ElectrochimicaActo. Vol. 39, No. 1l/12, pp.

1857-1862, 1994
Copyright 0 1994 Ekvier Scieaa Ltd.
Printedin Great Britain.All I&MSreserved
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0013-4686(94)E0107-B

ELECTROCATALYSIS IN THE ELECTROCHEMICAL

CONVERSION/COMBUSTION
OF ORGANIC POLLUTANTS
FOR WASTE WATER TREATMENT
CHRISTOS

COMNINELLIS

Institute of Chemical Engineering, Swiss Federal Institute of Technology, CH-1015 Lausanne,

Switzerland
(Received

24 September

1993; accepted

28 October

1993)

Abstrsti-The electrochemical oxidation (or combustion) of organ& with simultaneous oxygen evolution has been investigated using different electrode material (Pt, Ti/lrO,, Ti/SnO,). A simplified mechanism for the electrochemical oxidation or combustion of organics is presented according to which
selective oxidation occurs with oxide anodes (MO,) forming the so-called higher oxide MO,,, and
combustion occurs with electrodes at the surface oflwhich dH radicals are accumulated. Detection of
OH radicals formed by water discharge at different anodes using N,Ndimethyl-p-nitrosoaniline (RNO)
as a spin trap and preparative electrolysis confirm the proposed mechanism.
Key

words:

electrocatalysis, hydroxyl radicals, spin trap, oxygen evolution, oxidation of organics.

1. INTRODUCTION

Besides inorganic pollutants, industrial waste water

also contains organic pollutants which have to be
treated before the water can be discharged. Biological treatment is the most economic process and
is usually used for treatment of readily degradable
(Biocompatible) organic pollutants present in the
waste water. The situation is completely different
when the waste water contains toxic or/and refractory (Non-Biocompatible) organic pollutants. In this
case, another type of treatment must be used. The
electrochemical method for the treatment of waste
water containing organic pollutants has attracted a
great deal of attention recently[ l-31.
There are two main applications for the electrochemical treatment.
(i) The electrochemical conversion method in
which the Non-Biocompatible (NON-BIO) organics are transformed to Biocompatible (BIO) organics
before the biological treatment:
Elcctrochcm.

[NON-BIO]

Ckmvcrsion

Biolop.

[BIO] -CO,
trc.tm.
+

biomass.

The ideal electrode material which can be used in the

electrochemical conversion method must have
high electrochemical activity for aromatic ring
opening
(aromatic
compounds
are
nonbiocompatible) and low electrochemical activity for
the further oxidation of the aliphatic carboxylic acids
which are in general biocompatible.
(ii) The electrochemical combustion method, in
which the organics are completely oxidized to C02.
In this case, the electrode material must have high

electrocatalytic activity towards the electrochemical

combustion of organics to CO2 and H,O.
The electrochemical oxidation (conversion or/and
combustion) of all organic compounds is theoretically possible before oxygen evolution (due to Hz0
discharge) but in practice, the oxidation reaction is
very slow as a consequence of kinetic rather than
thermodynamic limitations.
To increase the electrochemical rate of oxidation,
electrocatalytic anodes have been proposed (Pt, Pd,
. ..) but the main problem during oxidation of
organics at a fixed anodic potential before oxygen
evolution, is the decrease of the anode activity as the
consequence of poison formation at the anode
surface[4]. These poisoning species can be oxidized
only at high anode potentials in the region of water
discharge with simultaneous
oxygen evolution,
which allows regeneration of the anode surface
during oxidation.
In previous works[5-81, the electrochemical oxidation of organic pollutants (phenol has been taken
as a model pollutant) was carried out under conditions of simultaneous oxygen evolution using different electrode
material.
Analysis
of reaction
intermediates and measurements of current efficiency
have shown that traditional anode material (Pt,
Ti/IrO, , Ti/RuO,) favour electrochemical conversion (carboxylic acids are the final oxidation
products) but with low current efficiency, contrary to
the Ti/SnO, anode, which not only gives high
current efficiency but favours also electrochemical
combustion.
In the present investigation, the aim is to elucidate
the mechanism of the electrochemical conversion/
combustion of organics, with simultaneous oxygen
evolution, to select candidate oxide anodes which

