ElecfrochimicaAcra, Vol. 35, No. 7, pp.

1125-I131, 1990 0013-4686/90

$3.00+ 0.00
Printedin Great Britain. 0 1990.PergamonPressplc.

A SPECIFIC ASPECT OF IMPEDANCE MEASUREMENTS

IN LOW CONDUCTIVITY MEDIA. ARTEFACTS AND
THEIR INTERPRETATIONS
S. CHECHIRLIAN,*P. EICHNER,*M. KEDDAM,? H. TAKENoUTIt and H. MAZILLE~
*RhBne-Poulenc Industrialisation 24, Av. Jean-Jauris, 69151 D&cines-CharpieuCedex, France
tLP 15 CNRS “Physique des Liquides et Electrochimie”, Laboratoire de l’Universit6 Pierre et
Marie Curie, Tour 22, 4, Place Jussieu, 75252 Cedex 05 Paris France
SINSA de Lyon, 20 Av. Albert Einstein, 69621 Villeurbanne Cedex, France

(Received 4 September 1989)

Abstract-Impedance measurements in the high frequency range beyond the electrolyte resistance, R,,
currently exhibit one or several loops irrelevant to the electrode process. For low conductivity media
encountered in spreading corrosion studies these relaxations appear in a lower frequency range
(l&l00 Hz) and can overlap the faradaic frequency range, thus leading to possible misinterpretation of
the data. This aspect was investigated in concentrated acetic acid solutions using two different kinds of
reference electrode. Solution resistivity as well as nature of the reference electrode and the distance between
working electrode surface and reference extremity were extensively investigated. The parasitic contribu-
tions of the different elements of the experimental setup on the measured impedance was modelled by a
unique electrical circuit which reproduces with an excellent precision the experimental data. This allowed
us to underline the various contributions of the electrical couplings occurring in the electrochemical cell,
especially between the reference electrode and the other elements.

Key words: low conductivity media, impedance measurement, acetic acid.

1. INTRODUCTION overlap those of the electrode’s response, which

In addition to steady-state techniques, the impedance
measurement is largely used in corrosion studies and
its application is quite naturally spreading to low
conductivity media (organic electrolytes, dilute
aqueous media . . .) [ 1,2]. In fairly conductive media,
the contribution of the electrolyte resistance is rather
negligible in the steady-state characteristics. Further-
more, the high frequency limit of impedance is iden-
tified with the electrolyte resistance. On the contrary,
in low conductivity media, steady-state polarization
techniques come up against difficulties which are
often insuperable due to the presence of ohmic drop.
Devices for the compensation of this term often need
to know, n priori, the value of the electrolyte resis-
tance itself. The impedance measurements are there-
fore primarily aimed at determining this quantity and
secondly at obtaining information on the electro-
chemical processes taking place at the electrode.
Unfortunately, the identification of the various
items contributing to the measured impedance be-
comes more and more difficult as the resistivity of the
solution increases. In particular, electrolyte resistance
no longer appears as the high frequency lin$ of the
impedance. The parasitic contributions by capacitive
as well as by inductive features intervene in the high
frequency range. A great vigilance is hence needed as
to their interpretation. We found that these artefacts
may appear even at much lower frequencies, for
instance at 10 to 100 Hz, in very low conductivity
media. From this point on, the frequency range
associated with these parasitic impedances can
makes the interpretation of the results rather difficult.
Several authors have examined these problems and
have demonstrated the role played by the time con-
stants arising from connections with the poten-
tiostat[ l-61. However, no publication completely
analyses this aspect, often misunderstood, of im-
pedance techniques and more generally of non-
steady-state techniques in low conductivity media.
The objective of the work presented here was firstly
to carry out an experimental study analysing the
various parameters involved in the frequency re-
sponse of a three-electrode cell. Apart from the
solution’s resistivity, two factors especially drew our
attention: the nature of the reference electrode and
the distance between the extremity of the reference
electrode and the working electrode, which deter-
mines, for a given resistivity, the value of the elec-
trolyte resistance R,. We were then able to produce
an electrical model which gave a coherent indication
of the behaviour observed.
2. EXPERIMENTAL DEVICE
2.1. Cell and electrodes
The cell is cylindrical and contains 200cm3 of
solution (cx Fig. 1). The counter-electrode is a plat-
inum mesh covering the side wall and the base of the
cell. The working electrode is an 11.3 mm diameter
disc enclosed in a PTFE sheath 20 mm in diameter.
An AISI 316 stainless steel electrode in concentrated
acetic acid solutions was used in this study. This

1125
1126 S. CHECIBRCLIAN
et al.

