b '

V15N I (03
Electrochemical Kinetic Parameters for the Cathodic - 7 1

Deposition of Copper from Dilute Aqueous Acid Sulfate

Solutions
J . T. HINATSU and F. R. FOULUS*

Depament of Chemical Engineering and Applied Chemistry, UnivetSity of Toronto, Toronto, On&ario,Canada MSS lA4
The use of linear-sweep voltammetry and chronopotentiometry for the determination of kinetic parameters for the
electrolytic recovery of copper from a simulated acid-copper electroplating waste solution was demonstrated. For the
electrodeposition of copper from solutions of 0.007-0.008 mol/L CuSO, + 0.5 mol/L H2SO4 at 25"C, the recom-
mended values of the transfer coefficient (a)and exchange current density (io)are Q = 0.46 f 0.06 (95%confidence
interval) and io = 11 f 4 A/m2. The close agreement between these values and the available literature values indi-
cates the reliabilaity of the voltammetric and chronopotentiometric methods.

On utilise la voltamttrie et la chronopotentiomttrie B balayage linhire pour dkterminer les paramhtres cinktiques
de rkcup6ration tlectrolytique du cuivre B partir d'une solution simulk d'blectroplacage au cuivre en milieu acide.
Les valeurs du coefficient de transfert (a)et de la densitk de courant d'6change (io)recommandks pour I'klectrodkpo-
-
sition du cuivre h partir de solutions t~0,007 0,008molell de CuS04 + 0,smold1 de H2S04B 25 deg. C, sont a =
0.46 + 0.06 (intervalle de confiance 95%)et io = 11 f 4 Aim'. Le bon accord entre ces valeurs et les valeurs pub-
liks dtmontre la fiabilitt des mtthodes voltamttriques et chronopotentiomktriques.

Keywords: copper electrodeposition kinetics, CuS0,-H2S04solutions, voltammetry. chronopotentiometry.

A cid-copper electroplating has a number of advantages
over other types of copper electroplating: it is relatively
fast, inexpensive, easy to maintain and control, less toxic
(cyanide-free), and produces deposits of good uniformity,
strength and ductility (Reid and David, 1987). For these
reasons, the use of acid-copper electroplating for the
manufacture of printed circuit boards is increasing in the elec-
tronics industry. However, the treatment of copper-
containing wastes is becoming more of a problem as regula-
tions and guidelines regarding effluents are tightened (Fleet,
1988). One method of removing the remaining copper from
depleted electroplating solutions is by electrodeposition. Con-
sequently, there has been renewed interest recently in the
electrodeposition of copper from CuS04-H2S04solutions
dilute in CuS04 (Scott, 1987).
The two-step reaction mechanism for the electrodeposi-
tion of copper from CuS04-H2S04solutions (Mattsson and
Bockris, 1962),
Cu++ + e- - CU+ (slow) . . . . . ., . . . . . . . . . . . (1)
Cu+ + e- - Cu (fast) . . . . . . . . . . , . . . . . . . . . . . (2)
-
~~
in CuS04. Linear sweep voltammetry (LSV) and
chronopotentiometry are frequently-used and reliable
methods, and the theory for their application to irreversible
reactions is well understood (Bard and Faulkner, 1980; Mac-
Donald, 1977). However, exact kinetic parameters for the
electrodeposition of copper from acid-copper solutions have
not been previously determined by these methods. Thus, in
the present study, we demonstrate the use and reliability of
LSV and chronopotentiometry as methods of determining the
kinetic parameters for the cathodic deposition of copper from
a simulated waste solution. We also compare our results with
those available in the literature, and give recommended
values of the kinetic parameters.
The simulated waste solution was 0.00789 mol/L in
CuS04 (- 0.5 g/L Cu) and 0.51 mol/L in H2S04 ( - 50
glL). These concentrations are similar to those which may
be found in waste solutions from acid-copper electropIating
(Scott, 1987). The relatively low CuSO4 concentration ren-
dered the effects of migration negligible (the transport
number for CU++ in this solution being 4.7 x 1 0 - ~
(Hinatsu and Foukes, 1989). Ohmic (iR) drops also were
negligible because of the high conductivity of the solution
(21.3 Slm), and the low current densities employed.

