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J. CHEM. SOC. FARADAY TRANS., 1994, 90(24), 3663-3668 3663

Hydrogen Adsorption-Desorption and Oxide Formation-Reduction

on Polycrystalline Platinum in Unbuffered Aqueous Solutions
Derek Pletcher" and Sotirios Sotiropoulos
Department of Chemistry, The University, Southampton, UK SO 17 IBJ
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The properties of microelectrodes are exploited to characterise hydrogen adsorption-desorption and oxide
formation-reduction at polycrystalline platinum in several aqueous electrolytes, especially unbuffered aqueous
media including water without the addition of electrolyte. In unbuffered solutions, the peaks for hydrogen
adsorption-desorption on a cyclic voltammogram are separated by several hundred millivolts. This separation
results principally from pH changes within the solution close to the electrode, induced by the surface reactions
themselves, although there is also a contribution from the slow kinetics of the electron-transfer processes. The
contribution from the irreversibility of the electron-transfer reactions has been estimated using rapid-scan volt-
ammetry in both acid and alkaline solutions. The influence of the mass-transport regime on the response is also
discussed,

An interest in the electrochemistry of oxygen in water
without the deliberate addition of any electrolyte has led us
to reexamine the adsorption-desorption of hydrogen and the
formation-removal of oxide from Pt electrodes in aqueous
media. We were especially concerned with these surface reac-
tions in water without added electrolyte. This is clearly a
neutral, unbuffered medium and such media have been little
investigated compared with acidic and alkaline solutions.
The adsorption and desorption of hydrogen on poly-
crystalline platinum in aqueous sulfuric acid have been
widely studied using voltammetric techniques '-' while more
recent investigations have employed spectroelectrochemical
methods6 and single-crystal surfaces7 to seek to obtain a
more detailed explanation of the multiple peaks on a cyclic
voltammogram. Generally, it is agreed that, in aqueous sul-
furic acid, hydrogen adsorption-desorption reactions are
rapid. The literature also contains many voltammograms for
Pt in aqueous sodium hydroxide and sodium carbonate but
they have generally been recorded at 20-100 mV s-' where
their appearance is similar to the voltammogram for sulfuric
acid. We are aware of only two papers, by Conway and co-
worker~,'.~which report the responses for Pt in aqueous
sodium hydroxide using fast potential scan rates and show
that the situation is more complex. They interpreted their
data in terms of slow electron-transfer reactions using theo-
retical expressions developed earlier."
Many of the experiments reported in this paper employ
microdisc electrodes (radii 5-12.5 pm) which extend consider-
ably the range of conditions where the surface chemistry of
Pt may be studied. Thus, cyclic voltammograms may readily
be recorded both at high potential scan rates (e.g. up to 1000
V s- ') and in media of low ionic strength without significant
distortion from IR or capacitance effects.' I-'
Experimental
The microdisc electrodes were prepared by sealing wires
(Goodfellow Metals) into soda glass. The disc surfaces were
cut and polished, initially on energy paper of decreasing
grades and then with 3, 1, 0.1 and 0.05 pm alumina powder
on a moistened polishing cloth. The electrode was then rinsed
well with water. Before studies in other electrolytes, the
potential of the Pt microelectrodes was cycled between -0.25
and +1.20 V in 1 mol dm-3 H 2 S 0 4 until a reproducible
voltammogram of the expected form4 was recorded. The elec-
trode was then again rinsed with water and transferred to the
medium under study. The cyclic voltammetry was carried out
in a two-electrode cell placed in a small bath held at 298 K
and placed within an A1 Faraday cage to minimise inter-
ference from electrical noise. The reference/counter electrode
was a Radiometer type K401 saturated calomel electrode and
it was separated from the microelectrode with a fine glass
sinter to minimise C1- contamination of the solution under
study. In addition, some experiments were carried out with a
Pt foil counter/reference electrode to ensure that C1- con-
tamination had not adversely affected the experimental data ;
in all cases, the responses were identical except for a shift
along the potential axis. The instrumentation has been
described elsewhere.'
Solutions were prepared with water from a Milli-Q/Milli-
Ro purification system and the resistivity of the resulting
water was checked to ensure that it met the specification
( > 18 MR cm). The sulfuric acid was ARISTAR grade while
sodium hydroxide and sodium sulfate were AnalaR grade.
