Eleclrochimica Acta, Vol. 38, No. 14, pp. 2121-2127. 1993 0013- 4686/93 $6.00 + 0.

00
Printed in Great Britain. f; 1993. Pergamon Press Ltd.

A KINETIC MODEL FOR THE DISSOLUTION

MECHANISM OF COPPER IN ACIDIC SULFATE
SOLUTIONS

DANNYK. Y. WONG,* BRUCEA. W. C~LLER~and DOUGLASR. MacFaRLaNEt

School of Chemistry, Macquarie University, Sydney, New South Wales 2109, Australia; TDepartment of
Chemistry, Monash University, Clayton, Victoria 3168, Australia

(Received 10 March 1993)

Abstract--Steady-state polarization curves and impedance data have been obtained for the electrochemi-
cal dissolution of copper in 1.0 M Na,SO, solutions at pH 1, 2, $4 and 5. The steady-state polarization
curves display only active dissolution in the potential range investigated (from the open circuit potential
up to + 1OOmVvs. see) and exhibit a Tafel range of 54.&55.6mV. Two time constants, over a wide
spectrum of frequencies (10-3-1@H~), have been observed in all complex impedance plots. The experi-
mental results have heen quantitatively fitted by a reaction mechanism model which provides an excellent
fit to the steady state data and is in qualitative agreement with the impedance data.

Key words: impedance electrochemistry, copper dissolution, kinetic and mechanism, rotating copper elec-
trode, acidic sulfate solutions.

INTRODUCTION tion (Cu + Cuz+ + e-) on the electrode, the steady

Anodic dissolution of copper is involved in
electrorefining[l], in electropolishing[2], in corro-
sion phenomena[2] and in maintaining the supply
for electroless deposition processes[l]. Many funda-
mental studies have been concerned with the mecha-
nism of corrosionC2, 33 and deposition[6-131 of
copper in various media, but very little has been
reported concerning the anodic dissolution of copper
at potentials other than the corrosion potential.
Mattsson and Bock&[61 and others[7, 81
employed a galvanostatic transient polarization
method to study the kinetics of deposition and disso-
lution of copper in CuSO, solution. According to
these authors, the dissolution of copper takes place
in a step-wise route in which Cu+ ion is the interme-
diate species (Model I).
Model I
kt
cu F Cu+ + e-
k-1
kz
cu+ \ Cu*+ + e-.
k-z
This dissolution mechanism was proposed because
the Tafel plot was found to be linear with a Tafel
slope of 40mV at 25C. In this model, the redox
process between Cu+ and Cu2+ (Ib) is therefore
regarded as the rate-controlling step and the reac-
tion steps relating to k,/k_, are supposed to equili-
brate very quickly compared to those relating to
k2/k_2. Impedance results of a copper electrode at
the equilibrium potential in a 0.56M CuSO,
+ 0.5 M H,SO, solution obtained by Dmitriev et
aL[14] also implied the slow electron exchange reac-
l Author to whom correspondence should be addressed.
rate of which was itself limited by diffusion of Cu+.
Brown and Thirsk[9] have found results support-
ing Model I using a potentiostatic transient tech-
nique with a rotating disk electrode in 0.3 M CuSO,
+ 0.2M H,SO,. The anodic current was observed
to increase with increased electrode rotation speed in
the overpotential range +5 to + lOmV, and the
local mass transport of Cu+ is considered in addi-
tion to the diffusion of Cu2+ from the electrode.
However, Glarum and Marshall[lS], reported an
admittance study of a copper rotating disk electrode
during deposition and dissolution processes in
0.25 M CuSO, + 1.75 M H,SO,, agreed that Model
I is applicable near the equilibrium potential if
allowance is made for the diffusion of Cu+ and Cu+
ions. The admittance results were used to infer that
Cu+ concentration is substantially decreased at
more anodic potentials due to a disproportionation
reaction (2Cu+ + Cu+ + Cu) and the growth of
metallic clusters in solution, while frequency disper-
sion was found at cathodic potentials due to a
double layer relaxation.
(If4 Slaiman and Lorenz[16] and Stankovic[ 171 have
carried out studies of copper dissolution in a solu-
tion of H,SO, + CuSO, using a galvanostatic
method. Slaiman and Lore&s results suggested that
step (Ia) in Model I be split in order to accommo-
date the presence of an adsorbed Cu+ species after
comparison with an equivalent circuit consisting of a
parallel arrangement of a double layer capacitance
with two polarization resistances in series, and one
of these two polarization resistances in turn, in
parallel with an adsorption capacitance. Slaiman et
al. found that, under their experimental conditions,
no significant evidence for diffusion polarization was
detected. Stankovic observed that the pseudocapaci-
tance increases with increase in potential and this
was suggested to be due to the adsorption of Cu+

