Elecrrochimica

Pergamon

Acta. Vol. 41. NW. l/8, pp. 957-965, 1996

Copyrigjxt 0 1996 Ehevicr Scima Ltd.
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CONTRIBUTION
OF ELECTROCHEMICAL
IMPEDANCE
SPECTROSCOPY
TO THE INVESTIGATION OF THE
ELECTROCHEMICAL
KINETICS
C.GABRIELLI*and M. KEDDAM
Laboratoire Physique des Liquides et Rlectrochimie, UPR 15 CNRS-Tour 22,5eme &age, Universite
Pierre et Marie Curie, 4 Place Jussieu-75252 Paris Cedex 05, France
(Receioed 8 May 1995)
general framework related to the investigation of electrochemical reaction mechanism under
linear regimes is established. The problem of the identification of the parameters of a model of heterogeneous reaction mechanism is discussed from the data obtained through the electrochemical impedance
and the electrogravimetric transfer function. If the model involves G independent differential equations
dealing with G coverage rates of the electrode surface by absorbed reaction intermediates, the impedance
provides 2d + 1 independant quantities which could lead to 21 + 1 kinetic rate constants. The electrogravimetric transfer function leads to I + 1 extra independent quantities. Therefore, by using simultaneously the two approaches, it can be. possible to obtain not only the rate constants but also the atomic
mass of the adsorbed reaction intermediates. Processes where only one adsorbed reaction intermediate is
involved is thoroughly anafyxed by cc electrogravimetry and the possible shapes of the transfer functions
which can be experimentally obtained is listed.
Abstrx-A

Kev words: electrochemical imnedance. electrochemical kinetics, ac electrogravimetry, electrochemical

reaction mechanism modelhng. a

INTRODUCTION

Electrochemical impedance spectroscopy has been

used for several decades for investigating electrochemical kinetics. This technique has demonstrated
its capability on many instances. It has been applied
in many fields ranging from metal or semiconductor
electrode-electrolyte
interface,
electrode/layer/
electrolyte system, porous electrodes, solid electrolytes [l-11]. One of the best successes of the
technique is related to the investigation of the reaction mechanism of iron dissolution in sulfuric
medium for pH ranging from O-5, where a model
was selected among 40 possible mechanisms [ 12, 133.
In spite of these results and even when mass transport is not the rate determining step some limitations to this technique can be observed. One of the
major drawbacks is related to the nature of the information obtained
about heterogeneous
reaction
mechanism. From electrochemical impedance measurements alone only quantities related to time constants and resistances to the flow of current can be
extracted. Sometimes the rate constants themselves
cannot even be obtained unambiguously. In any way
there is no information on the chemical nature of the
species involved in the reaction mechanism. Therefore an uc complementary technique to the electrochemical impedance which is based on the use of a
quartz crystal microbalance and called ac electrogravimetry can be proposed [ 141.

A general framework related to the investigation

of electrochemical reaction mechanism under linear
regimes will be established. Processes where only one
adsorbed reaction intermediate is involved will be
thoroughly analyzed by ac electrogravimetry and the
possible shapes of the transfer functions which can
be experimentally obtained will be listed.

GENERAL

FRAMEWORK

The chemical or electrochemical reaction kinetics

obey the same formalism (in the following, one of the
species is an electron as electrochemical reactions are
considered) and can be described in terms of fluxes.
Let us consider a general reaction mechanism
involving n chemical reactions between p species X,,
. ..( X,;
i$lvkixi

ifovkixi9

(I)

where the vti are the stoichiometric coefficients, and

Kk, K; the kinetic rate constants. If some Xi are not
involved in the kth reaction, eg, on the left hand side,
then vu = 0.
If 4: and 4; are the fluxes corresponding to the
kth reaction in the forward and backward directions,
then,
$,: = K, C~lCU ...C;

4; = K;Cv;,Cv;,
...Cv&

+ Author to whom correspondence should be addressed.

957

(2)

958

C. GABRIELLI

and

where Ci is the concentration of the species Xi. If Xi

is a reservoir [ie, is in large quantity compared with
Xi (j # i)], its concentration can be considered as a
constant and one can therefore replace the kinetic
rate constant K, (K;) by a new constant Kknvk,
(K;nv;,). If the kth reaction is irreversible, K; =
4; = 0.

