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Abstract

This paper shows the electrical conduction


characteristics of commercial diesel oil in solution
with surfactants. Theories usually considered with
pure hydrocarbons are able to explain satisfactorily
the behaviour of these complex mixture.

Introduction

In the past, there has been some attempts to assist the
injection of the oil in diesel engines with electric
fields. In our laboratory, we work on this very
problem [1]. Beside the theoretical study dealing with
stability of high speed jets of hydrocarbons, we have
been interested in the electrical properties of the diesel
oil. This paper relates the work we did on the
electrical conduction of the diesel oil.
Knowing that the diesel oil is, in fact, a complex
mixture of hydrocarbons and additives, whose
composition changes very often (as a result of its
origin), our experimental study uses the same sample
(the same origin). In order to get more information on
the behaviour of the diesel oil, we add an additive
(ASA3) which most of the components are
surfactants. More information about this additive can
be obtained for instance in [2].

Experimental device

A scheme of the experimental device is shown in
figure 1.The measuring cell we have designed, is
mainly composed of two planar parallel electrodes.
We can modify the distance d between them and the
liquid temperature T with an external circuit of water.
Our study concerns the transient and steady response
in current when we apply a voltage step. We analyse
them with the help of the theories usually considered
with dielectric liquids.

Figure 1



CHV source, CVoltmeter, CFaraday cage,
CMeasuring cell , CHV electrode, heat exchanger,
Coscilloscope, recorder, amperemeter, 1head of
amperemeter


Steady regime

The steady reponse is measured with a Keithley
electrometer 642, 5 minutes after applying the voltage
step. Electrodes were short-circuited between two
consecutive experiments.
Experiences at low electric fields (<10kV/m), show
that current density j is linear with voltage applied V
in the low voltage interval (ohmic interval). In this
region we can measure the dc conductivity of the
liquid = j
V
d
, the equivalent conductivity *
defined as

* =
c
(where c is surfactant
concentration) and the reduced equivalent
conductivity of the solution =

0
c
(where
0
is pure diesel oil dc conductivity at the same
conditions). These last parameters measure the degree
of dissociation of the additive and so show the effect
of surfactant on dc conductivity [Klinkenberg 3]. We
show in figure 2 the conductivity, the equivalent

CONDUCTION PHENOMENA OF DIESEL OIL


G. ARTANA
1
, H. ROMAT
1
, G. TOUCHARD
1,
B. DIKAREV
2


1
L.P.M.F., L.E.A., URA CNRS N191, Universit de Poitiers, 40 Av du Recteur Pineau, 86000, Poitiers,
FRANCE
2
Deparment of Physics, Civil Engineering Institute, Dniepropetrovsk, UKRANIE

conductivity and the reduced equivalent conductivity
as a function of the additive concentration.

We can see in this figure that conductivity of pure
diesel oil is highly increased when we incorporate low
amounts of surfactants, but at higher additiive
concentrations this effect diminishes.
Our results seem to agree with the theories that
consider the existence of reversed micelle structures
[4 Peersons]. In these structures the hydrophylic part
of the molecules of suractant form a central core
around a polar molecule of the liquid and the
hydrophobic part arrange in a radial configuration.
Reversed micelles structures were detected in some
hydrocarbons after a limit of surfactant concentration
is overcame named critical micellar concentration
(CMC). Then the initial equilibrium of ionic pairs AB
and free ions A
+
and B
-
.
AB
K
d
K
r
A B


+
+

(1)
is modified and the reaction can be considered as
2 ( AB)
n

K
d
K
r
AB
n
AB
n
1
1


+
+

( ) ( ) (2)
where ( AB)
n
represent the reversed micelle and
( ) AB
n
+
and ( ) AB
n

are the new charge carriers.



The CMC is usually detected by a sudden change in
conductivity curves as a function of concentration of
surfactant. As no sudden change is observed in figure
2 we can say that no critical micelle concentration
seems to be present.

A slight plateau of * shown in figure 2 is quite
similar to the one observed by Denat [5] and other
scientist. Denat has explained it considering that in the
pure hydrocarbons he has studied there was an
important amount of micelles and a negligible amount
of free ions and of ion pairs. When we analyse , that
excludes the effect of free ions existing in pure diesel
oil, the reduced equivalent conductivity exhibits a
much more evident plateau

Figure 3 shows as a function of the inverse of
absolute temperature T.
FIGURE 3) Diesel oil conductivty as a function of the
inverse of liquid temperature. Different concentartions
of additive.

We can see in this logarithmic plot that conductivity
depends exponentially on temperature. like


=

o
e
kT

The exponents are summarised in table I and they
are compatible with those corresponding with pure
hydrocarbons [6Adamczewsky].

