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

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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


rate of which was itself limited by diffusion of Cu+.
Anodic dissolution of copper is involved in Brown and Thirsk[9] have found results support-
electrorefining[l], in electropolishing[2], in corro- ing Model I using a potentiostatic transient tech-
sion phenomena[2] and in maintaining the supply nique with a rotating disk electrode in 0.3 M CuSO,
for electroless deposition processes[l]. Many funda- + 0.2M H,SO,. The anodic current was observed
mental studies have been concerned with the mecha- to increase with increased electrode rotation speed in
nism of corrosionC2, 33 and deposition[6-131 of the overpotential range +5 to + lOmV, and the
copper in various media, but very little has been local mass transport of Cu+ is considered in addi-
reported concerning the anodic dissolution of copper tion to the diffusion of Cu2+ from the electrode.
at potentials other than the corrosion potential. However, Glarum and Marshall[lS], reported an
Mattsson and Bock&[61 and others[7, 81 admittance study of a copper rotating disk electrode
employed a galvanostatic transient polarization during deposition and dissolution processes in
method to study the kinetics of deposition and disso- 0.25 M CuSO, + 1.75 M H,SO,, agreed that Model
lution of copper in CuSO, solution. According to I is applicable near the equilibrium potential if
these authors, the dissolution of copper takes place allowance is made for the diffusion of Cu+ and Cu+
in a step-wise route in which Cu+ ion is the interme- ions. The admittance results were used to infer that
diate species (Model I). Cu+ concentration is substantially decreased at
Model I more anodic potentials due to a disproportionation
reaction (2Cu+ + Cu+ + Cu) and the growth of
kt
metallic clusters in solution, while frequency disper-
cu F Cu+ + e-
sion was found at cathodic potentials due to a
k-1
kz
double layer relaxation.
cu+ \ Cu*+ + e-. (If4 Slaiman and Lorenz[16] and Stankovic[ 171 have
k-z carried out studies of copper dissolution in a solu-
tion of H,SO, + CuSO, using a galvanostatic
This dissolution mechanism was proposed because
method. Slaiman and Lore&s results suggested that
the Tafel plot was found to be linear with a Tafel
step (Ia) in Model I be split in order to accommo-
slope of 40mV at 25C. In this model, the redox
process between Cu+ and Cu2+ (Ib) is therefore date the presence of an adsorbed Cu+ species after
comparison with an equivalent circuit consisting of a
regarded as the rate-controlling step and the reac-
parallel arrangement of a double layer capacitance
tion steps relating to k,/k_, are supposed to equili-
with two polarization resistances in series, and one
brate very quickly compared to those relating to
of these two polarization resistances in turn, in
k2/k_2. Impedance results of a copper electrode at
the equilibrium potential in a 0.56M CuSO, parallel with an adsorption capacitance. Slaiman et
al. found that, under their experimental conditions,
+ 0.5 M H,SO, solution obtained by Dmitriev et
aL[14] also implied the slow electron exchange reac- no significant evidence for diffusion polarization was
detected. Stankovic observed that the pseudocapaci-
tance increases with increase in potential and this
l Author to whom correspondence should be addressed. 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). of the role of hydrogen ions in the dissolution
Several research groups[l&221 have provided evi- process. Results obtained from dc measurements
dence for the presence of Cu(1) in solution during the generally only indicate the overall reaction rate
dissolution process. Hence, these authors have pro- which depends on the slowest reaction path for a
posed a model for copper dissolution represented by series process, or on the fastest reaction path for a
Model II. parallel process in a particular reaction mechanism.
On the other hand, the uc impedance measurements
Model II provide additional information arising from the
kl intermediates involved in the reaction pathway, espe-
cu \ Cu(I),, + e- cially in the low frequency region where slow relax-
k-1 ation processes are more easily observed. The low
kz frequency region is here studied to frequencies an
Cu(I)ad= cut1) order of magnitude lower than in any previous work.
k-z
The present study has also covered potentials
h ranging from the vicinity of the potential of zero
cums Cu(II) + e-.