C U + ++ 2e- Cu ......................... (3)

has been verified in studies by Bockrk and Enyo (1962),
Turner and Johnson (1962), Bockris and Kita (1962),
Karasyk and Linford (1963), Brown and Thirsk (1965),
Damjanovic et al. (1966), Radovici and Vass (1967), Gor-
bunova and Thachik (1971), Chemenko and Litovchenko
(1971), Slaiman and Lorenz (1974), Kume (1976), Caban
and Chapman (1978), and Stankovic (1983). However, wide
ranges of values for the cathodic transfer coefficient
(0.31-0.57) and the exchange current density (standard
exchange current densities (io) -
of 2 850 A h 2 ) have been
reported by the above workers. Furthermore, relatively few
such data have been reported for acid-mpper solutions dilute
*Author to whom correspondence should be addressed.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, APRIL, 1991
Experimental
The pyrex cell was essentially of conventional three-
electrode design, and held about 150 cm3 of electrolyte.
The teflon lid had several openings for electrodes and gas
purging. The working and counter electrodes were copper-
plated platinum foil. All potentials were measured against
a saturated calomel reference electrode (sce), and are
reported as volts versus sce. Other equipment consisted of
a Princeton Applied Research (PAR) model 371 potentiostat,
a PAR model 175 universal programmer, a KeithIey model
614 digital electrometer, a Linear 800 series chart recorder,
a PAR model RE 0089 X-Yrecorder, and a Tektronix model
5 113 storage oscilloscope, the latter being used to record vol-
tammograms at sweep rates greater than 0.3 VIS.
571

1
 3.0 r -0.6 r

zE
v

*
c
2
5
2.0 - n
Q)
0
QI)

cri
-0.5

-0.4
1I I

>
0
-1.0 - -0.3
-a '

-
+
.
.

C
a
0
a
I

-0.2 -

0 4.2 -0.4
Potential (V vs. sce)
Figure 1 - Typical voltammogram for electrodeposition of Cu
+
from 0.00789 mol/L CuSO, 0.51 mol/L H,SO,. Sweep rate =
0.300 VIS, electrode area = 0.64,cm', 25C. The peak current
i
(i,) and the peak potential (Ep) are indicated. 0 4 8 12
The simulated waste solution was 0.00789 mol/L in Time (s)
CuSO4 and 0.51 mol/L in H2SO4. All solutions were pre-
pared using de-ionized water from a Millipore "Milli-Q" Figure 2 - Typical chronopotentiogram for electrodepositionof
water system (resistivity - 18 MQ cm), analytical grade
CuS04.5H20 (BDH AnalaR) and H2S04 (Baker Ana-
Cu from 0.00789 mol/L CuSO, + 0.51 moVL H'SO,. Electrode
area = 0.64,cm2, 2 5 T , constant current = 0.5 mA. The deter-
lyzed), and were deaerated with "oxygen-free" nitrogen for mination of the transition time, (r),and the locations of E,,,, E,,
and E,,,, are shown. 7 is given by the line segment AC; the length .
at least 15 min prior to the experiments. The temperature
of AB = 1/4 AC (Delahay and Mamantov, 1955).
was maintained at 25 f 0.2"C during the experiments using
a recirculating water bath.
The working electrode was electrolytically stripped of For two-step irreversible charge transfers where the inter-
copper and replated for each experiment. This preplating was mediate (Cu +) is more easily reduced than the initid reac-
carried out at a nominal current density of 200 A/m2 for 4 tant (Cu"), the characteristics of the voltammetric peak
+
min from a solution of 0.79 mol/L CuSO4 0.51 mol/L are primarily determined by the first charge transfer in the

