hydrometallurgy

ELSEVIER Hydrometallurgy39 (1995) 353-375

Kinetic aspects of galvanic interactions between

minerals during dissolution
P.R. Holmes *, F.K. Crundwell
Department of Chemical Engineering, University of the Witwatersrand, Johannesburg Private Bag 3 Wits 2050,
South Africa
Received 4 April 1995;accepted 29 May 1995

Abstract

A quantitative description of galvanic interactions between sulphide minerals based on thermody-

namic and kinetic parameters has been developed. A voltage balance over the galvanic couple provides
the basis for a mathematical description of the magnitude of the galvanic interaction. The contributions
to the voltage balance include the cell emf of the galvanic couple, kinetic descriptions of the anodic
and cathodic half-reactions, the voltage characteristics of mineral-mineral contacts and the voltage
losses across the solution. The rates of the anodic and cathodic half-reactions were modelled by the
Butler-Volmer equation and the diffusion equation.
The galvanic couples were constructed as rotating ring-disc electrodes so that solution voltage
losses were negligible. Two galvanic couples, copper-pyrite and galena-pyrite, were characterised
by initially determining the thermodynamic and kinetic parameters associated with the anodic and
cathodic half-reactions under different conditions of ferric concentration, electrode rotation rate and
temperature. A potentiostat was used to vary the voltages losses across mineral-mineralcontacts. The
effect that semiconducting properties of minerals have on the magnitude of the galvanic interaction
was described by examining the anodic dissolution of galena under illumination.
The thermodynamic and kinetic parameters were used in the mathematical model to obtain a
prediction of the magnitude of the galvanic interaction. The mathematical model is observed to be in
good agreement with the experimentally measured galvanic currents.

1. I n t r o d u c t i o n

Galvanic interaction occurs when electrically conducting minerals are in contact and are
present in a medium which facilitates charge transfer. The result of galvanic interaction is
to change the rates of the anodic and cathodic half-reactions that occur at the surface of

* Correspondingauthor.

0304-386X/95/$09.50 © 1995Elsevier ScienceB.V. All fights reserved

SSDI O304-386X ( 95 )00041-O
354 P.R. Hohnes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375

char9e transfer

2Fe3 +

pb2+ ~S°
~ 2Fe 2+

mineral contact

Fig.1.Galvanicnteractionbetweengalenaandpyrite.
each mineral. For example, when galena is in contact with pyrite in a ferric nitrate solution,
the rate of dissolution of the galena increases. The reason for this is as follows. When the
galena is not in contact with pyrite the dissolution reaction is coupled to the reduction of
ferric ions, which occurs on the galena surface. When the galena is in contact with the pyrite,
the dissolution reaction is coupled to the reduction of ferric ions which occurs on the pyrite
surface. Because the rate of the reduction of ferric ions is greater on the pyrite surface than
on the galena surface, there is an increase in the rate of dissolution of galena in this system
when galena is in contact with pyrite. This is illustrated in Fig. 1.
Galvanic interactions may occur in many minerals processing systems, especially in
leaching and flotation and in the opinion of Majima and Peters [ 1 ] "The galvanic effect
may be one of the most important electrochemical factors which governs the dissolution
rate of sulphide minerals in hydrometallurgical systems."
Although galvanic interaction is a well-known phenomenon, the exact processes and
mechanisms of this effect are not thoroughly understood in sulphide mineral systems.
Research to describe galvanic interaction in sulphide mineral systems is primarily qualita-
tive. Mehta and Murr [2] examined a number of galvanic couples, including chalcopyrite
and sphalerite in electrical contact with pyrite. The effect that galvanic interaction had on
the rate of bacterial leaching of chalcopyrite and sphalerite was investigated. The effects
that the particle size, the presence of bacteria and the pulp density have on the rate of
leaching of the minerals in contact with pyrite were described qualitatively. It was observed
that as the amount of pyrite in contact with another mineral increases, the rate of leaching
of this mineral increases. Mehta and Murr [2] explained the phenomenon of galvanic
interactions in terms of the rest potential of each mineral with respect to the standard
hydrogen electrode (SHE). The rest potentials of certain sulphide minerals are given in
Table 1. Sulphide minerals with more positive rest potentials (that is more noble minerals,
eg., pyrite 0.63 V vs. SHE), act as cathodes in a galvanic couple while minerals with more
negative rest potentials (that is less noble minerals, e.g., sphalerite - 0.24 V vs. SHE), act
as anodes. The cell emf, which is the magnitude of the difference between the cathodic and
anodic rest potentials, has been used as a measure of the magnitude of galvanic interaction.
This is an approximation since the description of the magnitude of galvanic interaction is
 P.R. Hobnes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375 355

