Aust. J. Chem.

, 1983, 36, 1695-704

Solvation of Ions. Some Applications. V*

Electrolytic Recovery of Silver
from Non-Aqueous Solutions Ag/EW Cu/EW

Sunil Jayasekera,* James A ~ r a a m i d e sand

~ , ~Alan J. ParkerA?
A School of Mathematical and Physical Sciences, Murdoch University, W.A. 6150.
Author to whom all correspondence should be addressed.

Abstract
Electrolysis of a dimethyl sulfoxide solution containing AgC1,- and CuC12- has been shown to
produce high-purity, adherent, non-dendritic cathode silver with a current efficiency of over 80%.
At the anode, CuC1,- was oxidized to CuZ+. An optimum electrolyte/solvent system was chosen
after a study of the various parameters contributing to the conductivity of the solution. Diffusion
coefficients and Tafel slopes were measured, as were the various potentials contributing to the cell
voltage. Good silver deposits were obtained by using 0.75 M CaCl2.2H,O, 0.5 M AgCl and 0.5 M
CuCl in dimethyl sulfoxide at 50°C at a cathode current density of 5 mA cm-2. A practical electrolysis
cell is proposed for use with a cyclic leach-electrowin process for recovering pure silver from various
high-grade secondary residues.

Introduction
In dipolar aprotic solvents such as dimethyl sulfoxide (Me,SO) and N,N-dimethyl-
formamide (Me,NCHO), the halo complexes of Cui and Ag' are much more readily
formed than in water.',, The equilibria
AgCl + C1- $ AgC1,- (1)
C U C ~ a-
+ F= Cucl2- @I
lie very much to the right-hand side in dipolar aprotic solvents owing to the higher
activity of the small C1- ion in these solvents compared with that in water.3 Large
polarizable complex ions like AgC1,- and CuC1,- are almost as well solvated by
dimethyl sulfoxide or N,N-dimethylformamide as by The equilibrium
constants for reactions (1) and (2) are related to the amount of water present and the
nature of the solvent, and are up to 6 log units larger in the dry solvents than in water.,,"

* Part I V , Hydrometallurgy, 1979, 4, 233.

f This paper is dedicated by S.J. and J.A. to the memory of Professor A. J. Parker who died on 30
August 1982.
Parker, A. J., Avraamides, J., and Clare, B. W., TMS Publication A81-42; 110th AIME Meeting,
Chicago, February, 1981.
Parker, A. J., Clare, B. W., and Smith, R. P., Hydrometallurgy, 1979, 4, 233.
Parker, A. J., Chem. Reo., 1969, 69, 1.
Ahrland, S., Blauenstein, P., Tagesson, B., and Tuhtar, D., Acta Chem. Scand., Ser. A, 1980,34,265.
 S. Jayasekera, J. Avraamides and A. J. Parker

In dipolar aprotic solvents, the Cu2+/CuC12-redox couple is a much more power-

ful oxidant than in water especially for metals which form complexes with C1- ion,
e.g., AgC1,-, CuC1,- and AuC1,-. This is because Cu2+ and C1- ions are less well
solvated, and Cu' (a dl0 cation) is better solvated by dipolar aprotic solvents than
by water. For these reasons, the following reactions proceed readily in dimethyl
sulfoxide or N,N-dimethylformamide:

These reactions can be used to prepare solutions of gold and silver from high-grade
materials such as anode slimes, residues from the photographic industry, scrap
jewellery, dental alloys, gold-silver bullion, zinc-box gold residues, and electronic
circuit boards.',' Addition of water to these solutions either precipitates gold metal
[reversal of reaction ( 5 ) ] or AgCl [reversal of reaction (I)], and thus provides a means
of producing pure gold powder and AgCl.' A cyclic process is only possible if the
added water is removed by distillation. Fig. 1 illustrates the steps involved in this
c ~ n c e p t . ' , ~The mixture of gold powder and AgCl may be separated by selectively
dissolving the AgCl in non-oxidizing media containing excess C1- ions. Gold is
soluble only in the presence of an oxidant, and remains behind.

Ap
Au0 bearing 1 a"d
inateriali
I

leach -
AgCI2-/AuC12-/

CuC12-/Me2S0
preclpltate
Fig. 1. Process concept
for sllver recovery.

