mea-
from Fig. 1. The values obtained were C0 = 28.2089 ±
suring frequency, namely: (1) The dielectric relaxation
0.0007 pF and Cp = 6.2168 ± 0.0003 pF at low frequency
due to polar molecules motions (rotation of large polar
and C0 = 2.6755 ± 0.0007 pF, Cp = 2.0399 ± 0.0003 pF
molecules) which do not involve long-range mobile large
at high frequency. polar molecules, characterized by τ1 and m, and (2) the
The estimation of the dielectric loss in this system is conductivity relaxation, or carrier response, associated
therefore based on Equation (3) with long-range conducting charge moving in heavy oil
described by τ2 and n. Consequently, The total complex
ε00 = tan δ × ε0 (3)
dielectric constant, ε∗ (ω), may be described as follows
[1,3] :
where tan δ is the measured tangent of loss angle.
Figures 2(a) and 2(b) present the variation of ε0 and ε∗ (ω) = ε∗ (ω)rotation + ε∗ (ω)carrier
ε00 versus frequency using a double logarithmic scale for εs − ε∞ σ0
ε∗ (ω) = ε∞ + m
+ [1 + (iωτ2 )n ] (4)
several heavy oils. ε0 and ε00 were obtained by Eqs. (2) 1 + (iωτ1 ) ε0 ω
and (3). The relaxational peak frequency of ε00 moves to The solid lines in Fig. 2(b) are theoretical curves ob-
a high-frequency region with increasing viscosity. More- tained by using Eq. (4). Only the data relative to the
over, another relaxational behavior appears partially in imaginary part were used in the fitting. The five parame-
the low frequency range (≤ 104 Hz). This implies the ters, ∆ε(= εs −ε∞ ), τ1 , τ2 , m and n were then introduced
Complex Dielectric Properties of Crude Oils in the Wide Frequency Range 10−2 Hz ∼ 109 Hz – Jong-Ho Park 695

increasing viscosity of the crude oils. This indicates that

the relaxation time at high frequency region is correlated
with the viscosity of the crude oils.

REFERENCES

[1] A. K. Jonscher, Dielectric Relaxation in Solids

(Chelsea Dielectric Press, London, 1983).
[2] R. H. Cole, Ann. Rev. Phys. Chem. 28, 283 (1977).
Fig. 3. Relaxation time(τ1 ) and asphalt contents of crude [3] R. H. Cole, J. G. Berberian, S. Mashimo, G. Chrys-
oils as a function of the viscosity.
sikos and A. Burns et al., J. Appl. Phys. 66, 793
(1989).
into the real part of the formula to check whether the cal- [4] T. P. Marsland and S. Evans, IEEE Proc. 134, 341
culated values are also in agreement with the measured
(1987).
value of ε0 .
[5] J. P. Grant, R. N. Clarke, G. T. Symm and N. M.
Shown in Fig. 3 is plot of relaxation time and asphalt
Spyron, J. Phys. E: Sci. Instrum. 22, 757 (1989).
contents of crude oils as a function of viscosity. Good cor-
[6] J. Hilland, Meas. Sci. Technol. 8, 901 (1997).
relations were obtained between fitting parameters and
[7] N. E. Hill, W. E. Vaughan, A. H. Price and M.
viscosity of the heavy oil. The τ1 was found to increases
Davies, Dielectric Properties and Molecular Behav-
with increasing viscosity of heavy oil. Also, the τ1 in-
ior (Van Reinhold Company Ltd., London, New
creases with increasing asphalt contents. The value of
York, 1969).
τ1 increased with increasing asphalt contents, suggesting
that the viscosity of the crude oil increased with asphalt [8] R. Bartnikas, Electrical Insulating Liquids (ASTM,
accumulation. As asphalt increased, viscosity also in- Chelsea, MI, 1994).
creased, and viscosity affected high-frequency dielectric [9] R. R. F. Kingdom, An Introduction to the Physics
relaxation. and Chemistry of Petroleum (John Wiley & Sons
Ltd., Chichester, New York, Brisbane, Singapore,
1983).
IV. CONCLUSION [10] H. P. Maruska and B. M. L. Rao, Fuel Csience &
Technology Intïl. 5, 119 (1987).
In conclusion, a cylindrical -type sample cell was de-
[11] F. Buckley and A. A. Maryott, Tables of Dielectric
signed and the correlation between heavy oil and di-
Dispersion Data for Pure Liquids and Dielectric So-
electric constant was investigated. The complex dielec-
lutions (New York: National Bureau of Standards,
tric constant of heavy oils was obtained by calibration
1958).
with several known fluids. From the complex dielectric
[12] R. C. Werst and M. J. Astle, Handbook of Chemistry
spectra of crude oil, we observed the dielectric consist-
and Physics (Boca Raton, FL:CRC, 1981).
ing of two regions for measuring frequency: the low fre-
[13] Y. Y. Akhaslov, Dielectric Propertis of Binary So-
quency region may be due to the diffusion charge trans-
port caused by impurities while the dielectric relaxation lutions (Oxford: Pergamon, 1980).
mechanism of high frequency region seems to be the non- [14] A. A. Maryott and E. R. Smith, Table of Dielec-
interacting Debye type. In the high frequency region, it tric Constant of Pure Liquids (New York: National
has been observed that the value of τ1 increased with Bureau of Standards, 1951).