Ag/AgCl reference which Z’ and Z” are the real and imaginary parts of
electrode 4 Platinum the impedance.
Wire

3. EXPERIMENTAL RESULTS
Rotating
device 3.1. Ag/AgCl electrode and Luggin capillary
Figure 2a shows the progression of the impedance
i diagram in relation to the distance x in an 80% acetic
CSCOOH acid solution. In the high frequency range of the
II
+ 0.1 M LiClO~ Platinum
electrode diagram (2.5-65 kHz) one sees a capacitive loop
whose diameter remains constant whatever x may be
and on which the frequency distribution does not
vary.
At low frequency (less than 100 Hz), the beginning
of a large diameter loop appears. This impedance is
Counter-electrode
relative to the faradaic impedance of the working
electrode. The intersection of its high frequency part
Fig. 1. Experimental device.
with the real axis leads to the electrolyte resistance R, .
May we recall that one can also calculate R, by
electrode was mounted on an ED1 Tacussel rotating comparing the value x with Newman’s equation
device whose speed was set at 1000 rpm for all the based on the distribution of the primary electrical
tests. The cell configuration adopted made it possi- field[7].
ble[2] to apply the analytical equations of Newman[q A third loop appears at the intermediate frequen-
for estimating the electrolyte resistance value at a cies (100 Hz-2.5 kHz): when x is greater than
given point in the cell. 2 mm, it is capacitive and its diameter grows with x.
Two types of reference electrodes were tried out: (i) When x becomes less than 2 mm the capacitive loop
A commercial Ag/AgCl electrode prepared in anhy-
drous acetic acid, saturated with LiCl and AgCl,
extended by a Luggin capillary filled with anhydrous
acetic acid + 0.1 M LiClO,. In order to limit ex-
changes with the solution, the extremity of the capil-
lary was plugged with asbestos fibre: (ii) A platinum
wire 0.5 mm in diameter, inserted in a glass capillary,
only the cross section of the platinum wire being in
contact with the electrolyte. This wire does not in
itself constitute a reference electrode but plays the
role of a low impedance alternating potential probe.
Its connection, via a capacitance, in parallel with the
reference electrode is generally recommended in order
to attenuate measurement difficulties at high frequen-
cies[l, 91. We shall see further on the reasons for the
improvement thus obtained. The extremity of the
reference electrode is located on the axis of the
working electrode. A screw device made it possible by
the use of a dial indicator to precisely check the
distance x between the surface of the working elec-
trode and the extremity of the reference electrode.

2.2. Electrolytes
60C
Two solutions with different resistivities were used: 1

(i) aqueous solution of acetic acid at 80% by weight

(p = 8-10.2 kf2 cm), (ii) 100% commerlcally pure
acetic acid @ = 8-12 MD cm).

2.3. Regulation-measurements
The measurements were carried out with a Solar-
tron-Schlumberger assembly (1286 potentiostat, 1250
frequency response analyser) controlled by an Apple
IIe personal computer.
The tests were carried out at room temperature.
For each reference electrode/solution couple, we
recorded the impedance diagram of the cell in galv- Fig. 2. Impedance diagram at different distances x between
anostatic mode for different values of x. A pseudo- the capillary tip (Ag/AgCl electrode) and the working
three-dimensional (Z’, Z”, x) display was adopted, in electrode: (a) 80% acetic acid; (b) 100% acetic acid.
 Impedance measurements in low conductivity media 1127

Fig. 3. Impedance diagram at different distances x between the extremity of the platinum electrode and
the working electrode: (a) 80% acetic acid; (b) 100% acetic acid.

