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Electrolytic processes and lead-dioxide anode

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 ELECTROLYTIC PROCESSES AND LEAD DIOXIDE ANODE (REVIEW)
INAM-UL-HAQUE*, ASIM KHAN AND SHERAZ ANWAR
Department of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan
*E-mail: inamul.haque@gmail.com Cell: 03014322989
ABSTRACT- Lead dioxide electrodes have low price compared to noble metals, possess stability against
chemical attack, exhibit high oxygen evolution overpotential, and are frequently employed as
electrocatalysts for such anodic processes as production of perchlorate, regeneration of chromium(VI),
oxidation of manganese(II), and incineration of organic pollutants . This article reviews the preparation
and use of lead dioxide electrodes.
Electrolytic production of perchlorate The mechanism of the anodic processes of aqueous mixtures
The anodic oxidation of chlorate to form perchlorate at a of acetate and acetic acid at platinum and lead dioxide
lead dioxide electrode was studied at the applied potentials anodes was investigated in the presence of styrene in the
more positive than 1.8 V vs. saturated calomel electrode, electrolyte. The shift in the current vs. potential curve due to
the current increased exponentially, and the currentemf addition of styrene in the solution was positive at the
curve showed no plateau or inflection. Perchlorate was platinum and negative at lead dioxide anode. The products
formed by the electrolysis at controlled potential even at the of controlled potential electrolyte at platinum were mainly
potential as negative as 1.8 V, and the maximum current 3,4-diphenylhexane (I), -hydroxy--acetoxyethylbenzene
efficiency (~80%) was at 2.0 V. These characteristics in the (II), and --diacetoxyethylbenzene (III). At lead dioxide, II,
case of lead dioxide electrode suggest a different mechanism III, and 1,4-diacetoxy-2,3-diphenylbutane were obtained, but
for the Kolbe reaction than that with a platinum or titanium no I. These results confirmed the formation of methyl radical
electrode [1]. at platinum as the intermediate of the process, but it was
In electrolytic process for the production of sodium impossible to prove the formation of methyl radical at lead
perchlorate by using a pure lead dioxide anode is described. dioxide. In the latter case, there may be a simultaneous
In this process, a saturated solution of sodium chlorate is discharge of acetate and hydroxyl ions [5].
electrolyzed batch wise at an anodic current density of 25 The electrolysis of aqueous solutions of acetic acid and
amp/dm2 at 50C to perchlorate; cell voltage was 4.5-5.0 V. potassium acetate containing pinacol was studied with
The process has been operated successfully for >2 years electrode of platinum and lead dioxide. The main products
without renewal of the anodes. The results of basic research of electrolysis with the platinum electrode are the Kolbe
on anode potential and current efficiency for perchlorate products, ethane and carbon dioxide, with a small amount of
formation from chlorate are also given [2]. acetone formed by the dehydrogenation of hydroxyl of
A reliable explanation of the practical electrolytic process pinacol. The product with lead dioxide electrode was only
and the establishment of reasonable operating conditions for acetone. The electrolysis of glacial acetic acid with lead
the production of sodium perchlorate from chlorate were dioxide electrode also gave a large amount of acetone. The
made by using a lead dioxide anode. The electrolyses were difference in the behavior of these two electrodes was
made to obtain current density vs. anode potential curves. ascribed to the difference in the apparent concentration of
Higher current densities induced lower current efficiency in free radicals present in the electrode-electrolyte interface.
the region of high conversion of chlorate. The effect of The adsorption of the radicals on the platinum electrode was
current concentration on current efficiency was almost larger than that on the lead dioxide electrode [6].
negligible. At higher temperatures the current efficiency The behavior of the methyl radical formed in the electrolysis
increased, especially at high conversion. Thus, the current of acetate solution was examined in the presence of CHCl 3,
efficiency rose ~10% when the 1st half of electrolysis was Cl3CMe and Cl3CCCl3 were formed together with ordinary
carried out at lower temperature and the latter half at higher Kolbe products (C2H6, CH4, AcOMe, etc.) by controlled
temperature. This behavior is the reverse of that reported for potential electrolysis. The formation of benzene was
the platinum anode process. Contamination of the electrolyte inhibited by adding chloroform while that of methane
by chromate showed a relatively negative effect on the increased. When lead dioxide was used, the above-
current efficiency. Addition of sodium fluoride contributes mentioned chlorides were also formed in glacial acetic acid
to maintain a high current efficiency [3]. but not in aqueous acetic acid solutions. The behavior of
The graphite substrate lead dioxide anodes have been AcO and Me on platinum anode is different from that on
developed for obtaining suitable size anodes for use in high the lead dioxide anode. AcO can be adsorbed on the
amperage cells in the production of chlorates and platinum anode surface, but not methyl radical. On the lead
perchlorates. The performance characteristics of the anodes dioxide anode, neither of the radicals is adsorbed [7].
in the preparation of chlorates and perchlorates are Regeneration of spent chromium(VI)
described. The use of graphite substrate lead dioxide anode The electrolytic oxidation of chromium(IIII) proceeds
in other inorganic preparations like bromates, iodates, and favorably, when the electrolysis is carried out with low and
periodates is also included [4]. Table 1 summarizes the high current density at the anode and cathode, respectively,
anodic processes carried out using lead dioxide electrodes. in the lower acidic bath of high temperature. The optimum
Oxidation of acetates conditions are as follows: bath composition 0.1 M chromic
sulfate, 0.5 M sodium sulfate, pH 2-4, temperature 60C,

1
current density 1A/dm2 at the anode, 100 A/dm2 at the
cathode. The conversion rate of chromium(III) to
chromium(VI) and the current efficiency were ~100 and 70-
80% respectively [8].