2121
2122 D. K. Y. WONG et al.
ions before the exchange of electrons as in step (Ib).
Several research groups[l&221 have provided evi-
dence for the presence of Cu(1) in solution during the
dissolution process. Hence, these authors have pro-
posed a model for copper dissolution represented by
Model II.
Model II
kl
cu \ Cu(I),, + e-
k-1
kz
Cu(I)ad= cut1)
k-z
h ranging from the vicinity of the potential of zero
cums Cu(II) + e-.
k-3
More recently, Balakrishnan and Venkatesan[23]
have investigated the anodic behaviour of copper in
various media including Na,SO,, NaCl, NaNO, ,
NH&l and (NH&IO4 solutions using rotating disk
and ring-disk electrodes under potentio-dynamic
conditions (potential scanning rate of 200mV
min-). These authors showed anodic polarization
curves of copper electrodes in acidic sulfate solutions
and observed that no passivation process occurred
in these systems. An anodic Tafel slope of 46 mV was
obtained in neutral sulfate solution and 40mM in
acidic solution (0.05 M HzSO,, + 0.2 M Na,SO,,
pH 1). Also, these authors reported an increased dis-
solution rate of copper with increased sulfate ion
concentration especially at high potentials. However,
no detailed discussion of a possible reaction mecha-
nism was given.
Awad er ~I.[241 carried out dissolution studies in
acidified aqueous solutions of various anions using a
potentiostatic method. Tafel plots were constructed
for the systems studied. The Tafel slopes (ranging
from 55 to 72mV in chloride, nitrate and sulfate
solutions) were found to depend on the nature of the
anion, indicating the possibility of anion partici-
pation in the anodic dissolution of the metal. Hence,
these authors proposed a reaction mechanism
involving the general anion, A-, based on the forma-
tion of intermediate Cu+ compounds (a fast
reaction). This was then followed either by a slow
electron exchange reaction or by a slow dispro-
portionation reaction (Model III).
Model III
kI
Cu+A-- _ CuA+e-
k-1
either CuA A Cu2+ + A- + e-
or 2CuA A Cu + Cu2+ + 2A-.
In the present work[25], the electrochemical dis-
solution of copper in acidic sulfate solutions has
been studied using ac impedance techniques. By
comparison with earlier work, results presented here
cover not only a wider range of pH (pH l-5), but
also a wider spectrum of frequencies (10-3-104H~).
Extending the range of H+ concentration to five
orders of magnitude allows investigation of the
dependence of the rate of reaction on pH and hence
of the role of hydrogen ions in the dissolution
process. Results obtained from dc measurements
generally only indicate the overall reaction rate
which depends on the slowest reaction path for a
series process, or on the fastest reaction path for a
parallel process in a particular reaction mechanism.
On the other hand, the uc impedance measurements
provide additional information arising from the
intermediates involved in the reaction pathway, espe-
cially in the low frequency region where slow relax-
ation processes are more easily observed. The low
frequency region is here studied to frequencies an
order of magnitude lower than in any previous work.
The present study has also covered potentials
current up to about + 1OOmV vs. see, in comparison
to earlier work in which attention has only been
centred around the potential of zero current poten-
tial (ie the corrosion potential). Hence, it is hoped
that more complete information can be obtained
through the present study and thereby the disso-
lution mechanism of copper in acidic sulfate solu-
tions will be clarified.
EXPERIMENTAL
Analytical reagent grade Na,SO, (anhydrous,
granular) and H2S04, purchased from Ajax Chemi-
cal, were used without further purification. Solutions
of l.OM Na,SO, and H2SO4 were prepared in
doubly distilled water. Electrolyte solutions of differ-
ent pH were prepared by mixing various proportions
of l.OM Na,SO, and H,SO,. All electrolyte solu-
tions were purged of oxygen by degassing with puri-
fied nitrogen for 16h[26] before steady state
measurements were commenced. The nitrogen was
purified by passing through a column of BASF
R3-11 copper catalyst and saturated by passage
through doubly distilled water. After deaeration a
blanket of nitrogen was kept over the solutions.
All experiments were performed in the poten-
tiostatic mode using a three-electrode cell. The refer-
ence electrode was a saturated calomel electrode
(see) and the counter electrode was a large piece of
platinum metal. A rotating copper (specpure grade
from Johnson & Matthey Chemicals Limited) disk
electrode (0.0194 f 0.0002 cm2) was employed as the
working electrode. The copper electrode was etched
in 20% (vol/vol) HNO, solution for 2min[27] and
rinsed with electrolyte solution before steady-state
measurements were commenced.
Steady-state measurements were made via a Solar-
tron 1186 Electrochemical Interface. Current mea-
surements were made when, at a set potential, the
current had reached a steady state. Impedance mea-
surements were performed using a Solartron 1250
Frequency Response Analyzer. The system was oper-
ated under automated control by a 6809
microprocessor-based computer system.
RESULTS AND DISCUSSION
The steady-state polarization curves of the disso-
lution of copper in l.OM Na,SO, solutions at
pH 1.0, 2.0, 3.0, 4.0 and 5.0 are depicted in Fig. 1. In
each case, the steady state was obtained within 5-
10min at a given potential and the Tafel slopes
 Electrochemical dissolution of copper 2123