disappears and is replaced by an inductive one whose 3.2. Platinum electrode

diameter increases when x decreases.
The diagram corresponding with x close to zero
shows up a particularity: part of the low frequency
loop crosses the field of the negative impedances (2”d
and 31d quadrants). When the reference electrode
approaches very close to the working electrode, the
glass capillary gives rise to a screening effect. A
similar phenomenon has already been observed and
interpreted by Fiaud et a/.[lO]. It appears when one
carries out impedance measurements on electrodes
covered with thin electrolyte layers.
The results obtained in 100% acetic acid are given
in Fig. 2b. The main difference compared with
the preceding results lies in the relative diameters
of the loops and the distribution of the frequencies.
The frequencies for which the various loops appear
are displaced downwards towards much lower
values. The diameter of the low frequency capa-
citive loop attributed to the corrosion process is
much smaller than that of the loops found at
medium and high frequencies, and it is practically
indistinguishable when x becomes greater than
0.5 mm.
The diagrams recorded with the platinum electrode
as reference electrode in acetic acid at 80 and 100%
are given in Figs 3a and b respectively. In the solution
at 80% the diagrams only show two loops in the
frequency range explored. The low frequency loop
originated in the working electrode. The second loop
whose diameter depends on the distance x transforms
from a capacitive to an inductive behaviour when x
becomes sufficiently small just as we have observed at
medium frequencies with the Ag/AgCl electrode. The
existence of this high frequency parasitic loop consti-
tutes the most specific feature of artefact generally
observed for electrolytes with a resistivity of less than
a few hundred of ohm cm and with a reference
electrode whose extremity is made up of a sintered
glass wall.
In acetic acid at lOO%, the shape of the diagrams
is similar to the one observed with the Ag/AgCI
electrode in the solution at 80%, except that the
diameters of the loops are greater. The low frequency
limit of the spectrum does not allow the visualization
of the faradaic loop, even when x is small.
1128 S. CHECHIRCLIAN et al.
4. DISCUSSION AND MODELLING
The whole experimental data indicates that: (i) the
high frequency limit of the impedance diagram is the
origin of the axes and not the electrolyte resistance
R,, (ii) generally speaking, two parasitic loops come
between the origin and R,: one capacitive high fre-
quency loop, independent of the position of the
reference electrode and one medium frequency loop,
depending on the position of the reference electrode.
This loop always becomes inductive when the latter
is close to the working electrode.
These phenomena appear at frequencies which are
generally associated with the variations of the inter-
facial impedances. One can therefore easily imagine
situations in which the overlap would prevent any
separation between the faradaic process on the one
hand and the parasitic impedances on the other hand.
In this case, determining R, would become totally
impossible.
The origin of these phenomena is to be found in the
fact that the reference electrode impedance is not
ideal and that it contributes to the measured
impedance. Electrical couplings between this elec-
trode and the other elements of the cell occur at high
frequencies. These couplings naturally depend on the
type and geometry of the reference electrode, and also
on its position by the way of the electrolyte resistivity.
Some of these couplings have been studied in the
literature on the subject and models have been pro-
posed[3-51. However, none of these models is able to
give a complete representation of our experimental
results described above. One must also take into