current up to about + 1OOmV vs. see, in comparison
k-3
to earlier work in which attention has only been
More recently, Balakrishnan and Venkatesan[23] centred around the potential of zero current poten-
have investigated the anodic behaviour of copper in tial (ie the corrosion potential). Hence, it is hoped
various media including Na,SO,, NaCl, NaNO, , that more complete information can be obtained
NH&l and (NH&IO4 solutions using rotating disk through the present study and thereby the disso-
and ring-disk electrodes under potentio-dynamic lution mechanism of copper in acidic sulfate solu-
conditions (potential scanning rate of 200mV tions will be clarified.
min-). These authors showed anodic polarization
curves of copper electrodes in acidic sulfate solutions EXPERIMENTAL
and observed that no passivation process occurred
Analytical reagent grade Na,SO, (anhydrous,
in these systems. An anodic Tafel slope of 46 mV was
granular) and H2S04, purchased from Ajax Chemi-
obtained in neutral sulfate solution and 40mM in
cal, were used without further purification. Solutions
acidic solution (0.05 M HzSO,, + 0.2 M Na,SO,,
of l.OM Na,SO, and H2SO4 were prepared in
pH 1). Also, these authors reported an increased dis-
doubly distilled water. Electrolyte solutions of differ-
solution rate of copper with increased sulfate ion
ent pH were prepared by mixing various proportions
concentration especially at high potentials. However,
of l.OM Na,SO, and H,SO,. All electrolyte solu-
no detailed discussion of a possible reaction mecha-
tions were purged of oxygen by degassing with puri-
nism was given.
fied nitrogen for 16h[26] before steady state
Awad er ~I.[241 carried out dissolution studies in
measurements were commenced. The nitrogen was
acidified aqueous solutions of various anions using a
purified by passing through a column of BASF
potentiostatic method. Tafel plots were constructed
R3-11 copper catalyst and saturated by passage
for the systems studied. The Tafel slopes (ranging
through doubly distilled water. After deaeration a
from 55 to 72mV in chloride, nitrate and sulfate
blanket of nitrogen was kept over the solutions.
solutions) were found to depend on the nature of the
All experiments were performed in the poten-
anion, indicating the possibility of anion partici-
tiostatic mode using a three-electrode cell. The refer-
pation in the anodic dissolution of the metal. Hence,
ence electrode was a saturated calomel electrode
these authors proposed a reaction mechanism
(see) and the counter electrode was a large piece of
involving the general anion, A-, based on the forma-
platinum metal. A rotating copper (specpure grade
tion of intermediate Cu+ compounds (a fast
from Johnson & Matthey Chemicals Limited) disk
reaction). This was then followed either by a slow
electrode (0.0194 f 0.0002 cm2) was employed as the
electron exchange reaction or by a slow dispro-
working electrode. The copper electrode was etched
portionation reaction (Model III).
in 20% (vol/vol) HNO, solution for 2min[27] and
Model III rinsed with electrolyte solution before steady-state
measurements were commenced.
kI Steady-state measurements were made via a Solar-
Cu+A-- _ CuA+e-
k-1 tron 1186 Electrochemical Interface. Current mea-
surements were made when, at a set potential, the
either CuA A Cu2+ + A- + e- current had reached a steady state. Impedance mea-
surements were performed using a Solartron 1250
or 2CuA A Cu + Cu2+ + 2A-. Frequency Response Analyzer. The system was oper-
ated under automated control by a 6809
In the present work[25], the electrochemical dis- microprocessor-based computer system.
solution of copper in acidic sulfate solutions has
been studied using ac impedance techniques. By
comparison with earlier work, results presented here RESULTS AND DISCUSSION
cover not only a wider range of pH (pH l-5), but The steady-state polarization curves of the disso-
also a wider spectrum of frequencies (10-3-104H~). lution of copper in l.OM Na,SO, solutions at
Extending the range of H+ concentration to five pH 1.0, 2.0, 3.0, 4.0 and 5.0 are depicted in Fig. 1. In
orders of magnitude allows investigation of the each case, the steady state was obtained within 5-
dependence of the rate of reaction on pH and hence 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 the size of this low frequency arc increases as the
55-72 mV reported previously[24]). In general, electrode rotation speed decreases, indicating the
all five polarization curves exhibit only active involvement of a diffusion process in determining the
dissolution behaviour in the potential range investi- ac response. On the other hand, no such electrode
gated, in agreement with those reported by rotation speed dependence has been observed for the
Balakrishnan[23] and Awad[24]. lower frequency arcs in low pH experiments (pH 1.0,
Impedance spectra for solutions of pH 1.0, 2.0, 3.0, 2.0 and 3.0). Therefore, while the high frequency arc
4.0 and 5.0 have been obtained at different polariza- corresponds to a faradaic impedance due to a charge
tion potentials. Two capacitive arcs were found in all transfer resistance in parallel arrangement with the
cases. Hence, only impedance spectra for solutions of double layer capacitance[28], the lower frequency
pH 1.0 and 5.0 at different polarization potentials, arc probably arises from a charge transfer interme-
labeled on each steady-state polarization curve, are diate adsorption at low pH and a process involving
displayed in Figs 2 and 3, respectively. In general, diffusion at higher pH.