Table 1
Rest potentialsof selected sulphide minerals (Mehta and Murr [2] )

Mineral Chemical formula Ee vs. SHE (V)

Pyrite FeS2 0.63

Chalcopyrite CuFeS2 0.52
Chalcocite Cu2S 0.44
Covellite CuS 0.42
Galena PbS 0.28
Sphalerite ZnS - 0.24

based solely on the thermodynamics of the galvanic cell and neglects the kinetic factors. In
order to fully understand galvanic interactions, the kinetics of the electrode processes must
be considered. For example, Dulrizac and MacDonald [3] observed that the dissolution
rate of chalcopyrite increased in the presence of molybdenite, which has a rest potential of
0.11 W vs. SHE. This is not consistent with the sulphide series presented by Mehta and
Murr [ 2].
Hepel [4] investigated the mechanisms which lead to selective leaching in sulphide
mineral systems and observed that galvanic cell formation between electrically conducting
minerals caused the suppression of the leaching of some sulphides. In order to quantify
galvanic interactions accurately, Hepel [4] concluded that consideration should be given
to both the thermodynamics and kinetics of electrode processes.
Nowak et al. [ 5 ] presented a number of mathematical models which describe the mag-
nitude of galvanic interaction in terms of thermodynamic and kinetic parameters. The
Butler-Volmer expression which describes the relationship between the rate of an
electrochemical reaction and its thermodynamic and kinetic parameters, was used to quantify
the magnitude of galvanic interaction between minerals. However, the mathematical models
are limited in that their applicability only extends to reactions which are controlled by the
reaction at the electrode surface. In addition, factors such as solution voltage losses and
voltage losses across mineral-mineral contacts, which affect the magnitude of galvanic
interaction, were not considered.
Hepel et al. [ 6 ] confirmed the presence of non-linear current-voltage characteristics at
the mineral-mineral contacts in the galena-chalcopyrite and chalcopyrite-pyrite galvanic
couples. It was concluded that the voltage loss across the mineral-mineral contacts may be
of sufficient magnitude to affect the operation of the galvanic cell.
The objectives of this research are therefore to provide a general basis for describing the
magnitude of galvanic interaction quantitatively based on thermodynamics and kinetics of
electrode processes. The solution voltage loss and mineral-mineral contact voltage loss are
included in the quantitative description of galvanic interaction. An important aspect of this
research is to experimentally verify the proposed mathematical model.

2. Chemistry

Two galvanic couples, namely copper-pyrite and galena-pyrite, were studied. The chem-
ical reactions in each of the galvanic couples are presented in this section.
356 P.R. Holmes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375

2.1. The copper-pyrite galvanic couple

The copper-pyrite galvanic couple was studied in acidified ferric sulphate solution. In
this couple, the pyrite forms the cathode and the copper forms the anode. The cathodic
reaction at the pyrite surface is the reduction of ferric ions to ferrous ions:
Fe 3+ + e - --*Fe 2+ (1)

