UC RESPONSE OF A ROTATING RING-DISK ELECTRODE:

APPLICATION TO 2-D AND 3-D FILM FORMATION IN

ANODIC PROCESSES
bi
Cd
&/dE
dQ/d-W)
El,
f
io
i,
&
Ko. i
Nd(w)
Nd(m)
NW)
NW)
NS
NW
NW
N'(w)
N(O)
N,
"0
RI
Q
r1
12
r3
z
=,
I-
Y
A
e
5:
w
;1;
N.BENZEKRI,M.KEDDAM and H. TAKENOUTI
LP 15 du CNRS Physique des Liquides et Electrochimie, Universitk P. & M. Curie, tour 22, 4 place
Jussieu, 75252 Paris Cedex 05, France
(Received 9 January 1989)
Abstract-The reaction mechanism for the metal dissolution often implicates the surface coverage by 2-D
adsorbed layer and for the passivation by 3-D film developing beyond the monomolecular layer. The surface
relaxatiop of which is revealed by a capacitive or by an inductive feature in the electrode impedance, but the
amount of these layers is hardly to be evaluated. The rotating ring-disk electrode (rrde) under a small
perturbation of the disk current describes quantitatively the kinetics of charge storing during the formation
of these films at the electrode surface. In this paper, first we examine theoretically this possibility, then
illustrate how to extract the available data from the rrde technique on the basis of reaction models, and
finally we apply it to the active dissolution and the passivation of iron in a molar sulfuric acid solution.
NOMENCLATURE
Tafels constant for K,, V-l
Double layer capacitance, F
Diffusion coefficient, cm* s-
Differential disk capacitance, F cm-*
Low frequency limit of dQ/dE, F crnm2
Disk electrode potential, V
Faraday constant, 96 500 C
Frequency of ac signal, Hz
Disk current, A
Ring current, A
Reaction rate of the i step, mol s-l cm-
Reaction rate constant at E=OV, mols-cm-*
Kinetic emission efficiency, C - 1
High frequency limit of Nd(w), C-
Low frequency limit of Nd(o), C 1
Kinetic efficiency of the ring process
Steadpstate collection efficiency
Hydrodynamic collection efficiency
Experimental collection efficiency under ac signal
N(w) corrected for Cd
Low frequency limit of N(w)
Steady-state collection efficiency relative to fluxes
Number of electrons involved in the disk reaction
Number of electrons involved in the ring reaction
Charge, C cm -
Disk radius, cm
Internal ring radius, cm
External ring radius, cm
Overall impedance including Cd, ohm
Faradaic impedance of the disk, ohm
Differential disk capacitance calculated from Z,,
F cm-
Maximum concentration of the adsorbed inter-
mediate, mol cm - *
Indicates a signal of small amplitude
Fractional surface coverage
Kinematic viscosity, cm2 s-
Flux of species leaving the disk, mol s- 1
Flux of species reaching the ring, mol s-
Angular frequency (2xf). rad s-
Dimensionless frequency
Rotation freqneyc, Hz
INTRODUCTION
The impedance techniques are nowadays largely used
in the electrode kinetics studies. The time constants
observed when not ascribed to bulk processes are
often interpreted by the relaxation of reaction inter-
mediate species covering the electrode surface in 2-D
or in 3-D layers. However the existence of such
intermediate species remains largely hypothetical and
their quantitative estimation is quite a hard task.
Albery and coworkers investigated extensively[ 11
in the late 60s the rotating ring-disk electrode (m-de).
In their final papers on this subject, they showed that
the rrde under an ac signal may give information
about the charge included by the adsorption of reac-
tion intermediates. If a certain number of experiments
were carried out on the basis of the steady-state rrde
techniques, one remarks only a few examples of use of
this technique in the transient regime[2,3]. These two
studies concern merely selection of reaction mechan-
isms and remained qualitative. The present paper is
aimed at evaluating the possibilities of the rrde tech-
niques in the quantitative investigation of electrode
processes. To achieve new information about the
electrode kinetics, the rrde data were coupled with the
results of impedance measurements on the disk elec-
trode.
PRINCIPLE
Let us consider that the species S transforms elec-
trochemically into B at the disk:
S A B+nue-.