the sixes of the arcs, and hence the corresponding Polarization curves and impedance spectra do not
scales of impedance, decrease as the potential allow direct determination of the chemical nature of
becomes more anodic at each pH. In addition, the reaction intermediate species, but do enable ideas to
lower frequency arc increases in size when the pH of be developed about the potential and time depen-
the solution becomes much more basic, eg pH 5.0, as dence of the concentrations and surface coverages of
shown in Fig. 3. Also, at higher pH (pH4.0 and 5.0), 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- from the dc current through the electrode interface.
posed and computer simulated in the present study Alternatively, Cu(I)*, probably anion-associated,
to generate theoretical steady-state polarization which can then be desorbed and diffuse into the bulk
curves and impedance spectra. The validity, though of the solution. A large number of simpler models
not the uniqueness, of a reaction mechanism can derived from this model, including Models I-III,
only be established when agreement is observed with were also investigated, but in each case a serious dis-
the polarization curve and a large number of imped- crepancy was observed between the simulated and
ance measurements at different points on the curve, observed results.
in terms of the magnitude of the impedance and fre- Computer simulations were performed by tran-
quency distribution. In this case, a model that scribing the proposed model into mathematical
accounts for the dissolution mechanism of copper expressions based on several assumptions described
must explain the various features in the steady-state previously[28]. For model IV, the current density
polarization curves and in the impedance spectra. expression and mass balance expressions are written
The simplest mechanism found to provide a sulll- aS:
cient explanation of the major features of the experi-
mental data presented in this paper is as follows: ; = 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 dC
y dt = t&k, + Ck-, - flux, (4)
&,, .
In this model, the reaction step (l/-l) represents where Or denotes the fractional electrode coverage
the electrochemical conversion of copper metal to an by Cu(I), & the fractional electrode coverage by
adsorbed Cu(1) species on the electrode surface. The Cu(II), and C the surface contact concentration of
latter is further oxidized to Cu(II), also adsorbed on Cu(I)*. /i and y represent the maximum number of
the electrode surface The reaction step relating to k, molecules adsorbed per unit electrode surface area
is a self-catalytic process and no consumption of and the perpendicular distance from the electrode
Cu(II), takes place. Such a catalytic step allows the interface occupied by a species in solution making
separation to the Cu(II),, relaxation time constant contact with the surface, respectively. Note that k,
Electrochemical dissolution of copper 2125

does not intervene in the mass balance because the found that good simulations of the experimental
related reaction neither produces nor consumes the steady-state polarization curves (Fig. 1) and imped-
intermediate species. The flux of each species in solu- ance spectra (Figs 2, 3) could be achieved using the
tion must satisfy the Nernst approximation set of kinetic parameters listed in Table 1. In general,
all simulated steady-state polarization curves (also
Flux, = - 2 (C: - C,) depicted in Fig. 1) show excellent fit to experimental
I data except at low potentials. This discrepancy prob-
in the time domain, and, in the frequency domain, ably arises from a shift of the corrosion potential
takes the form towards more positive values during the experiment.