The anodic reactions in the galvanic couple are the dissolution of copper and the reduction
of ferric ions on the copper electrode. The half-reaction describing the anodic dissolution
of copper is:
C u ~ C u 2+ + 2 e - (2)
Mattsson and Bockris [7] observed that the anodic dissolution of copper is a dual-step
process. In the first step copper is oxidised rapidly to cuprous ions. The second step, which
is the rate-determining reaction, consists of the oxidation of cuprous ions to cupric ions:
fast
Cu(s) ~ C u + + e - (3)
slow
Cu + ~ Cu 2+ + e - (4)

The anodic dissolution of copper was studied in sodium sulphate solutions and ferric
sulphate solutions. The reasons for this were twofold. Firstly, the amount of ferric reduced
at the copper anode can be determined by comparing the rate of copper dissolution in ferric
sulphate solution with the rate of copper dissolution in sodium sulphate solution. Secondly,
the study in sodium sulphate solution allowed a comparison of the kinetic parameters
obtained in this research with those of other researchers. The reaction describing the reduc-
tion of ferric ions on copper is:
Cu + 2Fe 3+ ~ C u 2+ + 2 F e 2+ (5)

2.2. The galena-pyrite galvanic couple

The galena-pyrite galvanic couple was studied in ferric nitrate solution. In this couple,
the pyrite forms the cathode and the galena forms the anode. The reduction of ferric ions is
the reaction which occurs at the cathode, while the reactions at the anode are the dissolution
of the galena and the reduction of ferric ions. The chemistry associated with the reduction
of ferric ions on the pyrite cathode has been discussed.
The anodic dissolution of galena results in the formation of plumbous ions, Pb z +, and a
solid sulphur film:
PbS ~ Pb 2÷ + SO+ 2e- (6)
Paul et al. [ 8 ] proposed that the dissolution of galena is a dual process involving a S -
intermediate:
PbS ~ P b 2÷ + S - + e - (7)
S- ~S°+e - (8)
 P.R. Holmes, F.K. Crundwell/ Hydrometallurgy39 (1995) 353-375 357

Furthermore, Paul et al. [ 8] observed that, as the sulphur film thickens, it becomes more
difficult for plumbous ions to diffuse through the pores and channels in the sulphur film.
This causes a high concentration of plumbous ions at the electrode surface which, in order
to maintain the charge balance, lowers the concentration of protons. This results in a localised
increase in pH where it is thermodynamically possible for the sulphur film to oxidise to
thiosulphate"

2S ° + 3H20 -~ $2032- + 6H + + 4e - (9)

Johnson et al. [9] observed that the dissolution of galena is controlled by the reaction at
the surface of the galena electrode.
The dissolution of galena was studied in sodium nitrate and ferric nitrate solutions. The
difference between the rates of galena dissolution in sodium nitrate and ferric nitrate solu-
tions yielded the rate of ferric reduction on galena. The reaction describing the reduction of
ferric ions on galena is:
PbS + 2Fe 3+ --* Pb 2 + + 2Fe 2+ + S o (10)

3. Mathematical modelling of galvanic interaction

3.1. Electrochemical theory o f galvanic interaction

A description of galvanic interaction based on the kinetics of the electrochemical reactions

occurring in the galena-pyrite couple is shown in Fig. 2.
In the absence of galvanic coupling the rate of galena dissolution is determined by the
condition that the anodic current, Ial, is equal to the cathodic current, Icl, at the corrosion/
mixed potential, Eco,.. However, pyrite, when coupled to galena, provides a more favourable
site for the reduction of ferric ions. As a result, the coupling of galena and pyrite causes the
corrosion potential to shift to the galvanic potential, Eg. This results in the anodic current

PbS - >pb2+ +S°+2e -

/

[a2

Eea Eco r E9
Icl Eec Elec%rode
PobenLlal

2Fe3++2e-->2Fe 2+ (PbS)

2Fe3++2e-->2Fe 2+ [FeS 2 )

Fig. 2. Electrochemicaltheory of galvanic interactionbetweengalenaand pyrite.