thickness of - -
H2SO4 at room temperature (22 23"C), to give a deposit
4 pm. The geometric surface area of the
working electrode was 0.400cm2. The electrochemicalsur-
face area of the Cu-plated working electrode was previously
determined by chronopotentiometryto be 0.643 cm2, which
corresponds to a roughness factor of 0.643 cm2/0.40,, cm2
= 1.6* (see Results and Discussion section below, and
Hinatsu and Foulkes (1989) for details).
ResuIts and discussion
A typical voltammogram and chronopotentiogram are
shown in Figures 1 and 2, respectively. Since the elec-
trodeposition of copper from CuS04-H2S04 solutions
involves two electron transfers, two voltammetric peaks or
chronopotentiometric waves might be expected, one for each
charge transfer. However, since Cu' is much more easily
reduced than Cu" in CuS04-H2SOd solutions, only one
peak or wave (corresponding to the overall two-electron
transfer) is observed, as indicated in Figures 1 and 2. The
observed Tafel behavior shows that the reaction is irrever-
sible (Mattsson and Bockris, 1955; Bockris and Enyo, 1%2).
sequence (Polcyn and Shain, 1966). In the electrodeposition
of copper, the first charge transfer (Equation (1)) is irrever-
sible, and thus the voltammetric peak essentially corresponds
to that of an irreversibletwo-electron charge transfer. Con-
sequently, the theory of LSV for irreversible reactions was
used in the present study. This theory should apply equally
well for soluble or insoluble products, since the nature and
fate of the reaction products are not important for irrever-
sible reactions (Bard and Faulkner, 1980). The chronopoten-
tiometric data were treated in a similar manner, using the
theory for irreversible reactions (MacDonald, 1977; Bard
and Faulkner, 1980). These equations for LSV and
chronopotentiomeayhave not been used previously to extract
kinetic parameters for the electrodeposition of copper.
DETERMINATION OF CATHODIC KINETIC PARAMETERS BY
LINEAR SWEEP VOLTAMMETRY
The peak potential (Ep, V vs. sce) and peak current tip.
A) in linear-sweep voltammetric investigations of irrevmible
reactions (at 25C) are described by (seeBard and F a h e r ,
1980; Nicholson and Shain, 1964)

572 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69. APRIL, 1991
 1
and

EP = Eo' - (RTIa n, F ) [ (0.00534 F/RO + In ( T I " ) 6.0

+ In ( D a n, F/ko2R7)"2 + In (v'12)] ) .. .. ... (5) n
a
E
where A is the electrode area (cm2), C and D are, respec-
-
W

a
tivel , the concentration (mol/cm3)and diffusion coefficient
Y
(cm /s) of the electroactive species, v is the potential sweep
rate (V/s), a is the cathodic transfer coefficient, n is the
number of electrons transferred in the overall reaction (n =
2 for the electrodeposition of copper from CuS04-H2S04
solutions), n, is the number of electrons transferred in the
rate-determining step (taken as l), Eo' is the formal poten-
tial (V vs. sce), ko is the standard rate constant (cm/s), R
.
is the gas constant (8.314 J/mol K), Tis the absolute tem-
(Sweep Rate)l'* ( V / S ) " ~
perature (298 K) and F is Faraday's constant (96487 C/mol).
In the above equations, ko is the value of the rate constant -
Figure 3 Variation of voltammetric peak current versus square
when the cupric ion concentration is 1 mol/L; that is, when root of sweep rate for electrodeposition of Cu from 0.00789 mol/L
E = E". Upon substituting the numerical values of F , R CuS04 + 0.51 mol/L HzSO4. Electrode area = 0.64, cm2,25C.
and T, Equations (4) and (5) become Error bars represent 95 % confidence intervals. The transfer coeffi-
cient was determined from the slope, according to Equation (6).
ip = 2.985 X lo5 n (an,)l12A C D1'2v''2 . . . . . . . (6)
and

Ep = Eo' - ([0.05915/(2 CY no)] [0.6777

-O*O
-0.1-1
I
I
+ log (38.925 D a no/ko2) + logv] ) . . . . . . . . . (7)
The sweep rate was varied from 0.010 to 2.00 V/s in order
to determine the transfer coefficient and the standard rate
constant in the usual manner from plots of ip versus v'" and
E versus lo v (Bard and Faulkner, 1980). The variation
of ip with 3" is shown in Figure 3. Each point is the
average from at least 4 experiments, each using a freshly-
replated Cu electrode. All error bars in this study represent
95%confidence intervals. The least squares slope is 4.61 X
A (s/V)'12. A cathodic transfer Coefficient of 0.432
was calculated using the values of D = 5.38 x cm2/s
-0.5
-3
' -2 -1 0 1
I

and A = cm2 (the true electrode surface area), which

were determined previously (Hinatsu and Foulkes, 1989).
The diffusion coefficient for Cu(II) was determined by
static mercury drop electrode polarography, since polaro-
graphic determination of D does not require prior knowledge
of the true surface area of a solid electrode. Our polaro-
graphic diffusion coefficients are in excellent agreement with
those reported by other workers (see Hinatsu and Foulkes
(1989)j . The true sufface area of the Cu-plated working elec-
trode was determined by chronopotentiometry,using a solu-
+
tion of 0.00393 mol/L CuS04 0.51 mol/L H2SO4, the
Sand Equation see uation (1 1) below) and a value of D
dEq
= 5.67 x 10- cm2/s, which was determined by polarog-
log (Sweep Rate) (V/r)
Figure 4 - Variation of voltammetric peak potential with logarithm
of sweep rate for electrodeposition of Cu from 0.00789 mol/L
+
CuS04 0.51 mol/L HzS04. Electrode area = 0.M3cm2,25C.
Error bars represent 95 96 confidence intervals. The transfer coeffi-
cient and the standard rate constant were determined from the slope
and intercept, respectively, according to Equation (7).
The formal potential (E") at 25C can be calculated
from the observed equilibrium potential (Erq = 0.00V vs.
sce for C = 0.00789 mol/L) and the Nemst equation