In addition, the parallel reaction of hydrogen pro-
duction also becomes less negligible in this potential
Aflux, = - m [ tanh- 1&j6i)c*- region. Indeed this effect shows significance with
increasing hydrogen concentration, as the least satis-
Here, A symbolizes a sinusoidal quantity and the factory fit is found in the simulation for the pH 1.0
barred quantity indicates a Laplace plane function of curve relative to other results of higher pH. The
the Laplace variable, s. simulated impedance spectra (Figs 2 and 3) display
The simulation task has been carried out using a two capacitive arcs which decrease in size as a func-
general matrix approach described previously[28]. tion of anodic potential. Also, the lower frequency
This general matrix approach is described briefly, arcs in the simulated impedance spectra for pH 5.0
together with the listing of matrix elements (Fig 3) are relatively larger in size, in comparison to
employed for this model, in the appendix. Hence, by those for lower pH, as observed experimentally. The
a simulate and compare technique, attempts are magnitudes of these simulated impedance spectra
made to fit the effective rate constants k;, kl,, kzff, compare qualitatively with those obtained experi-
k$, k;, kzff and Tafel slopes bl, b- 1, b2, b- 1, b, , mentally but severe impedance dispersion[29-321
b_, and b4 for all steady-state polarization curves (the impedance arcs being somewhat sunken than
and impedance spectra at each pH during the simu- semicircles) is encountered in the latter. The ratio of
lations. The values of the effective rate constants are the radius along the real axis to that along the ima-
chosen arbitrarily, aiming to reproduce the major ginary axis (treating the centre of a semicircle as
features observed in both the steady-state polariza- lying on the real axis), of the depressed semicircle of
tion curves and impedance spectra. The model must lower frequency, obtained in the present study
reproduce the general exponential increase of current ranges from about 1.5 to 1.9, as compared to an
in the potential range in the polarization curves (Fig. average of 1.6 in a similar study of dissolution of
l), exhibiting only active dissolution behaviour. Also, iron in acidic chloride solutions[33] and in the
the model must reproduce the observed impedance transpassive dissolution of nickel in acidic sulfate
spectra displaying two capacitive arcs, the imped- solutions[34]. A depressed semicircle, having its
ance scale of which becomes smaller as a function of centre below the real axis, will appear to have a
anodic potential at constant pH, and becomes larger reduced diameter along the real axis and exhibit a
when the solution becomes more basic (pH4.0 and higher frequency range along the arc length above
5.0). the real axis compared to the undepressed semicircle
With Model IV as our mechanistic model for dis- in the simulated impedance spectra. As a result, in
solution of copper in acidic sulfate solutions, it was 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-
Fig. 4. Contribution of each dissolution path to the overall
culated for the pH 1.0 solution. The metal seems to current, calculated for the pH 1.0 solution. C represents the
dissolve mainly through k, reaction path over the quantity (1 - 0, - 0,).
entire potential range investigated. This suggests that
the electrochemical dissolution of copper in acidified
sulfate solutions proceeds largely via a two-electron constants (which vary markedly with pH) was esti-
process. However, it is observed also that the mated such that no significant change in the magni-
branching path k,/k_, C gradually becomes more tude of the current density in the steady-state
important as a function of pH, suggesting a possible polarization curves and that of the impedances of the
onset of a new reaction involving the diffusion of spectra were observed.
Cu(1) away from the electrode. This is the expected The above analysis of the proposed model sug-
observation as a result of the formation of Cu,O in gests that the electrochemical dissolution of copper
alkaline solution [37-411. Also, this may be the to form Cu(I1) in acidic sulfate solutions is a two-
reason why the lower frequency arc has shown elec- electron autocatalytic process with Cu(1) as an inter-
trode rotation dependence in the pH4.0 and 5.0 mediate that can exist adsorbed on the surface and
solutions. However, this diffusion current probably in solution near the electrode and can be converted
does not arise from precipitation of any insoluble to Cu(II),, . This is consistent with Models I-III.
CuSO, film on the electrode as no such precipitate However, in Model II, insuflicient distinction is
film was observed. In addition, we have also not made between Cu(I),, and Cu(1) as to whether the
reached a high enough current density[42] to cause latter exists as another adsorbed intermediate or as a
precipitation of CuSO, . species in solution. Model III is similar to Model IV
All simulations have been performed by a visual in the possibility of anion participation during the
simulate-and-compare technique. Impedance disper- dissolution of copper in acidic sulfate solutions. On
sion has prevented us from performing statistical the other hand, it was not found necessary in the
evaluation of fitting between the simulated and present work to include a disproportionation of
experimental spectra. Hence, in this work the simu- Cu(1) species suggested in Model III.
