Electrochimica Acta. 1969. Vol. 14. PP. 981 to 989. Pergamon Press.

Printed in Northern Ireland

THE ANODIC BEHAVIOUR OF COBALT IN

ALKALINE SOLUTIONS*
R. D. COWLING-~ and A. C. RIDDIPORD
Department of Chemistry, The University of Victoria, Victoria, British Columbia, Canada

Abstract-The anodic polarization of cobalt in sodium hydroxide solutions has been studied under
potentiostatic and galvanostatic conditions. Only two stages in the oxidation were found. It is sug-
gested that these correspond to the transitions Co/Co(OH), and cO(OH),/Co(OH),. The nuclea-
tion and growth of the passivating layer of cobaltous hydroxide is discussed by analysis of the
current/time curves at various constant potentials.

R&sum&-Etude, sous de-s conditions potentiostatique et galvanostatique, de la polarisation anodique

du Co en solution sodique. Deux &apes seulement de l’oxydation ont Bte trouv&s. Ceci conduit
a penser qu’elles correspondent aux transitions Co/Co(OH), et Co(OI&/Co(OH),. Discussion de la
nucleation et de la croissance de la couche passive d’hydroxyde cobalteux par, analyse des courbes
courant-temps 11dit%ents potentiels constants.

Znaammenfamnng-Kobalt wurde in Natriumhydroxydlosungen anodisch unter galvanostatischen

turd potentiostatischen Bedingungen polarisiert. Es wurden nur xwei Oxydationsschritte gefunden.
Diese werden den Ubergangen Co/Co(OH), und Co(OI-&,/cO(OH), zugeschrieben. Durch Analyse
der bei verschiedenen konstanten Potentialen aufgenommenen Strom/Zeitkurven werden die Keim-
bildung und das Wachstum der passivierenden Kobalt(II) hydroxydschicht diskutiert.

INTRODUCTION
COMPARJZD to the large amount of work on nickel and iron electrodes, very few studies
have been made on cobalt. The anodic formation of particular oxides on the metal
was first reported by Grube and Feucht,r and later by Bessor? and by El Wakkad and
HicklingS The results of these workers, obtained with cobalt electrodes plated on to
platinum supports, have been collated by Deltombe and Pourbaix,4 who established
an equilibrium potential/pH diagram for the metal at 25°C. Later work includes that
of Schwabe and G&r6 The structure, phase-transitions and electrochemistry of the
Co(OH), electrode have been studied by Wynne-Jones and co-workers.7 A compre-
hensive survey on cobalt is availab1e.s
Previous investigations of the cobalt electrode were mostly concerned with anodic
charging curves at constant current densities, the existence of several oxides and
hydroxides being deduced from inflexions in these curves. The following forms are
generally considered possible :4 COO, CO(OH,), CosO,, Co(OH), or CoOOH and
Coos. It appears to be difficult to distinguish between anodically formed Co0 and
Co(OH),; thus, Bessons claimed to have found a potential corresponding to CO/COO,
while El Wakkad and Hi&h@ reported a value close to the theoretical equilibrium
potential for Co/Co(OH),. The highest oxide was observed in each case,1-3 but was
generally found to be unstable.
The aim of the present investigation was to study the anodic behaviour of spectro-
scopically pure cobalt electrodes in alkaline solutions, in the absence of oxygen. The
current/potential curve has been examined potentiostatically, as this does not appear
l Manuscript received 11 July 1968.
t Present address: Department of Chemistry, Laurentian University, Sudbury, Ontario, Canada.
981
982 R. D. COWLING and A. C. RIDDIFORD