raphy in a solution of the same comysition (Hinatsu and

Foulkes, 1989). The value 0.U3 cm was obtained as the
average of 29 determinations using constant nominal cur-
rent densities in the range 6 - 10 A/m2.
The variation of Ep with logv is shown in Figure 4. The
linear variation over a large range of sweep rates is indica-
tive of a kinetically-controlled reaction. The least squares
slope is -0.0688 V, which gives a cathodic transfer coeffi-
cient of 0.430, in excellent agreement with the value
obtained from the ip versus v1I2 data.
E"' = Eeq - (0.05915/2) log C . . . . .. ... . .. .. . (8)
where C is in mol/L. -Equation (7) and the values Eo' =
0.062 V vs. sce, a = o.431 (the average of the values from
the ip and Ep data), and the intercept of Ep versus logv
(-0.314 V vs. sce) were used to calculate a standard rate
constant of k, = 3.8 x cm/s.
The exchange current density, io (A/m2), was calculated
from ko as (B3rd and Faulkner, 1980)

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, APRIL, 1991 573
 -0.1 0 1 1 1 where 7 is the transition time (s) and t is the electrolysis time
(s) (Bard and Faulkner, 1980). If the values oft in Equation
L
(10) are replaced with the appropriate sub-multiples of 7,
-0.15 and then the Sand equation
-
n
a0
c
0 - p 2 = (n F A D'" 0 4 2 i) ......... ..... (1 1)
5 -0.20
c is used to eliminate r , the following expressions for the
e -0.25 - quarter-wave, half-wave and three quarter-wave potentials
I result:
&! Er14 = E'' + [(RTla n, F) [In (0.5 n F A k, C)
-0.30
t
I
II I
- In i] .................................
E,,' = Eo' + [(RTla n,, F) [In (0.2929 n F A k, C)
(12)

-3.5 -3.3 -3.1 -2.9

log i (amps)
- In i] ................................. (13)
E3r/4 = E'' + [(RTla nu F) [In (0.1400 n F A k, C)
Figure 5 - -
Plots of (E,,, E"'), (E, - E"') and - E"')
versus log i for electrodeposition of Cu from 0.00789 mol/L - In i] ................................. (14)
CuSO, 4- 0.51 mollL H2S0,. Electrode area = 0.64,cm2, 25OC.
Error bars represent 95X confidenceintervals. The transfer coeffi- The transition time was determined by the method of Delahay
cient and the standard rate constant were determined from the slopes
and intercepts, respectively, according to Equations (12) (14). - and Mamantov (1955); the validity of this method is indicated
by the constancy of the values of irv2Over the range of cur-
io = lo4 X nFk,C exp { [ -anF/RT]
rent densities investigated (6
- - 22 Alm'). Values of CY =
0.44 0.47 (average CY = 0.46) and k, = 5.7 x lov5 -8.1
- E " ' ) ) . ............................ x cm/s corresponding to io = 9.0 -lQ3 Nm', average
(Eeq .(9) io = 9.5 A/m$, or based on geometric surface area = 1.6,
x 9.5 A h 2 = 15.' Nm') were obtained from the slopes and
where (E, -
Eo' = -0.062 V, C is in mol/cm3 and the
factor 108 is used to convert A/cm2 to Alm2. Using the intercepts, respectively, of plots of (Er/,, - E"), (Era -
average value of CK = 0.43, yields a value of io = 4.6
E"'), and (&I4 - E") versus log i, shown in Fig. 5. Each
point represents the average of at kast 4 runs. The determina-
A/m2. This value is based on the true electrode area (rough-
tion of the kinetic m e t e r s by chronopotentiometry and LSV
ness factor = 1.61). The value of io based on the geometric
is summarrzed in Table 1, where the various plots, their slopes
surface area is l.61 X 4.6 A/m2 = 7.4 A/m2. and intercepts, and the resulting transfer coeficients and
exchange current densities are listed.
DETERMINATIONOF CATHODIC KINETIC PARAMETERS BY
CHRONOPOTENTIOMETRY
COMPARISON WITH LITERATURE VALUES, AND
The chronopotentiogram for an irreversible reaction is RECOMMENDED VALUES OF THE KINETIC PARAMETERS
described by:
The transfer coefficients obtained in the present study by
E = E"' + (RTIa nu F)(ln[2kJ(~D)''~] chronopotentiometry (CY = 0.44-0.47, average = 0.46)and
LSV (a = 0.43) are in good agreement with one another,
+ In (71/2 - t'")] ....................... (10) as well as with the value of a = 0.48 obtained by Bockris and