Regeneration of spent chromium(VI) solutions using lead
dioxide anodes has been discussed. Pure and copper(II)-
doped lead dioxide electrodes were prepared by
electrodeposition of lead dioxide on carbon-based substrates
using lead(II) nitrate bath at 1.5-1.75 V, pH 4-4.5,
temperature 60-70 C, and current density 0.0125-0.0175
A/cm2. Electrolyses of synthetic chromium(III) solutions
both in divided and undivided cells were used to investigate
the electrocatalytic activity, adhesion and stability of lead
dioxide electrodes, which can serve as industrial electrodes.
UV-visible spectrophotometry was used for estimating
conversion of chromium(III) to chromium(VI). The
electrocatalytic activity of lead dioxide was increased by the
doping of copper(II) ions [9].
Dense and uniform films of -lead dioxide were
electrodeposited on the surface of various types of stainless
steel. In strongly alkaline media, these films were found to
be very stable and exhibited significant electrocatalytic
activity for oxidation of chromium(III) and cyanide (CN).
In acidic media, -lead dioxide films deposited on type-416
stainless steel, which had been passivated by anodization in
a phosphate solution, were relatively stable and exhibited
catalytic activity for oxidation of manganese(II). Rate
constants for the anodic oxygen-transfer reactions of
chromium(III), cyanide and manganese(II) were estimated
from data obtained at rotated disk electrodes [10].
Voltammetric and coulometric results are described for
electrocatalytic oxidation of chromium(III) to chromium(VI)
at the mixed bismuth(V)-lead(IV) dioxide film electrodes
(designated Bi-PbO2) that are electrodeposited from acidic
solutions of lead(II) containing bismuth(III). A current
efficiency of 99.2% ( = 1.1%, N=12) was obtained for
galvanostatic generation of chromium(VI) at a pre-
conditioned bismuth-lead dioxide film electrode.
Preconditioning of the bismuth-doped lead dioxide film
merely involves the generation of chromium(VI) which,
based on scanning electron micrographs, is concluded
tentatively to achieve chemical stripping of non-catalytic
portions of the bismuth-doped lead dioxide films to produce
films having greater electrocatalytic activity for the desired
reaction. Electrochemical stripping of the bismuth-doped
lead dioxide electrode had a similar preconditioning effect.
Based on wavelength dispersive spectroscopy,
electrochemical stripping resulted in an increase in surface
bismuth concentration of 33% relative to lead [11].
Electrooxidation of manganese(II)
The heterogeneous rate constant for the anodic oxidation of
manganese(II) at lead dioxide-based mixed oxide electrodes
in 1.0 M perchloric acid was determined as a function of
high doping levels by the oxides of groups IIIA and VA
metals. Electrodes were prepared by electrodeposition from
solution containing lead(II) and the doping metal ions in 1.0
M perchloric acid. Doping with the group IIIA metal oxides
results in a slight decrease in the rate constant for
manganese(II) oxidation; however, doping with the group
VA metal oxides results in significant electrocatalysis of the
anodic oxygen transfer reactions as compared to a pure -
lead dioxide electrode. The rate constant at the mixed oxide
deposited from a solution of 1.0 mM Bi3+/1.0 mM lead(II)
was at least twenty five fold greater than that for pure -lead
dioxide, becoming virtually mass-transfer limited at the
mixed oxide electrode to rotation rates of 3600 rpm [12].
X-ray structural data, oxygen evolution overpotential (O2),
and constants (k) are compared for anodic oxidation of
manganese(II) (n=5 equiv/mol) and 2- thiophenecarboxylic
acid (2-TCA) at bismuth-doped lead dioxide in 1.0 M
perchloric acid. The rutile structure of pure -lead dioxide,
deposited anodically from 1.0 M perchloric acid containing
lead(II), is retained even as the bismuth(III) content is
increased to bismuth/lead 0.7, i.e., mole fraction of bismuth
= 0.4. There is no evidence of a new oxide phase being
forred. Crystallites of the bismuth-lead dioxide are deposited
with an increasing preferential orientation of the 020-plane
parallel to the gold substrate surface as the ratio
bismuth/lead is increased. Increasing values of k and
decreasing values of O2 are correlated with the increased
preferential orientation. However, the change in preferential
orientation is not the primary determining factor in the
electrocatalytic phenomena. The kinetic results are discussed
also on the basis of the so-called volcano plot of O2 as a
function of the heat of transition (H t) between the two
highest oxide phases for metal oxide electrodes [13].