to have been reported previously for alkaline solutions. Galvanostatic charging curves
have been obtained at fairly low current densities, and current/time curves have been
studied at several constant potentials in O-1 N and 1-ON NaOH.
EXPERIMENTAL TECHNIQUE
Cobalt electrodes
These were prepared from spectroscopically pure wire, supplied by Johnson,
Matthey and Co., Ltd. Electrodes 0.5 mm diameter and 2 cm long were mounted in
polystyrene tubing. Each electrode was cleaned anodically in a mixture of 1 part of
ethyl alcohol to 1 part of concentrated hydrochloric acid, washed with doubly distilled,
de-ionized water and transferred quickly to the cell. This gave very reproducible
results.
Solutions
Solutions were prepared from AnalaR reagents, using doubly distilled water, and
were de-aerated with “white-spot” nitrogen. It was found that the results were not
affected when the nitrogen was scrubbed by passage through a heated column of
copper on kieselguhr, then through a solution of vanadous sulphate in sulphuric
acid and finally through a potassium hydroxide solution.
Measurements
A Wenking potentiostat was used for determining current/potential curves. For
the galvanostatic experiments, voltages were measured with a Solar&on 1420 or 1440
digital voltmeter, connected to a print-out unit. A quinhydrone reference electrode
was used with suitable precautions to avoid contamination of, and by, the alkaline
electrolyte. To assist uniform current distribution at the working electrode, a large
cylindrical platinum counter-electrode was used.
All potentials in this paper are referred to the normal hydrogen electrode.
RESULTS
Current/potential curves
The steady open-circuit potential of cobalt in 1 N NaOH was about -0.63 V(she).
A typical anodic polarization curve from this rest potential, at room temperature, is
shown in Fig. 1. In calculating cd, the apparent surface area of the electrode was used.
The current/potential curve was obtained by increasing the potential in increments of
5 mV in the active regions and 25 mV in the passive region, and recording the steady
current at each potential. The current increased from the rest potential up to -0595
V(she), at which point it fell to zero (strictly, to less than lo-’ A/cm2) over a period of
3-4 h. Further increase of overpotential caused a small rise in the current which, again,
subsequently fell to zero. Between -0.595 and $0.200 V(she), the electrode was
clearly passivated. A second active/passive region occurred between +0*200 and
+0*265 V. At more positive potentials, oxygen evolution began.
In O-1N NaOH, the electrode became passivated at -0.535 V(she), the trans-
passive region beginning at +0*250 V.
Potential/time curves
Constant-current charging curves were obtained on electrodes in NaOH solutions
ranging from O-1 to 2 N. The cd varied between 50 and 500 pA/cm2. The curves
 Anodic behaviour of cobalt in alkaline solutions 983

I Lo-_b
-650 -600 -550
E, mV (she)
FIG. 1. Potentiostatic anodic polarization curve for cobalt in 1 N NaOH, saturated
with nitrogen.

-600

I I 1 I
9 30 4L 50 60
r, min

FIG. 2. Galvanostatic anodic polarization curves for cobalt in 1 N NaOH, saturated

with nitrogen.
1,400; 2, 310; 3,250; 4,200; 5, 150,uA/cma

obtained for a 1 N solution are shown in Fig. 2. Except at the higher cds, the
plateaux which preceded passivation occurred at -0.590 to -0.600 V(she). A
second process, marked by a considerable overshoot of potential, followed by a slight
pause, was found in the region where the potential changed rapidly; this appears as a
change of slope between about +a300 and +0*450 V, depending on the cd.
984 R. D. C~WLINOand A. C. RIDDIFORD

In O-1 N NaOH, at cds less than 80 PA/ cm2, the initial plateau occurred at about
-0.530 V(she), the second process being shown by a marked inflexion in each curve
at +0.300 to +OMO V.

Current/time curves
The current/time relationship during the initial Glm formation was studied at
various constant potentials in solutions of 1.0 N and 0.1 N NaOH. The curves
obtained for a 1 N solution are shown in Fig. 3. As the overpotential was increased,

3oc

Q 2oc
i

<

IOC

1 I I
C 2 4 6 0 IO 12
t, min

Fro. 3. Potentiostatic i/t curves for cobalt in 1 N NaOH, saturated with nitrogen.
1, -535; 2, -545; 3, -555; 4, -565 mV (she).

the maximum current also increased, the peak shifted to shorter times and both the
rise and fall of the current were more rapid. Attempts to obtain potentiostatic current/
time curves for the second oxidation process were not successful.