M. KEDDAM

If the reaction intermediates are all related to the

substrate
Mi = MS + Ma,,

where M,,, is the atomic mass of the adsorbed

species which is associated with the substrate to form
the intermediate i:

The mass balance of Xi, applied for the kth reaction which consumes (vLi- vii) molecules in the
forward direction and produces (vki - $3 in the
backward direction, gives:

dG_- -(Vki - vjJ#: + (Vki- V;i)d;.

dt

(8)

p-1

dm

1
i=Z+rl+r*

Tt=

BiWs

hi)

$+

Msk$,%(d:
- 4;)

(3)
p-1
=

Therefore, for the n reactions the set of the concentrations Ci of species i obeys

&Ma,,$

1
i=Z+rl+rz

MS

(4)
+ i

where

wk,(h+

4;)

8i

k=l

(5) as

-vki+v;..

oki=

Among the p species there are:

1 which is the substrate (numbered l),
rl which adsorb on the electrode surface,
r2 which are issued by desorption from the electrode surface,
1 which is an electron (numbered p),
p - 2 - rz - rl which are reaction intermediates
absorbed on the electrode, having surface concentration C,, .
The coefficients vLPand v& are generally equal to 0
or 1 as monoelectronic elementary steps are often
considered.
The mass balance of the pth species (ie, electron)
leads to the Faradaic current

p-1
0,

1.

i=2+rl+r*

p-1
i=2;,+,,

(10)

-2.

If the rz species which are issued by desorption

from the electrode surface leave free a substrate site
and if the pi are equal, pi = j?, then :

(11)

(6)

k=l

where F = 96500 C.
The mass change m(t) per surface unit of the electrode can be split into two terms:
(i) mass change of the adsorbed coverage phase

ie,

(12)
In the case of an inert metal
(ii) mass change of the electrode material itself
M

rr+r2+1
2
j=r,+2

dt

I
1 wk,(#:
k=l

4;)

(13)

and

ie,

(14)

(7)
where the surface concentrations

are equal to Cs, =

/I, 0, A, M, =
is the atomic
M, is the atomic mass of the species i whose cover-

age is 8, and b1 is the maximum number of moles of

i on the electrode surface of area A.

species

It will be seen in the following examples that the

previous hypotheses are often assumed in the
models.

dBi
At quasi steady state t = 0 and
dm,
dt

-=MM,i

k= ,wk,bh+

4;)

Investigation of the electrochemical kinetics

ie

959

where the adsorbed

coverage 6.

Me(OH), has a

intermediate

m,(t)= Mst t ~~(44- 4;) + m(O) (1%

k=l

= BMMetO~*
$ - M,,(K,(l

- 0)

the quantity
+ K,(l - 0) - K; 0)

I, = -F f

k=l

?&&+ -

(16)

4;)

= (M,,

- M,,(K,(l

can be considered as a Faradaic current assigned to

the steps related to the substrate.
In some simple mechanism I, = I, and the
Faraday law is found.
m,,(t) = -M,

+ m(0).

(17)

The derivation of the mass change relationship

will be exampled on some commonly dealt with
reaction mechanisms :

+ ZM,,)(K,(l

= 2jIM,,$

- 0) - K; 0)

- 0) + K,(l - 0) - K; 0)

- M,, K,(l - 0).

iii. Metal deposition

Me++ + 20H-

Me(OH),
K2

Me(OW,

where the adsorbed

coverage 0
i. Bockris reversible mechanism of iron dissolution

Me+20H-+2e

intermediate

= BMwoH,, ;

Me(OH),

has a

+ Mu, K, 0

KI

Fe+OH-_

WW,,,

lFe+++OH-+e.

Here, n = 2, p = 5, r, = r2 = 1, species 1 is Fe; 2:

OH-; 3: (FeOH),,,,; 4: Fe++; 5: e.
vtt = 1, VIZ = 1, v;s = 1, v;s = 1, VZJ= 1, v;.$ = 1,
v;~ = 1, vi5 = 1 all other vii and vii are equal to zero.
4; = Kt8;

= &eon@:

The change of the electrode mass is equal to

+ M,, K,(l - 0).

iv. Adsorption on an inert electrode

KI

r& = K,tI

- 4; - 42).

de

= 2BM,

Me + OH-

The change of the mass of the adsorbed phase is

equal to
PM,,,,

- 0) - K,t?)