(1)
The species B leaves the disk, is transported by
convective diffusion up to the ring, where it is trans-
formed into P:
1159
1160 N.BENZEKRI eta1
B A P+n,e-.
(2)
The product R may be identical to S, the initial
species, as in the case of a redox system, or different, as
it is actually the case in this paper. The number of
electrons concerned in the Reaction (1) or (2), ie n, or
nR, is positive for an anodic and negative for a cathodic
process. It can be seen that the rrde operates in three
distinct processes: electrochemical reaction at the disk,
coupling between the disk and the ring through the
convective diffusion and collection at the ring.
What one measures experimentally in the rrde
experiments is the disk and the ring current respect-
ively in and i,. At the steady-state, the corresponding
collection efficiency (Ns) can be defined as:
Ns=.
in
(3)
In a similar way, the collection efficiency under an ac
signal at the angular frequency w is to be defined by:
N(w) ~2
Al,
(4)
where A indicates a signal of small amplitude. In the
low frequency limit, one has the general relation
between the real quantities:
AN, AiR
i, Ai,
AE,
------.
i,AE, i:, AE
D
One obtains, if ANs/ AE,=O:
i, Ai,
_=__.
i, Ai,
ie Ns = N(0).
rt is worth emphasizing that the steady-state collec-
tion efficiency Ns is identical to the zero frequency
limit of the dynamic collection efficiency N(w) only if
Ns is independent of En. In other words, if the disk
process changes with potential, for instance the val-
ency of the disk dissolution varies with the potential,
then Equation (6) is no longer valid and deviations
with respect to this equation are given by Equation (5).
As stated above, the disk and the ring currents are
linked through three distinct steps. N(w) can hence be
split in the following fashion:
= Nd(w) . Nt(w)/ Nr(w),
(7)
Nr(w), ie A&/ Aik, is the kinetic efficiency of the ring
process (2). If this process is fast enough that its
kinetics is entirely controlled by the convective diffu-
sion, then Nr(w)= l/ n,F, where F is the Faraday
constant. The applicability of the rrde is, in fact, closely
dependent on the possibility of finding a suitable ring
material and electrochemical system for which Nr(w)
is to be considered constant.
Nt(w), ie A4J A4,, is determined completely by
mass transport. This term was actually the main object
of the extensive work carried out by Albery[l]. The
steady-state collection efficiency N, in terms of fluxes
can be expressed by:
N,= 1 -F $ +/ 123(1 -F(a))
0
-_(I +a+@ I{ I-F(i)(l+a+p)},
where:
F(@=~ln(~)+~tgg(~)+~.
(8)
From this equation, it can be seen that N, depends
only on the geometry of the ring-disk electrode,
namely rJ r, and r,/ r,: rl, r2 and r3 stand for the disk
radius, the inner and outer radii of the ring, respect-
ively.
In the transient regime, Nt(w) exhibits a compli-
cated frequency dependence and no analytical ex-
pression is available. However, on a very general basis,
Nt(o) can be reduced by the dimensionless frequency
W:
I%=157 $
0
1/J
f
-,
R
where v is the kinematic viscosity, D the diffusivity, f
the frequency of perturbing signal at the disk and fi
the rotation speed of the rrde. The last two terms are
expressed in Hz. Albery[l] proposed an approached
expression of Nt(w) for a thin ring valid for W ranging
between 1 and 16.
Nd(w), ie A&/ A&,, is the kinetic emission efficiency
depending only upon the kinetics at the disk electrode,
and contains the information we are interested in. At
the steady-state provided that the overall valence be
independent of electrode potential the Faraday law
will be respected, hence:
lim Nd(w) =&
(10)
0-o D
In the transient regime, a fraction of the disk current
Air, may be stored at the disk surface as the charge AQ,
implied in the faradaic process through the formation
of adsorbed intermediate species (2-D) or of films (3-
D). From the conservation of electrical charge, one
can derive[4]:
(11)
Under a sine-wave perturbing signal, dAQ/ dt =jwAQ,
then Equation (11) becomes:
n,F 3 +jw $ = n,F Nd(w) +jw $ = 1.