Except for one experiment, all solutions were thoroughly
deoxygenated with a fast stream of fine N, bubbles. The cell
and other glassware were cleaned and then washed thor-
oughly with water to remove all ionic species.
Results and Discussion
Preliminary Experiments
Throughout this study, cyclic voltammograms were recorded
at microdiscs with radii of 5 and 12.5 pm.In all solutions, the
definition of the peaks for the adsorption-desorption of
hydrogen on Pt improved with potential cycling within the
medium under study (even after cycling in sulfuric acid) and
when the positive potential limit was chosen to allow oxide
formation-reduction. Except where otherwise discussed, all
features on the voltammograms as well as the current den-
sities were independent of the electrode size, as expected for
adsorptiondesorption reactions. The peaks associated with
hydrogen adsorption-desorption could always be distin-
guished from those for oxide formation-removal by appro-
priate shortening of the potential limits.
Fig. 1 reports a cyclic voltammogram recorded at 0.1 V
s-' for an aqueous solution of 1 mol dm-3 Na,S04 at a Pt
microdisc electrode, radius 5 pm. The scan towards negative
potentials shows a large peak for the reduction of platinum
oxide at -0.20 V us. SCE which overlaps H adsorption to
some extent, although a shoulder at -0.50 V and a peak at
-0.64 V for H adsorption can be clearly discerned. The
reverse scan shows two well defined H desorption peaks at
-0.29 and -0.16 V us. SCE and the formation of oxide at
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3664 J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

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-80 1 I I I I
-0.5 0.0 0.5 1 .o
E/V vs. SCE
Fig. 1 Cyclic voltammogram at a Pt microdisc electrode (radius 5
pm) in 1 mol dm-3 aqueous Na,SO,. Potential scan rate 100 mV
S-'.

potentials more positive than +0.20 V. As expected, the

cathodic and anodic charges for both H adsorption-
desorption and oxide formation-reduction are approximately
equal. The interesting feature is, however, the apparent irre-
versibility of H adsorption-desorption with the major peaks
separated by 360 mV. Voltammograms were also recorded at
higher potential scan rates; the separation of the peaks for 0.0 0.5 1.o
both H adsorption-desorption and oxide formation-removal EIV vs. SCE
are even greater and hence by 5 V s - l the hydrogen adsorp- Fig. 2 Cyclic voltammograms at a Pt microdisc electrode (radius 5
tion region is distorted by overlap from oxide reduction. It pm) in (a) 1 mol dm-3 H,S04 and (b) 0.5 mol dm-3 aqueous
should be emphasised that the separation of the H H,S04-0.5 mol dm-3 aqueous Na,SO,. Potential scan rate 100 mV
adsorption-desorption peaks increases by the adsorption S-I.
peak moving to negative potentials as well as the desorption
peak shifting to positive potentials. This is indicative of a a Pt disc in 0.1 mol dm-3 Na2S0, when the disc is station-
slow electron-transfer process. ary and rotating at 1600 rpm. The curve at the rotating elec-
In order to confirm that these data are not influenced by trode has many similarities to the voltammogram in Fig. 1 at
impurities in the sodium sulfate (e.g. chloride ion), voltam- the microdisc electrode. The response at the stationary elec-
mograms were recorded for the Pt microdisc in solutions of 1 trode is, however, markedly different. The H adsorption-
mol dm-3 H2S04 and 0.5 mol dm-3 Na2S0,-0.5 mol dm-3 desorption process now appears to be fairly reversible (i.e. the
H2S04, see Fig. 2; the responses are identical except for peak separations are small, <50 mV) and there is an addi-
minor potential shifts and have the classical form widely tional broad cathodic peak at +0.32 V us. SCE.
described for 1 mol dm-3 H2S04 in the l i t e r a t ~ r e Further-
.~ We believe that the difference can be understood in terms
more, a series of voltammograms were obtained in 1 mol of the pH changes at the electrode surface resulting from the
dm-3 NaClO, solution and they were essentially identical to electrode reaction themselves. In the unbuffered medium, the
those in 1 mol dm-3 Na2S0,, confirming that anion adsorp- two reduction processes
tion is not an important factor in determining the voltam-
metry.