Ratios of the change in surface mass corresponding to a
change in charge (m/q) were determined for
electrodeposition of thin films of pure lead dioxide and
bismuth-doped lead dioxide at gold-film electrodes in 0.1 M
perchloric acid, using an electrochemical quartz
microbalance. The value m/q = 1.26 0.04 mg/C
obtained for pure lead dioxide films is in good agreement
with the theoretical value of 1.24 mg/C. A large value,
m/q = 1.32 0.03 mg/C, obtained for the bismuth-doped
lead dioxide films, is concluded to result from the
codeposition of some perchlorate with bismuth(V) in the
mixed-oxide film. Bismuth(III) was determined to be
anodically absorbed as bismuth(V) at pure lead dioxide
surfaces for E > 1.45V vs. silver/silver chloride with m/q
= 1.72 0.02 mg/C in 0.1 M perchloric acid and 1.30 0.03
mg/C in 1 M nitric acid. The lead dioxide-film electrodes
with adsorbed bismuth(V) are active for various anodic
oxygen-transfer reactions, including the oxidations of
manganese(II) to permanganate and dimethyl sulfoxide to
dimethyl sulfone. Experimental results are interpreted to be
consistent with mechanism proposed previously, in which
the bismuth(V) sites have a lower overpotential for anodic
discharge of water to produce oxygen. It has been proposed
that adsorbed hydroxyl radicals generated in the oxygen
evolution mechanism are consumed by oxygen-transfer
steps, required in many oxidation processes [14].
Details are reported for the synthesis and characterization of
composite materials prepared from powdered Bi3Ru3O11 and
polymeric adhesive fashioned into disk electrodes. The
structure of the synthesized material is that of the cubic
KSbO3 type from single-crystal and powder x-ray
diffractometry. The surface morphology of a composite
2
electrode is quite porous from micrographs obtained using
SEM. Voltammetric data obtained for various anodic
reactions at these electrodes were examined for evidence
that oxidation can occur with transfer of oxygen to oxidation
products in the potential region corresponding to onset of
anodic discharge of water. Model reactants include dimethyl
sulfoxide, tetramethylene sulfoxide, and manganese(II). The
electronic band structure of Bi3Ru3O11 was calculated;
mixing of Ru 4d and O 2p orbitals in an antibonding band at
the Fermi level facilitates oxygen transfer [15].
Anodic oxidation of cyanide
Films of copper oxide were readily deposited
electrochemically on conductive surfaces from alkaline
solutions containing copper(I,II) cyanide. The resulting
copper oxide-film electrodes showed catalytic activity for
the anodic oxidation of cyanide to cyanate in alkaline media.
The half wave potential was pH-dependent, indicating the
involvement of hydroxyl ions in the reaction mechanism.
Electrocatalysis was concluded to occur by oxygen transfer
mediation facilitated by formation of copper(III) sites in the
copper oxide surface. The deposited films were only loosely
adherent to the substrates and were susceptible to chemical
dissolution in the presence of excessively high cyanite
concentrations (ca.>>1 mM) over a long time period (ca.30
min.) [16].
Electrooxidation of dimethyl sulfoxide
The electrolytic activities were compared for pure and
chloride-doped -lead dioxide film on gold and platinum
substrates. Rate constants were increased significantly for
oxidations of manganese(II), toluene, benzyl alcohol,
dimethyl sulfoxide, and benzaldehyde in acidic media by the
incorporation of chloride (Cl) into the oxide films. These
reactions occur by the electrocatalytic transfer of oxygen
from water to the reaction products. Result of x-ray
diffraction studies indicates that the chloride-doped -lead
dioxide continues to have the slightly distorted rutile
structure of pure -lead dioxide. The observed
electrocatalytic phenomenon is a beneficial consequence of
the surface defects generated when chloride aids in charge
compensation within the surface matrix and, thereby,
increases surface sites capable of adsorbing hydroxyl
radicals which are transferred in the electrocatalytic oxygen
transfer reactions [17].
The electrocatalytic effect of added bismuth(III) was studied
for the anodic response of dimethyl sulfoxide (DMSO) at
lead dioxide- film electrodes in 1.0 M perchloric acid.
Dimethyl sulfoxide was virtually unreactive at pure lead
dioxide-film electrodes electrodeposited from acidic media.
However, well-defined anodic waves with transport-limited
current plateaus were obtained for up to 100 mM dimethyl
sulfoxide by addition of as little as 10 M bismuth(III). The
product of dimethyl sulfoxide oxidation was determined to
be dimethyl sulfone (DMSO2). The electrode activity is
concluded to be the result of absorbed bismuth(III) and/or
bismuth(V) which function to mediate the oxygen-transfer
step in the anodic reaction mechanism. The E1/2 values for
dimethyl sulfoxide and several additional compounds were
determined to be virtually equivalent (1.65-1.71 V vs.
saturated calomel electrode) in spite of large differences in
the E0 values for respective half reactions. This is explained
as the consequences of a common rate-controlling step
which is discharge of water at the bismuth sites to produce
adsorbed hydroxyl radicals which are subsequently
consumed in the oxidation process. Large concentrations of
bismuth(III) (>>10 M) severely inhibited the
electrocatalytic oxidation of dimethyl sulfoxide; however,
the concentrations required to produce transport-limited
signals were much larger than needed for bismuth(III) [18].
Ultrathin films (0.5 m) of lead monoxide were generated
on the surfaces of gold, platinum, titanium, and glassy
carbon electrodes during rapid voltammetric dissolution of
thick films (>10-100 m) of -lead dioxide deposited from
acidic solutions containing lead(II). These lead monoxide
films were stable at potential values >0.5 V negative of the
peak of potential for cathodic stripping of bulk lead dioxide.