D D n
(12)
It can be seen easily that at the steady-state (w=O),
Equation (12) reduces to Equation (lo), based merely
ac Response of a rotating rrde 1161
on the Faraday law. Provided that AQ/ Ai, be deter-
mined, one can calculate dQ/ dE, the faradaic capaci-
tance of the disk electrode:
dQ dQ din AQ 1
_=-.__=_._
dE din dE, Ai, Z,
(13)
where Z, is the faradaic impedance of the disk process.
dQ/ dE is an important kinetic parameter, which al-
lows us to evaluate the frequency dependence of the
amount of charge stored at the electrode surface.
Furthermore, the integration of its low frequency limit
dB/ dE(O) allows us to evaluate the charge stored at the
electrode surface between E, and E,:
As shown by Equation (13), to obtain this information
experimentally, the disk impedance must be measured
together with the ac collection efficiency N(w).
EXPERIMENTALS
The disk was made of Fe (J ohnson Matthey), the
radius of which was 1.4 mm. The platinum ring (Lyon-
Alemand) was mounted on a stainless-steel holder.
The inner and the outer radii of the ring was respect-
ively 1.5 and 2.1 mm. The collection efficiency N, was
calculated to be equal to 0.48 according to Equation
(8). The lateral surface of these electrodes was covered
with a cataphoretic paint providing an excellent pro-
tection against infiltration of electrolyte between me-
tal and insulator. One obtains thus a stable and
reproducible passive current. The gap between the
disk and the ring was filled up with a wax. The outer
part of the ring was surrounded by a large epoxy resin
cylinder, the radius of which was 9.5 mm.
The counter electrode was a large platinum net (ca
200 cm*) and the reference electrode was Hg/ Hg,SO,
in sat. K,SO,. The disk potential is given as measured
without any correction. The cylindrical electrolytic
cell contained about 300 ml of a molar sulfuric acid.
Experiments were carried out at 25C under Ar
atmosphere.
The electrode interfaces (disk and ring) were polar-
ized by a home-made bi-potentiostat including a
correction circuit for the ohmic coupling between the
disk and the ring[4]. The collection efficiency and the
disk impedance were measured simultaneously by the
4-Channel Frequency Response Analyzer (Solartron
FRA-1254). These measurements were controlled by a
personal computer (SORD M68), also used to
perform numerical simulations of models and post-
processing of results to calculate, for instance Nd(w)
and dQ/ dE.
MODELS
It will be shown below how Nd(w) and dQ/ dE can
be calculated from a reaction model. For this sake,
models for active dissolution and passivation were
dealt with, both of them concern 2-D film formation:
Active dissolution
It is now generally admitted that iron dissolves
through two consecutive and irreversible steps in
acidic media. Fe(I) species adsorbed at the electrode
surface, is considered to be the reaction inter-
mediate[5-77:
Fe -% Fe(I),, + e - ,
Fe(I) x2
WJ -
Fe(H),,, + e -. (13
The reaction rates Ki are assumed to obey the Tafel
law, ie Ki=Komi exp(biE). K,,i is the reaction rate
constant at E =O V for an arbitrary potential scale.
The charge and mass balances of this reaction can be
written by:
i,=F{K,(l--B)+K,B},
(16)
where y stands for the maximum concentration of the
adsorbed intermediate and 0 its fractional surface
coverage. The calculation of the electrode impedance
for this model was given elsewhere[5-7]. The peculiar
equation to the rrde is the flux of final species leaving
the disk which can be expressed by:
&=K,8.
(18)
The Taylor expansion of Equation (18) gives:
d&=(blK,8)dE+K,d0,
hence:
W,
dE=b2K2e+K2 ;.
Then the Faraday law allows us to calculate directly
dQ/ dE:
dQ
de
~=v@~ (20)
On the other hand, the following relationship can
easily be derived:
>
ZF,
(21)
where Z, stands for the faradaic impedance. From this
equation it can be seen that the time constant involved
in Nd(o) is the same as in the electrode impedance.