PtO + H 2 0 + 2e- -+ Pt + 20H- (1)
and
Influence of Mass Transport on the Response in Unbuffered Pt + H,O + e- -+ Pt-H + OH- (2)
Media lead to the formation of a hydroxide ion and hence cause the
The mass transport to or from a microdisc electrode is pH close to the surface to increase. In contrast, the coupled
always efficient because the mass-transfer coefficient is pro- oxidation reactions will be
portional to D/r, where D is the diffusion coefficient of the
Pt + H 2 0 - 2e- -+ PtO + 2H' (3)
reactant and t the radius of the disc; for a 5 pm disc the
mass-transfer coefficient is ca. 8 x lo-, m s-'. Hence, in and
order to study the voltammetry over a wide range of mass- Pt-H - e- + Pt + H+
transport conditions, experiments were carried out at station- (4)
ary and rotating-disc electrodes (at 1600 rpm, k, x 1 x lo-, Both reactions lead to the formation of protons and a
m s - l ) . Fig. 3 compares voltammograms run at 0.1 V s-' for decrease in pH close to the surface. Albery and CalvoI4 have
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 3665

port regime. For example, hydrogen desorption from an

30 -
(4 RDE or a microdisc is completed at potentials expected for
an acidic medium (the protons again resulting from the elec-
trode reaction itself) since the hydroxide formed during
0 hydrogen adsorption and evolution has already been swept
away from the surface. At a stationary electrode, see Fig. 3(a),
the hydroxide ion remains close to the surface and hydrogen
-30 desorption occurs at the potentials expected for a basic solu-
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tion Overall, adsorption-desorption is relatively reversible at

the stationary electrode while a large peak separation
-60. appears when the conditions lead to the removal from the
surface of the hydroxide formed during adsorption. Exactly,
4 4
the same trends are discernible for oxide formation-removal
301 (b) A except that it is the proton formed which controls the pH at
the electrode. Moreover, this reaction is always irreversible
and little oxide thickening occurs on the scan back from posi-
tive potentials. As a result, the response for the unbuffered
neutral solution shows two peaks for oxide removal; that at
+0.33 V corresponds to the reduction in an acid environ-
ment while that at -0.18 V corresponds to the reduction of
oxide after all the protons have been consumed or lost from
the surface. A similar effect relating to hydrogen desorption
can be seen on voltammograms employing a higher scan rate
of 5 V s- at the microdisc when hydrogen desorption occurs
in two distinct potential regions: some of the hydrogen is
~~~

4.5 0.0 0.5 1 .n

Fig. 3 Cyclic voltammograms at a Pt disc electrode (radius 2.5 mm)
(a) stationary (b) rotating at 1600 rpm in 0.1 mol d m P 3 aqueous
Na,SO,. Potential scan rate 100 mV s - '.
confirmed experimentally that such changes in pH occur in
the case of a gold electrode in neutral solution using a
rotating-disc electrode (RDE) with a pH-sensitive ring elec-
trode. The pH at the electrode surface will, however, also
depend on the mass-transport regime; with increasing mass-
transfer coefficient, the protons and hydroxide ions will leave
the surface more rapidly and there will be a smaller pH
change within the layer adjacent to the surface. More impor-
tantly, once the generation of proton or hydroxide ceases, in
well mixed systems the layer at the surface will rapidly return
to neutrality. Experimental data from voltammetric experi-
ments for Pt in acidic, basic and neutral solutions using
several types of electrode are reported in Table 1. It can be
seen that in the unbuffered neutral solution, the deposition
reactions, hydrogen adsorption and oxide formation always
occur at a potential expected for the pH environment created
by the electrode reactions themselves, basic from H adsorp-
tion and acidic from platinum oxide formation. In contrast,
with a relatively low potential scan rate, e.g. 0.1 V s-', the
potential for the reverse reactions depend on the mass trans-
desorbed in an alkaline environment before all the hydroxide
escapes from the electrode surface while the remainder is
desorbed in an acidic environment resulting from formation
of protons in the electrode reaction.
Overall, it can be seen that the mass-transfer regime has a
strong influence on the response for unbuffered neutral media
and such effects will predominate in studies of water without
electrolyte.