1857

CH. COMNINELLIS

1858

favour electrochemical conversion or combustion

organics for waste water treatment.

of

2. MECHANISM OF THE
ELECTROCHEMICAL
CONVERSION/COMBUSTION
OF
ORGANICS WITH SIMULTANEOUS
OXYGEN EVOLUTION

work of Rosenthal[9] who used so as a tracer to

show that portion of the evolved gas comes from
oxygen already present in the oxide film. This view
was put forward several times with other electrodes
(RuO, , IrO, , NiCo,O,, NiOOH)[ lo].
Such a result may be explained in terms of the
equations (MO = oxide anode):
2MsO + 2H, I60 + 2M180(16OH) + 2H+ + 2e,
2M1*0(16OH) + 2M1s1602 + 2H+ + 2e,

In Fig. 1, a generalized scheme

chemical

conversion/combustion

of the electroof organics

on

oxide anode (MO,) is presented. In the first step

[equation (l)], Hz0 (or OH-) in acid (or alkali)
solution is discharged at the anode to produce
adsorbed hydroxyl radicals according to the equation :
kl
MO, + H,O -MO,(OH)

+ H+ + e. (1)

In a second step, equation (2), the adsorbed hydroxyl

radicals may interact with the oxygen already
present in the oxide anode with possible transition of
oxygen from the adsorbed hydroxyl radical to the
lattice of the oxide anode forming the so-called
higher oxide MO,, i, equation (2):
k2
+ H+ + e.
MO,(OH) -MO,+,
(2)
Thus, we can consider that at the anode surface two
states of active oxygen can be present :
(i) physisorbed
active
oxygen
(adsorbed
hydroxyl radicals, OH); and
(ii) chemisorbed active oxygen (oxygen in the
oxide lattice, MO,, i).
In the absence of any oxidizable organics, the physisorbed and chemisorbed active oxygen produce
dioxygen according to the equations (3) and (4):
Lo
MOJOH) 50, + H+ + e + MO,,
(3)
kd
302.
(4)
MO,+ t -MO,+
Direct evidence for the last route of oxygen evolution at platinum oxide (PtO,) is provided by the

H++c

MOx(OH)

MO,+,

H++c-

Fig. 1. Generalized

schema
of the electrochemical
conversion[6]/combustion[!j]
of organics with simultaneous oxygen evolution[3, 41: (1) H,O discharge; and (2)
transition of 0 from OH to the lattice of the oxide anode.

2M8/0,

+ Ms0 + Ml60 + 18i602.

In the presence of oxidizable organics we speculate

(by similarity with the heterogeneous catalytic oxidation with 0, on oxide catalyst[ll])
that the physisorbed active oxygen (OH) should cause
predominantly the complete combustion of organics,
equation (5), and chemisorbed active oxygen
(MO,+,) participate in the formation of selective
oxidation products, equation (6):
kc

MO,(OH), -

CO2 + ZH+ + Ze + MO,,

(3

R + MO,+,

k.
-RO+MO,.

(6)

2.1. Selective oxidation (conversion) of organics,

equation (6)
For the selective oxidation of organics, the concentration of adsorbed hydroxyl radical on the
anode surface must be almost zero. To satisfy this
condition, the rate of transition of oxygen into the
oxide lattice, equation (2), must be much more faster
than the rate of hydroxyl radicals formation, equation (1):
rate of hydroxyl radical formation = k,[MO,],
rate of transition of oxygen in the oxide lattice =
k2C 1,

k,C 1% k,CMO,l,

(7)

where :
= electrochemical rate constant for H,O discharge;
k2
= electrochemical rate constant for transition of oxygen into oxide lattice;
[MO,] = concentration of active sites on the oxide
anode; and
Cl
= concentration of oxygen vacancies in the
oxide lattice.
k,