In the literature, sometimes the iron dissolution
mechanism through a catalytic reaction is proposedC8,
91. In this case, the first step is reversible and the
second step does not consume Fe(I),,:
x1
Fe - Fe(I), +e-,
x-1
Fe + Fe(I).,
z Fe(I),, + Fe(II),, + 2e -. (22)
Then, the charge and mass balance can be written by:
i,=F{K,(l-e)-K_,e+2K,e),
(23)
y$+K,(l--8)--X_,e.
(24)
1162 N. BENZEKRI et ~1.
The particularity of this reaction lays on the fact that
the mass balance [Equation (24)] does not contain
K,0 giving the dissolution rate of iron. The flux of
Fe(II),,,
is expressed by Equation (18). Formally,
Equations (20) and (21) remain valid though dB/ dE
and ZF are different from the consecutive mechanism.
Passivation
The mechanism for the passivation of iron was
studied by Keddam et aI.[6]. and is rather compli-
cated. For the sake of simplicity, we will consider in
this paper an approximated model which includes two
adsorbates: Fe(H),, as a dissolution intermediate and
Fe(III),, as a passivating species:
K,
Fe - Fe(II),,, +2e-,
Fe - Fe(II),, + 2e-,
(25)
WW,,
2 Fe(II),,, (non-catalytic),
or:
K.
Fe(II),, + Fe _+
Fe(II),, + Fe(II),,,
+ 2e-(catalytic process),
K4
Fe(II),, - Fe(III),, + e -,
K-4
KS
FWW,, - WIW,,,
(chemical dissolution of passive film).
The equations for charge and mass balances in the
case of non-catalytic process are given below:
i,=F(2(K, +K,)~+K,e,--K_-482}, (26)
Y~=~,Z-(K,+K,)H,+K~,B,, (27)
$f-f=K,e,-(K_,+K,)e,, (28)
where 0, and O2 are the fractional surface coverage of
Fe(II),, and Fe(III),, respectively, and E = 1 - o1 - e2.
As for the specific equations for the rrde, the flux of
Fe(II),,, and Fe(III),,, should be distinguished:
4, = K,C+ K,B, (fl ux of FeQU,,,), (29)
& = K,B, (flux of Fe(III),,).
(30)
From Equation (26H28), the steady-state charac-
teristics and electrode impedance can be derived along
the same usual procedure. For the charge stored at the
electrode surface, Fe(II),, and Fe(III)., cannot be
distinguished hence, dQ/ dE becomes:
(31)
By contrast, the flux of ferrous and ferric species may
be distinguished according to the ring reaction selec-
ted then:
W, dE
Nd(w&,,= -p*-=
dE din
b,K,C+b,K,O,)
--(K, -K,)$K,$f
I
2,
(32)
Wz
Nd(w),.u,,, =di =
b,K,H,+K,~ ZP (33)
D >
In the case of the catalytic process, Equations (26) and
(27) may be modified in the similar way to the active
dissolution.
This paragraph illustrates the close similarity be-
tween the modelling for the rrde, in particular for the
calculation of kinetic emission efficiency Nd(w) and
that of the electrode impedance. No additional hypo-
thesis is necessary to calculate the parameters specific
to the rrde technique compared with the well-estab-
lished electrode impedances derivation.
RESULTS AND DISCUSSION
Simulation calculations
Active dissolution. Figure 1 displays the results of
simulation calculation for the consecutive two-step
dissolution given above, for three polarization points
marked by A to C on the steady-state polarization
curve. In the impedance diagrams (upper row), the
contribution of the double layer capacitance Cd to the
overall impedance 2 was included by the following
relation:
i = $ +jwCd.
F
(34)
As was stated in[5], the faradaic impedance is induc-
tive in low potentials where K, -z K,, and capacitive
for high anodic overvoltage (cf diagram C). The
diagram for Nd(w) (lower row) is a semi-circle in the
upper half plane (negative imaginary part). It can be
remarked that its shape and size is independent of the
polarization potential. The low frequency limit of Nd,
2FNd(O), is equal to unity in agreement with Equa-
tion (12). Its high frequency limit, 2FNd(oo), is equal
to 0.22, value determined solely by b, and b,. Only the
characteristic frequency, defined by that at the maxi-
mum of the imaginary part, changes with the poten-
tial. This frequency is close to that observed in the
faradaic impedance.
