Journal of the Korean Physical Society, Vol. 47, September 2005, pp.

S255∼S258

Dependence of Salt in Water-in-Crude Oil Emulsion System

Jong-Ho Park and Nam Gwon Back

Department of Science Education, Chinju National University of Education, Jinju 660-756

Ho-Soon Yang
Department of Physics, Pusan National University, Busan 609-735

Byung-Chun Choi
Department of Physics, Pukyong National University, Busan 608-737

Jeong-Bae Kim
School of Computer Aided Science, Inje University of Education, Kimhae 621-749

K. S. Hong∗
Busan Center, Korea Basic Science Institute, Busan 609-735

(Received 13 February 2005)

A cylindrical-shape sample cell was prepared to investigate the dependence of salt amounts in
a water-in-crude oil emulsion system by measuring the dielectric properties in the frequency range
from 10−2 Hz to 107 Hz with an impedance analyzer. High-sensitivity complex dielectric constant
measurements were obtained after calibration with several fluids having known dielectric constants.
From complex dielectric spectra, we observed two regions for frequency characteristics: conduction
relaxation in the low-frequency region due to diffusion by charge transport caused by impurities
such as resins and asphaltenes in the continuous phase, and the dielectric-relaxation mechanism in
the high-frequency region due to the modified Debye type where the relaxation time was in linear
proportion to the salt content in the disperse phase of the water-in-crude oil emulsion system.

PACS numbers: 77.22.-d, 77.84.Nh

Keywords: Water-oil emulsion, Dielectric constants, Dielectric relaxation, Emulsion stability