Ultrathin films of lead dioxide were produced, in turn, by
anodization of the lead monoxide films in lead(II)-free
solutions. Results are emphasized here for the voltammetric
and microscopic characterization of these thin films at gold
electrodes. The formation of stable lead monoxide film
during cathodic dissolution of thick lead dioxide films is the
result of a deficiency of H+ in the interfacial region between
the substrates and the porous thick oxide films. Ultrathin
lead monoxide films were oxidized to ultrathin lead dioxide
films during a positive potential scan and were
electrocatalyticlly active for oxidation of dimethyl sulfoxide
at E >1.5V vs. saturated calomel electrode when
bismuth(III) was present in the test solutions [19].
Voltammetric and kinetic results are described for
electrocatalytic oxidations of various compounds at doped
lead dioxide-film electrodes on titanium substrates.
Compounds tested include dimethyl sulfoxide and several
thiophene derivatives. Results are emphasized for lead
dioxide films doped with iron(III) (Fe-PbO2), and with
silver(I) and bismuth(V) (Ag-Bi-PbO2), that were
electrolytically deposited on titanium substrates with the
presence of an interlayer of lead dioxide deposited from
acidic solutions of lead(II) and sodium fluoride. These
laminar film electrodes are quite stable and offer
significantly improved catalytic activity for various anodic
oxygen-transfer reactions in comparison to pure lead
dioxide-film electrodes [20].
Oxidations of dimethyl sulfoxide, toluene, and p-xylene at
pure lead dioxide-film electrodes were determined to be
under extreme kinetic control with values of the apparent
heterogeneous rate constant (kapp<<1103 cm/s). However a
significant increase in kapp was observed at acetate-doped
lead dioxide-film electrodes in 1 M sulfuric acid. X-ray
diffraction data indicated the acetate-doped lead dioxide
films retained the slightly distorted rutile structure of the -
form of pure lead dioxide. Catalysis of the anodic discharge
of water to produce adsorbed hydroxyl radicals is concluded
to account for the enhanced catalytic activity of the acetate-
doped lead dioxide films for the anodic oxygen-transfer
reactions in sulfuric acid [21].
3
 Table 1: Oxidations at lead dioxide anodes

Sr No. Electrodes Conditions Processes Properties References

1 Lead dioxide Applied potential more Chlorate to Perchlorate was formed by the electrolysis [1]
electrode positive than -1.8 V vs. perchlorate at controlled potential even at the potential
saturated calomel as negative as 1.8 V, and the maximum
electrode current efficiency (~80%) was at 2.0 V.
2 Pure Lead A saturated solution of Electrolytic The process has been operated successfully [2]
dioxide sodium chlorate is production of for >2 years without renewal of the anodes
electrode electrolyzed batch wise sodium
at an anodic current perchlorate
density of 25 amp/dm2 at
50C to perchlorate; cell
voltage was 4.5-5.0 V
3 Lead dioxide ---- Production of The current efficiency rose ~10% when the [3]
anode sodium 1st half of electrolysis was carried out at
perchlorate lower temperature and the latter half at
from chlorate higher temperature
4 Graphite ---- Production of ---- [4]
substrate lead chlorate and
dioxide anodes perchlorate
5 Platinum and Anodic oxidation of Oxidation of The products of controlled potential [5]
lead dioxide aqueous mixtures of aqueous electrolyte at platinum were mainly 3,4-
anodes acetate and acetic acid in mixtures of diphenylhexane (I), -hydroxy--
the presence of styrene in acetate and acetoxyethylbenzene (II), and --
the electrolyte acetic acid diacetoxyethylbenzene (III). At lead
dioxide, II, III, and 1,4-diacetoxy-2,3-
diphenylbutane were obtained, but no I
6 Platinum and ---- The The adsorption of the radicals on the [6]
lead dioxide electrolysis of platinum electrode was larger than that on
electrodes aqueous the lead dioxide electrode
solutions of
acetic acid and
potassium
acetate
containing
pinacol
7 Lead dioxide ---- The ---- [7]
electrolysis of
acetate solution
8 Lead dioxide The optimum conditions The The conversion rate of chromium(III) to [8]
are as follows: bath electrolytic chromium(VI) and the current efficiency
composition 0.1 M oxidation of were ~100 and 70-80% respectively
chromic sulfate, 0.5 M chromium(III)
sodium sulfate, pH 2-4,
temperature 60C,
current density 1A/dm2
at the anode, 100 A/dm2
at the cathode
9 Pure and Electrolyses of synthetic Regeneration The electrocatalytic activity of lead dioxide [9]
copper doped- chromium(III) solutions of spent was increased by the doping of copper(II)
lead dioxide both in divided and chromium(VI) ions
undivided cells solutions
10 Lead dioxide ---- Oxidation of ---- [10]
chromium(III)
and cyanide
(CN).