TABLE1
Summary of Experimental Determination of Kinetic Parameters
io ("'1
Based on Based on
true surface geometric
Method* Plot Slope Q Intercept area surface area
LSV ipvs.v I n 4.6, x 1 0 - ~ 0.432 -- -_ I

LSV Epvs.logv 0.0688 0.430 -0.31, 4.6 7.4

CHRPOT (Ed4.E" '1 -0.129 0.459 -0.577 9.5 15.2
vs. log i
CHRPOT (E,,,-E" '1 -0.125 0.47, -0.598 8.7 13.9
vs. log i
CHRPOT (E3r14-E"'1 -0.134 0.44, -0.66, IO., 16.5
vs. log i
*LSV = linear sweep voltammetry.
CHRPOT - chronopotentiometry.
x Roughness factor = 1.61

514 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69. APRIL, 1991
 TABLE 2
Literature Values of Transfer Coefficients for Cu Electrodes in CuS0,-H2S04 Solutions Obtained by Various Methods
[CUSO*1 [ H2SO4 1 Temp.
Reference Method* (mol/L) (mol/L) ("C) a
Reid and David AC 0.24 I .8 ? 0.52
Mattsson and GP 0.01 1- 0.5 30 0.49
BQCkriS 0.5
Bockris and Enyo GP 0.007- 0.5 30 0.47'
0.46
Bockris and Kita GP 0.05 1 .o 30 0.51 +

Brown and Thirsk RDE/PS 0.1-0.3 0.2-0.47 25 0.43'

Radovici md Vass GP 0.05-0.5 0.5 2545 0.48
Chernenko and PC 0.01-0.2 0.5 25 0.31,'
Litovchenko
Karasyk and GDP 0.75 0.5 25 0.57
Linford
Kume GP 1 0.5 25 0.49
Caban and RDElPS 0.010-0.10 0.20-2.o 21 0.39
Chapman
Milora et al. RDEfLSV 0.10 1.o 25 0.35
Stankovic GP 0.05-0.7 0.5-2.0 30 0.51
Average a = 0.46f0.05**
* -
AC AC impedance.
GDP - galvanostatic double pulse.
GP - galvanostatic pulse.
-
LSV linear sweep voltammetry.
-
PC programmed chronopotentiometry.
-
PS potentiostatic.
-
RDE rotating disk electrode.
+ Average value.
**95%confidence interval using t-test.

TABLE 3
Literature Values of Exchange Current Densities for Cu Electrodes in 0.007-0.008 mol/L CuS04+ -0.5 mol/L H2S04Solutions
I
[ cuso41 [ H2S041 Temp. i
Reference Method* (mol/L) (mollL) ("C) (A/%)
Bockris and Enyo GP 0.007 0.5 30 24**
I Caban and RDE/PS 0.00789 0.51 21 5.0+
ckitermtn
Stankovic GP 0.00789 0.51 30 2.5''
Pearson and Schrader AC 0.00736 0.5 23 15.9
Average ifi = 12
* AC - AC impedance.
GP - galvanostatic pulse.
I
-
PS potentiostatic.
-
RDE rotating disk.
** Average value.
j
+ Calculated using Caban and Chapman's equation iq = 156 (Cc )0.67 exp(-0.37CA) (A/m2), where CCuis the CuSO, concentration
(0.00789) mol/L), and C, is the H,SO, concentration (0.51 mh/L).
A Calculated using Stankovic's equation io = 36 (a,-,+t)0.67(A/m2).The cupric ion activity of 6.14~10-,mol/L was calculated
from the Nernst equation as follows: the observed rest potential = 0.00 V vs. sce and Eo = 0.095 V vs. sce; therefore, 0.00 V
= 0.095 + (0.05915/2) log a,--+ t.