I. INTRODUCTION phase (oil region) and disperse phase (water region).

The systems commonly called ‘emulsions’ are complex
systems relevant to applications in the oil, food, or paint-
ing industries, and their properties are studied empiri-
cally in relation to various fields of science and engineer-
ing [1]. The behavior of emulsions depends on the nature
of the disperse phase [2], and the properties of obtained
emulsions strongly depend on the size of drops and their
concentration.
Dielectric spectroscopy is a powerful technique in ana-
lyzing heterogeneous systems of water-in-oil (W/O) and
oil-in-water (O/W) emulsions. The conductive and di-
electric properties of emulsions have been extensively
studied theoretically and experimentally [1–6]. Dielec-
tric relaxation was investigated in several materials re-
cently [7–10], but this is not known in W/O and O/W
emulsions. We can divide an emulsion into continuous
∗ E-mail: kyongsoo@kbsi.re.kr; Fax: +82-51-517-2497
-S255-
The main dielectric characteristics of a W/O system
are: conducting continuous and disperse phases which
do not exhibit intrinsic dielectric relaxations in the high-
frequency region in the case of non-polar phases; the
disperse phase exhibiting a Debye-type relaxation. Sys-
tematic calculations proved that Hanai’s formula can be
transformed into Cole-Cole-type dielectric relaxation for
a non-conducting dispersive phase [11]. When the dis-
perse phase is conducting, the system exhibits two kinds
of dielectric relaxation: one connected with the disperse-
phase Debye relaxation and the other arising from inter-
facial polarization phenomena; as well as a conducting
continuous phase where the system exhibits a steady con-
ductivity caused by charge diffusion in the low-frequency
region.
However, crude oil is a mixture of aliphatic and aro-
matic hydrocarbons, oxygen, nitrogen, and sulfur. Usu-
ally, it contains conducting compounds such as resins and
asphaltenes. These are large polar molecules forming ag-
-S256-
gregates or inverse micelle structures. It is reasonable to
believe that these polar compounds are the source of the
dielectric dispersions measured in crude oil [12], and the
measured spectra show relaxation behavior in the mega-
hertz region and a low-frequency conductivity. If the
conductivity of the disperse phase is high enough, con-
duction phenomena interfere with dipolar relaxation and
the total dielectric relaxation of the system results from
overlapping of the dielectric relaxation of dipolar origin.
In this paper, we calibrated the sample cell by mea-
suring dielectric-constants of known samples. We investi-
gated dielectric relaxation behavior in salt-water/crude-
oil emulsions and the relationship between salt content
and electrical parameters by using an impedance ana-
lyzer.
II. EXPERIMENTAL DETAILS
1. The impedance cell and the estimation of
complex dielectric constant
The impedance cell was designed to be sensitive to
small changes in the dielectric constant, which means
that the geometric capacitance must be maximized. In
order to minimize the influence of impurities in the liq-
uid, a large sample volume is needed. Based on this, a
cell with geometric capacitance of approximately 11.60
pF and mechanical length (lm ) of 60 mm, with a = 4.5
mm and b = 6.0 mm, was designed as shown in Figure
1.
Since the development of an exact analytical model
for the measurement cell is difficult, the system is based
upon a numerical calibration of the relationship between
measured capacitance Cmeas and the real part of the com-
plex dielectric constant of the fluid. The parameters Cp
and C0 are determined by linear regression on fluids with
known dielectric constants, where Cp is the stray capac-
itance and C0 the geometric capacitance of the cell. The
dielectric constants of several fluids used in the calibra-
tion are given in Table 1. We plotted the capacitance of
Fig. 1. Schematic diagram of cylindrical-shape sample cell
for the dielectric measurements.
Journal of the Korean Physical Society, Vol. 47, September 2005
Table 1. Dielectric constants of the standard samples at
20 ◦ C.
Medium Dielectric constant (ε0 ) References
Air 1.0005 ± 0.0002 [12]
n-heptane 1.924 ± 0.01 [13]
Carbon tetrachloride 2.238 ± 0.002 [14]
Chloroform 4.82 ± 0.02 [15]
Monochlorobenzene 5.699 ± 0.008 [14], [15]
1,2-dichloroethane 10.65 ± 0.05 [13], [14]
the samples as a function of frequency, and found that
capacitances of the samples used were almost indepen-
dent of measuring frequency. The numerical calibration
depends on accurate data of the real and imaginary parts
of the complex dielectric constant. The real part of the
dielectric constant is determined from the measured ca-
pacitance, Cmeas . The imaginary part of the dielectric
