Oxidations involving silver. I.

Kinetics of the anodic oxidation of

silver in alkaline electrolytes
T. G. CLARKE, J. B. LEE, J. R. MORLEY,
N. A. HAMPSON, AND B. SCANLON
Department of Clzetnistry, Ut~iversityof Technology, Lolrghboroug/z,Leicestersllire, England
Received March 5 , 1968

-
The kinetics of the electrochemical oxidation of silver to A g 2 0 in NaOH have been studied at different
temperatures and hydroxyl ion concentrations. Theenthalpy of activation was found to be 5 kcal/rnole.
The kinetics of oxidation of A g 2 0 to A g o are discussed.
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Canadian Journal of Chemistry, 46, 3437 (1968)

Introduction tion of these oxides ]nay have an effect on the

Investigations in organic electrosynthesis have,
in general (see e.g. ref. l), paid little attention to
the behavior of the electrode; in contrast, prog-
ress in physico-chemical studies of electrodes
has depended upon scrupulous cleanliness of
electrolyte, cell, and electrode materials, to a
degree not readily achievable or economically
feasible for industrial organic reactions. As a con-
sequence organic and physico-chemical studies
have been largely divorced.
Interest has grown rapidly, in industrial and
academic laboratories, in the applications of con-
trolled electrosynthesis (2). We have undertaken
a conjoint organo- and physico-chemical study
of the behavior of solid electrode systems applied
to organic oxidations of laboratory and industrial
interest.
A prerequisite of a valid extrapolation of
results to a new situation, is a clear understanding
of all the contributing factors. The first papers
in this series will analyze the factors affecting
oxidations occurring at a solid silver electrode.
Results for other systems will be discussed
separately.
Silver in the Ag(1) state has long been used (see
e.g. ref. 3), for the oxidation of organic com-
pounds, and higher valency states appear to be
the cause of the catalytic effect of silver in per-
sulfate oxidations (see e.g. ref. 4).
A silver anode is not inert (as is platinum) but
participates in the electrode reaction. In acidic
solutions Agf ions are in equilibrium with the
electrode (EO = 0.799 V normal hydrogen elec-
trode) and therefore it is not feasible to carry out
oxidations in acid electrolytes. In alkaline solu-
tions two electrochemically well-defined oxides
are formed: Ag(1) oxide, Ag,O (EO= 0.338 V)
(15), and a higher oxide with the stoichiometric
formula A g o (EO = 0.599 V) (16). The forma-
oxidation of organic dompounds; a n under-
standing of this effect requires a knowledge of
the kinetics of oxidation of the silver electrode
itself.
Studies of the differential capacitance of silver
in neutral electrolytes (5) have indicated that the
electrode-electrolyte interphase is uncomplicated
by the intrusion of films, provided that the elec-
trode has been pretreated under carefully con-
trolled conditions. Further, over a considerable
range of potential, electrode capacitance measure-
ments appear to be characteristic of a n uncom-
plicated metal-electrolyte interphase at which
adsorption is absent. (The p.z.c. was readily
identified by a capacitance minimum a t - 0.7 V).
These measurements have recently been extended
to electrolyte of high p H (6). The properties of
the electrode-electrolyte interphase are generally
similar in neutral and alkaline electrolytes; al-
though there is some evidence for weak OH-
adsorption at potentials on the anodic side of
the p.z.c. in electrolytes of high pH. A carefully
prepared silver electrode provides a metal-elec-
trolyte interphase essentially uncomplicated by
surface films over a considerable range of
potentials.
Subjecting the electrode to positive potentials
in alkaline electrolytes results in the formation
of Ag,O
11I Ag + OH- -> 9Ag20 + $ H 2 0 +e
Dirkse et al. (7) have examined this reaction in
35% KOH and concluded that for the low over-
potential region (q,, < 40 mV) the exchange
current io (measured by the linear slope ofcurrent
density (i)-overpotential (qo) plots
 3438 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968

where R, T, and F have their usual significance), is -

washed and inserted into the cell. (Taking 17 pF ~ m
for the double layer capacitance of a smooth Hgelectrode,
- ~
approximately 2 x A cm-'. No value of
a, the charge transfer coefficient, has been
reported (see also ref. 14).
-
values for the electrode capacitance of silver in neutral