DISCUSSION
The potential at which passivation first becomes possible in both 1 N and O-1 N
NaOH was found to be very reproducible. The Flade potential for cobalt in these
solutions is therefore taken as -0.595 and -0.535 V(she), respectively. In neither
solution was a reactivation potential observed. The equilibrium potential/pH dia-
gram4 shows that the only oxides (or hydroxides) which can be formed from the metal
at these potentials are Co0 and Co(OH),, the corresponding equilibrium potentials
at pH 14 being -0.662 and -0.733 V(she), respectively. Thus, while many workers
report passivation potentials close to reversible values for particular metal/metal-oxide
equilibria,s*10 in the present case there is a large difference between the passivation
potential and the nearest equilibrium potential. The change of 60 mV for a pH change
of 1 suggests that passivation is due to a simple oxidation reaction in which the
stoichiometric coefficients of hydroxyl ions and electrons are equal.
 Anodic behaviour of cobalt in alkaline solutions 985

The second stage of the anodic oxidation began at +0*200 V(she) in 1 N NaOH
and at +0*250 V in O-1 N NaOH. In view of the fact that only two steps were found
in the oxidation of the metal, it seems unlikely that the unstable oxide COO, was
formed under the conditions of these experiments. This, at first, seems surprising, as
other authors1-3 have reported the existence of this oxide. The probable explanation is
that while Coos is stable on a substrate of inert platinum (or platinum oxide), it is
not likely to be formed in contact with cobalt, which would immediately reduce it to a
lower oxidation state. It can be assumed, then, that the second stage in the potentio-
static oxidation of cobalt is due to the transition Co0 or Co(OH), to Co(OH), or
CoOOH.
The galvanostatic potential/time curves, such as those in Fig. 2, also indicate the
occurrence of only two stages in the oxidation. The potential of the first plateau in
1 N and O-1N NaOH corresponds closely to the potential of the first process found in
the potentiostatic examination. For the second stage, however, the inflexions in the
charging curves occur at somewhat more positive potentials than the corresponding
process in the current/potential curves. This is due, in part, to the overshoot of the
potential beyond the equilibrium value as the thin film on the electrode surface
becomes oxidized,ll and in part to the effect of the cd through the film. The higher the
cd, the further will the potential be displaced from the reversible value (see Fig. 2).
In the charging of the cobalt electrodes, the overpotential associated with the second
state was undoubtedly greater in 1 N NaOH than in the 0.1 N solution, since in the
latter case the cds were considerably lower. Wynne-Jones et ~1’ examined plated
Co(OH), electrodes, and found a potential of 0.25 V(she) for the transition Co(OH),+
CoOOH, in 1 N NaOH. In O-1N NaOH, one would therefore expect a plateau at
about $0.31 V, in reasonable agreement with the present observations. It is suggested
that the second stage in the oxidation therefore corresponds to Co(OH),/CoOOH, the
initial passivation reaction being due to the formation of Co(OH), rather than COO.
This implies an overpotential of about 130 mV for each stage in the potentiostatic
oxidation of cobalt, a magnitude which is often associated with nucleation overpoten-
tials. When the electrode is forced to sustain a constant current, the overpotentials
may increase.
The general form of the current/time curves at constant potentials, Fig. 3, indicates
that the rate of formation of the passivating film is controlled by the rate of growth of
the nuclei, rather than by the rate of dissolution of the metal.12 Figure 4 shows that
during the initial stages of growth in 1 N NaOH, the current at lower overpotentials
(with respect to the equilibrium potential for Co/Co(OH)d is proportional to P.
Using a simple model for the geometry of growing nuclei,ll this implies that three-
dimensional (hemispherical) growth occurs, with progressive nucleation. The partic-
ular case of the initiation, and growth, of three-dimensional nuclei upon a bare solid
metal surface has not been fully treated in the literature with respect to the calculation
of the exact amount of overlap of the growing centres. The ensuing discussion, there-
fore, follows the lines of Fleischmann and Thirsk’s13 treatment of the growth of lead
dioxide nuclei in a lead sulphate layer. As such, it must be regarded as a first approxi-
mation.
It is assumed that the growing nuclei effectively reach a limiting size at a fixed time
after formation, this time being equal to the maximum in the i/t curve. The physical
limit to the growth of nuclei would, in the present case, be the grain boundaries of the
 R. D. CCWLING and A. C. RIDDIFORD

120-

IOO-

60-
a
3.
60-
.<

0
L I
I.0
I
2.0
131 min3

FIG. 4. Dependence of current on (time)” during the initial stages of film formation
in 1 N NaOH.
1, -555; 2, -575 mV (she).

metal substrate. If the nucleation law can be represented as diV/dt = AN, exp (--At),
and the growth law by i = Bu2, where N is the number of nuclei at time t, N,, is the
maximum possible number of sites, A is the nucleation rate constant, B is the growth
rate constant and u is the age of a centre, the@

rate = AN$u2 exp [-A(t - u)] . du,

where uz is the time of the rate maximum. For u, > t,

BN, . At3
rate -h
3 ’
and for uz < t,

rate = BN, exp [-A(t - uJ] ula - 2 + $ - $ exp1.