constant of low-loss fluids involves large uncertainties;
hence, an accurate linear regression model is difficult to
obtain.
2. Sample preparation and test of emulsion sta-
bility
To make emulsion samples, 50 ml of distilled water
and crude oil are prepared. A small amount of salt is
melted in the distilled water(50 ml). Melted salt water
and crude oil are mixed for 5 minutes with an ultrasonic
homogenizer. We divided salt-water/crude oil emulsion
samples into 5 classes (0.0, 0.2, 0.4, 0.6 and 0.8 PTB-
crude oil/water, where 0.5 PTB is 1.427 mg/l = 1.427
ppm). Sometimes, thermal reaction happens by super-
sonic waves when the mixture is made into emulsion. It
is very difficult to obtain dielectric spectra in a stable
state because particles are moving until thermal equilib-
rium is achieved. We checked the stable condition of the
emulsion by measuring the time dependence of capaci-
tance at 104 Hz for a 0.0 PTB-crude oil/water emulsion
sample.
Figure 2 shows the time dependence of capacitance
and tan δ in 0.0 PTB-water/crude oil emulsion. We can
observe that the capacitance increases abruptly and sat-
urates after 10 minutes. Although the time dependence
of tan δ was opposite to capacitance, it also saturates af-
ter 20 minutes. This means that the emulsion becomes
stable because of the decrease of particle mobility. Thus,
we made emulsion samples and obtained dielectric spec-
tra in the emulsion after a stabilizing time of 20 min-
utes. The dielectric spectroscopy of salt-crude oil/water
emulsion is measured in a frequency domain (10−2 ∼ 107
Hz) with an impedance analyzer (Solatron, SI1260). The
data were taken at 20 ◦ C in atmosphere, and the tem-
perature of the sample was measured with a platinum-
rhodium thermocouple with stability ±0.1 ◦ C.
Dependence of Salt in Water-in-Crude Oil Emulsion System – Jong-Ho Park et al.
Fig. 2. Time dependence of capacitance and tan δ in 0.0
PTB-water/crude oil emulsion.
Fig. 3. Schematic diagram of continuous and disperse
phases in salt-water/crude-oil emulsion system. S means salt,
white circles are water drops, and small black circles are im-
purities.
III. RESULTS AND DISCUSSION
Figure 3 shows a schematic diagram of the salt-crude-
oil/water emulsion system, where we can distinguish the
crude-oil region (continuous phase) and the salt-water
region (disperse phase). The continuous phase includes
conducting materials such as asphaltenes, resin, and non-
conducting materials. Water holds salt (conducting ma-
terial) in the disperse phase.
When we consider water only, as for Debye-type ideal
materials, the measured complex dielectric constant as a
function of angular frequency can be described by
ε s − ε∞
ε∗ (ω) = ε∞ + , (1)
1 + iωτ
where ε∞ is the high-frequency dielectric constant, εs the
static dielectric constant of the liquid, and τ the relax-
ation time of the Debye process. When we consider the
orientation of polarizations caused by molecules and in-
terfacial polarizations of the disperse phase at the bound-
-S257-
Fig. 4. ε0 and ε00 vs. frequency characteristics of salt-water
/crude oil emulsion.
ary, the dielectric constant (1) can be rewritten as
εs − ε∞
ε∗ (ω) = ε∞ +
1 + (iωτ )1−α
εp − εs
+ , (2)
1 + (iωτp )1−αp
where τ and τp are the relaxation times and α and αp
are parameters describeing the distribution of relaxation
times. A conductivity term was fitted to complex dielec-
tric constant spectra for conducting materials; thus, the
expression for dielectric constant (2) becomes
εs − ε∞
ε∗ (ω) = ε∞ +
1 + (iωτ )1−α
ε p − εs iσ
+ − . (3)
1 + (iωτp )1−αp ε0 ω
The first two terms on the right-hand side are the original
Cole-Cole model, which is dielectric relaxation caused by
dipole orientation polarization of polar molecules in the
frequency range 100 MHz ∼ 10 GHz. The third term
accounts for a low-frequency relaxation due to the inter-
facial polarization effect at the grain boundary. The last
term is purely empirical, and is the conductive loss in
the liquid, depending on the measurement cell, and σ is
the dc conductivity.
Figure 4 shows variations of the real (ε0 ) and imaginary
00
(ε ) parts of the dielectric constant versus frequency in
log-log scale for several salt contents. The real part ε0
decreases slowly in the frequency range from 10 to 106 Hz
with salt content. The characteristic peak in the imagi-
nary part ε00 , which is shifted towards higher frequencies
when salt content increases, indicates the presence of a
relaxation process.
The values ε0 and ε00 decrease rapidly with frequency.
The absolute values of the slopes below 104 Hz are larger
than those above 104 Hz and seem to be independent of
the salt content. These two tendencies in frequency de-
pendence suggest that two dispersion mechanisms are