-
(pH 7) electrolytes (5) indicate that the ratio of
true area: superficial area is 2.5.)
Barradas and Fraser (8) have investigated the
Polarizariot1 Procedure
reaction Electrodes were polarized only once; thus each point on
[2] +Ag20 + OH- -> Ago + QH,O + e the current density - overpotential plots (Figs. 3 and 5)
corresponds to a new electrode.
in the high overpotential region using both Current density - overpotential data corresponding to
current-step and potential-step techniques. The the formation of Ag,O [I], was obtained by the applica-
tion of a singlc galvanostatic current pulse (duration
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charge transfer coefficient was found to be 0.5

but a value for the exchange current could not
-- 30 ms, rise-time < 1 ps) to a clean Ag electrode.
For the study of the formation of A g o [2], the electrode
be obtained from their results. was first electrolytically oxidized, in the cell, at a current
Organic oxidations at electrodes, when used density of 2.5 mA ~ m until - ~ the electrode potential
as a preparative technique, are usually carried began to rise to that of A g o formation. The application
of a single galvanostatic current pulse to this electrode
out at high current density and therefore at high provided the required overpotential data.
overpotentials. Information is required on the
kinetic parameters in this potential region. Results
This paper records the results of galvanostatic Potential Sweep
and potential sweep measurements made with The application of a potentiostatically con-
solid silver electrodes in aqueous sodium hydrox- trolled potential ramp to a silver anode resulted
ide.
in a current-potential curve of the form shown
Experimental in Fig. 1. The curves contained three peaks. Two
Electrolytes were continuously purified by circulation peaks were very pronounced and were inde-
through activated charcoal (9). The purification chamber pendent of electrode-electrolyte contact time.
was incorporated in a side limb of the electrolytic cell Their positions in the potential range indicated
(Pyrex glass) and circulation of the electrolyte effected by
means of a nitrogen lift pump (10). Electrolytes were
that these peaks correspond to faradaic current
maintained under an atmosphere of purified nitrogen (11) flow due to reactions [ l ] and [2].
presaturated to the necessary relative humidity by passagc The third peak appeared on the cathodic side
through a bubbler containing cell electrolyte. of the other two and was strongly dependent on
The construction of the silver microelectrodcs (- 2.5 electrode-electrolyte con'tact time and electrode
x lo-' cm2) used has been described elsewhere (5).
The counter electrode was either platinum gauze or a pretreatment. he peak was absent from the
silver rod (for experiments using a pulse generator).
The electrical circuits for galvanostatic polarization
experiments and switching techniques have been described
previously (10). Potentiostatic measurements were made
using a fast response potentiostat coupled with a linear
sweep generator (Chemical Electronics Ltd.).
Potential measurements were made against an AgzO/
Ag NaOH (1 M) reference electrode in conjunction with
a Luggin capillary.
The potential-time response under galvanostatic
conditions was recorded on an oscilloscope (Hewlett
Packard 130 C, and camera 196 B). The current-potential
response during potentiostatic experiments was recorded
either from an oscilloscope or by means of a chart
recorder.
All chemicals were of analytical reagent quality;
water was twice distilled in quartz from deionized stock.
Experiments were made under conditions of controlled
temperature ( k 0 . 5 "C).
Electrode Pretrearmetlr
FIG. 1. Potentiostatic current-potential curve for
silver in M NaOH at 23 "C. Electrode area = 2.22
The electrode was polished on roughened glass under
conductivity water and chemically etched in 15%
x ~ m - Potential
~ . sweep rate = 0.070 V min_ .
Peak a is the formation of Ag,O and peak b, theformatlon
aqueous nitric acid (5). The electrode was thoroughly of Ago.
 CLARKE ET AL.: OXIDATIONS INVOLVING SILVER. I 3439

TABLE 1
Variation of kinetic parameters with temperature for the formation of Ag,O in M NaOH
--- -- ----
Upper
limit
Tafel slope Z(l - a) a of Tafel
Temperature aq/a log i = b blT io or reglon
("K) (mV) (mV OK-') (mA cm-') h(l - a) If h = 1 If h = 2 (mV)
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current response curve if the electrode was held In the low overpotential region (qD < 10 mV)
in solution for approximately 10 min before the attempts to use this technique introduced a large
start of the potential sweep. The peak was greatly uncertainty in the value of qD.Attempts to make
enhanced if an already completely oxidized elec- measurements on an electrode containing suffi-
trode (Ago formation complete) was electro- cient Ag,O to be satisfactorily defined against a
chemically reduced. The magnitude of the peak standard gave results complicated by uncertainty
appeared to be independent of whether the elec- concerning the electrode area.
trode was just mechanically polished or polished The activation overpotential, qo, was plotted
and etched before insertion into the cell. against log,, i, a Tafel plot. A typical Tafel plot
is shown in Fig. 3. The exchange current, i, is
Galvanostatic Experiments obtained as the intercept of the extrapolated
The Formation of Ag,O linear region of the curve at q, = 0. The product
A typical overpotential-time transient is
shown in Fig. 2. The trace rises from a potential
value more negative than the Ag,O/Ag equilib-
rium potential (line A-B). (After polarization
the electrode potential falls back to line A-B.)
Extrapolation of the linear portion of the curve
to zero time (the intersection of the trace and
line A-B), when adjusted for the pseudo-ohmic
overpotential yields qD.