Figure 2 shows the results of simulations for the
catalytic model. Since the metal is likely to dissolve
according to the consecutive step mechanism, the
values of kinetic parameters are arbitrary. At more
anodic potentials than those given here, the faradaic
impedance exhibits a capacitive feature. Nd(w) is a
semi-circle. 2FNd(O) is unity as in the case of the
former model. On the contrary, 2FNd(m) depends on
the potential, and approaches to unity with the in-
creasing anodic voltage. Thus the diameter of Nd(w)
becomes vanishingly small with increasing anodic
potential. Though this was not shown here, the low
frequency limit of dQ/ dE fairly smaller in this catalytic
mechanism than in the case of consecutive step one, as
can be expected by the very nature of the reaction.
ac Response of a rotating rrde 1163
-8,0 . .
I 1 I I
-I,2 , , , , , , ( ,
-0;l
III. I
A
B
C
REAL PART; 2F b
dd (w) ; dimensionless
Fig. 1. Simulation results: active dissolution of Fe (Model III). Constants corresponding to 1 M H,SO,.
y=lO-sm~lcn-~, Cd=100~Fcm-2, K,=4x105 exp (38.4 E), K, = 8 x lo- exp (7 E). Upper row:
impedance, lower row: ZFNd(w); (A)-(C) correspond to the points marked on the I-E curve.
- 1
o.otf. # I I 1 I
,100 Hz
A1 o.ot,
0 100H-r
f, I I1 .r .I o.ot , o-L1 I I .1 I I -I
0 100 7
0.2lkHz 11 08 105 098
REAL PART;2F Nd (w) ; dimQnsiontess
I,01
Fig. 2. Simulation results: active dissolution of Fe (Model 22). K, = 1Oexp (19.2E), K_ 1 = 1.5 x 10-l
exp( - 19.2 E), others cf Fig. 1.
Thus, it can be concluded that the rrde technique
may constitute a useful tool to check the reaction
mechanism as suggested by other authors[2, 31. It is
also noteworthy that Nd(w) diagram is located in the
upper plane, that is dQ/ din >O [cf: Equation (12)]. In
other words, the increase of current is accompanied
with that of the charge at the electrode interface. This
is also an important feature directly accessible to ac
rrde techniques.
Passivation. Figure 3 displays the results of simu-
lations for the passivation process 25 with non-
catalytic reaction. The set of kinetic parameters
chosen here is rather rough since the model given
above was found to be oversimplified to describe
accurately the experiments. The impedance diagrams
shown here (upper row) do not contain the contribu-
tion of the double layer capacitance, since introducing
it makes the high frequency loop of faradaic impe-
dance difficult to visualize in certain cases. The impe-
dance diagrams show then two capacitive loops corre-
sponding to the surface relaxation of the two inter-
mediates. Furthermore, the low frequency limit of the
impedance is negative in agreement with the slope of
the polarization curve. As expected Nd(o) shows also
two loops. The high frequency behaviour can be
related to the dissolution intermediate Fe(II),,. On the
contrary, that showing up at low frequencies is to be
attributed to the passivation process. In relation with
Equation (12), it can be concluded that if the increase
of the surface coverage makes decrease the current,
then Nd(w) should be displayed in the lower part of the
plane (positive imaginary part). In other words, there
is a straight forward relationship between the feature
1164 N. BFNZEKRI et al.
REAL PART 1 2F Nd (OI Fc c nj , di mensi onl ess
Fig. 3. Simulation results: passivation or iron [Model 25). K 1 = lo- exp (12 E), K, = 5 x lo- exp (6 E), K,
=2x IO-, K,=3 x 1O-9 ~~~(19.2 E), K_,= 10-l exp( ~ 19.2 E), K,= 10-r. Double layer capacitance
was neglected. Others cf Fig. 1.
of Nd(w) and the kinetic role of the adsorbed species.
This contrasts definitively with the electrode impe-
dance where the adsorption of a same species may give
rise to either an inductive or a capacitive loop accord-
ing to the kinetic parameters. 2FNd(O) is unity even in
the fully passive range, whereas the main process is
essentially the passive dissolution, forming Fe(III),,,.
