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Electroreduction of nitrobenzene to p-aminophenol using voltammetric and

semipilot scale preparative electrolysis techniques

Article in Journal of Applied Electrochemistry · February 2002

DOI: 10.1023/A:1014725116051

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 Journal of Applied Electrochemistry 32: 217–223, 2002. 217

2002 Kluwer Academic Publishers. Printed in the Netherlands.

Electroreduction of nitrobenzene to p-aminophenol using voltammetric and semipilot

scale preparative electrolysis techniques

K. POLAT1*, M.L. AKSU2 and A.T. PEKEL1

1
Ankara University, Faculty of Science, Department of Chemistry, 06100 Tandogan-Ankara, Turkey
2
Gazi University, Faculty of Education, Department of Chemistry, 06500 Besevler-Ankara, Turkey
(*author for correspondence, e-mail: [email protected])

Received 8 January 2001; accepted in revised form 27 November 2001

Key words: cathode materials, cyclic voltammetry, electrochemical reduction, p-aminophenol, preparative elec-
trolysis, rotating disc electrode

Abstract

This paper describes an investigation of the reduction of nitrobenzene to p-aminophenol by the use of CV, RDE and
preparative electrolysis with Cu and Cu(Hg) electrodes. The preparative electrolyses of nitrobenzene were carried out
at controlled current and controlled potential conditions using copper and amalgamated copper using a new semipilot
(laboratory) scale system in the absence of an organic cosolvent. The effects of redox reagents and the concentration of
nitrobenzene in catholyte added to the medium were also examined. The best results were obtained with 2.3% BiCl3 at
nitrobenzene concentration of 0.144 g cm)3 catholyte. The most suitable electrode material was found to be
amalgamated copper and the reduction of nitrobenzene to p-aminophenol was found to follow an ECE mechanism.

1. Introduction

The electrolytic reduction of nitrobenzene to p-amino-

phenol was first carried out by Gattermann using a Pt
cathode, ambient temperature and highly acidic reaction
medium [1,2] where nitrobenzene (I) was converted into
p-aminophenol (III) by the rearrangement of the phenyl-
hydroxylamine (II) intermediate as follows:

C6 H5 –NO2 ! ðC6 H5 –NHOHÞ ! NH2 –C6 H4 –OHðpÞ

ðIÞ ðIIÞ ðIIIÞ

ð1Þ

The Gattermann method was modified by Darmstadler

Here, we report the effects of cathode material,
[3] and Thatcher [4], and used by Eastman Kodak [5] for
electrode rotation speed, the concentration of the
the large-scale production of p-aminophenol. Although
electroactive compounds and additives such as SnCl2
this method was more popular than the chemical
and BiCl3 on the yield of p-aminophenol.
method it was not as commercially promising as the
method developed by Dey et al. [6]. These workers
developed a new method using cheap cathode materials 2. Experimental details
such as copper, monel and nickel and H2SO4 at very low
concentration. Wilson and Udupa [7] obtained high Copper (Johnson Mathey, 99.9% with dia. 1 mm),
current densities by rotating the electrodes at very high graphite (IR grade with dia. 5 mm) amalgamated copper
speeds. Fleishmann et al. [8] proposed the following and copper-coated copper electrodes were mounted in
reaction scheme: Teflon rods filled with an acryl (Merck) polymer. The
After these studies, much attention has been given to amalgamation and bismuth coating of copper electrodes
the effects of temperature, H2SO4 concentration, cath- were carried out as described in the literature [15, 18, 19].
ode material, type of diaphragm and the reducing agent The supporting electrolyte used in the CV and RDE
employed, on the reduction of nitrophenol to the p- studies was 2 M H2SO4 in a solution of 50% organic
aminophenol [9–17]. solvent/50% water (v/v).
218
All the voltammetric studies were carried out with a compartment was a ceramic porous cup with dimension
Wenking Lb75L laboratory model potentiostat, a Wen- 16 cm · 2.8 cm · 0.4 cm. The capacities of the anode
king model V5G72 wave generator, a Yokogowa and cathode compartments were 200 and 120 cm3. The
Technicorder 3077 type recorder and a 1KA-WERK anolyte was 20% H2SO4 and the catholyte was 20%
TYP RM 18 rotating disc electrode using a standard H- H2SO4 containing nitrobenzene at various concentrations.
type cell. The counter electrode was a helical Pt wire in The catholyte was transferred to the cell using a
the CV and a cylindrical Pt cage placed around the peristaltic pump (Prominent Electronics) with an output
working electrode in the RDE experiments; the refer- rate of 8.9 dm3 h)1. The solution was purged with
ence electrode was the saturated calomel electrode purified nitrogen for two hours with constant stirring.
(SCE). The preparative electrolyses were carried out by circu-
Except for the electrolytically coated electrodes, all lating the electroactive compound over the surface of
the electrodes used in the voltammetric studies were first the cathode without using organic cosolvent. The use of
subjected to mechanical treatment using rough and then organic cosolvent proves to be a problem when high
fine emery paper, and then kept in trichloroethylene to temperatures are employed. The system used here is a
remove any grease from the surface. They were shaken in novel one and avoids these problems. The circulation of
doubly distilled water for a few minutes and wiped with the catholyte also reduces the cost of the raw material,
drying paper before being placed into the electrolytic namely sulphuric acid. The catholyte temperature was
cell. The electrolytic cell was purged with oxygen-free kept constant at 70–75 C using a thermostat. The
nitrogen for thirty minutes prior to the electrochemical charge passing through the circuit in constant potential
experiments. It was observed that the reduction peak electrolyses was monitored with an electronic integrator
currents decreased with the number of scans to an (Sistem Teknik, model 274). The constant current
increasing extent when the electrodes had not been electrolyses were carried out using a 250V/25A power
subjected to this pretreatment. The curves obtained with source (Deniz Elektronik ve Makine Sanayi Tic.).
the pretreated electrodes were found to be highly
reproducible.
All the reagents used in the experiments were analyt- 3. Results and discussion
ical grade (Merck) and used without further purifica-
tion. All the solutions were prepared with double 3.1. Cyclic voltammetric investigation
distilled water.
The preparative electrolyses were carried out using the The cyclic voltammetric curves obtained with Cu are
system depicted in Figure 1. The cathode was a Cu or shown in Figure 2. The curves show a single irreversible
Cu(Hg) plate with the dimensions of 13 cm · 9 cm · peak at all scan rates; the peak shifts in the negative
0.1 cm rolled into a cylindrical form. The anode direction as the scan rate is increased.