358 P.R. Hobnes, F.K. Crundwell / Hydrometallurgy 39 (1995)353-375

increasing from la~ to Iaz and the cathodic current increasing from I~1 to Ic2-At the galvanic
potential, the sum of the partial currents at the anode is equal to the sum of the partial
currents at the cathode. The galvanic current is equal to either of these two quantities. Fig.
2 illustrates that the kinetics of the anodic and cathodic reactions in a galvanic couple
primarily determine the magnitude of the galvanic current flowing through the couple.

3.2. Voltage balance over the galvanic cell

The basis of the electrochemical model of galvanic interaction is contained in Kirchoff' s

Voltage Law (Hine [ 10] ). The law equates the sum of the voltage gains to the sum of the
voltage losses in a closed electrical circuit. The following four factors, which affect the
magnitude of the galvanic interaction, can be identified:
l. the magnitude of the difference between the cathodic and anodic rest potentials, referred
to as the cell emf;
2. the magnitude of the overpotential at each electrode, determined by the rates of the
anodic and cathodic reactions in the galvanic couple;
3. the magnitude of the resistance between the two electrodes. The nature of the electrical
contact between the two electrodes in a galvanic couple may be ohmic or rectifying;
4. the magnitude of the voltage drop across the solution. The conductivity of the solution
determines how readily charge is transferred through the solution.

The existence of voltage drops across the mineral-mineral contact and the solution results
in the electrode potentials of the anode and cathode occurring at Ea and E¢, respectively.
This is shown in Fig. 3. As the voltage losses across the mineral-mineral contact and
solution increase the anodic and cathodic overpotentials decrease which results in a further
decrease in galvanic current. The difference between the cathodic rest potential and the
anodic rest potential is equal to the sum of the absolute values of the electrode overpotentials,
the solution voltage loss and the mineral-mineral contact voltage loss:
E~,c- E~.a= Cell emf = I r/c I + I r/a L+ IVsolutionI "1- [VcontactI ( 1 1)

PbS - >pb2+ +S°+2e

I9 - I ~ ~ r)c
E ea . . ~ . ~ TEa Ec o

Da VconLacL V ~ Eec

/
E_lecLpode
_ PoLenLlal

j//2Fe:3++2e - _>2Fe2 + (FeS 2)

Fig. 3. The influence of mineral-mineral contact and solution voltage losses on the magnitude of galvanic
interaction.
 P.R. Holmes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375 359

where:
Ee,~ = the rest potential of the half-reaction at the cathode;
Ee,a = the rest potential of the half-reaction at the anode;
"0c = E~ - Ee,~ = the cathodic overpotential;
r/a= E a - Ee, a = the anodic overpotential;
Vsotution = the solution voltage loss;
Vcontact = voltage loss across mineral-mineral contact.

Eq. ( 11 ) is valid for a galvanic couple in which there are no cathodic processes on the
anode and no anodic processes on the cathode. The voltage balance for a galvanic couple
in which anodic and cathodic processes occur on both the anode and cathode is given by
Eq. (12):

E~.... - E ~ .... = Irl'~l + Ir/'al + IVsoluao,I + IV~o,~ctl (12)

where:
E~or,c = the corrosion potential of the cathode;
E~.... = the corrosion potential of the anode;

n'~= Ec- Ecor.c;

n;,= Ea- Ecor,..
Each of the voltages on the right hand sides of Eqs. (11) and (12) can be related to the
galvanic current flowing through the couple.

3.3. Kinetics of electrode reactions

The Butler-Volmer equation describes the rate of a half-reaction which is controlled by

the transfer of charge, and is given by:

i= i"{exp[(1-~RT)Fr/1-J
ex~-~)} (13)

where:
i = current density;
io = exchange current density;
R = universal gas constant;
T = temperature;
c~ = charge transfer coefficient;
F = Faraday's constant.