Influence of Slow Electron Transfer on the Response at
Microelectrodes
It was considered interesting to assess the contribution of
slow electron transfer to the peak separations in neutral
unbuffered media. This cannot be achieved directly because
of complex variation of proton-hydroxide availability with
potential scan rate and the size of the microdisc. Hence,
experiments were carried out in both acidic and basic condi-
tions.
At slow potential scan rates in 1 mol dm-3 H,SO,, the
voltammograms recorded between + 1.2 and -0.25 V had
the classical features for hydrogen adsorption-desorption and
oxide formation-reduction in addition to a well defined
double-layer region (see Fig. 2 and the literature review, ref.
4). In the hydrogen region and at the higher scan rates, the
response is dominated by two sharp adsorption and desorp-

Table 1 Peak potentials for H adsorption-desorption and oxide formation-reduction on Pt in water and various aqueous solutions

EJV vs. SCE

oxide oxide
medium electrode H adsorption H desorption formation reduction

1 rnol dm-3 H,SO, RDE, disc, 0.00, -0.14 -0.14, -0.05, 0.00 + 0.66 +0.55
microdisc
0.1 mol dm - NaOH RDE, disc, -0.65, -0.75 -0.70, -0.58 0.00 -0.20
microdisc
0.1, 0.5 or 1 disc (0 rpm) -0.50, -0.62 -0.57, -0.43 +0.52 +0.33, -0.18
rnol dm-3 Na,SO,
RDE (1600 rpm) -0.43, -0.58 -0.35, -0.22 +0.48 -0.18
microdisc (r = 5 pm) -0.49, -0.63 -0.29, -0.16 +0.46 -0.20
pure H,O microdisc (r = 12.5 pm) -0.40, -0.54 -0.20, -0.13 +0.54 -0.17
pure H,O + 0, microdisc (r = 12.5 pm) -0.61, -0.80 -0.55, -0.50

Potential scan rate 0.1 V s-'.


3666
tion peaks. At low scan rates, the peak potentials for the
paired cathodic and anodic processes are identical. Even at
the 5 pm radius microdisc where iR drop is totally negligible,
as the potential scan rate is increased, however, peak separa-
'
tion begins to occur. At a scan rate of > 100 V s- the separa-
tion of the peaks for both weakly and strongly adsorbed
hydrogen approaches 50 mV. Hence, even in sulfuric acid,
there is an influence on the voltammetry from the kinetics of
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the formation and cleavage of Pt-H bonds.
In aqueous sodium hydroxide and at slow potential scan
rates (50 mV s- '), the response in the hydrogen region clearly
shows two cathodic and two anodic peaks although the peak
for weakly adsorbed hydrogen is always smaller than that for
strongly absorbed hydrogen. Indeed, the voltammogram has
a general similarity with that in sulfuric acid under similar
conditions and the separations between coupled peaks are
small. Fig. 4(a) shows the voltammogram at 500 mV s-'.
Already, there are significant changes. The adsorption peak
at more positive potentials is greatly diminished in impor-
tance and appears only as a shoulder on the major cathodic
peak at -780 mV. While there are still two well formed
desorption peaks, they are shifted significantly to positive
potentials and are observed at -690 and -570 mV. With
increasing potential scan rate, there is a shift of the major
cathodic peak to more negative potentials and both anodic
shift in a positive direction. Fig. 4(b) shows the response at 50
V s - and the quality of the voltammograms at the microdisc
electrode should be noted. It can clearly be seen that the
hydrogen adsorption and desorption peaks are now well
separated. The major cathodic peak is seen at -900 mV and
the anodic peaks at - 550 and -440 mV. The separation of
the major anodic and cathodic peaks with potential scan rate
is illustrated in Fig. 5 and the shape of the curve clearly con-
firms that the kinetics of the adsorption-desorption have
become a major factor in determining the shape of the volt-
ammogram (Fig. 5 also shows the variation of the peak
-60 1
-1 .o -0.5 0.0 0.5
EIV vs. SCE
Fig. 4 Cyclic voltammograms at a Pt microdisc electrode (radius 5
pm) in 0.1 mol dm-3 aqueous NaOH. Potential scan rates ( a ) 100
mV s - ' and (b) 50 V s-'.