Fig. 1. The experimental set-up for the preparative electrolyses. Key:

(A) electrolytic cell, (B) cathode, (C) thermostat, (D) peristaltic pump, Fig. 2. Cyclic voltammograms of nitrobenzene (3.0 mM) in 2.0 M
(E) electrolyte reservoir, (F) magnetic stirrer with a heater, (G) anode H2SO4 containing 50% water – 50% 2-propanol (v/v) on Cu at: ()
compartment, (H) N2 inlet, (I) N2 outlet. 10, (h) 20, (j) 40, (·) 80, (s) 160 and (d) 320 mV s)1.
 219
Table 1. Cyclic voltammetric results of NB (3 mM) on graphite in a medium of 2 M H2SO4 in 50% water – 50% 2-propanol (v/v)

m/mV s)1 Ep/mV Ep/2/mV Ip/mA Ip/m1/2 C E1/2/mV ana Ep ) Ep/2/mV

10 320 245 1.686 178 285 0.640 75

20 330 250 2.033 152 290 0.600 80
40 335 255 2.772 146 295 0.533 90
80 350 260 3.788 141 305 0.533 90
160 365 260 5.036 133 315 0.533 90
320 380 260 7.346 137 320 0.384 125

Fig. 3. Change of current function with scan rate on Cu (m) and

graphite (j).
Fig. 4. Cyclic voltammograms of nitrobenzene (2.0 mM) on coated Cu
at a scan rate of 40 mV s)1 (·) Bi coated Cu; (d) Cu coated Cu; (h)
Table 1 lists the cyclic voltammetric data obtained amalgamated Cu.
with graphite under the same conditions employed for
Cu. Figure 2 and Table 1 show that the results obtained
with both these electrodes are similar, except for a more tained with Cu and graphite. The reduction peak of
negative reduction potential, higher current and current nitrobenzene to phenylhydroxylamine appears at
function values and lower charge transfer coefficient 225 mV with Cu/Cu and Cu(Hg) and 250 mV with
(ana ) with graphite. Cu/Bi. The rate of hydrogen evolution reaction is
The plot of Ip against m1=2 gave a straight line, while highest on Cu(Hg) and almost the same on Cu/Cu and
the graph of current function against the scan rate was a Cu/Bi.
concave curve decreasing towards the higher scan rates The effect of salts such as SnCl2 and BiCl3 as reducing
for both copper and graphite (Figure 3). agents on the reduction of nitrobenzene on Cu and
In another study with copper the effect of the graphite was also investigated. The data obtained by the
concentration of the nitrobenzene in the electrolyte addition of these salts into the reaction media using
was investigated. copper and graphite are given in Table 2. The highest
Figure 4 gives the cyclic voltammograms obtained current efficiency was obtained with BiCl3. It appears
with coated electrodes. The peak potential shift towards that the peak potentials in media without reducing agent
more positive values and the current and hydrogen shift to more positive values and hydrogen evolution
overvoltage is much higher compared with those ob- takes place at more negative potentials.