11 Mixed ---- Electrocatalytic A current efficiency of 99.2% ( = 1.1%, [11]
bismuth(V)- oxidation of N=12) was obtained for galvanostatic
lead(IV) chromium(III) generation of chromium(VI) at a pre-
dioxide film to conditioned bismuth-lead dioxide film
electrodes chromium(VI) electrode

4
 Table 1: coninued

Sr No. Electrodes Conditions Processes Properties References

12 Lead dioxide-based Anodic oxidation of Anodic oxidation of ---- [12]
mixed oxide manganese(II) manganese(II)
electrodes solutionin 1.0 M
perchloric acid
13 Bismuth-doped Oxidation of Anodic oxidation of ---- [13]
lead dioxide manganese(II) (n=5 manganese(II) (n=5
equiv/mol) and 2- equiv/mol) and 2-
thiophenecarboxylic thiophenecarboxylic acid
acid (2-TCA) solution (2-TCA)
in 1.0 M perchloric acid
14 Bismuth-doped ---- Oxidations of ---- [14]
lead dioxide manganese(II) to
electrode permanganate and
dimethyl sulfoxide to
dimethyl sulfone
15 Lead dioxide film ---- Oxidation of dimethyl ---- [18]
electrodes sulfoxide
16 Iron(III) (Fe-PbO2), ---- Oxidation of dimethyl ---- [20]
and with silver(I) sulfoxide and several
and bismuth(V) thiophene derivatives
(Ag-Bi-PbO2)
doped lead dioxide
electrode
17 Pure lead dioxide- ---- Oxidations of dimethyl ---- [21]
film electrodes sulfoxide, toluene, and p-
xylene
18 -lead dioxide In acidic media oxidation of dimethyl ---- [22]
electrodes and sulfoxide, phenol, and
bismuth-doped lead benzene in acidic media
dioxide electrodes
19 Iron(III)-doped lead In acetate buffer media Electrochemical Carbon dioxide is a product of [23]
dioxide films on (pH 5) incineration of p- electrochemical process
titanium substrates benzoquinone
20 Copper doped-lead ---- Electrochemical About less than 100-ppm of [24]
dioxide electrode incineration of p-aniline aqueous aniline solution upon
constant current electrolysis,
using a lead dioxide anode and
steel cathode, leads to complete
electrochemical incineration of
aniline
21 Mixed silver-lead In carbonate buffer (pH Electrochemical ---- [25]
oxide films 10) incineration of selected
organic amines
(ethylamine, N-
ethylmethylamine,
trimethylamine,
ethanolamine, and L-
alanine)
22 Lead dioxide ---- Electrolysis of an aqueous ---- [29]
electrode mixture of 1 mol/dm3
propionate and 0.5 or 5
mol/dm3 nitrate solution

The electrocatalytic activities are compared for pure -lead
dioxide electrodes and bismuth-doped lead dioxide
electrodes for oxidation of dimethyl sulfoxide, phenol, and
benzene in acidic media. A correlation is observed for
conversion of dimethyl sulfoxide to dimethyl sulfone. The
oxidation of phenol occurs at a transport-limited rate for
both the lead dioxide and bismuth-doped lead dioxide film
electrodes; however, the bismuth-doped lead dioxide
electrodes exhibit significantly greater stability against
surface fouling by polymeric films. This is a direct benefit of

5
the greater electrocatalytic activity for oxidation of phenol
beyond the phenolic radical. A ring-disk experiment for
benzene oxidation at a bismuth-doped lead dioxide disk
demonstrates that o-benzoquinone and p-benzoquinone (neff
= 6 equiv/mol) are produced at he disk in the ratio ~0.25.
However, the total ring current for reduction of these
products from the disk reaction is significantly below that
predicted from the disk current, and it must be concluded
that a significant amount of electroinactive species is
produced at the disk. This production is speculated to occur
with neff > 6 equiv/mol and probably corresponds to a ring-
opening reaction with production of one or more organic
acids. The product solution from exhaustive electrolysis of
benzene contains p-benzoquinone as the only electroactive
product; hence, the o-benzoquinone is concluded to undergo
further oxidation at the bismuth-doped lead dioxide electrode
to one or more electroinactive products [22].
Incineration of organic pollutants
The electrochemical performance of several anode materials
is compared for the electrochemical incineration of p-
benzoquinone in acetate buffer media (pH 5). The COD
estimated for benzoquinone by titration with standard
permanganate solution can be decreased to virtually zero by
electrolysis at electrodes comprised of iron(III)-doped lead
dioxide films on titanium substrates. Carbon dioxide is a
product of electrochemical process; however, the possibility
of other volatile products cannot be dismissed. Addition of
solid benzoquinone to acetate media is followed by slow
formation of a brownish black colour that results from one
or more humic compounds produced by condensation of
benzoquinone; however, it cannot be concluded whether the
condensation reaction is necessary prerequisite to successful
electrochemical incineration of benzoquinone in acetate
buffer include heating of the anode (e.g. 60 oC) to increase
the rate of anodic discharge of water and, thereby, decrease
the anodic overpotential. Evidence also is presented that the
rate of electrochemical incineration is enhanced slightly by
the addition of a traces of iron(III) with reduction of oxygen
to hydrogen peroxide at a cooled stainless steel cathode (e.g.
15oC) in an undivided cell [23].
A simple electrochemical reactor to treat aqueous effluents
for the total mineralization (conversion of aniline to carbon
dioxide and water) of an organic pollutant is described.
Results show that about less than 100-ppm of aqueous
aniline solution upon constant current electrolysis, using a
lead dioxide anode and steel cathode, leads to complete
electrochemical incineration of aniline.