I\

CuCI2/CaCI2/
Me2S0
dlstll -
a

v
v pure
rnsolubles
II
Au0 and AgCl

heat

However, the AgCl precipitate requires further treatment to convert it into pure
metal. This can be done by (A) melting with Na2C0, at 1 100°C, (B) reducing a slurry
of AgCl in water with zinc dust at 60-80°C, or (c) reducing AgCl with hydrogen at
3 0 0 - 4 0 0 " ~ . ~All of these procedures require another refining step to obtain pure
silver. Other disadvantages of the concept are the energy-intensive nature of any
pyrometallurgical steps and the sensitivity of the organic solvents to oxidation during
the distillation.' Dimethyl sulfoxide is prone to violent decomposition in the presence
of oxidants like Cu2' even at 80°C, and therefore N,N-dimethylformamide was
recommended for operations above 50°C.'
If silver can be recovered directly by electrolysis of the leach solution, then the
water addition/distillation steps can be eliminated. This will allow the use of the
preferred solvent, dimethyl sulfoxide, which has superior solvating properties to
 Solvation of Ions. Some Applications. V

N,N-dimethylformamide. It was the purpose of this study to examine the feasibility

of the electrolytic recovery of silver from typical leach solutions. In theory, silver
metal is plated out on the cathode and the oxidant regenerated at the anode:
cathode AgC1,- + e- + Ago + 2C1-
anode CuC1,- -t Cu2'+2C1-+e-
This allows the spent electrolyte to be recycled directly to the leaching stage to dis-
solve more silver, and leads to a cyclic process which does not consume any reagents
other than electricity. A similar investigation on gold electrolysis is being carried out
and will be reported at a later date.

Experimental
Salts
Silver chloride was prepared from A.R. silver nitrate and hydrochloric acid. The precipitate was
thoroughly washed with deionized water, and dried at l103C. A.R. cuprous chloride was washed
with 0.01 M hydrochloric acid until white, then with water, and finally with ethanol. It was dried
under vacuum at 140'C and stored under nitrogen.
All other salts were A.R. grade and were used without further purification.

Dimethyl sulfoxide and N,N-dimethylformamide were purified by drying overnight over 4A

molecular sieves, and distilling under nitrogen at reduced pressure (c. 7 mmHg). Both solvents
contained less than 0.1 % water by weight, measured by Karl Fischer titration, and were stored over
4A molecular sieves.

Instrumentation
Conductivity measurements were made by using a Philips PW9501 conductivity bridge and a
PW9.511 conductivity cell.
Viscosities of solutions were determined by using an Ostwald viscosimeter, and absolute viscosities
determined by comparison with water.
Density measurements were performed on an Anton-Paar precision densitometer.
Potential and current were measured with a Keithley 177 multimeter. Thoroughly cleaned pure
silver, copper and platinum wires were used as indicator electrodes for the AgC1,-/Ago, CuC1,-/CuO
and Cu2+/CuC1,- couples, respectively.
Electrochemical measurements were made by means of a Princeton Applied Research (PAR) 170
electrochemical system in conjunction with a platinum rotating-disc assembly. Solutions were main-
tained at constant temperature in a Metrohm cell, and were kept free of oxygen by a slow stream of
nitrogen throughout the current-potential measurements.
The electrolysis equipment consisted of a Metrohm constant-temperature cell into which were
placed a high-purity silver cathode (Johnson-Matthey) and a carbon or platinum anode. Electrode
areas were determined by the silver coverage, but were generally about 9 cm2. Current was supplied
by a Hewlett-Packard 6226B power source. Voltages were recorded on a Linear Instruments chart
recorder. Electrode potentials were measured against a saturated calomel reference electrode con-
nected to a Luggin capillary through a salt bridge containing 0.1 M tetraethylammonium picrate
dissolved in the solvent of interest.
Analysis of solutions and silver deposits for copper and silver was carried out by atomic absorp-
tion spectrophotometry.