Table 2. Effect of redox compounds on the reduction of nitrobenzene (2 mM) in 2 M H2SO4 containing 50% water – 50% 2-propanol (v/v) on
copper and graphite at a scan rate of 40 mV s)1

Redox compounds Electrodes )Ep/mV Ip/mA )EH/mV

SnCl2 Cu 325 1.35 520

BiCl3 Cu 325 1.50 520
– Cu 375 1.28 500
SnCl2 Graphite 210 3.00 600
BiCl3 Graphite 210 3.30 600
– Graphite 335 2.80 580
220
The current increases linearly with scan rate and that these ions were capable of reducing the nitro
nitrobenzene concentration with Cu and graphite indi- compounds in the solution [9, 12]. This was also
cating that the reduction process is diffusion-controlled. observed in our study and the addition of SnCl2 and
The current function does not correlate with the scan BiCl3 to the reaction medium changed the shape of the
rate, which shows that the electron transfer is preceded voltammograms obtained with both electrodes em-
by a chemical reaction. Otherwise, these two parameters ployed (Cu and graphite) and increased the hydrogen
would be expected to correlate linearly [22]. The overvoltage and the current densities as mentioned
parameter (dEp/2)/ d log m was found to be 35–45 mV previously.
which complies well with the criterion of (dEp/2)/
d log m ¼ 30=ana (mV) for ECE reactions [23]. 3.2. Rotating disc electrode results
The charge transfer coefficient ðana Þ for the irrevers-
ible system was calculated using The RDE studies were carried out with Cu and Cu(Hg)
at a rotation speed of 200–2000 rpm (Figures 5 and 6).
Ep  Ep=2 ¼ 48=ðana Þ ð3Þ
The voltammograms obtained with both electrodes are
similar in appearance. However, the current and hydro-
The ðana Þ values at scan rates ranging between
gen overvoltage on Cu are much lower than on Cu(Hg).
10 mV s)1 and 320 mV s)1 were found to be 0.640–
The current increases with rotation speed and the peaks
0.800 on Cu and 0.384–0.640 on graphite. The fact that
become broader as the rotation speed is increased. The
the value of charge transfer coefficient is lower on
plots of I=x1=2 C against x1=2 and 1/Ip against 1=x1=2
graphite compared to one on copper is probably due to
gave a curve and a straight line, respectively, which
the stronger adsorption and blockage of the products on
shows that reaction is ECE type and diffusion con-
graphite.
trolled.
The transfer coefficients decrease and the Ep values
The kinematic viscosity of the solution under the
shift to more negative potentials, as is known to be the
experimental conditions was 0.0435 cm2 s)1. The hetero-
general case for irreversible reactions [25]. This was
geneous rate constant was obtained in the usual manner
observed for both electrodes.
from the intercepts of the linear 1/I against 1=x1=2 plot
The fact that there was no anodic peak after reversal
[26].
from the hydrogen evolution potential shows that the
total reduction process and the chemical reaction are 1 1 1
irreversible and the product of chemical reaction is ¼ þ ð4Þ
I Ik 0:62 nFAC 1 D2=3 m1=6 x1=2
electrochemically inactive. In previous reports on the 0 0
same reaction it was pointed out that the total reduction
and the chemical reaction was totally irreversible and
the rate of chemical reaction was 100 times higher than
that of the electrochemical reaction [16].
The reduction of phenylhydroxylamine to aniline by
taking an electron from the cathode surface and its
conversion to p-Ap though a chemical rearrangement
reaction in the solution is competitive [9, 16, 17, 25].
Therefore the higher the rate of the chemical reaction
the higher the yield of p-aminophenol.
Studies carried out in this area show that the
reduction of phenylhydroxylamine into aniline takes
place in parallel with hydrogen evolution [6]. Therefore,
the yield of p-aminophenol is expected to be higher on
metals having a higher hydrogen overvoltage. Accord-
ingly, graphite, which has a higher hydrogen evolution