C6H5NH2 + 7O2 6CO2 + NH3 + 2H2O
The electrolyte, for electrodeposition of lead dioxide, was a
saturated solution of lead nitrate and copper nitrate, i.e. 325-
350 g/L lead nitrate and 25-30 g/L copper nitrate with an
initial pH 4-4.5. Titration with standard N-
bromosuccinimide solution was used to confirm that
following electrolysis, total organic carbon in the aqueous
solution reduces to background level [24].
Results are described from research directed to the discovery
of new anode materials suitable for obtaining stable and
sensitive response when applied at constant potential for the
amperometric detection of organic amines. Voltammetric
and amperometric results are compared for detection of
selected organic amines in carbonate buffer (pH 10) at
mixed silver-lead oxide films prepared by electrodeposition
on platinum substrates and by anodization of silver-lead
alloys. Anodic response is observed at both electrodes for
ethylamine, N-ethylmethylamine, trimethylamine,
ethanolamine, and L-alanine. However, data indicate that the
oxide electrode formed by anodization of silver-lead alloys
is superior with regard to stability of response. From flow-
injection detection using constant applied potential in
carbonate buffer, linear dynamic ranges (r2 > 0.99) are at
least three decades for selected primary, secondary, tertiary,
alkanol-amine, and amino acids in carbonate buffer (pH 10) ,
with the detection limits (S/N=3) of ~0.3 M (i.e. 6 pmd per
20 L injection). Results are presented for the
characterization of these films using x-ray diffractometry,
XPS, and SEM [25].
Values of the activation energy (H act) for oxidation of
ethylamine and alanine are 17 and 7.2 kJ/mol, respectively,
from temperature effects on the apparent heterogeneous rate
constants estimated from Koutecky-Levich plots for
anodized silver-lead eutectic disk electrodes in carbonate
buffer (pH 10). The value of H act for oxidation of aquated
ammonia is 39 kJ/mol from data obtained in a flow-through
reactor. The anodic peak potential for ethylamine is
observed to vary linearly with the overpotential for anodic
evolution of oxygen as a function of temperature. This is
interpreted from the coupling of these anodic processes via
the adsorbed species (OH) produced by anodic discharge of
water as a prerequisite of both processes [26].
Oxidation of ammonia
Ammonia in alkaline media is oxidized to nitrate at anodized
silver-lead eutectic alloy electrodes (2.4% silver by weight).
The anodic signal is diminished for pH < ~8, and this
attenuation is attributed to the protonation of ammonia to
from ammonium. Protonation of ammonia at silver sites in
the electrode surface is the initial step in the electrocatalytic
oxidation mechanism. For pH > ~10, the anodic signal
decreases with time because of the loss of ammonia by
volatilization. The heterogeneous rate constant for oxidation
of ammonia to nitrate is significantly smaller than that for
oxidation of ethylamine (EA) to acetaldehyde and ammonia
(kapp, NH3 / kapp, EA = ~0.2). Hence, ammonia is a product of
ethylamine oxidation at a rotated disk electrode whereas
acetaldehyde and nitrate are the final products of the
exhaustive electrolysis of ethylamine [27].
Electrolyses of aqueous solution of propionate
The anodic behavior of platinum, lead dioxide, and graphite
was studied in an aqueous solution of propionate. The
normal Kolbe process, the formation of butane and carbon
dioxide, is observed only on platinum anode in the potential
range above 1.9 V vs. saturated calomel electrode. At less
noble potential than the above, no normal Kolbe products
were obtained, even on the platinum anode, but some
abnormal Kolbe products, such as ethylene, ethyl
propionate, and ethyl alcohol were obtained. On lead dioxide
anode, the oxidation process and oxygen evolution
6
predominated, with the abnormal Kolbe process occurring
only to a small extent. In the case of graphite anode, the
abnormal Kolbe products without ethane were mainly
obtained. An anode potential more noble than 1.9 V vs.
saturated calomel electrode was required for the normal
Kolbe reaction [28].
Controlled, potential electrolysis of an aqueous mixture of 1
mol/dm3 propionate and 0.5 or 5 mol/dm3 nitrate solution
was carried out on a lead dioxide anode at 1.70-2.10 V vs.
saturated calomel electrode. Nitrate ester, EtONO2 and
O2NOC2H4ONO2 were obtained when the nitrate
concentration was 5 mol/dm3, but no nitrate esters were
obtained at any potential when it was 0.5 mol/dm3. Propionic
acid is oxidized to carbon dioxide by nitrate radicals
electrogenerated at high positive potential. The influence of
the anode potential and the nitrate concentration on the
amount of nitrate esters indicated the simultaneous
formation of nitrate and ethyl radical as intermediates which
gave rise to EtONO2 and O2NOC2H4ONO2 [29].
A gold rotated ring-disk electrode was applied for the
detection of soluble intermediate products during the anodic
electrodeposition and cathodic dissolution of -lead dioxide
in solutions of perchloric acid. A soluble species which only
can be reduced at the ring electrode is produced during the
anodic nucleation and deposition processes for lead dioxide
at the disk electrode. This soluble intermediate product is
concluded to be lead(IV) which is probably associated with
oxygen, e.g., PbO2+ or Pb(OH)22+.The cathodic ring current
from detection of the soluble lead(IV) species was studied as
a function of the concentrations of lead(II) and perchloric
acid, and variation of rotational velocity. The results are
consistent with chronoamperometric data for lead(s)
deposition described previously. Soluble lead(IV) and
lead(III) as well as lead(II) , are concluded to be products of
the cathodic dissolution of lead dioxide [30].