Results and Discussion

Solubility, Conductivity and Viscosity Considerations of Potential Electrolytes
In the proposed cyclic leach-electrowin system it is important to choose a solution
composition which gives high efficiencies in both the dissolution and electrolysis
 S. Jayasekera, J. Avraamides and A. J. Parker

stages. The efficiency of the leaching stage depends on the amount of oxidant (i.e.,
Cu2') and complexing agent (i.e., C1-) which will dissolve in the solvent, whereas it
is the conductivity of the solution which directly affects the efficiency of the electro-
lysis. The conductivity of the leach solution will depend on temperature, concentra-
tion and nature of dissolved salts, viscosity, water content, and choice of dipolar
aprotic solvent.
A comparison of the relevant physical and electrochemical properties of the two
solvents of interest suggests that N,N-dimethylformamide is the more suitable,
particularly in view of its lower viscosity and, therefore, higher cond~ctance.~How-
ever, the solubilities of a wide range of metal salts are generally higher in dimethyl
s u l f ~ x i d e . ~For
- ~ practical reasons CaC12.2H,0 seems to be the preferred source of
C1- owing to its cheapness and high solubility, but for the purposes of directly
comparing the two solvents anhydrous LiCl was chosen.

Table 1. Conductivities (K), at 25 and 50°C, of various solvent systems containing equimolar CuCl
and AgCl
Values given are 1 0 3 (S +
~ cm-I). [CuCl] [AgCI] in the solutions are: (A) none; (B) 0 . 1 M + 0. l ~ ;
(C) 0.3 M+@3 M; (D) 0.5 M+@5 M

Electrolyte (A) (B) (c) (Dl

solutions 25°C 50°C 25°C 50°C 25°C 50°C 25'C 5OCC

A Compositions of salts are beyond the solubility limits.

The data obtained are presented in Table 1. Conductivities were measured for
three different concentrations of equimolar AgCl and CuCl in the presence of various
concentrations of LiCl or CaC12.2H20. The effect of LiCl concentration on conduc-
tivity in the two solvents is shown in Fig. 2. A maximum in conductivity occurs at

Sawyer, D. T., and Roberts, J. L., Jr, 'Experimental Electrochemistry for Chemists' (John Wiley:
New York 1974).
Janz, G. J., and Tomkins, R. P. T., 'Non-aqueous Electrolytes' Vol. 2 (Academic Press: New York
1973).
Martin, D., and Hauthal, H. G . , 'Dimethyl Sulphoxide' (Van Nostrand-Reinhold: Berkshire
1975).
Muir, D. M., and Parker, A. J., Proceedings of 112th AIME Annual Meeting, Atlanta, Georgia,
U.S.A., March 6-10, 1983 (Eds K. Osseo-Asare and J. D. Miller) p. 341.
Aylward, G. H., and Findlay, T. J. V., 'SI Chemical Data' 2nd Edn (John Wiley & Sons,Australasia,
Pty Ltd, 1975).
Solvation of Ions. Some Applications. V

a LiCl concentration of about 1 M, as noted by ~ut1er.l' This may be due to either

ion-pairing or a large viscosity increase at high salt concentrations. Butler has shown
that the viscosity of dimethyl sulfoxide solutions increase sharply at LiCl concentra-
tions around 0.8 M. This is consistent with our own observation that increasing the
temperature from 25 to 50°C lowers the viscosity by a factor of nearly four and
increases the conductivity in comparable solutions. In fact, dimethyl sulfoxide is
almost as conductive as N,N-dimethylformamide at higher temperatures (Fig. 2).
CaC1,.2H20 behaves similarly to LiCl at equivalent C1- concentrations in dimethyl
sulfoxide.

Fig. 2. C o n d u c t ~ \ ~ t ~( Ke)s of d~rnethcl

sulfoxide and .V, \ -dnneth>lforrnarn~de 7
solut~onaconta~ningLlCl at 25 and 50°C $
L?
Me,NCHO, 25'C

The addition of AgCl and CuCl to solutions containing LiCl increases the conduc-
tivity. However, excess C1- (above that required for complexation of silver and copper
ions) tends to lower the conductivity. Table 1 indicates the amount of C1- needed to
dissolve a certain amount of AgCl and CuCl. An excess of 0 . 5 M C1- (i.e., 1.5 M
LiCl or 0.75 M CaC12.2H20) is quite sufficient to dissolve 0 . 5 M AgCl and 0 . 5 M
CuCl. The identity and relative concentrations of the various chloro complexes of
copper(1) and silver(1) were not determined. For convenience we refer to them as
CuC1,- and AgC1,-, although higher complexes may also be p r e ~ e n t . ~ , "
Table 2. Conductivity (K) of a partly electrolysed leach solution
containing 0 . 7 5 M CaCI2.2H20 in dimethyl sulfoxide at 25 and
50°C