In the potential range examined here, the dissolution
valence changes from two to three, hence Ns is no
longer equal to N(0). Furthermore when the potential
increases, 8, tends to unity, and the modulation of
potential modifies neither 8, value nor the dissolution
rate of the passive film. Only a small change of 0, and
Fe(I1) dissolution are made. However this argument
may be no longer valid if the passivation process is
described by the formatuion of a 3-D film.
Experimental results
Active dissolution. Figure 4 is relative to the exper-
imental results obtained during the anodic dissolution
or iron in 1 M H,SO,. The impedance diagram A and
B are in a good agreement with that of simulation
showing one inductive loop in low frequency range.
On the contrary, on the diagram C two inductive
loops can be clearly seen, as reported in[6]. On the
second row of this figure, the results of N(w) are
displayed. These curves have a half-cardioidal shape ie
Nt(w) is predominant in the frequency dependence of
N(w). From these uncorrected results, it is difficult to
foresee Nd(w). The calcuiation of Nd(w) is performed
first by correcting for the contribution of the charge of
the double layer in the overall current: experimental
N(w) is replaced by N(o):
N(w) =
N(w)
1 -jwCdZ
(35)
where Z is the overall disk impedance. Nd(o) is then
calculated according to Equation (7).
Preliminary work performed in various conditions
indicated that the best manner to achieve Nd(w) is to
determine Nt(w)/Nr(w) together in the same solution
as that used for performing the rrde experiments. In
the particular case given here, 1 M H,SO,+
10 mM Fe,(SO,), solution was prepared. The Fe(II),,,
is produced at the disk then reoxidized at the ring.
The results of calculation were given in the lower
row of Fig. 4. The results diverge significantly for the
frequencies higher than several Hz. This phenomenon
can be attributed to Nt(w): in fact, Nt(w) behaves as a
low-pass filter, and a vanishingly small UC signal was
observed in raw N(w) data for frequencies higher than
several Hz.
Nd(oo), though depending somehow on potentials,
remains small which is in the favour of the two-step
consecutive mechanism. However ZFNd(0) is signifi-
cantly small than unity. It was also found that the
higher is the rotation speed, the smaller is Nd(O), and
also when the solution pH increases, Nd(0) decreases.
This unexpected feature was interpreted by the pres-
ence of at least two reaction paths to produce Fe(II),,,
in agreement with our previous work[6]. The reaction
path, major at low anodic potentials, produces a
divalent species Fe(II),,, easily oxidizable at the ring,
whereas the other, through a catalytic process, forms a
species unable to be collected at the ring. The latter
species transforms into usual Fe(II),,, by an homo-
geneous chemical step taking place meanwhile the
transport from the disk to the ring. The relative weight
of two paths depends both on the potential and the
solution pH, as was suggested in[6].
The high frequency cut-off behaviour of Nt(o) and
the complication observed for the collection of
Fe(II),,, at the ring make further quantitative analysis
hazardous. At the present time no derivation of Nt(w)
taking into account this homogeneous step is avail-
able.
Passiuation. Figure 5 exhibits the results obtained
in the passivation range of iron in sulfuric acid. The
electrode impedance is quite similar to those predicted
by numerical simulations. N(o) displays, at higher
current (diagram C), a very depressed feature. The
(IC Response of a rotating rrde
Zd (o), 0hm.c t -n
REAL PART, 2F Nd(w ), di mensi onl ess
Fig. 4. Experimental results. Active dissolution in 1 M H,S04, 900 rpm. Disk: Fe, polarized at points
(AHC) marked on the I-E curve, AE,= +2 mV, Ring (Pt): Fe(II)-rFe(III), E,=0.8 V. Upper row:
impedance, middle: N(o) and lower: ZFNd(w).
1
.
k
*C
2
E
El
\
-5
VO
+5q
-75 0
E ,,mVufS.S.E
~~~~~~~~~~
I
1,2 / -0,3 1, Z- 0, 6
REAL PART, 2F Nd (W) , dl mensl onl ess
O/ 9
Fig. 5. Experimental results. Passivation in 1 M H,SO,, 620 rpm. Disk: Fe, AS,== k 10 mV, Ring:
Fe(II)dFe(III), E=0.8 V. Upper, middle and lower rows, see Fig. 4.
correction for double layer effects according to
Equation (35) has a little effect due to the low frequen-
cies while correction for Nt(w) restitutes the Nd(o)
data shown in the lower row. In agreement with
simulated data, the diagrams are located in the lower
half-plane exhibiting directly the passivating role of
the surface process involved in the charge storing. The
frequency corresponding to the maximum imaginary
part is equal to that shown by the low frequency
impedance at the same polarization point.