potential than copper, is a more suitable cathode
material for p-Ap synthesis.
The fact that hydrogen overvoltage and current are
higher on Cu(Hg) than on Cu/Cu and Cu/Bi can be
explained on the basis of a stronger adsorption of p-Ap
on the amalgamated surface. That is why Cu(Hg)
appears to be a more suitable electrode material in the
synthesis of p-Ap.
Fig. 5. RDE curves of nitrobenzene (3.0 mM) in 2.0 M H2SO4
The addition of redox compounds such as SnCl2, containing 50% water – 50% 2-propanol (v/v) on Cu at: (d) 200,
TiCl3 and BiCl3 has a synergistic effect on the yield of (s) 400, (·) 600, (.) 1000, ( ) 1200, (j) 1600 and (h) 2000 rpm
p-Ap as indicated in previous studies and it was claimed keeping the scan rate at 40 mV s)1.
 221
range of rotation speeds in the reduction of nitroben-
zene to p-Ap was 600–1200 rpm.
The literature indicates that the rotation speed has a
marked effect on the yield of p-Ap [7, 9, 16]. It was also
found that the current function 1=x1=2 C was indepen-
dent of rotation speed.
The sharp peaks obtained at lower rotation speeds can
be explained by the fact that the intermediates remain at
the surface of the electrode for a much longer period,
which increases their chance of reaction and reconvert-
ing to aniline. This makes the total number of electrons
transferred correspond to n1 + n2. The increase in
rotation speed apparently increases the rate of phen-
ylhydroxylamine molecules leaving the electrode surface
by diffusion, and convection and this leads to a decrease
in reaction time for organic molecule reduction. In other
words, the amount of phenylhydroxylamine on the
surface increases. The reason why the peaks get broader
at higher rotation speeds is possibly the result of the fact
that the reduction of nitro compounds is continuing
while phenylhydroxylamine is leaving the electrode
surface to give chemical reaction in the solution. This
shows that chemical reaction competes with electro-
chemical reaction.
Fig. 6. RDE curves of nitrobenzene (3.0 mM) in 2.0 M H2SO4
containing 50% water – 50% 2-propanol (v/v) on Cu(Hg) at: (d) 3.3. Preparative electrolyses
200, (s) 400, (+) 600, (h) 1000, (j) 1200, (,) 1600, (.) 1800 and ( )
2000 rpm keeping the scan rate at 40 mV s)1.
The electrolyses were carried out at constant potential
and current conditions using Cu and Cu(Hg) and the
where effects of the current, redox reagents and the concen-
tration of nitrobenzene in catholyte were investigated.
Ik ¼ nF ~
k C01 ð5Þ The parameters such as acid concentration and temper-
ature were not separately examined and kept at 20%
n is the number of electrons transferred, C01 is the bulk H2SO4 and 75 C. The same parameters were employed
concentration of the reactant, x is the rotation speed of in previous studies [12, 20, 21].
the electrode, m is the kinematic viscosity of the solution The results obtained in constant potential electrolyses
and A is the surface area of the electrode. The diffusion are given in Table 3 which shows that the highest yield
coefficient and the heterogeneous rate constant for of p-Ap in preparative electrolyses was obtained with
nitrobenzene were determined as 5.98 · 10)6 cm2 s)1 Cu(Hg) at potential controlled conditions which is
and 9.24 · 10)8 cm s)1. supported by the cyclic voltammetric and RDE data.
The rotating disc electrode experiments revealed that The formation of resinous compounds remained low
the number of electrons transferred was 6 at low (200– at nitrobenzene concentration less than 0.144 g cm)3
600 rpm), 4 at medium (600–1200 rpm) and 2 at high and increased at concentrations higher than that.
rotation speeds above (>1200 rpm) as calculated by the The amount of aniline formed remained constant. The
use of the Levich equation. Thus, the most suitable increase in nitrobenzene concentration increases the