pH 4.0

Fig. 1. Experimental (dashed lines) and simulated (solid lines) steady-state polarization curves of disso-
lution of copper in a mixture of various proportions of l.OM Na,SO, and 1.0 M H,SO,. Electrode
rotation speed = 25OOrpm.Marked points indicate the polarization potentials at which the impedance
was measured. The kinetic parameters used in simulations are tabulated in Table 1.

observed range from 54.8 to 55.6mV (compared to
55-72 mV reported previously[24]). In general,
all five polarization curves exhibit only active
dissolution behaviour in the potential range investi-
gated, in agreement with those reported by
Balakrishnan[23] and Awad[24].
Impedance spectra for solutions of pH 1.0, 2.0, 3.0,
4.0 and 5.0 have been obtained at different polariza-
tion potentials. Two capacitive arcs were found in all
cases. Hence, only impedance spectra for solutions of
pH 1.0 and 5.0 at different polarization potentials,
labeled on each steady-state polarization curve, are
displayed in Figs 2 and 3, respectively. In general,
the sixes of the arcs, and hence the corresponding
scales of impedance, decrease as the potential
becomes more anodic at each pH. In addition, the
lower frequency arc increases in size when the pH of
the solution becomes much more basic, eg pH 5.0, as
shown in Fig. 3. Also, at higher pH (pH4.0 and 5.0),
the size of this low frequency arc increases as the
electrode rotation speed decreases, indicating the
involvement of a diffusion process in determining the
ac response. On the other hand, no such electrode
rotation speed dependence has been observed for the
lower frequency arcs in low pH experiments (pH 1.0,
2.0 and 3.0). Therefore, while the high frequency arc
corresponds to a faradaic impedance due to a charge
transfer resistance in parallel arrangement with the
double layer capacitance[28], the lower frequency
arc probably arises from a charge transfer interme-
diate adsorption at low pH and a process involving
diffusion at higher pH.
Polarization curves and impedance spectra do not
allow direct determination of the chemical nature of
reaction intermediate species, but do enable ideas to
be developed about the potential and time depen-
dence of the concentrations and surface coverages of
each species. Several hypothetical mechanisms for