Enyo (1962) using a galvanostatic pulse technique, which dilute solutions of copper in sulfuric acid. As can be seen
is the only literature value for a solution similar to the one from Table 2, this recommended value is essentially iden-
! employed in the present work (0.007 mol/L CuS04 0.5 + tical to the average of the available literature values obtained
mol/L H2S04). The average of our two values and the using a variety of methods. However, this exact agreement
single literature value gives CY = 0.46i0.06(95% confi- likely is fortuitous, since not only different concentrations,
I dence interval using t-test). This value is recommended for but also different temperatures were used for many of the
LIJe in work involving the electrodeposition of Cu from results listed in Table 2. However, the value is close to
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, APRIL, 1991 575
the expected theoretical value of 1/2 for the accepted two-
step mechanism. This close agreement confirms that the reac-
tion mechanism remains unchanged for a wide range of
CuS04 activities, and indicates the reliability of the LSV
and chronopotentiometric methods.
The nominal exchange current densities (basedon the geu-
metric electrode surface area) obtained in the present study
by LSV (io = 7.4 A/m2) and chronopotentiometry (io =
15.2 f 3.2 A/m2) are in reasonably good agreement with
one another, and with the available literature values for com-
parable solutions (Table 3). The literature values are quite
scattered, ranging from io = 2.5 A/m2 to 29 A/m2.
However, the average of the literature values is io = 12 A
me, which is very close to the average value of io = 11
A/m2 obtained by LSV and chronopotentiometry. This
close agreement, in spite of variations in the temperature
-
(21 30C), the CuS04 concentration (0.007 mol/L to
0.0079 mol/L), and the electrode surfaces, as well as the
fact that some of the literature values were extrapolatedfrom
fitted equations, gives added confidence to the values
obtained by LSV and chronopotentiometry . Consequently,
the average value of 11 f 4 A/m2 determined in the present
work may well be the best value that can be recommended
for the electrodeposition of copper from dilute solutions of
CuS04 in H2SO4 at about 25C.
The values of a and io obtained in this study by LSV and
chronopotentiometry were calculated using carefully checked
experimental results, as well as accurate values of the diffu-
sion coefficient for Cu(II) and the true surface area of the
Cu-plated cathode (Hinatsu and Foulkes, 1989). The close
agreement between the experimental and literature values
demonstrates the reliability of the voltammetric and
chronopotentiometric methods. Consequently, these methods
may now be used with confidence to study various aspects
of the electrodeposition of copper from dilute waste solu-
tions, for example, the effects of residual electroplating
additives.
Summary
The use of linear-sweep voltammetry and chronopoten-
tiometry was demonstrated for the determination of the
kinetic parameters for the electrodeposition of copper from
CuS04-H2S04solutions dilute in CuS04. The recommended
values of the kinetic parameters for electrodeposition of
copper from solutions of 0.007-0.008 mol/L CuS04
0.5 mol/L H SO4 at 25C are a! = 0.46 f 0.06 and io =
1 1 f 4 A/m;1 (based on the geometric surface area).
Acknowledgements
The authors gratefully acknowledge the financial support of the
Natural Sciences and Engineering Research Council of Canada.
Nomenclature
A = electrode area (m2 or cm2)
C = concentration of electroactive species (mol/L or
mol/cm3)
D = diffusion coefficient of electroactive species (cm2/s)
E = electrode potential (V vs. sce)
Eeq = observed equilibrium potential (V vs. sce)
peak potential (V vs. sce)
3E =
= standard reduction potential (V vs. sce)
= formal potential (V vs. sce) = E + (RT/2F)
My,+ +lYcu.)
576 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. VOLUME 69, APRIL, 1991
= quarter-wave potential (V vs. sce)
= half-wave potential (V vs. sce)
= threequarter wave potential (V vs. sce)
= Faraday constant
= current (A)
= exchange current density (A/m2)
= standard exchange current density (A/m2);the
exchange current density when the cupric ion con-
centration is 1 moUL
= peak current (A)
= standard rate constant (cmls); the rate constant when
the Cu(II) activity is 1 mol/L
= number of electrons transferred in overall reaction
= number of electrons transferred in ratedetermining
step
= gas constant
= absolute temperature ( K )
= cathodic transfer coefficient
= sweep rate (V/s)
= cupric ion activity coefficient
= copper metal activity coefficient
= transition time (s)
References
Andricacos, P. C. arid H. Y.Cheh, The Application of Linear
Sweep Voltammetry to a Rotating Disk Electrode for the Rever-
sible Depositionof an Insoluble Species, J. Electrochem. Soc.
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