account the specific nature of the reference electrode
used. In the case of the’platinum electrode, one must
introduce an additional capacitance, located at the
extremity of the electrode, resulting from the double
layer capacitance at the platinum/acetic acid inter-
face. Also, one must introduce a resistance and a
capacitance representing the coupling between the
reference electrode and the counter-electrode.
This finally leads us to consider the network shown
on Fig. 4[2, 111. In this circuit, & represents the
electrolyte resistance between the reference electrode
and the working electrode, R, + R: = R,,, the elec-
trolyte resistance between the working electrode and
c2T
? ..zQR~l
Zf 7
Fig. 4. Equivalent circuit dealing with experimental results.
R,, C,: working electrode impedance. R, + R: = R,,,: elec-
trolyte resistance between the counter-electrode and the
working electrode. C,, R,: series capacitance and resistance
of the reference electrode. C,, R:: coupling elements be-
tween the reference electrode and the counter-electrode. C,:
coupling capacitance between the reference electrode and
the working electrode.
the counter-electrode. R: is an electrolyte resistance
localized on the one hand between the reference
electrode and the counter-electrode, and on the other
hand in the capillary. R, is the charge transfer resis-
tance of the working electrode and C,, the double
layer capacitance. The resistance R, represents the
actual resistance of the reference electrode which is
localized mainly at the capillary tip. This resistance
varies depending on the geometry of the capillary tip
and also on the resistivity of the solution. In the case
of the platinum electrode, this resistance represents
the frontal electrolytic resistance of the platinum
wire. The capacitor C, is due to the coupling between
the reference electrode and the counter-electrode.
Capacitor C, represents the capacitive coupling be-
tween the reference electrode and the working elec-
trode. The input capacitance of the potentiostat and
of the connecting cables can also contribute to in-
creasing the value of C,.
May we point out that this model, representative of
our cell behaviour, does not contain any self-induc-
tive element whereas on the experimental diagrams
one observes large inductive loops. The contribution
of the real inductance of the working electrode or of
the connecting cables has already been shown in very
special cases, for example when the impedance of the
system studied is very low[6]. However, in our case
the amplitude of the inductance observed is such that
it cannot be linked with that of the cables or the
working electrode. Giihr ef u1.[3], in a study similar
to ours, demonstrated in fact that this pseudo-induc-
tive effect is a consequence of the capacitive coupling
between the working electrode and the counter-elec-
trode. In fact, at high frequencies, a potential derived
from the counter-electrode by the way of the capaci-
tance C1 is added to the potential measured by the
reference electrode (point B). Whereas the impedance
of C, decreases when the frequency increases, the
amplitude of the derived potential increases. This
results in a rise in the impedance modulus measured
with the frequency, which causes the inductive be-
haviour observed at high frequency in the aqueous
acetic acid solution or at medium or even low fre-
quency in the concentrated acetic acid.
4.1. Analytical expression of the impedance
To check the validity of our model, we calculated
its impedance. The apparent impedance measured
was equal to the ratio of the voltage in C to the total
current crossing the cell:
According to the Kirchoffs law, the sum of the
currents arriving at the nodes A, B and C is nil and
let:
Z,=R:+i
jd, ’
5= R,+,&, I
z,= R,
jr&R,+ 1’
(5)
 Impedance measurements in low conductivity media 1129