TABLE I

concent. 0 ppm 1ppm 10ppm 100ppm
0.31eV 0.36eV 0.31eV 0.25eV

Figure 4 shows the relationship of j with electric field
E=V/d. At higher electric fields than those
corresponding to the ohmic interval, the diesel oil
without additives shows a saturation of the current
whit electric field. These results are in good
agreement with the prediction of current density j
s
and voltage saturation V
s
of Thomson's theory [7]
j
s
d
V
s
j
s
d
= =


2
2
and
that is usually applied to some dielectric liquids.
With solutions of diesel oil with additives no clear
saturation. In this case, applying Thomson's theory,
saturation should occur at electric fields higher than 1
MV/m. However for these fields other phenomena
like increase of bulk creation of charge carriers or
injection.
Theoretical models of both phenomena are reported in
several works[4]. First one is described with the
theory of Onsager of field enhancement of
dissociation constant of equilibrium 1.
K
d
K
d
I e E U
e E U
=

0
1 0
2
0
4
2
/ ( )
/ ( )


In this formulae K
d0
is the dissociation constant at
the thermodynamic equilibrium, I
1
is the modified
Bessel function of first kind and order 1 and
L e E U =
0
2
/ ( )
where e
o
is the electron charge and U the thermal
potential equal to kT/e
0,
with k Boltzman's constant.
In solutions of hydrocarbons with surfactants this
theory has been also applied to describe the
enhancement of constant K
d1
of equilibrium 2 [8]
Current density j of some injection models where free
ions must escape from the image barrier [4] are
expressed by
j K
ech
q
a
=
with K
ech
D x
i
x
a
x
a
E
o
U
K L L
=
+ 2
1
2
exp ( / / )
( / )

where D mean diffusion constant of ions, x
a
is the
minimum distance of approach of an ion to the
electrode wall, x
i
e
U
=
0
16
and q
a
is the charge
density at the plane x
a.
This charge density is usually
estimated with q
a
A =

2
with A a coefficient taht
depends on liquid caracteristics.[Castellanos]
Both theories give similar results in our case and these
predictions fits well with our experiments. However
this theoretical analyses can not distinguish the role of
each phenomena. Transient reponse enable us to
explain this.

Transient regime

Transient reponse is obtained with the system of
figure 1 operating with an oscilloscope Tektronic
P7001. Time constants of the whole measurement
systems are about 1 ms.
At low electric fields transient phenomena are faster
than the time constants of the measurement system
and from the decay of current with time no useful
information can be obtained.
A typical transient reponse at higher electric fields is
shown in figure 5. It is composed by an initial plateau
of current Io with time, then an increase of it until
time T
t
when a maximum I
mx
is recorded and then a
decrease towards the steady value.
In figure 6 we show the dependence of T
t
with
electrode voltage. In a first region of these curves time
T
t
depends linearly with voltage. In a second region
this linearity is lost. The expression of transit time of
ions from one electrode to the other of injection
models in isolating liquids with the simpler models is
T
t
d
V
=
2

(3)
where we see that T
t
is inversely proportional to V as
can be verified in the first region of our curves.
Non linearity in the second region is usually explained
by the influence of electroconvection phenomena.
In figure 7 we show the dependence of T
t
with
electrode spacing. It is observed that time Tt
dependence with d is not quadratic as should be
expected from formulae (3). This and the initial
plateau of current Io with time shows that residual
conduction phenomena is also present.
Figure 8 and figure 9 shows the quotient of I
mx
with
Io as a function of V for pure diesel oil and diesel oil
with additives respectively. This quotient is a good
parameter to estimate the relative importance of
injection and residual conduction.
As this quotient is higher for pure diesel oil than for
diesel oil with additives, we can think that injection is
much more important in the first case.
For diesel oil solutions with additives this quotient is
quite close to 1 so a low level of injection seems to
occur. This agrees with other researcher's results of
some pure hydrocarbons with surfactants where no
injection is observed. This ihas been explained by the
large size of this micelles and its difficulty to have a
close approach to the electrode.
So, for diesel oil with additive, at high electric fields
we think that at least two kinds of charge carriers are
present, one minoritary proceeds from injection
(maybe the same of pure diesel oil) and the other
majority, of larger size, from the dissociation of the
reversed micelles.
Though transient response is only qualitatively
predicted by theories of injection in isolating liquids, a
rough estimation of a kind of mean ionic mobility
can be obtained with formulae 3
Table 2 shows us this mean mobilities. Also we show
in the third and fifth column the product of this mean
mobility and coefficient of dynamic viscosity .
Walden's law predicts that his product should be
constant at different temperatures. This table shows us
that this law is satisfactorily verified.

TABLE 2
T
K
10
-8
m
2
/Vs
10
-8
cPo m
2
/Vs
10
-8
m
2
/Vs
10
-8
cPo m
2
/Vs
0 ppm 10 ppm
293 1.05 2.81 1.66 4.44
303 1.21 2.44 2.22 4.48
313 1.59 2.56 2.50 4.02
323 1.96 2.7 2.86 3.94


Conclusions

In this paper we have studied the behaviour of a
commercial diesel oil with a surfactant.
It is shown the influence of liquid temperature and
surfactant concentrartion on some useful electrical
parameters as dc conductivity and mean ionic
mobility.
We have verified that theories usually considered for
pure hydrocarbons can be used to describe the
electrical behaviour of this complex mixture at low
and high electric fields.

Acknowledgments

We are very greatful to Dr P.Atten with whom we
have held very fruitful discussions.

References

1. G.Artana, Thse doctorale, Universit de Poitiers,
1995.
2. Douwes Van der Waarden
3. Klinkenberg
4. Peersons
5. Denat, Thse doctorale, Universit de Grenoble
6 Adamczewsky
7 Thomson
8 Randriamalala, Thse doctorale, Universit de
Grenoble

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