E
m3---;~
0 100 200 300 400 SW 600

k- I 811

1:_,
y 1
0 100 200 300 400 5&I

REALPART,Ohm REALPART,Ohm
Fig. 2. Experimental (left) and simulated (right) complex impedance plots in pH 1.0 solution. Polarization
potentials at which the impedance was measured are marked on the pH 1.0 polarization curve in Fig. 1
by the corresponding letters. Parameter is frequency in Hz
2124 D. K. Y. WONG et al.

I/-.I\.
0 200 400 600 800 1'000

E
6 2oo1 B5

11,&f-f?yk~
0 100 200 300 400

REAL PART, Ohm REAL PART, Ohm

Fig. 3. Experimental (left) and simulated (right) complex impedance plots in pH 5.0 solution. Polarization
potentials are.marked on the pH 5.0 curve in Fig. 1.

copper in acidic sulfate solutions have been pro-
posed and computer simulated in the present study
to generate theoretical steady-state polarization
curves and impedance spectra. The validity, though
not the uniqueness, of a reaction mechanism can
only be established when agreement is observed with
the polarization curve and a large number of imped-
ance measurements at different points on the curve,
in terms of the magnitude of the impedance and fre-
quency distribution. In this case, a model that
accounts for the dissolution mechanism of copper
must explain the various features in the steady-state
polarization curves and in the impedance spectra.
The simplest mechanism found to provide a sulll-
cient explanation of the major features of the experi-
mental data presented in this paper is as follows:
from the dc current through the electrode interface.
Alternatively, Cu(I)*, probably anion-associated,
which can then be desorbed and diffuse into the bulk
of the solution. A large number of simpler models
derived from this model, including Models I-III,
were also investigated, but in each case a serious dis-
crepancy was observed between the simulated and
observed results.
Computer simulations were performed by tran-
scribing the proposed model into mathematical
expressions based on several assumptions described
previously[28]. For model IV, the current density
expression and mass balance expressions are written
aS:
; = k, - Bl(kl + k-, - k2)

cu + Cu(II),, t4 Cu(II),, + Cu(II),, + 2e-

- &(k, + k_, - 2kJ (1)
k-,!lk,
kI de,
cu -
B dt = k, - f+(k, + k_, + k, + k3)
Cu(I),,
k-1
- 8,(k, - k_,) + (Ck_,) (2)
k-3 tlk,
Cu(I)zd p 2 =elk2 - e2(k_ 2) (3)

dUf
&,, .
In this model, the reaction step (l/-l) represents
the electrochemical conversion of copper metal to an
adsorbed Cu(1) species on the electrode surface. The
latter is further oxidized to Cu(II), also adsorbed on
the electrode surface The reaction step relating to k,
is a self-catalytic process and no consumption of
Cu(II), takes place. Such a catalytic step allows the
separation to the Cu(II),, relaxation time constant
dC
y dt = t&k, + Ck-, - flux, (4)
where Or denotes the fractional electrode coverage
by Cu(I), & the fractional electrode coverage by
Cu(II), and C the surface contact concentration of
Cu(I)*. /i and y represent the maximum number of
molecules adsorbed per unit electrode surface area
and the perpendicular distance from the electrode
interface occupied by a species in solution making
contact with the surface, respectively. Note that k,
 Electrochemical dissolution of copper 2125