Thus, efficient anodes for selective oxidation

(conversion) of organics must have low concentration of active sites on the anode surface and must
have a high concentration of oxygen vacancies in
the oxide lattice.
Oxides forming the so-called higher oxide
(MO,,,)
at potentials above the thermodynamic
potential for O2 evolution can be considered as
oxides having a high concentration
of oxygen
vacancies and can favour selective oxidation
(conversion) of organics.
The current efficiency depends on the relative rate
of the selective oxidation of organics, equation (6) to

1859

Electrochemical conversion/combustion of organic pollutants

rate of oxygen evolution (side reaction) by decomposition of the higher oxide, equation (4):
rate

of

selective

oxidation

rate of O2 evolution
MO,+ I = kAYI,

by

of

organics =

decomposition

of

where :
= stoichiometry factor for selective oxidation;
= rate constant for the selective oxidation of
organics, equation (6);
= rate constant for 0, evolution, equation (4);
k,
[0] = steady state concentration of active oxygen
in the oxide lattice; and
[R], = concentration of organics at a given time, t.

The Instantaneous Current

be given by the relation:
ICE =

Efficiency (ICE) can

k,CRI,
Z, k,CJU+ kc,
4

(8)

This relation shows that the ICE for the selective

oxidation is independent of the anode potential (k,
and kd are chemical rate constants) and depends on
the reactivity of organics (kJ, on its concentration
and on anode material (kd).
High ICE can be obtained with reactive organics
and with anodes having low rate for the decomposition of their higher oxide.
2.2. Combustion of organics, equation (5)
For the combustion of organics, high concentration of hydroxyl radicals on the anode surface must
be present. This is the case when the rate of hydroxyl
radicals formation, equation (l), is much faster than
the rate of oxygen transition into oxide lattice, equation (2).
The following relation must be satisfied:

k,CMO,I,> k2[ 1.
Thus efficient oxide anodes for combustion
of
organics must have a large number of active sites for
the adsorption of hydroxyl radicals and must have a
very low concentration of oxygen vacancies in the
oxide lattice.
Oxides in which the oxidation state of the cation
is the highest possible and/or which contains an
excess oxygen in the oxide lattice (this can be
achieved for example by doping the oxide with
another metal oxide in which the oxidation state is
higher than the base oxide) can be considered as
oxides (or mixture of oxides) at the surface of which
the hydroxyl radicals are accumulated and favour
the combustion of organics.
The current efficiency for the combustion of
organics depends on the relative rate of combustion
of organics, equation (5), to the rate of oxygen evolution (side reaction) by discharge of the adsorbed
hydroxyl radicals, equation (3):
rate of combustion of organics = Z, kJOH][R],
,
rate of 0, evolution by discharge of OH =

WOW,
where :

= stoichiometry factor for complete combustion of organics;

= electrochemical rate constant for the comk,
bustion of organ& equation (5);
= electrochemical rate constant for 0, evolko
ution, equation (3);
COH] = steady-state concentration
of adsorbed
hydroxyl radicals at the oxide anode; and
= concentration of organics at a given time,
PI,

ZC

The Instantaneous Current Efficiency (ICE) can be

given by the relation
ICE =

z, kCR1,
ZckCRl,
+ k,

(10)

This relation shows that the ICE for the combustion

of organics depends on the nature of organ&, on its
concentration, on the anode material and on the
anode potential. High ICE for the combustion of
organics can be obtained with anodes having low
electrochemical activity for 0, evolution by discharge of hydroxyl radicals, equation (3).
We have to note that it is very probable that
dioxygen participates also in the combustion of
organics according to the following reaction schema:
Formation of organic radicals by a hydrogen
abstraction mechanism :
RH + OH + R + H,O;
Reaction of the organic radical with dioxygen
formed at the anode:
R+O,+ROO;

Further abstraction of a hydrogen atom with

the formation of an organic hydroperoxide
(ROOH) and another organic radical.
ROO + RH + ROOH + R.