FIG. 2. Typical overpotential-time curve for the

galvanostatic polarization of silver in M NaOH at 23 "C. FIG.3. Typical Tafel plot for the formation of
Applied current density = 46 mA ~ m - ~ . Ag,O in M NaOH at 23 "C.
 3440 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968

Z(1 - a) was calculated from the slope of the

linear region using
-- arl D - 2.303R T
c31
a log,, i ZF(1 - a)
(1 - a)Z increased at the higher temperatures
as shown in Table I. At 23 "C the value of the
exchange current increased with increasing OH-
concentration (Table 11).
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TABLE I1
Variation of exchange current, io, with OH-
concentration for Ag20 formation at 23 "C

OH- concentration( M ) Exchange current,io ( m A

0.28 1.4
1.OO 2.8
4.86 7.2

Figure 4 shows a plot of log,, i, against 1/T.

Assuming that the Arrhenius equation holds over
the temperature range, the value for AH*, the
enthalpy of activation, is 5.5 4 2 kcal/mole. The
value for i, at the highest temperature studied
(60 "C) was only approximate as there was a
greater than normal scatter of points on the Tafel
plot; probably due to variations of temperature
within the cell.
T h e Formation of A g o
Short time (-30 ms) potential-time tran-
sients were very complex, irreproducible, and
difficult to interpret unambiguously. This could
be ascribed to the highly resistive properties of
the Ag20 surface and to variation in this surface
immediately before the perturbing pulse was
applied. The requirement that the whole of the
Potential Sweep Experiments
FIG. 4. Temperature dependence o f Ag,O exchange
current in M NaOH.
FIG. 5. Tafel plot for the formation o f Ago in M
NaOH at 23 "C.
electroactive surface should be A g 2 0 at zero
time was uncertain.
Examination of the charging characteristics
during the time of transition from reaction [I ]
to reaction [2] indicated that the transition is
relatively slow ( w 2-5 s) at low rates.
Consequently, experiments made by applying
long time pulses (-- 10 s) to an A g 2 0 electrode
on the point of rising to the overpotential charac-
teristic of the AgO/Ag20 system should give
potentials, in the later stages, pertaining only t o
this system in the absence of effects due to re-
action [I].
The final 'steady-state' overpotential plotted
as a function of log,, current density for the
reaction in M NaOH at 23 "C is shown in Fig. 5.
The value of the exchange current is found to be
0.02 mA and the charge transfer coeffi-
cient -- 0.6 assuming that 2 electrons are involved
in the process (8).
Discussion
Dirkse and De Vries (12) ascribed the first
anodic peak on the current-potential curve to
the formation of AgOH. The experimental re-
sults reported here suggest that whatever is
concerned in the oxidation process is readily
removed by contact with the electrolyte. Differ-
 CLARKE ET AL.: OXIDATI(3NS INVOLVING SILVER. I
ential capacitance measurements (6) indicate
that, in alkaline solutions, strong interaction of
negative ions with the silver surface does not take
place until -- +0.2 V (n.h.e.). It seems likely,
therefore, that the peak is due to removal of
hydrogen (adsorbed in the electrode pretreat-
ment) by the process
OH- + Had,-> H,O +e
The observation that electrodes only mechan-
Can. J. Chem. Downloaded from cdnsciencepub.com by 148.218.97.129 on 05/03/23
ically polished under conductivity water exhibit
a similar extra peak during the early stages of
electrode-electrolyte contact does not necessarily
vitiate the argument. Even in pure water the
establishment of a double layer might involve
sufficient transfer of electrons to form hydrogen
atoms at the electrode surface (17).
Galvanostatic Experiments
The Formation of Ag,O
The form of the potential-time transient (Fig.
2) is as expected for double layer charging fol-
lowed by charge transfer. The initial "jump", a
pseudo-ohmic overpotential, caused by the elec-
trolyte resistance between the test electrode and
the tip of the Luggin capillary is insignificant
compared with the activation overpotential.
After the "jump", the potential rises very rapidly
with a rate, at zero time, determined by the
double layer capacitance, C,, and the current
density applied to the electrode
The value of C, found from overpotential-time
+
transients (85 20 pF cm-,) agreed reasonably
with the value found by differential capacitance
measurements at this potential (70 20 p F +
c m - 7 (5, 6).
The absence of a significant concentration of
potential determining species on the silver elec-
trode means that, in our experiments, the potential
of the silver electrode is initially undefined in the
polarizable region. This unduly complicates
measurements at low overpotential. A t high
overpotential (- 100 mV a t 23 "C) the log-linear
relationship breaks down (Fig. 3). This might be