does not intervene in the mass balance because the
related reaction neither produces nor consumes the
intermediate species. The flux of each species in solu-
tion must satisfy the Nernst approximation
Flux, = - 2 (C: - C,)
I data except at low potentials. This discrepancy prob-
in the time domain, and, in the frequency domain,
takes the form
Aflux, = - m [ tanh- 1&j6i)c*-
Here, A symbolizes a sinusoidal quantity and the
barred quantity indicates a Laplace plane function of
the Laplace variable, s.
The simulation task has been carried out using a
general matrix approach described previously[28].
This general matrix approach is described briefly,
together with the listing of matrix elements
employed for this model, in the appendix. Hence, by
a simulate and compare technique, attempts are
made to fit the effective rate constants k;, kl,, kzff,
k$, k;, kzff and Tafel slopes bl, b- 1, b2, b- 1, b, ,
b_, and b4 for all steady-state polarization curves
and impedance spectra at each pH during the simu-
lations. The values of the effective rate constants are
chosen arbitrarily, aiming to reproduce the major
features observed in both the steady-state polariza-
tion curves and impedance spectra. The model must
reproduce the general exponential increase of current
in the potential range in the polarization curves (Fig.
l), exhibiting only active dissolution behaviour. Also,
the model must reproduce the observed impedance
spectra displaying two capacitive arcs, the imped-
ance scale of which becomes smaller as a function of
anodic potential at constant pH, and becomes larger
when the solution becomes more basic (pH4.0 and
5.0).
With Model IV as our mechanistic model for dis-
solution of copper in acidic sulfate solutions, it was
found that good simulations of the experimental
steady-state polarization curves (Fig. 1) and imped-
ance spectra (Figs 2, 3) could be achieved using the
set of kinetic parameters listed in Table 1. In general,
all simulated steady-state polarization curves (also
depicted in Fig. 1) show excellent fit to experimental
ably arises from a shift of the corrosion potential
towards more positive values during the experiment.
In addition, the parallel reaction of hydrogen pro-
duction also becomes less negligible in this potential
region. Indeed this effect shows significance with
increasing hydrogen concentration, as the least satis-
factory fit is found in the simulation for the pH 1.0
curve relative to other results of higher pH. The
simulated impedance spectra (Figs 2 and 3) display
two capacitive arcs which decrease in size as a func-
tion of anodic potential. Also, the lower frequency
arcs in the simulated impedance spectra for pH 5.0
(Fig 3) are relatively larger in size, in comparison to
those for lower pH, as observed experimentally. The
magnitudes of these simulated impedance spectra
compare qualitatively with those obtained experi-
mentally but severe impedance dispersion[29-321
(the impedance arcs being somewhat sunken than
semicircles) is encountered in the latter. The ratio of
the radius along the real axis to that along the ima-
ginary axis (treating the centre of a semicircle as
lying on the real axis), of the depressed semicircle of
lower frequency, obtained in the present study
ranges from about 1.5 to 1.9, as compared to an
average of 1.6 in a similar study of dissolution of
iron in acidic chloride solutions[33] and in the
transpassive dissolution of nickel in acidic sulfate
solutions[34]. A depressed semicircle, having its
centre below the real axis, will appear to have a
reduced diameter along the real axis and exhibit a
higher frequency range along the arc length above
the real axis compared to the undepressed semicircle
in the simulated impedance spectra. As a result, in
this work, comparisons between the experimental