As the electrolysis proceeds, the concentration of AgC1,- decreases and CuC1,-

is oxidized to Cu2+. Table 2 gives the conductivities for intermediate concentrations
of copper and silver species. During the course of electrowinning there is a decrease

lo Butler, J. N., J. Electroanal. Chem. Zntevfacial Electrochem., 1967, 14, 89.

l1 Alexander, R., KO,E. C . F., Mac, Y. C . , and Parker, A. J., J. Am. Chem. Soc., 1967, 89, 3703.
 S. Jayasekera, J. Avraamides and A. J. Parker

in conductivity which may be due to the formation of larger less mobile complexes
such as CU(M~,SO),~+.It is unlikely that in practice the electrolysis would be per-
mitted to continue until the AgC1,- concentration had fallen to 0.1 M. In the proposed
cyclic process the electrolyte would be returned to the leaching stage well before
complete depletion of AgC1,-.
The initial solution composition which appears to be best suited for both electro-
lysis and leaching is 0 . 5 M CuC12.2H20and 0.75 M CaC12.2H20in dimethyl sulfoxide.
Such a solution readily dissolves metallic silver at 50°C producing an electrolyte
containing 0 . 5 M AgC12-, 0 . 5 M CuC12-, 0.5 M C1- and 0.75 M Ca2+. The conduc-
tivity of this solution is 1 . 7 x S cm-' at 50°C, about the same as that of 0.1 M
KC1 in water at 25°C.

A&+/A~" Fig. 3. Effect of water on

300 1 C u : + / ~ u ~ ~ , - electrode potentials of interest in

dimethyl sulfoxide solutions at 25°C.
4

Electrode Potentials
In order to produce high-purity cathode silver, the reduction of AgC1,- must occur
at a more positive potential than the reduction of CuC1,-. In fact AgC1,- is less
well solvated by dimethyl sulfoxide than is CuC1,-, so we expect the two electrode
reactions to be (6) and (7). From the data presented in Fig. 3 it is apparent that
the redox couples AgC1,-/Ago and CuC1,-/CuO are sufficiently well separated, even
in the presence of water, so that AgC1,- can be cathodically reduced without the
problem of copper codeposition. Unfortunately, the reduction potential for the
Cu2+/CuC12- couple is more positive than for AgC1,-/Ago; this suggests that the
efficiency of the electrowinning cell will be low if the Cu2+ concentration is allowed
to build up. A cell design incorporating separate anode and cathode compartments
is necessary to prevent significant concentrations of Cu2+ reaching the cathode.
Fig. 3 also illustrates the effect of water on the reduction potentials of the species
of interest in dimethyl sulfoxide. Almost identical data were obtained in N,N-dimethyl-
formamide. On addition of water, both the AgC1,-/Ago and CuC1,-/CuO couples
shift anodically, i.e., the metals become more difficult to oxidize. However, the
important implication presented in Fig. 3 is that, in practice, total removal of water
from the solvent system is unnecessary, and the water content of commercially
available solvents is tolerable. In fact it is advantageous to have some water in the
Solvation of Ions. Some Applications. V

solution because the overall cell potential becomes smaller with increasing water
content. However, this advantage is limited owing to the lowering of the solubility
of silver as the amount of water increases. For example, dimethyl sulfoxide containing
10% water by volume (corresponding to 40 mole % water) can still dissolve up to
0.6 M silver.' Water also lowers the viscosity somewhat and thereby improves the
conductivity of the solution. The use of CaC12.2H20 and CuCl2.2H2O at 0.75 and
0.5 M concentrations, respectively, would produce a solvent system containing less
than 5 % water by volume which does not limit the solubility of silver.

Diffusion Coe$cients and Tafel Parameters

The mobility of AgC1,- and CuC1,- complex ions in the electrolyte is an important
factor in determining the limiting current density. Tafel parameters provide infor-
mation relating to the kinetics of electron transfer, which are useful in choosing
electrode materials. The experimental technique employed a rotating platinum disc
electrode, and, because of the similarity of the system to that studied by Muir, his
method was closely f~llowed.~'Like Muir, we were working with high concentrations
of dissolved copper and silver corresponding to practical solutions, and were interested
only in obtaining comparative data.