Since the organic hydroperoxides formed are relatively unstable, decomposition of such intermediates
often leads to molecular breakdown and formation
of subsequent intermediates
with lower carbon
numbers. These scission reactions continue rapidly
until the formation of carbon dioxide and water.

3. EXPERIMENTAL

DETAILS

3.1. Detection of hydroxyl radicals during electrolysis

The direct detection of hydroxyl radicals formed
by water discharge at the oxide anode, equation (l),
by electron spin resonance (esr) is possible only if the
OH radicals are produced in relatively high concentration in the esr cavity by in situ electrolysis.
The indirect technique for the detection and identification of low concentration
of OH radicals
involves trapping of the OH radical by an addition
reaction (spin trap) to produce a more stable radical
(spin adduct):
OH + spin trap -+ spin adduct.

1860

CH. COMNINELLIS

A number of OH radical spin traps are available

the literature[12]
but N,N-dimethyl-p-nitrosoaniline
(RNO) has the following advantages[ 131:

in

(i) The reaction of RN0 with OH radicals has

been reported to be very selective as neither singlet
oxygen (0,)
nor various Peroxo
compounds
destroyed the chromophoric
group of RNO[ 131.
(ii) The high rate of the reaction with OH radicals
(k = 1.2 x 101oM-ls-l).
(iii) The ease of application as one merely observes
the bleaching of the sensitive adsorption
band at
440nm(& = 3.44 x 10-4M-1cm-i).
Another advantage of RN0 for the detection of
OH radicals formed by water electrolysis is that
RN0 is electrochemically
inactive at Pt, IrO, and
SnO, anodes as has been shown by cyclic voltamsimilar results have been
metry measurements;
reported
in the literature
at Pt and
PbOz
anodes[14]. In our experiment, RN0 has been used
as spin trap and the bleaching of the yellow colour
was measured during electrolysis:
RN0

+ OH + R-NO

OH
3.1.1. Electrolytic cell and measuring method. A
two-compartment
cell of 50ml capacity was used,
the anode was in the form of plate (4cm*) and the
cathode was a platinum spiral enclosed in a lOm1
porous porcelain pot; stirring was provided by a
magnetic bar. The anodic compartment
contains
also a Fiber-optic
spectrophotometer
(Guide wave,
Inc. Model 260) for the measure of the bleaching of
RN0 at 440nm during constant current electrolysis
with different electrodes. Owing to the large extinction coefficient of RN0 (in neutral and alkaline
solution) it was possible to measure accurately very
small changes in concentration.
The screening test of
anodes has been carried out in phosphate
buffer
(pH = 7.1) containing 2 x 10m5 moldme
RNO. All
experiments were done at room temperature (25C).
In order to study the OH radical reaction with
phenol (PhOH), studies were carried out at pH9
(Na,B,O,
solution) in the presence of both, RN0
and PhOH in the electrolyte.
Under these conditions,
RN0 and PhOH are
simple competition reactions for OH radicals:
koH
RN0
PhOH
For competitive

+ OH -

kom
+ OH -product.
reactions

product,

it is easily shown that:

Go
(PhOH)
(RNO)

3.2. Electrochemical oxidation of organics

3.2.1. Determination of the current efficiency. The
Instantaneous
Current Efficiency (ICE) for the electrochemical oxidation of organics with simultaneous
oxygen evolution is given by the relation:
ICE

= bleaching rate of RN0 in the presence

of phenol ;
= bleaching rate of RN0 in the absence of
phenol;
= phenol concentration
in the electrolyte;
and
= RN0 concentraton
in the electrolyte.