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J. CHEM. SOC. FARADAY TRANS., 1994, VOL 90
400
T
T
I
E
300
>
.E..
kIn
d
200
100
P
0 0
0
0 ,
0
-1 0 1 2
log(v/v s-1)
Fig. 5 Variation of the peak separation, AEp, between the major
adsorption and desorption peaks with potential scan rate for V, 0.1
mol dm-3 NaOH and 0 , 1 mol dm-3 H,SO,. Data taken from
voltammograms at a Pt microdisc electrode, radius 5 pm. The error
bars indicate the reproducibility during a number ( > 6) of experi-
ments.
separation for weakly adsorbed hydrogen in sulfuric acid and
it is always much smaller). A similar plot has been reported
by Sharpel' and the scan-rate dependence in a base by
Conway and c o - ~ o r k e r s *but
~ ~ the reliability of the data
from experiments with microelectrodes should be higher.
Clearly, the kinetics of electron transfer do contribute to the
voltammetry of hydrogen adsorption-desorption, especially
at high scan rates and maybe in all experiments with
enhanced mass transport.
Voltammetry at 50 V s- clearly shows two other features.
First, hydrogen gas evolution is no longer observed in the
same potential region; it is shifted to more negative poten-
tials with increasing scan rate. Secondly, during the scan
towards negative potentials, the shoulder appears at a poten-
tial negative to the major peak whereas at 500 mV s- it is at '
more positive potentials. This indicates either (i) a marked
change in the relative importance of the types of adsorbed
hydrogen with potential scan rate or more likely (ii) that the
kinetics of adsorption-desorption are slower at sites with
strongly absorbed hydrogen than at those with weakly
absorbed hydrogen.
It would appear that the kinetics of hydrogen adsorption-
desorption are important in determining the cyclic voltam-
metric response at fast scan rates; it cannot be assumed that
these electron-transfer reactions are rapid, particularly from
neutral or basic solutions where, for example, the adsorption
process involves bond cleavage within the water molecule.
Surface Chemistry of Platinum in the Absence of Added
Electrolyte
Fig. 6 illustrates the voltammetry of water without added
electrolyte at a Pt microdisc (r = 12.5 pm). The general fea-
tures are the same as with the other unbuffered aqueous solu-

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Fig. 6 Cyclic voltammograms at a Pt microdisc electrode (radius
12.5 pm) in pure water without added electrolyte. Potential scan rate
100 mV s-'.
tions with only a slight decrease in peak sharpness. The peak
potentials for H adsorption-desorption and oxide formation-
reduction are also shown in Table 1. The major H
adsorption-desorption peaks are again separated by some
340 mV. Therefore, the surface chemistry of Pt once again
I cesses. It has been confirmed that there is a significant influ-
-1 0
S2-
-0.5 0.0 0.5
EIV vs. SCE
Fig. 7 Cyclic voltammograms at a Pt microdisc electrode (radius
12.5 pm) in pure water, without added electrolyte, in equilibrium
with air. Potential scan rate 100 mV s-'. The inset shows an expan-
sion of the H adsorption-desorption region while oxygen reduction
is occurring at a mass-transport-controlled rate.
View Article Online
3667
reflects the pH environment created by the electrode reac-
tions themselves as they occur.
The surface chemistry for unbuffered solutions is also very
sensitive to competing electron-transfer reactions. Fig. 7 illus-
trates the behaviour when the solution without added elec-
trolyte contains oxygen, so that oxygen reduction can take
place. First, it may be noted that oxygen reduction gives a
well formed wave16 at -330 mV us. SCE. At more negative
potentials in the plateau region for this wave, a hydrogen
adsorption peak can be clearly identified. Likewise, on the
reverse scan, see inset recorded on a more sensitive scale, the
H desorption peaks can be seen and the cathodic-anodic
peak separation is only ca. 150 mV. Both the adsorption and
desorption peaks occur in the potential region expected for
an alkaline medium. The mass-transport-controlledreduction
of 0, from air-equilibrated water would be expected to create
a pH of ca. 11 at the Pt surface. Indeed, it is clear that the
hydroxide ions produced by oxygen reduction are sufficient
to produce an alkaline environment close to the surface
which determines the potential for H adsorption (note that
oxygen reduction continues to occur on the back scan nega-
tive to its reduction wave). A more exact estimate of the pH is
not possible because of the slight IR distortion of the voltam-
mogram. It must also be emphasised that these experiments
do not give any indication of the nature of the cations in
solution leading to overall charge balance; this is a funda-
mental problem in electrochemical experiments involving
solutions of very low ionic strength17v1*but does not cause
practical difficulty provided that a microelectrode is used.