Table 3. Diffusion coefficients (D) of copper and silver complexes in 1 . 5 M LiCl solutions

SpeciesA Solvent Temperature ("C) 10IOD (m2 s-I)

0.01 M CuC12- Hz0 25 7.9

0.10 M CuC12- Hz0 25 6.7
0 . 10 M CuC12- Hz0 50 17.3
0.10 M CuC12-, 4 M NaC1, 1 M HCl H20 25 7.3B
0.01 M CuC1,- Me2S0 25 2.6
0.01 M CuClz- Me2S0 50 3.9
0.10 M CuC12- Me2S0 25 2.9
0 . 10 M CuCl2- Me2S0 50 5.0
0.01 M AgClz- Me2S0 25 2.1
0.01 M AgC12- MezSO 50 3.2
0.10 M AgClz- MezSO 25 1.9
0.01 M AgC12- Me2NCH0 25 3.3
0.01 M AgC12- Me2NCH0 50 4.4
A Exact nature of complex ions was not determined. Species shown were assumed to predominate.
Muir, D. M., Warren Spring Laboratory Report LR416 (ME), Stevenage, U.K., 1982.

Diffusion coefficients were determined from the Levich equation. The data
(Table 3) show that the mobility of CuC1,- is considerably greater in water than in
the dipolar aprotic dimethyl sulfoxide. As expected, there is a significant increase
in diffusion coefficient at higher temperatures. The results for AgC1,- are not pre-
sented with the same confidence owing to the changing area of the platinum disc as
silver metal was deposited during the course of the current-potential measurements.
By using the same procedure as ~ u i r , " Tafel slopes were determined for the
CuZ'/CuCi2- redox couple in water and dimethyl sulfoxide containing 1.5 M LiCl
and 0.1 M CuC1. Oxidations of CuC1,- in both solvents have similar Tafel slopes,

l2 Muir, D. M., Warren Spring Laboratory Report LR416 (ME), Stevenage, U.K., 1982.
 S. Jayasekera, J. Avraamides and A. J. Parker

which implies that the rates of electron transfer are comparable. Although a more
specific interpretation is not justified with the limited data available, our results
parallel those of other workers who found similar rates of electron transfer for the
anodic dissolution of copper and silver metal in similar C1- solutions of dimethyl
sulfoxide and water.13
It is the high viscosity of the dimethyl sulfoxide-based electrolyte which limits the
current densities at which silver may be electrowon from solution rather than the
rates of electron transfer. The results obtained in this part of the study must not be
regarded as an attempt to obtain any absolute values. Comparisons were made of
the behaviour of the two dipolar aprotic solvents and water at practical concentrations
of AgC1,-, CuC1,- and C1-. It is apparent that the electrowinning stage will need
to be operated under conditions which will minimize the low diffusion rates of the
electroactive species, i.e., high temperature and vigorous stirring.

Table 4. Effect of electrolysis conditions on nature of cathode silver deposit

Platinum anode, silver cathode; separation 3 mm; plating time 2 h

Temperature Stir- Current density Cell voltage EfficiencyA Quality of

("c) ring (mA cm - ') (mV) ( %) deposit
-- - -

0.75 M CaC12.2H20, 0 . 5 M CuCl, 0.5 M AgCI, Me2S0

50 no 5 684 82 adherent, smooth (good)
50 no 10 13OOB 80 dendritic (fair)
25 no 5 980 87 adherent, smooth (good)
25 Yes 5 685 57 adherent, smooth (good)
0.75 M MgC12.6H20, 0 . 3 M CuCI, 0.3 M AgCI, Me2NCH0
50 no 5 675 90 adherent, smooth (good)
50 no 10 1150B - -
A Based on weight of silver deposited. Unstable-this is the starting voltage.

Operating Cell Voltage

As predicted, the cell voltage was lowered by increasing the temperature or by
stirring (Table 4). The contribution of the equilibrium potential (E") to the overall
cell voltage is rather small; this implies that correct choice of operating conditions
is important in keeping the cell voltage as low as possible, and therefore minimizing
the electrical energy cost. It was found that the stirring rate had a more pronounced
effect on the electrode potential of the platinum anode than on the silver cathode ; this
suggests that it is the anodic oxidation of CuC1,- which is rate limiting. At the anode
diffusion layer, the transport of CuC1,- to the anode surface is hindered not only by the
buildup of C1- ions but also by the presence of complexes such as CU(M~,SO),~+
which are moving away from the anode.
Recent studies in aqueous C1- solutions have shown that the electrode kinetics of
the Cu2+/CuC12- couple are faster on platinum than on glassy carbon.12 A final
choice of the anode material cannot be made without a more systematic study.
However, we have found that carbon of high surface area polarizes less readily than
bright platinum and may be a more practical choice for a working cell.

l 3 Benari, M. D., Hefter, G. T., and Parker, A. J., Hydvometalluvgy, in press.