10- Uo,),
IO

where:
= electrolysis current; and
Ir,,), = partial current for 0, evolution
time, t.

at a given

Two methods have been used for the determination of the partial current for 0, evolution; the
Oxygen Flow Rate (OFR) method (in which the
oxygen flow rate was measured during electrolysis)
and the Chemical Oxygen Demand (COD) method
(in which the Chemical Oxygen Demand was measured during electrolysis). From the ICE-t curve, the
average current efficiency (defined as the Electrochemical Oxidation
Index, EOI) and the Electrochemical Oxygen Demand (EOD) can be calculated.
Details concerning these methods are given in a previous paperf61.
3.2.2. kectiode material, electrochemical cell and
analvsis. The Ti/IrO, electrode was oreoared bv the
thermal decomposition
technique which consists of
the following steps: dissolution in isopropanol of the
coating components;
varnish application
on the
pretreated titanium base by brush; drying at 80C;
thermal decomposition;
cooling and repeating the
above operations
until the desired amount of the
coating is reached, finally post-heat
treatment
for
1 h. Many more details concerning
electrode preparation and characterization
are given elsewhere[l&
163.
The SnO, film electrodes doped with Sb were prepared on titanium base metal by Stucki by the standard spray hydrolysis method; the best composition
of the spray solution found by Stucki was log SnCI,
x SH,O, 0.1 g SbCl, in lOOm1 of ethanol; details of
the preparation are given elsewhere[ 171.
A two compartment
cell of 150ml capacity was
used; the anode was made of Pt, Ti/IrO,
or
Ti/SnO, , and the cathode was a platinum spiral
enclosed in a 10 ml porous porcelain pot; stirring
was provided by a magnetic bar.
The disappearance
of phenol and the appearance
of its oxidation products were monitored by HPLC
(Shimazu 8A). The progress of the electrochemical
oxidation
was monitored
by measuring
the Total
Oxygen Carbon (TOC, XERTEX, Dohrman)
and
the Chemical
Oxygen Demand
(COD, Hach Dr
2000).
The oxygen formed in the anolyte during electrolysis was measured by a gas burette and analysed by
gas chromatography.

1 (11)

where :
G(-RNO)

Thus a plot of l/(G(-RNO)

vs. (PhOH)/(RNO)
should
yield
a
straight
line
with
slope
(l/G,) .(ko,/k,,),
from which the relative rate constant for the reaction of OH radicals with phenol
(/con) can be calculated.

Electrochemical conversion/cc rmbustion of organic pollutants

4. RESULTS

AND DISCUSSION

4.1. Anode screening for the selective

oxidation/combustion of organics
According to the proposed model (Fig. 1) high
concentration of OH radicals on the anode surface
favours complete combustion of organics.
For screening tests of anodes we have used RN0
as spin trap of OH radicals (see experimental part).
Figure 2 shows the adsorption spectrum of aqueous
RN0 solution (2 x 10-5moldm-3)
at pH = 7.1
during galvanostatic electrolysis (20 mA cm - ?) with
different anodes.
With Pt and Ti/IrO, anodes, there is only a slight
decrease in optical density at 440nm during electrolysis contrary to the Ti/SnO, anode, for which there
is a rapid decrease in the optical density.
The rate constant ken between phenol and OH
radicals has been calculated from Fig. 3 using equation (11). The calculated value (3 x 10s M - s- ) is
in good agreement with those reported in literature
from y-radiolysis studies[18].
These results show that there is accumulation of
OH radicals at the SnO, anode surface contrary to
IrO, and Pt anodes for whichthe surface OH
radical concentration is almost zero. Thus, according
to the proposed model (Fig. l), the SnO, anode
favours complete combustion contrary to the IrO,
and Pt anodes which favour selective oxidation.
4.2. Electrochemical oxidation of organics
To confirm the proposed mechanism for the electrochemical conversion/combustion
of organics with
simultaneous oxygen evolution (Fig. 1) and the
screening test using RN0 (see Section 4.1) the oxidation of organ& has been investigated at platinum
(selective oxidation) and SnO, (combustion) anodes.
4.2.1. Selective oxidation (conversion) of organics.
In a previous paper[6], the electrochemical oxida-

I
372

30

[PhOH)/[RNO]
Fig 3. Determination of the rate constant between phenol
and OH radicals at pH 9 using equation (11). NB : The rate
constant between RN0 + OH has been taken as
1.2 x lOM-s-t.