involved in the dielectric-constant measurement. There-
fore, the conductivity term in Eq. (3) should be im-
proved, because the slopes of ε0 and ε00 at low frequency
-S258-
are not unity. Since diffusion occurs in these emulsion
systems, two polarization mechanisms are possible: the
dielectric relaxation due to continuous/disperse-phase
interfacial polarizations which do not involve long-range
mobile droplets, characterized by τ1 and m, and the con-
ductivity relaxation or carrier response associated with
conducting charges moving in the continuous phase, de-
scribed by τ2 and n, where τ1 and τ2 are the relaxation
times in the order of µs and ms, respectively. Therefore,
the total complex dielectric constant can be described as
ε s − ε∞
ε∗ (ω) = ε∞ +
1 + (iωτ )m
σ0
+ [1 + (iωτ )n ]. (4)
ε0 ω
After evaluating all the frequency-dependent complex-
dielectric-constant data fitted with Eq. (4), we found
that the carrier polarization mechanism was weakly dis-
persive, while the interfacial polarization mechanism was
somewhat more dispersive. From the calculated values
of τ1 and τ2 in the emulsion system, we observed that
the relaxation time τ1 was in linear proportion to salt
content while τ2 was independent of the salt content in
the emulsion systems. These facts suggest that the high-
frequency dielectric relaxation is not related to resins
and asphaltenes in the continuous phase, but is related
to the salt in the disperse phase. Since τ1 and σ do not
depend on salt content, salt cannot move from disperse
phase to continuous phase and can be trapped strongly
to droplets. A dielectric response relation, which is con-
sidered as a generalization to the Cole-Cole dielectric ex-
pression, has been proposed. The influence of the charge-
carrier contribution on the complex dielectric constant is
significant, as is demonstrated when both interfacial and
carrier polarization mechanisms are simultaneously con-
sidered.
IV. CONCLUSIONS
A cylindrical-shape sample cell was prepared to in-
vestigate the dependence of salt amounts in a water-
in-crude-oil emulsion system by measuring the dielec-
tric properties in the frequency range from 10−2 Hz to
107 Hz with an impedance analyzer. The characteris-
tics of the measurement cell are optimized to give high
sensitivity. High-sensitivity complex-dielectric-constant
measurements were obtained after calibration with sev-
eral fluids having known dielectric constants. From com-
plex dielectric spectra, we observed two regions for fre-
quency characteristics: conduction relaxation in the low-
Journal of the Korean Physical Society, Vol. 47, September 2005
frequency region due to diffusion by charge transport
caused by impurities such as resins and asphaltenes in
the continuous phase, and the dielectric-relaxation mech-
anism in the high-frequency region due to the modified
Debye type. In the high-frequency region, it was ob-
served that the relaxation time, τ1 , was in linear pro-
portion to the salt content in the disperse phase of the
water-in-crude-oil emulsion system.
ACKNOWLEDGMENTS
This work was supported by Korea Science and Engi-
neering Foundation Grant R05-2003-000-10451-0.
REFERENCES
[1] N. A. Mishchuk, A. Sanfeld and A. Steinchen, Adv. Col.
Int. Sci. 112, 129 (2004) and references therein.
[2] B. P. Binks, Modern Aspects of Emulsion Science (Cam-
bridge, The Royal Soc. Chem, 1998).
[3] J. Sjöblom, N. Aske, I. H. Auflem, O. Brandal, T. E.
Havre, O. Saether, A. Westvik, E. E. Johnsen and H.
Kallevik, Adv. Col. Int. Sci. 100, 399 (2003).
[4] K. Kumar, A. D. Nikolov and D. T. Wasan, Ind. Eng.
Chem. Res. 40, 3009 (2001).
[5] N. Aomari, R. Gaudu, F. Cabioch and A. Omari, Col.
Surf. A 139, 13 (1998).
[6] O. V. Gafonova and H. W. Yarranton, J. Col. Int. Sci.
241, 469 (2001).
[7] C. S. Kim, B. E. Jun, H. H. Baek, D. J. Kim, Y. H.
Hwang, H. K. Kim, G. S. Jeen and J. N. Kim, J. Korean
Phys. Soc. 42, S1038 (2003).
[8] J. S. Kim, H. S. Lee and C. H. Jeong, J. Korean Phys.
Soc. 42, S1042 (2003).
[9] J. Oh, J. A. Seo, G. S. Jeen, H. K. Kim, Y. H. Hwang
and S. Kojima, J. Korean Phys. Soc. 44, 527 (2004).
[10] B. Kim, C. Lee and I. Yu, J. Korean Phys. Soc. 44, 908
(2004).
[11] C. Boned, J. Peyrelasse, M. Clausse, B. Lagourette,
J. Alliez and L. Babin, Colloid Polym. Sci. 257, 1073
(1979).
[12] R. C. Weast and M. J. Astle, Handbook of Chemistry and
Physics (CRC, Boca Raton, 1981).
[13] A. A. Maryott and E. R. Smith, Table of Dielectric Con-
stants of Pure Liquids (National Bureau of Standards,
New York, 1951).
[14] F. Buckley and A. A. Maryott, Table of Dielectric Dis-
persion Data for Pure Liquids and Dilute Solutions (Na-
tional Bureau of Standards, New York, 1958).
[15] Y. Y. Akhadov, Dielectric Properties of Binary Solutions
(Pergamon, Oxford, 1980).