Solvation of Ions. Some Applications. V

Ohmic polarization (iRdrop) has been dealt with in the discussion on conductivity
and can be effectively reduced by increasing the temperature or by minimizing the
spacing between anode and cathode.

Current Eficiencies
Electrowinning experiments were carried out with two different electrolyte systems
(Table 4) in order to determine the operating conditions which gave a satisfactory
deposit of silver in terms of adherence, purity, and cathodic current efficiency at a
fixed electrode separation of 3 mm. Current efficiencies ranged from 75 to 85 % in
still solutions but were considerably lower (i.e., below 60%) in stirred electrolytes.
The first experiment in Table 4 gave the most satisfactory silver deposit with a copper
content < 0 . 5 ppm. Current densities above 5 mA cm-2 tended to give dendritic,
non-adherent cathode deposits.
Current efficiencies, based on weight of silver deposited, were never above 90%
and were much lower in stirred electrolytes owing to concurrent leaching of the silver
deposit by anodically generated Cu2+. In a series of experiments with a 50 % electro-
lysed solution it was shown that the chemical dissolution of silver was strongly
dependent on stirring and rather less on temperature (Table 5). From the smooth
surface of the silver deposits it appeared that chemical leaching rather than the reduc-
tion of Cu2+ at the cathode was the major contributor to the low current efficiencies
in stirred solutions.

Table 5. Effects of temperature and stirring on the rate of leaching of

silver by Cu2' in chloride solution
Solvent system: 0.75 M CaC1,.2H20, 0.25 M CuCl, 0.25 M CuC12.2H20,
Me2S0. A current density of 5 mA cm-= corresponds to a theoretical
rate of cathode silver deposition of c. 20 mg cm-2 h-I

Temperature ("C) 25 25 50 50
Stirring no yes no yes
Leaching rate (mg cm-2 h-') 3 25 5 50

Precautions were taken to exclude air from all electrowinning experiments because
of the oxidation of CuC1,- by atmospheric oxygen. This would lead to a lowering
of the Faradaic efficiency and an increase in cell voltage if the CuC1,- concentration
was allowed to decrease sufficiently to allow other anodic processes to take place.
In practice, the proposed cyclic process would take place within sealed leaching and
electrolysis vessels or else under an inert gas atmosphere.

Conclusions
Smooth, adherent, high-purity cathode silver may be recovered by electrolysis of
a dimethyl sulfoxide solution containing 0.75 M CaCl2.2H2O and 0.5 M each of silver
and copper as AgC1,- and CuC1,- complexes. The optimum current density at
which the electrolysis could be carried out in an unstirred solution was found to be
5 mA cm-2 at a temperature of 50°C. Stirring tended to lower the current efficiency
of the electrolysis, and it is proposed that in practice a diaphragm cell be used to
which anolyte and catholyte are kept apart during the electrolysis and then recycled
 S. Jayasekera, J. Avraamides and A. J. Parker

to the leaching stage. Selective stirring of the anolyte would therefore be possible,
which should result in an improvement in the anode kinetics without lowering the
cathode efficiency. Two such cell designs are depicted in Figs 4a and 4b.

c"?+to
leach tank
t

Fig. 4. Schematic diagram.; of t w o prcqmsed elsctron.inning cells

AgC12-/CuCI2-
from leach circuit

It is recognized that the practical current density of our process is low and would
necessitate a large electrode surface area for a reasonable silver throughput, e.g., a
'Swiss roll cell' design. However, the electrolysis stage must be sized to the leaching
stage, and, as yet, we have no data on the kinetics of silver dissolution from actual
residues.
Problems which have not yet been examined are the choice of materials and the
actual construction of a suitable electrowinning cell, and the effects of impurity build-
up in a typical leach-electrowin circuit. More fundamental investigations, such as
the evaluation of Tafel parameters for different electrode materials and a thorough
electrochemical study of the reduction of AgC1,- in dimethyl sulfoxide, need to be
performed for a better understanding to be gained of the electrode processes.

Acknowledgments
We thank Dr D. M. Muir, Dr P. Singh and Mr M. D. Benari for their invaluable
comments and advice, and Mr D. A. Clarke, Mr D. J. Clair and Mr B. Kilpatrick for
technical assistance.

Manuscript received 28 February 1983