Table 1. Kinetic parameters used in simulation calculation for Model IV

PI-I 1 2 3 4 5
k~ff/molcm-2s-1 9 x lo- 1x 1o-3 3x 10-S 5 x 10-Z 5.5 x 10-l
&?!/molcm-2s- 2 x lo-lo 2x lo-0 2 x lo-0
: ; ;;I:
2 x lo-lo
k$/molcm-2s-1 8x 1o-g 5x 1o-g 4 x lo-g ;: ; $
E~/molcm-* s-l 8.5 x 1O-9 8.5 x lo- 8.5 x 10-g 8.5 x 10-g
k, /molcm-s-l 1.5 x 1o-g 1.5 x 10-g I.5 x lo+ 2.5 x 1O-9 4 x lo+
k /ems- 5x 10-p 5x 10-g 5x lo+ 5 x 1o-g 5 x lo+
kf$molcm-s-l 1.3 x 10-s 1.5 x lo-* 1.6 x 10-s 1.9 x 10-s 2.5 x IO-
WV- I9 19 19 19 19
-19 -19 -19 -19 -19
19 19 19 19 19
-19 -19 -19 -19 -19
0 0 0 0 0
0 0 0 0
b,/V- 38 38 3: 38 38
Double layer
Capacitance/Fcm-2 5 x 10-S 5 x lo- 5 x 1o-s 5 x 1o-5 5 x lo-
j/m01 cm2 1 x 10-s 1 x lo-* 1 x 10-8 1 x 10-s 1 x lo-*
Y/cm 6 x lo- 6 x IO+ 6 x lo- 6 x lO-9 6 x lo+
Rotation speedjrad s - 261.8 261.8 261.8 261.8 261.8
Diffusion coefficient/cm2 s-l I x 10-S 1 x lo- 1 x lo- I x lo- I x lo-S
Kinematic viscosity/cm2 s-l 1 x 1o-6 1 x lo+ 1 x 10-e I x lo+ 1 x 10-6
Cb/mol cm -3 0.0 0.0 0.0 0.0 0.0
 2126 D. K. Y. WON0 et al.

and simulated results have been made with emphasis

on similarity of shape, orders of magnitude and fre-
quency distributions in the impedance diagram,
although the latter will tend to be higher in the
experimental results due to the reasons just men-
tioned.
For an elementary charge transfer process, the
value of bJ=a,F/RZ) is 19.5V- for a symmetry
factor (a3 of 0.5. Values of b, of 19V- for all elec-
tron transfer steps and OV- for non-electron trans-
fer steps are employed in all simulations carried out
in this work. This represents a usual symmetric reac-
tion profile of an activated complex. However, values
of the order of 0.1 or less were found to be necessary
in other work[34-36) in which case the reaction 0.10 0.08 0.02

profile would take a highly asymmetric shape.

In Table 1, the optimum value found for the /3
parameter employed in the simulations is
1 x lo-* mol cm-* and this is comparable in magni-
tude to those used by Keddam et al.[35] and Mac-
Farlane et al.[33] of lo-* and 5 x 10-*molcm-*,
respectively, and of the order expected for mono-
layers of atoms on the electrode surface. The double
layer capacitance has been assigned a value of
50Fcm-*, compared to 70Fcm-* obtained by
Bockris et al.[lO] and 30Fcm-* by Pearson et
al.[ll] for a copper electrode in CuSO, + H,SO,
systems. A typical value of the diffusion coefficient
has been used for ions and likewise of the kinematic
0.06 0.02
viscosity for ions in aqueous solutions. 0.10