due to a change in the charge transfer mechanism,
alternatively it might indicate the limit of the
expkimental technique. The former explanation
seems to be indicated by the observation that the
-
upper limit of the l'afel region is extended to
200 mV at low temperatures (Table I).
3441
The general shape of the Tafel curves at higher
overpotentials suggests there is no specific ad-
sorption of the anion in this potential region.
-
The slope of the linear portion of the Tafel
plot yields a value of (1 - a)Z 0.9 at 23 "C
(Fig. 3). At higher temperatures this rises tovalues
> 1 (Table I) which indicates that Z (the number
of unit charges transferred in the rate determining
step) is greater than unity.
(In this connection potentiometric studies of
the Ag,O/Ag. OH- electrode show a dependence
of electrode potential (E) on OH- concentration
(Con-) corresponding to Z = 2, (aE/a log,, Con-
= 29 mV), although the change in oxidation
state of the silver is only + 1.)
An interpretation for this difference can be
given in terms of the transmission coefficient
(13). This concept is useful in reactions of this
type in which both the reactant and product sides
of the electrode equation involve species which
are not discrete ionic entities.
For a simple charge transfer reaction involving
one ion of charge difference Z between oxidized
and reduced forms the charge transfer equation,
connecting faradaic current density, i, and acti-
vation overpotential, qD,is
where a and p are respectively the cathodic and
anodic charge transfer coefficients (ct + P = 1
for the same reaction), i, is the exchange current,
and F, R, and T have their usual significance.
In this reaction the reactant is the metal lattice
and the overall product, the Ag,O crystal. The
transmission coefficient, h, is defined as the num-
ber of unit charges conveyed through the double
layer each time the rate-determining step occurs
once (13). Equation [4] then becomes
[51 i = io exp (- uhF
=)qD - io exp (%)TI,
If h has the value 2 the results are self-consistent.
The value of h/Z = 2, is commonly observed (13)
and interpreted in terms of two metal ions in-
volved, at once, in the activated state.
For a general reaction, 0 + Ze = R, the
exchange current, i,, is given by i, = 2Fk°C,"-
Col-". For eq. [I ] using h we have
Since we can consider the activities of solid Ag
 3442 CANADIAN JOURNAL OF
and Ag20 as unity and taking h = 2, eq. [6]
becomes
Correlation of io and OH- concentration data
-
(Table 11) yields an OH- dependence of io con-
sistent with a value of a 0.3 (at 23 "C) using
eq. 171. From Table I, a obtained from the Tafel
slope at 23 "C has a value 0.55.
This difference in values for a can be inter-
Can. J. Chem. Downloaded from cdnsciencepub.com by 148.218.97.129 on 05/03/23
preted in terms of simple adsorption of OH-
ions at the electrode (18). If the adsorption obeys
a simple Freundlich isotherm (it should be noted
that there is no theoretical justification for using
this isotherm, however, it appears to hold in
similar cases) eq. [7] becomes
where n is the Freundlich exponent and k' a
constant involving h and kO. A value for n = 2, Boots Pure Drug Co. Ltd., J.R.M. from Lough-
at 23 "C, would give a self-consistent a. This value borough University of Technology, and B.S.
for n indicates only weak adsorption of OH-.
The variation of Tafel slope function (b/T) Professor R. F. Phillips for his continued interest
with temperature (Fig. 6) is probably a reflection and encouragement.
of changes in adsorption with temperature.
The value of AH" (- 5 kcal mole-') is lower
than that generally found for simple charge
transfer reactions (- 10 kcal mole-'). This low
value might be explained by the adsorption of
electroactive species. The occurrence of a charge
273 293 313 333
Temperature, OK
FIG.6. Temperature dependence of .the Tafel slope
parameter (b/T)for the formation of Ag,O in M NaOH.
CHEMISTRY. VOL. 46, 1968
transfer reaction in the adsorbed state is often
associated with a low enthalpy of activation (19).
The Formation of Ago
The Tafel plot obtained for the formation of
-
A g o (Fig. 5) confirms the results of Barradas
and Fraser (8) that hp is 1. Taking h as 2, P
becomes 0.5 (i.e. a = 0.5).
The value of the exchange current obtained in
this investigation is only very approximate in
view of the difficulties involved in the production
is -
of a homogeneous electrode surface. The value
2 decades smaller than for the io involving
the formation of Ag20. The large difference in
these values confirms that the method of electro-
lytically producing Ag20 containing only mini-
mum amounts of A g o is feasible.
Acknowledgments
T.G.C. acknowledges financial assistance from
from the Science Research Council. We thank
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