lated results were accepted when the least deviations
from the experimental results were observed. A
variation of approximately 50% in the values of SUMMARY AND CONCLUSIONS
effective rate constants, presented in Table 1, which
remain comparatively insensitive (these effective con- In summary, the electrochemical dissolution of
stants do not vary markedly with pH) during simula- copper in acidic sulfate solutions of pH l-5 has
tions was tolerated before any obvious change in the been studied using impedance techniques over a
simulated results was observed. A maximum of 20- wide spectrum of frequencies (lo--lo4 Hz). Two
40% variation in the values of sensitive effective rate capacitive arcs including the high frequency arc due
Electrochemical dissolution of copper 2127

to the double layer capacitance in parallel with a 28. D. R. MacFarlane, D. K. Y. Wong and B. A. W. Caller,
faradaic impedance have been observed experimen- Bull. Electrochem. 6,893 (1990).
tally. Successful simulations of the experimental 29. J. A. Harrison and P. J. Stronach, J. electroanal. Chem.
interfacial. Electrochem. 72,239 (1976).
polarization curves and impedance spectra using
30. W. H. Mulder and J. H. Sluyters, Electrochim. Acta 33,
Model IV suggest that the electrochemical disso- 303 ( 1973).
lution of copper to form Cu(II) in acidic sulfate solu- 31. K. Nisancioglu and J. Newman, J. electrochem. Sot.
tions proceeds mainly via a two-electron 120, 1339 (1973).
autocatalytic process with Cu(I),, as a precursor of 32. I. Epelboin, M. Keddam, J. electrochem. Sot. 117, 1052
Cu(II)., * However, when the pH of the solution (1970).
becomes more alkaline, the simulated results suggest 33. D. R. MacFarlane and S. I. Smedley, J. electrochem.
that the formation of Cu(I)* will be favored and this Sot. 133,224O (1986).
may indicate the onset of a different reaction mecha- 34. M. Keddam, H. Takenouti and N. Yu, J. electrochem.
Sot. 132,256l (1985).
nism.
35. M. Keddam, 0. R. Mattes and H. Takenouti, J. elec-
trocheml Sot. 128,257 (1981).
36. H. Schweickert, W. J. Lorenz and H. Friedburg, Elec-
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8. J. OM. Bockris and H. Kita, J. electrochem. Sot. 109, general current density expression for a proposed reaction
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13. I. R. Burrow, J. A. Harrison and J. Thomoson. J. elec- where K is a scalar rate constant arising from the term inde-
troanal. C&L interfacial. Electrochem 58,541 (i975). pendent of 0 and C.
14. Y. S. Dmitriev, A. A. Murtazina and A. S. Kolosov, Similarly, mass balance for the surface intermediate can
Elektrokhimiya 5, 106 (1969). be expressed in matrix form via
15. S. H. Glarum and J. H. Marshall, J. electrochem. Sot.
128,968 (1981).
16. Q. J. M. Slaiman and W. Lorenz, Electrochim. Acta 19, @] g = [@II + [f&C + R
791 (1974).
17. Z. D. Stankovic, Electrochim. Acta 28, 109 (1983). and for the species in solution making contact with the
18. G. W. Tindall and S. Bruckenstein, Anal. Chem. 40, surface
1051 (1968).
19. G. W. Tindall and S. Bruckenstein, Anal. Chem. 40,
1403 (1968).
[jq 2 [/?$I + [l$JC - fliix,
20. G. W. Tindall and S. Bruckenstein, Anal. Chem. 40,
where the square-bracketed terms are square matrices
1637 (1968).
formed from rate constants and stoichiometric coefficients.
21. N. A. Hampson and R. J. Lathan, Trans. Faraday Sot.
Hence, the following scalar quantity and (1 x 1) vectors
67, 1440 (1971).
are constructed from the current density and mass balance
22. W. J. Albery and M. L. Hitchman, Ring-Disc Elec-
expressions (equations 4-6) written for Model IV.
trades, p. 78.-Oxford University Press (197lj.
23. K. Balakrishnan and V. K. Venkatesan, Trans. SAEST $ = [-(k, + k-, - k2) - (k, + k-, - 2k,)]
12,221 (1977).

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,].