Figure 4 shows the contribution of each disso- PotentialIV versus SCE

lution path in the model to the overall current, cal-
culated for the pH 1.0 solution. The metal seems to
dissolve mainly through k, reaction path over the
entire potential range investigated. This suggests that
the electrochemical dissolution of copper in acidified
sulfate solutions proceeds largely via a two-electron
process. However, it is observed also that the
branching path k,/k_, C gradually becomes more
important as a function of pH, suggesting a possible
onset of a new reaction involving the diffusion of
Cu(1) away from the electrode. This is the expected
observation as a result of the formation of Cu,O in
alkaline solution [37-411. Also, this may be the
reason why the lower frequency arc has shown elec-
trode rotation dependence in the pH4.0 and 5.0
solutions. However, this diffusion current probably
does not arise from precipitation of any insoluble
CuSO, film on the electrode as no such precipitate
film was observed. In addition, we have also not
reached a high enough current density[42] to cause
precipitation of CuSO, .
All simulations have been performed by a visual
simulate-and-compare technique. Impedance disper-
sion has prevented us from performing statistical
evaluation of fitting between the simulated and
experimental spectra. Hence, in this work the simu-
lated results were accepted when the least deviations
from the experimental results were observed. A
variation of approximately 50% in the values of
effective rate constants, presented in Table 1, which
remain comparatively insensitive (these effective con-
stants do not vary markedly with pH) during simula-
tions was tolerated before any obvious change in the
simulated results was observed. A maximum of 20-
40% variation in the values of sensitive effective rate
Fig. 4. Contribution of each dissolution path to the overall
current, calculated for the pH 1.0 solution. C represents the
quantity (1 - 0, - 0,).
constants (which vary markedly with pH) was esti-
mated such that no significant change in the magni-
tude of the current density in the steady-state
polarization curves and that of the impedances of the
spectra were observed.
The above analysis of the proposed model sug-
gests that the electrochemical dissolution of copper
to form Cu(I1) in acidic sulfate solutions is a two-
electron autocatalytic process with Cu(1) as an inter-
mediate that can exist adsorbed on the surface and
in solution near the electrode and can be converted
to Cu(II),, . This is consistent with Models I-III.
However, in Model II, insuflicient distinction is
made between Cu(I),, and Cu(1) as to whether the
latter exists as another adsorbed intermediate or as a
species in solution. Model III is similar to Model IV
in the possibility of anion participation during the
dissolution of copper in acidic sulfate solutions. On
the other hand, it was not found necessary in the
present work to include a disproportionation of
Cu(1) species suggested in Model III.
SUMMARY AND CONCLUSIONS
In summary, the electrochemical dissolution of
copper in acidic sulfate solutions of pH l-5 has
been studied using impedance techniques over a
wide spectrum of frequencies (lo--lo4 Hz). Two
capacitive arcs including the high frequency arc due
 Electrochemical dissolution of copper 2127

to the double layer capacitance in parallel with a
faradaic impedance have been observed experimen-
tally. Successful simulations of the experimental
polarization curves and impedance spectra using
Model IV suggest that the electrochemical disso-
lution of copper to form Cu(II) in acidic sulfate solu-
tions proceeds mainly via a two-electron
autocatalytic process with Cu(I),, as a precursor of
Cu(II)., * However, when the pH of the solution
becomes more alkaline, the simulated results suggest
that the formation of Cu(I)* will be favored and this
may indicate the onset of a different reaction mecha-
nism.
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APPENDIX
Based on the assumptions described previously[28], a
general current density expression for a proposed reaction
mechanism model can be written in terms of the column
vectors[28], f? and I?, listing the surface adsorbed interme-
diate coverages and the reactant/product surface contact
concentrations, respectively, and the row vectors, k, and kc,
listing the appropriate combinations of rate constants and
electron numbers, such that
where K is a scalar rate constant arising from the term inde-
pendent of 0 and C.
Similarly, mass balance for the surface intermediate can
be expressed in matrix form via
@] g = [@II + [f&C + R
and for the species in solution making contact with the
surface
[jq 2 [/?$I + [l$JC - fliix,
where the square-bracketed terms are square matrices
formed from rate constants and stoichiometric coefficients.
Hence, the following scalar quantity and (1 x 1) vectors
are constructed from the current density and mass balance
expressions (equations 4-6) written for Model IV.
$ = [-(k, + k-, - k2) - (k, + k-, - 2k,)]

1
24. S. A. Awad. Kh. M. Kamel. Z. Abd El-Hadi and H. A. -(k, + k-, + k, + k, -(k, -k-2)
Bayumi, J.electroanal. Ch;m. interfacial. Electrochem. [l& =
k, -(k-z)
199,342 (1986).

1
25. D. K. Y. Wang, B. A. W. Coller and D. R. MacFarlane, k-, 0
Proc. of the 7th Australian Electrochemistry Conference, C&l= o o

February, Sydney, Australia, p. 154 (1988). [

26. M. Braun and K. Nobe, J. electrochem. Sot. 126, 1666

(1979). [I;;;] = ; ;
27. R. Sethi and D. T. Chin, J. electroanal. Chem. inter- [ 1
facial. Electrochem. MO,79 (1984). K = k, ri- = [k,].