A comparative study of electrodeposition of lead dioxide
from 1.0 M perchloric acid, 1.0 nitric acid, 1.0 M acetic
acid-1.0 M sodium acetate and 3.0 M potassium hydroxide
solutions containing 0.1 M lead(II) salts, on glassy carbon
electrodes was carried out using cyclic voltammetric and
chronoamperometric measurements. The oxidative
formation of lead dioxide is found to follow 3-D nucleative
growth with the same order of nucleation over voltage in
these media involving pH variations between 0 and 14.5.
Multisweep cyclic voltammetric studies indicate that the
medium influence comes primarly through the chemical
dissolution process following lead dioxide nuclei formation.
In alkaline media, smaller nuclei undergo continuous
chemical dissolution, leading to the growth of large-sized
crystals. In acidic media, since chemical dissolution is less
likely, a phase of different crystal sizes with a more compact
structure evolves [31].
The effects of added cations and anions on the nucleation
and growth of lead dioxide were studied at a gold rotating
disc electrode. The accumulation of electrodeposited lead
dioxide in the presence of a high concentration of
arsenic(III) does not proceed because the chemical stripping
rate of lead dioxide by arsenic(III) is greater than its
deposition rate. Among anions, sulfate and nitrate greatly
enhance the rate of deposition of lead dioxide whereas
phosphate decreases the rate of deposition. It is shown that
the growth of lead dioxide on the gold substrate is not a
uniform process, but proceeds by preferential growth on
specific sites on the surface of the substrate [32].
The effects were examined of copper(II) cations and acetate
anions on the nucleation, growth and electrochemically
active surface area of lead dioxide on a SnO2/Ti electrode.
The nucleation rate of electrodeposited lead dioxide was
greater in the presence of copper(II), but smaller in the
presence of acetate anions when compared with that of pure
lead dioxide. The growth rate of the nuclei of lead dioxide
was greater for acetate-doped lead dioxide but it was smaller
for copper(II)-modified lead dioxide in comparison with
pure lead dioxide. The acetate-doped lead dioxide was
grown in the form of hemispheres, whereas the copper(II)-
modified lead dioxide was in the form of multi-sided
pyramids whose growth axes are directed towards the center
of the sphere. The average size of crystal aggregates for
electrodeposited lead dioxide became enlarged in the
presence of copper(II). The morphology of the lead dioxide
film was smooth in appearance in the presence of acetate
anions. The growth of lead dioxide on the SnO2/Ti substrate
was demonstrated not to be an instantaneous process, but is
preceded by progressive nucleation with preferential island
growth. Lead dioxide doped with the acetate anion resulted
in a significant increase of the electrochemically active
surface area (Q*); by contrast, values of Q* for lead dioxide
modified with copper(II) decreased [33].
Kinetic parameters of the system, -lead dioxide/lead(II)
voltage region were obtained by using the galvanostatic
single step and the current interrupter methods. The single-
step mechanism: -PbO2+4H++2e = Pb2++2H2O, was
considered on the basis of the current-overvoltage relation
and the activation energy value observed [34].
The transient curves of the -lead dioxide/lead(II) system
were observed in nitric acid-sodium nitrate solution by using
a galvanostatic single-pulse method. The activation
overvoltage was estimated and rate equations were
determined empirically in the high overvoltage region. The
reaction mechanism of the -lead dioxide/lead(II) system is
explained from the results of the differences in the exchange
current density and the transfer coefficient obtained by both
anodic and cathodic polarizations. The reaction mechanism
is [35]:
Pb2+ +H2O PbO(2H+)ad.,
PbO(2H+)ad., PbO+(2H+)ad + e-
PbO+ (2H+)ad PbO2+(2H+)ad + e-,
PbO2+(2H+)ad + H2O -PbO2 + 4H+ ,
Transition time, , on the galvanostatic overvoltage-time
transient was observed on -lead dioxide electrodeposited on
a platinum microelectrode in the potential region of
reduction of -lead dioxide in lead nitrate-nitric acid-sodium
nitrate system. An inflection was observed on the current I
7
vs. 1/2 curve. In the system i>i1, the I vs. 1/2 curve had a
linear relation whose slope depended on the bulk
concentration, of H+, but not on that of lead(II). Thus, the
reaction rate is controlled by diffusion of H+ and i1, the
diffusion current. The diffusion coefficient obtained by
applying diffusion equations was of reasonable magnitude
for H+. The thickness of the diffusion layer was 810 3 cm
[36].
The electrolytic treatment of waste water from chemical
processes was examined with a lead dioxide anode in
sodium sulfate solutions to prevent the contamination of
water by alcohols such as methyl alcohol [67-56-1], ethyl
alcohol [64-17-5], and ethylene glycol (I) [107-21-1]. The
oxidation efficiency of I was very high, but decreased in the
order of I, methyl alcohol, and ethyl alcohol with decreasing
alcohol concentration <0.25 M at 5 A/dm2. The current
density had small effect on the oxidation efficiency in the
range of 2.5 to 10.0 A/dm2. The dissolution of the lead
dioxide anode, forming the plumbic ion, during electrolysis
was negligible (<5.6 g/Ahr). The lead dioxide anode was
superior to a platinum anode in terms of the high oxidation
efficiency and the very low yield of carbon monoxide [37].