1 1 The calculation of this impedance in the frequency

-= I+‘+_ (6)
z cqu. R: 5 R,+ Z,’ range 1 Hz-100 kHz was done with a personal com-
puter. The corresponding impedance diagrams were
we obtain: drawn after having attributed to the elements of the
model various consistent values and in such a way

zapp.=
($+ I)(_!.&;_;9
(7) that the simulated diagrams are close to the experi-
mental diagrams.
The variation of the distance between the working
electrode and the reference electrode was simulated
RI 1 by modifying the ratio RJR; whilst keeping the sum
R, + R: constant. The values adopted for R, were
*+ (8) chosen from the experimental diagrams shown
B
in Figs 2 and 3 whereas the sum R, + R: was esti-
mated in accordance with the Newman’s equation:

-2-lkC-S

60
i

Iktiz

I I
*
2
3 Z’(kCU

R* (km
f

I I )

WC
m Z’(kra

Fig. 5. Simulated diagrams corresponding with the situation of the Ag/AgCl electrode with the capillary:
(a) 80% acetic acid; (b) 100% acetic acid.
1130 S. CI~ECH~RCLIAN
et al.

Table 1. Values attributed to the various elements of Fig. 4 in the case of the Ag/AgCl electrode with the capillary
AidAtSl 4 R,+R: RI R* R, Cd C, G C,
80%
CH,COOH &2kf2 4kQ 2MQ 2MR 1OOkI-I @IJF 10 pF 30pF IMF
100%
CH,COOH O-O.5MR 2MR 2MfJ IOOMR 1OOk.Q 6OpF 10 pF 3OpF 1MF

Table 2. Values attributed to the various elements of Fin. 4 in the case of the platinum electrode
Platinum R R+R: R:’ R. R, C.4 C, c, c.
80%
CH,COOH &1.5kf-& 4kR 0.1 MR 0.1 M&I 0.1 MR MpF 1OpF 30pF O.lpF
100%
CH,COOH &I .2 MR 2MR 2MQ 1OOMR 0.1 MR 6OUF 10~F 30~F O.luF

R, + R: = p/4,,, in which r,, is the radius of the
working electrode.
4.2. Digital simulation
Figure 5 represents the diagrams simulating the
behaviour of the Ag/AgCl electrode. They were ob-
tained by attributing to the elements of the model
the values given in Table 1. In the same way, the
values in Table 2 make it possible to simulate the
behaviour of the platinum electrode (Fig. 6). The
choice of these values provides a very good similar-
ity between the diagrams obtained experimentally
and those calculated from the chosen model, this
being for both concentrations of acetic acid and
both electrodes. Below we give some arguments on
the consistency of the values attributed to the ele-
ments of the model.
The values adopted for C,, and R, concern the
faradaic impedance of the working electrode; the
values are in fair agreement with those found
during experiments which we have carried out
elsewhere.
In the case of the Ag/AgCl electrode with the
capillary the presence of the capacitance C, is
not justified, and this is why we attribute a high
value to it which gives it a negligible impedance
in the frequency range in which we are interested.
For the platinum electrode, the value adopted
(0. I pF) corresponds with the double layer capaci-
tance of the platinum in acetic acid. Experimental
determination of the latter by impedance measure-
= 41.4 PF cme2 that is for
ment gave us: CdPI,AeOH80s,,
our 0.5 mm diameter electrode: C = 0.093 ~IF. R:I
does not vary when the resistivity of the solution
changes. This indicates that it is not totally depen-
dent on the test solution, but rather on the
electrolyte contained in the capillary. However, in
the case of the platinum electrode it is not negli-
gible which makes us think that it may to a large
extent be localized in the internal circuits of the
potentiostat.
Capacitances C, and C2 are independent of the
resistivity of the solution. We chose to give C, a
higher value than C, to allow for the potentiostat
input capacitance. In order to check if the values
attributed to C, and C2 were consistent with reality,
we estimated the capacitance presented by the glass
tube used for the capillary. The latter had an exter-
nal diameter of 4 mm, a wall thickness of 1 mm
and was submerged to about 80mm. By applying
the equation which allows us to calculate the
capacitance of a cylindrical capacitor, we found:
C = 32pF. This value matches quite well those
chosen for C, and C, (considering that the calcu-
lation was approximate, given that the potential
field around the capillary was probably not
uniform).
The qualitative interpretation of the shape of the
diagrams observed appears quite clearly if one notes
that the diameter of the high frequency capacitive
loop is equal to: (R, + R:). C,/(C, + C,). Capaci-
tances C, and C, therefore constitute a dividing
bridge acting on the potential V of the counter-
electrode (c$ Fig. 4). The existence of two loops
is a consequence of the antagonistic effect of
capacitances C, and C, on the potential V, measured
by the reference electrode. C, introduces at this
level a part increasing with the frequency of the
voltage of the counter-electrode. In parallel, C, re-
duces V, to zero when the frequency goes towards
infinity.
5. CONCLUSION
A thorough knowledge of the phenomena ob-
served in the range of high frequencies when
measuring impedance in low conductivity media
is essential for interpreting experimental diagrams.
The role of the conductivity of the electrolyte, the
design of the reference electrode and the geometry
of the cell on the artefacts altering the impedance
measurements at the high frequency limit of the
spectrum is correctly described by a unique electrical
circuit. The values attributed to the elements corre-
spond with physical consideration and/or direct
measurements.
The increases in the resistivity of the solution can
to a certain extent be compensated by the use of a
low impedance potential measurement probe such
as a platinum wire, keeping in mind that this type
of electrode does not constitute a real reference
electrode.
 Impedance measurements in low conductivity media 1131

(W

Fig. 6. Simulated diagrams corresponding with the situation of the platinum electrode. (a) 80% acetic
acid; (b) 100% acetic acid.

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