+ M~cKze

4; = K,(l - 6);

= (MMc+ 2M,,)(K,(l

(FeOHLiS + e

x1

-Me-OH+e
Kl
-

Me-OH
where the adsorbed
coverage 0
$

= PM,,,,

Me+OHintermediate

$ - M,,(K,(l

= (Muc + M,,XK,(l
- M,,(K,(l
Therefore,

Me-OH

has

- 0) - K, 0)

- 0) - K, 0)

- 0) - K, 0)

de
= /TM,, -.

dt

(MF~+ Mod@:- 4; - d-4- Mdb: - 9;)

= jIMoH +f - M,, Kz 8.

If sufficiently small perturbations A&, BE, Am and

AI, about the quasi steady state are considered,
ma(t) and IF,, stay in a linear regime (only the first
order is kept in the expansion of all the quantities).
From equation (4) the concentration change ACi is
given by:

ii. Schuhmann passivation mechanism

KI
Me -Me+++2e

x1
Me+20H-

Kz

(Me(OH)&,

+ 2e

where ( )s means the value of the quantity

brackets is taken at steady-state.

between

960

C.

GABRIELLI

and M.

KEDDAM

There are only 8 = p - r, - rz - 2 independent

differential equations on the Ci = &t$ as AC&) # 0
for these species.
Therefore, in the frequency domain:

Therefore, the same time constants can be found

in the admittance YF(w)and in the Am/BE(w) electrogravimetric transfer function.
The problem of the identification of the parameters of a model from the electrochemical impedance
joA = AA6 + BAE
(19) and the electrogravimetric transfer function data can
now be discussed.
where the matrix A has component:
As there are / = p - rl - rz - 2 A&s, there are /
independent equations which lead to L loops in the
Aij = i
low frequency part of the electrochemical impedance
measured at one polarization potential. Each loop
(20) provides two quantities: one time constant and one
resistance. Therefore, 2! quantities are available from
and column vectors A0 and B have components
the measurement plus another one given by the high
frequency limit (if the double layer capacitance is
ABi = fliABi and Bi
eliminated) namely the charge transfer resistance.
(21) Consequently, if the reaction mechanism involves
=
2L + 1 kinetic rate constants there will be a possibility for identifying them unambiguously. The meaIn the same way
surement of the impedance at several potentials
along the current-voltage curve allows the voltage
AI, = F i o,,(A&+ - A&)
(22) dependance of the parameters to be found.
L=l
However, even if this criterium is verified it is not
ie
sure that the rate constants can be individually
Al, = CAB + DAE
(23) obtained as the time constants and the resistances
are often very complicated functions of the rate conwhere
stants.
In this domain Berthier et al. [16] have shown
that the identifiability of the rate constants depends
D=Fi
(24)
-kp[(s>,
- ($!$)A
k=l
on the structural properties of the mode1 of the reaction mechanism. Generally, the number of the rate
and the column vector C has component:
constants will be larger than 21 + 1 and an indeterminacy remains. The measurement of the electroCj=Fi
(25)
ak.v[($$s
- ($$)d.
gravimetric transfer function Am/AE will provide
k=l
e + 1 new quantities as the time constants are the
Similarly from equation (7), the mass change in the
same as those of the admittance. Therefore, it will be
frequency domain is equal to :
possible to obtain not only the rate constants but
also the atomic mass of the adsorbed reaction interp-1
jwAm = jo
1
fiiMiABi
mediates as this transfer function leads to informai=rl+r*+l
tion on the chemical nature of the reaction
mechanism through the atomic masses Mi .
+ MS i %dAd:- A&-)
(26)

&%i[(fg),
- (%)A.

k=l

ie,

Am = E(o)AB + F(w)AE
where the matrix E(w) has component
E&o) =

Mi +

3 i
.%

k=l

@ki[(%y).