(-AU,)
Thus, during the initial stages of growth, the current should be proportional to t3, as
observed.
For uz < t, a plot of log (rate) us t should be linear, the gradient giving the nuclea-
tion rate constant A. Figure 5 shows the experimental log i us t plots for cobalt at
various potentials in 1 N NaOH. The variation of A with potential is shown in Fig.
6(A). As A is very small, the exponential in the expression

Ul2 - 2 +5 - f exp (-Au,)]

was expanded to obtain
log (rate) = log BN, + log F + Au, - At,
 Anodic behaviour of cobalt in alkaline solutions 987

P20 -

* 2.00 -
x

.= I.80 -
B

I.60 -

I.401
0
I
2
I
4
I
6
I
8
I
IO 12
I J
14
1, min
FIG. 5. Dependence of log i on t dutiNt;k later stages of film formation in 1 N

1, -535; 2, -545; 3, -555; 4; -565; 5, -575 mV (she).

and the plots of log i us t shown in Fig. 5 were extrapolated back to t = 0, log BN,
being calculated from the intercept. Figure 6(B) shows the dependence of log BN,,
upon potential. For the assumed model of growing hemispheres, it can be shownu
that BN,, is proportional to k3, where k is the rate constant for the growth process in
mole/s/cma. Hence, if 7 is the overpotential for the growth process,

dq 1 . dq
d log BN, =5%$

Since the slope of Fig. 6(B) is dg/d log BN, = 28.2 mV, then dq/d log k = 84.6 mV.
If ,5 is the transfer coefficient for the anodic reaction, and z the number of electrons
involved in the rate-determining step, then
2.303 RT O-059
dg/d log k =
/3zF = 7’
In the present case, pz = O-69. Therefore, if z = 1, /? = O-69, or if z = 2, p = O-35.
If the rate-determining step involves a two-electron transfer, a possible mechanism
would be
Co + 2 OH- = Co(OH), + 2 e-,
although an effectively termolecular reaction such as this seems unlikely. Since the
basis of the foregoing discussion is that Glm growth, rather than metal dissolution, is
rate-determining, the reaction Co + Co s+ + 2 e- is not considered as the slow step in
the process. A possible mechanism for the growth of the passivating Urn on cobalt
in 1 N NaOH, is
Co + OH- = Co(OH),, + e-,
Co(OH),,, + OH- = Co(OH), + e-,
988 R. D. Coma and A. C. RDDIFORD

o.kl-1--10
E, mV (she)

-7.oor

N
E -670-
Y
e
3!
ii -640-
_
-0
5 -6.10-

4
-560-

E, mV (she)

Fro. 6. Dependence of (A) nucleation rate constant, and (B) log of composite growth
rate constant, on potential, in 1 N NaOH.

where the first step, the formation of adsorbed OH at cobalt sites, is rate-determining,
with /I = O-69.
A similar analysis of the current/time curves in O-1 N NaOH was not successful.
Further studies are being made on this.
SUMMARY
The results of the present studies have shown that the oxidation of a clean cobalt
surface takes place in two stages. This is supported by both potentiostatic and galvano-
static experiments, and in no case was a significant third process found between the
rest potential and the point of oxygen evolution. The two oxidation stages are attrib-
uted to the transitions Co + Co(OH), and Co(OH), + CoOOH. The current/time
curves show that in 1 N NaOH the passivating layer grows in three dimensions (on
the simple model, hemispherical growth being assumed), and that progressivenucleation
occurs. From the analysis of these curves, a simple mechanism for growth is proposed.
 Anodic behaviour of cobalt in alkaline solutions 989

Acknowledgment-R. D. C. thanks Energy Conversion Ltd. for the provision of a Research Grant,
during the tenure of which the present work was undertaken.

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