Lead dioxide anodes were prepared by electrodeposition of
lead(II) on titanium in acidic lead nitrate solutions at 30, 50,
70, 90 and 130C. The electrodes plated at higher
temperatures revealed a progressive increase in the content
of -lead dioxide relative to -lead dioxide. The individual
crystals were larger and a higher O2/O3 overpotential was
observed during the electrolysis of water on such anodes in
0.5 M perchloric acid. At higher temperatures the 110
orientation parallel to the geometrical plane of the electrode
predominates for the crystallographic planes. An opposite
trend can be established for the crystallographic planes 200
and 101 [38].
Current efficiencies are compared for the generation of
ozone simultaneously with oxygen during anodic discharge
of water at pure and iron(III)-doped -lead dioxide film
electrodes in phosphate buffer (pH 7.5, 10C) containing 2.5
mM potassium fluoride. Also examined is the effect of
applied current density. A current efficiency of 14.6 % was
obtained for the iron(III)-doped lead dioxide film electrode
deposited on an internally cooled (10C) tubular titanium
substrate at a current density of 200 mA/cm2 as compared to
only 6.1 % at the undoped lead dioxide electrode under the
same conditions. This result is tentatively explained from a
mechanism involving the transfer of oxygen from hydroxyl
radicals adsorbed on lead(IV) sites adjacent to iron(III) sites
in the surface of the iron(III)-doped lead dioxide electrodes
[39].
The surface composition and vibrational properties of lead
dioxide and bismuth-doped lead dioxide electrode were
studied using Auger electron spectroscopy and high
resolution electron energy loss spectroscopy. Deposition
from perchlorate solution yields chlorine-rich oxides. For
lead dioxide, chlorine tends to segregate at the surface. For
bismuth-doped lead dioxide, chlorine does not segregate at
the surface, but the concentration of chlorine throughout the
bulk of the oxide is about three times that in the lead
dioxide. This suggests that bismuth and chlorine may
chemically bind in the doped oxides. Hydroxyl groups and
hydrocarbon fragments are also present throughout the bulk
of both films. Both oxides exhibit distinct photon loss
spectra, similar to those observed by other authors with
EELS for many other oxides. Subtle differences between
vibrational frequencies of the two oxides may be related to
differences in surface crystallographic orientation or to
differences in chemical composition [40].
The polarographic oxidation of the plumbous ion at a
rotating platinum electrode was studied. In the voltage
scanning towards the positive direction, the oxidation was
diffusion-controlled with an activation energy of 5.2
kcal/mol, and the wave height was proportional to the
concentration and also to the square root of the rate of
rotation. In acid media, E1/2/pH = 0.114 V, while E1/2
was independent of pH in alkaline media. The value of n (n
is number of electrons) was 2 at concentrations <0.4 mM
lead(II) and it was <2 at higher concentrations. From the
discrepancy of the decomposition potential between the
positive and negative scan, the reaction mechanism was
assumed to be: Pb2++2H2O=PbO2+4H++2e at the platinum
electrode; Pb2++PbO2=2PbO+ and
+ +
PbO +H2O=PbO2+2H +2e at the lead dioxide electrode
[41].
Lead dioxide electrodeposited under optimized conditions
on carbon paste provides an electroanalytically useful
electrode, with an anodic working range extending to 1.9 V.
Voltammograms for sulphite are used to study electrode
lifetime and reproducibility; calibration graphs are linear up
to 10-3M sulphite in 0.5 M sulphuric acid [42].
The results of a potentiostatic study of a porous lead dioxide
electrode indicate that the degree of oxidation of the lead
dioxide increases with an increase in the anodic potential,
approaching some limit value. A decrease in the anodic
potential results in cathodic reduction of some of the oxygen
from the crystal lattice of the oxide. Use of the data from the
electrostatic and potentiostatic study of the electrode permits
calculating the dependence of the oxygen activity in the lead
dioxide phase on the anodic potential and degree of
oxidation of the oxide [43].
The electrodeposition of -lead dioxide from perchloric acid
solutions of lead(II) at a gold rotated disk electrode was
studied as a function of applied potential, rotational velocity,
and the concentrations of perchloric acid and lead(II). A
long induction period (i.e., i 0) is associated with high
acidity, low concentration of lead(II) and high rotational
velocity. Following the induction period, the current rises to
a steady-state value which is significantly lower than the
mass transport-limited value for lead(II). The steady-state
value of electrode current decreases as rotational velocity is
increased, contrary to expectations for a mass transport-
controlled process at a rotated disk electrode. The generation
of a soluble intermediate species is proposed to account for
these observations. Repeated cycles of deposition and
stripping of lead dioxide at the gold rotated disk electrode
result in a decreasing induction period for subsequent lead
dioxide deposition. This is concluded to result because a
lead(II) ad-layer (possibly lead monoxide) is formed which
is stabilized by interaction with the gold substrate and is not
8
dissolved following the negative potential scan to 0.3 V. The
original state of the clean gold surface is regenerated by
cathodic hydrogen evolution, chemical stripping with
hydrogen peroxide or potassium permanganate, or by
mechanical abrasion [44]
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