ELECTROGRAVIMETRIC
FUNCTION

(27)

(%f)J

(28)

TRANSFER

As an example of the simplest electrochemical

process which could be found to example the electrogravimetric transfer function, a mode1 of reaction
mechanism where only one coverage 8 is involved
will be considered. In these conditions equation (26)
can be written

and the column vector F(o) has component

F(w) =

M,
jw

;,wki[(~),

jwdm = juM,/IAB

($$)A*(29)

+ +

i wk(A&+ - A#;).
k-l

(32)
From these equations it can be found that [ 151:
AI,
= YF = Cowl-

AE

Am
G = E(w)(jd

A)-B

+ D

Therefore, the mass of the electrode can be decomposed in two parts:

(30)
l
l

- A)-B

where I is the identity matrix.

+ F(o)

(31)

The mass of the substrate (metal): M,

The mass of the film or layer (2-D or 3-D): ML.

The change of the mass of the substrate can be

related to the Faraday law applied to the components AI, of the global current which participates

961

Investigation of the electrochemical kinetics

to transformations
from or towards
state of the electrode, ie,

the metallic

Asymptotic behaviours of Am/AE

(i) When the frequency tends to infinity (o + 00)

where zt is the number of electrons exchanged in the

kth electrochemical reaction.
I, is positive for an anodic dissolution and negative for a cathodic deposition in agreement with the
IUPAC convention. This expression can be simplified by assuming that all the steps related to the
metal involve the same number of electrons zS then:
MS
Am, = --AI,
joz, F
where
AI, = ; Aif.
Generally, I, is a function of the potential E and
coverage 8.

(39)
ie

Am
~=Re+jIm.

When w increases, Im/Re tends towards - 00 and

Arc tg(Im/Re) tends towards + 42. Therefore, the
Am/AE(o) diagram tends to the origin, tangentially
to the imaginary axis in a quadrant depending on
the parameters.
In the case where M, = 0, as g, > 0, Im(Am/
AE) < 0 whatever the sign of Re(Am/AE), and therefore Am/AE approaches the origin tangentially to the
imaginary axis from the bottom of the complex (Re,
- Im) plane.
(ii) When the frequency tends to zero (w --t 0)

I, = @, 6)

Re N 9

g;r + MLB

ie
(35)
Therefore, the change of mass due to a potential
perturbation can be calculated

and separated in three contributions.

l

The g; term corresponds to the mass change

associated to the impedance HF limit (charge
transfer resistance of the involved steps).
The g; term corresponds to the Faradaic contribution due to 0 on the current component related to
the metal.
The M, term corresponds to the actual contribution of the film.

$)

Ae
gk + sb E (0)
(
>

Im N - +&
s

(40)

ie,
Im=_M,.L
zswF

4,s

where R, = AE/AIJO) is a pseudo polarization

resistance relative to the sole steps which are related
to the metallic phase. This quantity is generally different from the global polarization resistance R, .
In the particular case where the steps which
modify the film do not change the mass of the metal
then R, = R, (adsorption).
In Figs 1 and 2 the calculated Am/AE (w) diagrams are plotted in the plane (Re, -1m) for various
.4

It can be noted that even if the film material has a

negligible mass (ML #0), Am/AE is not confounded
with the imaginary axis but has a real part. For a
reaction mechanism with only one coverage A0/
AE(w) can be written under the general form:
A0
-=
AE

Ae/AE(O)
1 +jwT

(37)
-. 4

and then
Am
X6=

--

MS
juzs F

+M,B-

REAL PART 1 10-j g V-

Ae/AE(O)
gi + g; 1 +jor

Ae/AE(O)
1 +jwr

(38)

Fig. 1. Electrogravimetric transfer function Am/AE(o) calculated for M, = 0 and for the parameters listed in Table 1
(T > 0): Curve A corresponds to parameters 1 and 1; curve
B to 2 and 2 and curve C to 3 and 3 (frequency is indicated in Hz).

C. GABRIELL~ and M. KEDDAM

962
.4

Table 2. List of parameters used for calculating the electrogravimetric transfer function for T r 0
Am

-. 4

-. 2

0.0

.2

.4

REAL PART I lo- g V-

Fig. 2. Electrogravimetric transfer functions Am/A,?(o) calculated for M, = 0 and for the parameters listed in Table 2
(r < 0): Curve D corresponds to parameters 4 and 4, curve
E to 5 and 5 and curve F to 6 and 6 (frequency is indicated in Hz).

conditions, M = 0, M, = 179, /I = lo- mole cmm2

and the parameters listed in Tables 1 and 2.
As, now:

3.2

3.2

0.8

0.8

Table 1. List of parameters used for calculating the electrogravimetric transfer function for 5 > 0

Am

$(O)

sb

*-I

y-1

3.2
;3.2

500
+100
-100
-500

0.01
+0.01
-0.01

0.2
0.2
1

20
ro
>o

3
3

3.2
3.2

+500
-500

-0.01
+0.01

0.2
0.2

co
<o

A,

R;,

QE

100

s;

R,

-1

>o

0.01

-I

>o

0.01

-0.2

>o

-0.01

-0.2

20

-0.01

-I

<o

+O.Ol

-I

<o

-0.01

-100
500
-500
100
-100

In Fig. 3(A-C) are plotted the transfer functions

Am/AE (0) deduced from the diagrams A, B and C in
Fig. 1 (T > 0) for increasing values of M,. Similarly
in Fig. 4(DF) are plotted the curves deduced from
curves D, E and F in Fig. 2 (T -c 0) for increasing
values of ML. For the diagrams plotted in Figs. 3
and 4 the following quantities are kept constant:
M, = 17 g, /I = 10-smolecm-2.
Tables 3 and 4 give the schemes of the impedance
diagrams where the double layer behaviour is shown
in dotted line which has to be associated with the
Am/AE diagrams of Figs. 3 and 4 and examples of
the corresponding electrochemical processes. In the
simple case where I, = I,, the electrochemical
impedance is equal to

(41)
g; and AB/AE (0) contribute to Am/AE by their
product, ie, Am/AE does not change when these
parameters simultaneously change sign by keeping
the same absolute value.
It is noticeable that the diagrams calculated for
T < 0 (Table 2 and Fig. 2) correspond to autocatalytic kinetics related to multi steady state electrochemical systems with reduced observability.
When M, # 0 the number of possible shapes
increases. First of all when w + co the imaginary
part of Am/AE (w + co) can change sign when M,
increases. Then Am/AE approaches the origin
tangentially to the imaginary axis from any of the
four quadrants.
Concerning the low frequency limit, only the real
part of AmJAE (w + w) depends upon M,. From
the curves plotted for M, = 0, Re.(Am/AE) will
increase or decrease following the sign of AB/AE (0).

g (0)
V-L

sH
*-I

E
g

1
z,=g;+g,

, WAE (0)
1 +jwT

1
=-+-

R,

A
(42)

l+jCOT

ie,

1
1
-=R+A
RP
1
where A = g; - AB/AE (0) and R; = gk.
In Fig. 5 are plotted the transfer functions.
. Am

JO E

MS

= - z,~

Sk + S;

A0/AE (0)
1 +jwr

in the case of parameters 2 in Table 1.

The low frequency limit is independent of M,,
only the high frequency one depends on M,. The
shapes are very similar for the other sets of parameters. This type of plotting emphasizes the high frequency part of the Am/BE behaviour (related to the
coverage behaviour) although the direct plot of
Am/AE is largely obscured by the low frequency
behaviour which reflects the continuous change of
the electrode mass (me(t)).
Some examples of the simultaneous analysis of the
electrogravimetric transfer function can be found in
the literature [14, 17-211. They demonstrate the
interest of such an approach as it supports the model
tested by impedance techniques and gives information on the chemical nature of the species involved.

Investigation of the electrochemical kinetics

963

0
REAL PART I IO-3 g V-1

REAL PART I IO- g V-

.5
I

-r-

1.0

-+!._

-.

-1.0

0.0

REAL PART 1 lo-

.5

at:0

-..5
REAL.PART

0.0

.5

1.0

500 1 d

-400
I lo-

75

REAL PART I IO-3 g V-1

1

-1.0

g V-

2.0
-

-1.5

g V-1

Fig 3. Electrogravimetric transfer function Am/AE(o) calculated for the parameters listed in Table 1 and M, = 0 (a,
a: M, = 2Og; b, b: M, = 908; c, c: M, = 2oOg; d, d:
M, = Soog) (frequency is indicated in Hz): A: curves a, b, c
and a, b, c deduced respectively from parameters 1 and 1
in Table 1 (curve A); B: Curves b, c, d and b, c, d deduced
respectively from parameters 2 and 2 in Table 1 (curve B);
C: Curves a, b, c and a, b, c deduced respectively
from
-.
parameters 3 and 3 in Table 1 (curve C).