tion of phenol was studied at platinum anode (at the

surface of which an oxide PtO, is formed during
oxidation); the obtained results[6] have shown that
the current elkiency for phenol oxidation is independent of current density (and anode potential) but
increases with phenol concentration
and with
increasing pH. It has also been found[5] that at Pt
anode benzene derivatives which contain electron
withdrawing groups (-COOH, -NO,, -SO,H) are
oxidized with low current efficiency, contrary to
benzene derivatives of which the substituents are

436

A,
Fig. 2. Adsorption spectra of aqueous RN0 solution (2 x 10-smoldm-3)
during 2 h galavanostatic electrolysis with different anode material:
T = 25C.

nm
obtained at 5min intervals
i = 20rnAcn1-~; pH = 7.1;

1862

CH.

COMNINELLIS

Figure 5 shows the evolution of phenol, aromatic

intermediates and aliphatic acids during the electrochemical oxidation of phenol at the SnO, anode; the
amount of CO, also formed is given.
5. CONCLUSION

20

40

60

80

100

Ah dm-
Fig. 4. Evolution of: (1) phenol; (2) aromatic intermediates;
(3) aliphatic acids; and (4) CO, during the electrochemical
oxidation
of phenol
at Pt anode:
i = 50mAcm-*,
T = 70C. pH = 2 (const). NB: The progress of electrolysis
is expressed in specific electrical charge (Ahdm-s)
and all
concentrations are expressed in mg Cl-.

donating
(-NH,, -OH) which increase the
reactivity of the benzene derivates and are oxidized
with high current effkiency[5]. These results are in
concordance with those expected using relation 8
(the influence of pH can be explained by the fact that
the phenate ion is much more reactive than phenol).
Analysis of the oxidation products during electrolysis of phenol at platinum anode[6] shows that oxidation occurs in two steps: in the first step aromatic
intermediates
(hydroquinone,
catechol,
benzoquinone) are formed and in the second step
aromatic ring opening occurs with the formation of
muconic acid which is further oxidized to C4 and C,
aliphatic acids (maleic, fumaric and oxalic acid) these
acids are stable toward further oxidation. Figure 4
shows the evolution of phenol, aromatic intermediates and aliphatic acids (expressed in mgC l- )
during the electrochemial oxidation of phenol at Pt
anode; the amount of CO* (mg C l- ) also formed is
given in the same figure.
4.2.2. Combustion of organics. The electrochemical
oxidation of phenol has been studied using SnO,
anodes[8]. Analysis of the oxidation products during
electrolysis has shown that aliphatic acids (fumaric,
maleic, oxalic) are the main intermediate products
which are further oxidized to CO? (combustion).
electron

20

40

60

80

100

Ah dmm3
Fig. 5. Evolution of: (1) phenol; (2) aromatic intermediates;
(3)
. , alinhatic acids; and (4) CO, during the electrochemical
oxidaiion of phenol at thk Sn6* anode: for conditions see.
Fig. 4.

A simplified mechanism for the electrochemical

selective oxidation or combustion of organics with
simultaneous oxygen evolution is presented. According to this mechanism, selective oxidation of organics occurs with electrodes forming the so-called
higher oxide MO,, 1 (chemisorbed active oxygen)
and combustion occurs with electrodes at the surface
of which OH radicals are accumulated (physisorbed
active oxygen).
The detection of OH radicals formed by water
discharge at different anodes using N,N-dimethyl-pnitrosoaniline (RNO) as a spin trap has shown that
at Pt and IrO, anodes the surface OH radical concentration is almost zero, contrary to the SnO,
anode for which there is accumulation of OH radicals at its surface. Thus, according to the proposed
mechanism, the SnO, anode favours complete combustion contrary to the IrO, and Pt anodes which
favour selective oxidation. The model has also been
confirmed by preparative electrolysis.
Acknowledgement-The
author acknowledges
ance of M. Vincent Schaller for the hydroxyl
trap measurements.

the assistradical spin

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