Conclusions
In unbuffered, neutral aqueous solutions, both hydrogen
adsorption-desorption and oxide formation-removal on a
platinum surface appear to be unusually irreversible pro-
ence from the rate of the electron-transfer reactions,
particularly at high potential scan rates. The major contribu-
tion to the peak separations in cyclic voltammetry at < 1 V
s-' is, however, the difference in the local pH at the electrode
surface (basic for reductions and acidic for oxidations) due to
the electrode reactions themselves. As a result, the form of the
response is very sensitive to the mass-transport regime.
Recording the response in conditions where the products of
the electrode reactions are rapidly lost from the surface (i.e.
using an RDE or especially a small microdisc) accentuates
the pH differences and hence the apparent irreversibility of
the reactions. Competing electrode reactions can also create
the pH environment controlling the surface reactions and the
example of H adsorption in the presence of oxygen reduction
has been presented. Finally, it has been shown that water
without added electrolyte behaves as a typical neutral,
unbuffered medium.
The authors would like to thank Solomat Ltd (a member of
the Neotronics Technology plc Group) for financial support
of this work.
References
1 S. Gilman, in Electroanalytical Chemistry, ed. A. J. Bard, Marcel
Dekker, New York, 1967, vol. 2.
2 R. Woods, in Electroanalytical Chemistry, ed. A. J. Bard, Marcel
Dekker, New York, 1976, vol. 9.
3 J. F. Lopis and F. Colom, in Encyclopedia of the Electrochem-
istry of the Elements, ed. A. J. Bard, Marcel Dekker, New York,
1976, vol. VI.
4 H. Angerstein-Kozlowska, in Comprehensive Treatise of Electro-
chemistry, ed. E. Yeager, J. O'M. Bockris, B. E. Conway and S.
Sarangapani, Plenum Press, New York, 1984, vol. VII, p. 26.

3668
5 B. E. Conway, H. Angerstein-Kozlowska and F. C. Ho, J. Vac.
Sci. Technol., 1977, 14, 351.
6 A. Bewick and J. W. Russell, J. Electroanal. Chem., 1982, 132,
329.
7 J. Clavilier, D. Armand and B. L. Wu, J . Electroanal. Chem.,
1982,135,159.
8 H. Angerstein-Kozlowska and B. E. Conway, J. Electroanal.
Chem., 1979,95, 1.
9 B. E. Conway, H. Angerstein-Kozlowska and W. B. A. Sharp, J.
Chem. SOC.,Faraday Trans. I , 1978,74,1373.
Published on 01 January 1994. Downloaded by The University of Auckland Library on 26/12/2017 10:22:42.
10 H. Angerstein-Kozlowska, J. Klinger and B. E. Conway, J. Elec-
troanal. Chem., 1977,75,45.
11 Ultramicroelectrodes, ed. M. Fleischmann, S. Pons, D. R.
Rolison and P. P. Schmidt, Datatech Systems, Morganton, NC,
1987.
View Article Online
J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90
12 Microelectrodes: Theory and Applications, ed. M. I. Montenegro,
M. A. Queiros and J. L. Daschbach, NATO AS1 Series, volume
197, Kluwer, Dordrecht, 1991.
13 M. I. Montenegro and D. Pletcher, J. Electroanal. Chem., 1986,
200,371.
14 W. J. Albery and E. J. Calvo, J. Chem. SOC., Faraday Trans. I ,
1983,79,2583.
15 W. B. A. Sharpe, Ph.D. Thesis, Ottawa, 1976.
16 D. Pletcher and S. Sotiropoulos, to be published.
17 K. B. Oldham, J. Electroanal. Chem., 1988,250, 1.
18 J. C. Myland and K. B. Oldham, J. Electroanal. Chem., 1993,
347,49.
Paper 4/04537H; Received 25th July, 1994