-200

200

400

600

i
I30 0

REAL PART I 10-S g V-1

Fig. 4. Ekctrogravimetric transfer function Am/AE(o) calculated for the parameters listed in Table 2 and M, # 0 (a,
a: M, = 20g; b, c: M, = 90g; c, c: M, = 2OOg; d, d:
ML = SOOg)(frequency is indicated in Hz); D: Curves b, c,
d and b, c, d deduced respectively from parameters 4 and
4 in Table 2 (curve D); E: Curves a, b, c, d and a, b, c, d
deduced respectively from parameters 5 and 5 in Table 2
(curve E); F: Curves a, b, c, d and a, b, c, d deduced
respectively_ from narameters
6 and 6 in Table 2 (curve F).
.

964

C. GABRIELLIand M.

KEDDAM

Table 3.

Schemes of the impedances associated with the electrogravimetric transfer functions (double layer behaviour is plotted in dotted line) and examples of related electrochemical systems for 5 > 0 corresponding to the
diagrams A, B and C [A = g;(AfI/AE)jO)]
4
nmlnE

A < 0, IA/

large
: anodic

*
> o,
eE = dE

gle < o

elE = i+

ge > 0 :

< 0,

passivation

cathodic

blocking

A c 0, 1Al small

de

~-~ > 0,
@E = dE

ge -c 0

: anodic

dissolution

de
8B = dYE< 0, ge > 0 : cathodic

deposition

A>0

dB
BE = z > 0, ge > 0 : anodic

dissolution

de
eE =aE < 0, ge < 0 : cathodic

deposition

Table 4. Schemes of the impedances associated with the electrogravimetric transfer functions (double layer behaviour
is plotted in dotted line) and examples of related electrochemical systems for 5 < 0 corresponding to the diagrams D,
E and F [A = gb(A0/AE)(O)]

&dttE
E

AExlIF
A > 0 =1 Z-shaped
elk = g

curve

(in

the

diagonal

> 0, ge > 0 : autocatalytic

desorption
of an anodic activating
species
de
BE =dE < 0, ge < 0 : autocatalytic
formation
of a blocking

species

A < 0, 1 A/ large

+ S-shaped
diagonal)

BE = g

(in

the

> 0, g0 < 0 : autocatalytic

desorption
BE =g

curve

of

an

anodic

blocking

species

< 0, ge > 0 : autocatalytic

adsorption

of

a cathodic

blocking

A c 0, 1Al small*

species

Super
S-shaped
curve
(multisteady
states
for potentiostatic
and
galvanostatic
polarisation)
de
8c =G > 0. ge < 0 : non observable
de
BE = di < 0, ge > 0 : non

observable

Investigation

of the electrochemical

400

by impedance technique alone and give information

on the chemical nature of the species involved.

5
00
?

300

200

2
d

100

965

kinetics

REFERENCES
/

2
2
;j

-100

1. C. Gabrielli, Identi$cation of Electrochemical Processes

by Frequency
Response Analysis (Ed.). SolartronSchlumberger
(1981).
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Electrochemical
Materials
Science. (Edited by B. E.
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Vol. 4, p. 151. Plenum Press (1981).
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Experimental
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Press (1984).
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Use and Applications of Electrochemical
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(1990).
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Marcel Dekker Pub. Co, p. 243 (1995).
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iI,,,,,
Jc+-:;,,

-200
-400

-300

-200
REAL

-100

100

;:

PART 1 1O-6 g V-s-

Am/AE(w)transfer function calculated for parameter 2 listed in Table 1 and (a): M,, = 0; (b): M, = 1OOg;
Fig. 5. jw

(c): M,, = 300g and (d): M, = 500g (frequency

in Hz).

is indicated

Case of adsorption on an inert electrode

Now from equation (14)

where M,, is the atomic mass of the adsorbate.

The plot of the Am/AE electrogravimetric transfer
function gives a semi-circle centered on the real axis
with low frequency limit

and high frequency limit

Am
-&wc+o.

CONCLUSION
Some examples of the simultaneous analysis of the
and
electrochemical
impedance
the
electrogravimetric transfer function can be found in the literature [ 14, 17-211. They demonstrate the interest of
such an approach as they support the models tested