For a thorough description of the thermodynamics and kinetics of electrode processes

refer to Bockris and Reddy [ 11] and Bard and Faulkner [ 12].
A reaction which is limited by mass transfer and electrochemical processes is termed a
mixed-controlled reaction. In the derivation of an expression to describe mixed-control
behaviour, it is assumed that, near the electrode surface diffusion is the only mode of mass
360 P.R. Holmes, F.K. Crundwell / HydrometaUurgy 39 (1995)353-375

transport. For example, consider the reduction of ferric ions at an electrode. The diffusion
of ferric ions to the surface of the electrode is described, at steady state, by:
FD
i = - ~ ( [Fe 3+ ]~-- [Fe 3+ ]b) (14)

where:
D = diffusion coefficient;
6 = diffusion film thickness;
[Fe3+]s = the concentration of ferric ions at the electrode surface;
[Fe3+]b = the concentration of ferric ions in the bulk solution.

The diffusion equation is combined with the Butler-Volmer equation to obtain Eq. (15)
which relates the cathodic overpotential to the thermodynamic and kinetic parameters of
the cathodic process. It has been assumed in the derivation that no anodic processes occur
on the cathode. This is because the potential was sufficiently cathodic in this research to
disregard anodic processes on the cathode. The entire derivation of the mixed-control
equation was presented by Li et al. [ 13 ] :

FI • /]
In[ ~,C(A )]
RT ll,c A~
(15)
ilx + 1

where:
a¢ = charge transfer coefficient for the half-reaction at the cathode;
io,c = exchange current density for the half-reaction at the cathode;
i~,~ = limiting current density for the half-reaction at the cathode;
Ac = the surface area of the cathode.

3.4. Overall mathematical expression f o r galvanic interaction

The mathematical model of galvanic interaction, for a galvanic cell in which there is only
anodic reaction on the anode which is controlled by the rate of the electrochemical reaction
and only one reaction on the cathode which is controlled by both reaction and mass transfer,
is given by Eq. (16). It has been assumed that an ohmic relationship exists at the mineral-
mineral contact and across the solution. The model describes the magnitude of galvanic
interaction in terms of the thermodynamic and kinetic parameters of the anodic and cathodic
electrode processes and the voltage losses across the mineral-mineral contact and solution:

tl,c Ac RT [ I ~ , ,
- In/ +--lnl---zt--I+IgRcomct+IgRsol,ao. (16)
, e,--- cqF \io.dtJ
• a~F /i,c(/.~. +1
L ' Vtc/o c
 P.R. Holmes, F.K. Crundwell/ Hydrometallurgy 39 (1995) 353-375 361

where:
Ig = galvanic current;
R'co°~ct = resistance across the mineral-mineral contact;
R'sol,~o, = solution resistance.

Eq. (16) can be derived for various other situations depending on the rate controlling
processes at the anode and cathode and current-voltage characteristics of mineral-mineral
contacts.

4. Experimental

4.1. Description of reagents

The copper used in the copper-pyrite galvanic couple was 99.9% pure. The pyrite had a
polycrystalline structure and was obtained from Navajun, Spain. The galena and pyrite used
in the galena-pyrite couple were obtained from single crystals from Black Mountain, South
Africa and Navajun, Spain, respectively. The types of conduction that the mineral samples
exhibited were determined by a thermoelectric effect measurement and energy dispersive
X-ray analysis (EDXA). The thermoelectric measurement, also used by Springer [ 14],
involved placing the two probes of a voltmeter on opposite sides of the surface of the mineral
electrode. One side of the mineral was heated and the variation in the voltage output
monitored. The direction in which the voltage increases determines the type of conductance
of the mineral electrode. Both pyrite electrodes and galena were observed to be n-type
conductors. Further confirmation of n-type conduction was obtained from EDXA measure-
ments by determining the quantities of species present on the surfaces of solid samples. The
results indicated that galena was rich in lead and the pyrite electrodes were rich in iron,
suggesting that both these minerals are n-type semiconductors.
Analytical grade ferric sulphate, ferric nitrate, sodium sulphate and sodium nitrate crystals
were used in the experimental investigation. Sulphuric acid (98%) and nitric acid (55%)
were used to obtain the desired pH in each experiment. Doubly distilled water was used to
prepare all solutions.