Table 3. Results of constant potential electrolyses of nitrobenzene on Cu and Cu(Hg)

Cathodes E/mV Product yields Conversion/% Selectivity/% Unreacted Resinous

NB/mol Compounds/g
p-Ap AN p-Ap AN

/mol /% /mol /%

Cu 375 0.160 68.4 0.062 26.4 94.8 72.2 27.8 0.0122 1.05
Cu(Hg) 225 0.180 76.9 0.044 18.8 95.7 80.4 19.6 0.0098 0.92

Catholyte: 20% H2SO4 (200 cm3) + 0.144 g NB/cm3 catholyte; anolyte: 20% H2SO4, anode: graphite; temperature: 75 C; Q: 85 603 C
(4 F mol)1).
222
Table 4. Effect of nitrobenzene concentration in catholyte for electrolyses carried out on Cu at 375 mV (the electrolyses was carried out at the
same conditions set in Table 3)

NB Q/C Product yields Conversion Selectivity/% Unreacted Resinous

/g/catholyte (4 F mol)1) /% NB/mol Compounds/g
p-Ap AN p-Ap AN

/mol /% /mol /%

0.144 85603 0.160 68.40 0.062 26.40 94.80 72.20 27.80 0.0122 1.04
0.300 175992 0.296 60.66 0.160 32.79 93.45 64.91 35.09 0.0320 2.70
0.400 235814 0.375 57.69 0.236 36.31 94.00 61.37 38.63 0.0390 3.20

Table 5. Results of constant current electrolyses of nitrobenzene on Cu and Cu(Hg), cf. Table 3, i = 5.85 mA cm)2, Q = 90 312 C (4 F mol)1)

Cathodes Product yields Conversion/% Selectivity/% Unreacted Resinous

NB/mol Compounds/g
p-Ap AN p-Ap AN

/mol /% /mol /%

Cu 0.097 41.50 0.126 54.00 95.50 43.50 56.50 0.0106 1.90

Cu(Hg) 0.158 67.40 0.070 29.90 97.30 69.30 30.70 0.0065 1.50

Table 6. Effect of redox compounds added to reaction medium in the reduction of nitrobenzene on Cu (E = )325 mV) and all other conditions
are as same as those listed in Table 3)

Redox compounds % Product yields Conversion/% Selectivity/% Unreacted NB/mol

(· 10)3)
p-Ap AN p-Ap AN

/mol /% /mol /%

SnCl2 1.7 0.100 42.70 0.128 54.70 97.40 43.80 56.20 6.00
BiCl3 1.7 0.130 55.60 0.099 42.30 97.90 56.80 43.20 5.00
SnCl2 2.3 0.168 71.80 0.062 66.50 98.30 73.00 27.00 4.00
BiCl3 2.3 0.175 74.80 0.055 232.90 98.72 75.80 24.20 3.00
SnCl2 5.2 0.112 47.90 0.120 51.30 99.10 55.20 44.80 2.00
BiCl3 5.2 0.115 49.10 0.117 50.00 99.10 49.50 50.50 2.00

chance of nitrobenzene intermediate phenylhydroxyl- and product yield of p-Ap were obtained when the
amine giving reaction at the cathode surface. This amount of both redox agents was 2.3% and BiCl3 gave
reaction is promoted as the amount of undissolved better results compared with SnCl2.
nitrobenzene increases.
The I–Q graph of potential controlled electrolysis 3.3.1. Separation of the electrolyses product
data gave the number of electron as 4. The unreacted NB was separated from the reaction
The effect of the nitrobenzene concentration was also medium by steam distillation, purified with ether ex-
investigated at constant potential (all the other para- traction and dried over CaCl2 after evaporation of ether.
meters being the same as Table 3) and the results are The remaining solution was neutralized with NH4HCO3
given in Table 4. Table 5 lists the results obtained from to pH 6–7 and resubjected to steam distillation to
the constant current electrolyses of nitrobenzene Cu separate aniline. Aniline was extracted with ether from
and Cu(Hg). The effects of the reducing agent added the aqueous solution. The solution was then boiled with
to the catholyte are given in Table 6. It is observed active carbon, filtered and cooled to 0 C. The p-
that the p-Ap yield is dependent on the potential aminophenol crystals were filtered off, washed with
employed according to the data presented in Table 3 benzene and 1% sodium bisulfite, recystallized from hot
and Table 4. water and dried in a vacuum dessicator (mp 188–189 C
Table 6 indicates that the addition of redox com- lit., [28] mp 189.5–190 C). The flow chart of the system
pounds to the reaction medium increases the p-Ap yield is depicted in Figure 7.
and percentage conversion, which proves that these In conclusion, the highest p-Ap yield is obtained by
redox species reduce the nitro compounds in the using Cu(Hg), BiCl3 and 0.144 g cm)3 catholyte con-
solution. It was observed that the highest selectivity centration, respectively.
 223

Fig. 7. Flow-chart for the electrochemical production of p-aminophenol.

This is a preliminary study for the continuous 10. J.E. Slaqer, German Patent 1 066 589 (1959).
electrolyses of nitrobenzene to p-aminophenol on an 11. J. E. Slaqer and J. Mirza, French Patent 1 416 966 (1965).
12. K. Jayaraman, K.S. Udupa and H.V.K. Udupa, Trans. SAEST 12
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scale up this semipilot (laboratory) system to pilot scale 13. J. Marquez and D. Pletcher, J. Appl. Electrochem. 10 (1980) 567.
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