The less anodic the potential, the more visible is the
derivation with respect to the model prediction.
2FN40) becomes significantly lower than unity and it
was verified that correlatively 3FNd(w) corresponding
to the flux of Fe(III),, increases. At the same time the
real part of Nd(o) becomes negative in the high
1166 N. BENZEKRI et ul.
frequency range. In perchloric medium this high fre-
quency feature is even more apparent and the Nd(w)
diagram turns around the origin, Nd(oo) being posi-
tive. The model given above is clearly unable to
explain in details the Nd(w) data, and particularly the
fastest processes of passivation, whilst the impedance
is correctly restituted. This illustrates the highest
selectivity of the rrde under ac polarization. Nd(w) was
processed further according to Equation I I to yield
the complex ratio AQ/ AE(w) describing the frequency
response of the surface charge. The low frequency limit
is of particular interest and is shown as a function of E
in Fig. 6.
In the range investigated dQ/ dE decreases with
increasing E and tends towards a value of about
6 mFcm_ at about 0 V, then increases again. Ac-
cording to the model based on a 2-D passivating layer
this quantity should vanish as the coverage is com-
pleting to unity. This discrepancy is obviously due to
the 3-D character of the passive film developing
beyond the active-passive transition. The value ob-
tained is in reasonable agreement with calculation on
the basis of normally assumed thickness voltage de-
pendence.
On the same figure, the capacitance r determined
from impedance data at low frequencies[lO] is also
displayed. This value increases monotonously with
potential and reaches ca 20 mF cm- at 0.6 V. A close
examination of the faradaic impedance expression for
a film forming process showed actually that the charge
stored at the surface cannot be determined with
accuracy by impedance technique. The rrde technique
applied in this field shows again a definite advantage
compared with the impedance method.
CONCLUSION
The n-de technique under a small ac perturbation of
the disk current was applied in the study of the anodic
processes leading to the formation of 2-D or 3-D
layers. The theoretical examination of the operating
parameters allowed us to distinguish three factors: the
kinetic emission at the disk, the mass transport coup-
ling between the disk and the ring and the collection at
the ring. The relevant quantity is the kinetic emission
efficiency of the disk, since it gives directly the amount
of charge involved at the disk interface, in the course of
a faradaic process a parameter of outstanding import-
ance for the electrode kinetics investigation.
By applying the technique to the active dissolution
of iron, it was found that the time constant exhibited
by this system is too short to get the whole informa-
tion with the present performance of the rrde. The
decrease of Nd(0) with respect to the increasing poten-
tial and solution pH was interpreted consistently with
the reaction paths previously introduced in the impe-
dance modelling.
The passivation process will be a promising field to
be investigated by the rrde. The time constants in-
volved are large enough and Nd(w) can be calculated
30
I I I I
+
20 _
l-4
k

LL
E )I
fc
0 *
o,%
p - _t(f_+
/
L
. P
0
0
0 I I I I j
- 100 -50 0 50 100
E
D / mV5sE
Fig. 6. Differential capacitance for the formation of passive
film Fe/lM H,SO,, c/ Fig. 5. dQ/dB deduced from the rrde
and disk impedance measurements. r calculated from low
frequency data of the disk impedance, *, 0: 620rpm; f, 0:
900 rpm.
with a good accuracy. Then the formation of anodic
film leading to passivity was evaluated more satis-
factorily than by the impedance method. It is worth to
emphasize that the coupling of N(w) measurements
with the disk impedance is absolutely necessary to
achieve quantitative analysis of the results.
Acknowledgement-This work was performed in the frame-
work of the thesis of one of the authors (N. B.). She is grateful
to the Ministry of the Education of Morocco for providing
a scholarship.
5.
6.
7.
8.
9.
10.
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