4.2. Apparatus

The three-electrode cell was used to characterise the electrochemical kinetics of the anodic
and cathodic half-reactions. The cell consists of a central rotating working electrode on
which the half-reaction of interest occurs. A platinum electrode was used as a counter
electrode to complete the electrical circuit and thus, under steady-state conditions, ensure
charge neutrality. A Schott-Gerade saturated calomel electrode (SCE) was used as a ref-
erence electrode. A CV27 BAS potentiostat was used to obtain the polarisation data for the
half-reactions.
For the galvanic cell, an electrode system was constructed to minimise the voltage drop
across the solution. This was achieved by a rotating ring-disc electrode [ 15 ]. The electrodes
of the galvanic cell were connected through the potentiostat. This is illustrated in Fig. 4.
362 P.R. Hohnes, F.K. Crundwell / HydrometaUurgy 39 (1995) 353-375

POTENTIOSTAT
WE : w o r k i n 9 e l e c L r o d e
CE : c o u n L e r elecLrode
RE : r e f e r e n c e electrode
Vr : tin 9 volLage
Vd : d i s c voltage
V c : cell voltage
19 : 9 a l v a n i c currenL

~ rin 9
disc

Fig. 4. Electrical circuit configuration used to investigate the galvanic couples.

The anode of the cell was connected as the working electrode, while the cathode was
connected as the counter electrode. The potentiostat was used to vary the load of the galvanic
circuit, representing a variation in the resistance of the mineral-mineral contact. This is
illustrated in Fig. 5. A thorough description of the electrical circuit configuration and setup
is given by Holmes [ 16].
The copper-pyrite rotating ring-disc electrode consisted of a copper ring surrounding a
disc of pyrite. The copper ring had a surface area of 0.34 cm 2 while the pyrite disc had a
surface area of 0.78 cm 2. The galena-pyrite rotating ring-disc electrode consisted of a ring
of pyrite surrounding a disc of galena. The surface area of the pyrite ring was 1.1 cm 2 and
the surface area of the galena disc was 0.76 cm 2. Electrical contact to each electrode was
made by using a silver impregnated glue to attach a brass strip to the back of each electrode.
A contact wire was then soldered to each of the brass strips.
The electrochemical cell had a jacket into which water, at the desired temperature, was
fed from a Thermomix 1460 Braun temperature control bath. The rotation of the working
electrode was controlled by a Pine AS2RE speed control assembly. The polarisation data
were recorded by a 3421A Hewlett Packard Data Acquisition Control Unit. A UNOMAT
LX500GS lightmeter was used to illuminate the surface of galena in the study of the effect
of semiconducting properties on the rate of galena dissolution.

2e-
.

2ro pb 2+

2Fe 2+ L
PUp Le Galena
FeS 2 PbS

Fig. 5. The external load representing a variation in the resistance of the mineral-mineral contact.
 P.R. Holmes, F.K. Crundwell/ Hydrometallurgy39 (1995)353-375 363

4.3. Electrode and solution preparation

The electrodes were prepared by polishing with a 600 and 1200 grade silicon carbide
paper. The electrodes were then rinsed in distilled water and washed in acetone to remove
any species which remained on the electrode surfaces after polishing. The electrodes were
further washed and polished with a 5-micron alumina polishing compound. The polishing
compound was removed by distilled water before the electrodes were studied.
Solutions were prepared by placing the required amount of ferric sulphate or ferric nitrate,
obtained from 1 M standard solutions, in a 250-ml volumetric flask. The required amount
of sulphuric acid or nitric acid was placed in the flask. The solution was made up to 250 ml
by adding doubly distilled water. The hydrogen ion concentration in all solutions was 0.5
M. Nitrogen was sparged into all solutions for approximately ten minutes to remove dis-
solved oxygen. The minor oxygen impurity in the nitrogen from the gas cylinder was
removed by passing the gas mixture through a scrubber of copper pellets in sulphuric acid.

5. Results and discussion

The kinetics of the half-reactions in each couple are presented and discussed. Then the
electrochemical action and the model prediction of galvanic interaction of each couple are
discussed.

5.1. The copper-pyrite galvanic couple

Reactions at the copper anode

The rate of copper dissolution does not vary with an increase in the rate of electrode
rotation in sodium sulphate solutions which implies that the reaction is controlled by the
reaction at the surface. Mattsson and Bockris [7] observed that the anodic dissolution of
copper is controlled by the electrochemical reaction at the surface of copper. The value of
the anodic charge transfer coefficient obtained in sodium sulphate solutions of between 1.28
and 1.44 compares favourably with that obtained by Mattsson and Bockris [7] of 1.35. The
anodic charge-transfer coefficient has a value greater than unity suggesting that copper
dissolution occurs as a dual-step mechanism. The anodic exchange current density for copper
dissolution cannot be compared to the exchange current densities of other researchers since
a different solution was used in this study.
Fig. 6 illustrates that the presence of ferric ions causes the overall rate of the anodic
process to be very weakly dependent on the rate of rotation of the electrode. As the rate of
rotation is increased there is a slight increase in the rate of dissolution of copper. This can
probably be attributed to the catalytic effect of ferric ions oxidising the cuprous ion inter-
mediate:
Cu + + F e 3+ ---~Cu 2+ + F e 2+ (17)

The rate of copper dissolution was observed to increase with increases in temperature
whilst increases in ferric concentration had a minimal effect on the rate of the reaction.
364 P.R. Holmes, F.K. CrundweU/ Hydrometallurgy 39 (1995) 353-375

o
x x 0.15 V vs SCE
x
O ........... ~ O . 3 0 V vs SCE
1,60 - + ............ + O . 4 5 V vs SCE
E
u

9e_____~ X x
1.20 -

~,
g
0.80 -
c
t..

<_)
0.40 (3~ . . . . . . . . . . . . . . . . . . . . . . . . --O ......... -O .............. ---O- ................................... (9
_t2
"o
o 4- ....................... -t- ............................. + ....................... -f- ................................... +

0.00 I I t I I I I I
0.i4 0.16 0.16 0.20 0.22 0.24 0.26 0.28 o.ao 0.32

I/Rotation Rate 0"5 (rpm -0.5) x 101

Fig. 6. The dependence of copper dissolution on the rate of electrode rotation. Conditions: 298 K, 0.2 M Fe3+,
0.5 M H + , scan rate 1 mV s- 1.

The kinetic expression for the dissolution of copper in ferric solutions is derived as
follows• It is assumed that the first term of the Butler-Volmer equation describes the rate
of copper dissolution:

Similarly, it is assumed that the second term of the Butler-Volmer equation describes
the rate of reduction of ferric ions on copper:

The net anodic current is given by the sum of the anodic and cathodic currents on the
anode:

• I . (
i=to,aeXp~--~Ta J -- to,cexp~ -- - ~ - r / e ) (20)

Eq. ( 2 0 ) cannot be rearranged to express the overpotential in terms of current. However,

the rate of ferric reduction is small relative to the rate of copper dissolution. The difference
between the two exponentials can be approximated by a single exponential expression• Eq.
(21 ) relates the net current at the anode to the kinetic parameters associated with the overall
anodic process:

,
r/a = ' ~
RTIn ( .-;---'7-.
I (21)
otaF ~to,aAa]
where:
 P.R. Holmes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375 365

• t
lo,a = the exchange current density for the overall anodic process;
!
0/a = the charge transfer coefficient for the overall anodic process;
I = current;
Aa = the surface area of the anode•

Reactions at the pyrite cathode

The effect of the rate of rotation of the electrode is shown, at high overpotentials, in Fig.
7. As the rate of rotation of the electrode is increased, the rate of the reduction of ferric ions
on pyrite at high cathodic overpotentials increases. At low cathodic overpotentials, near the
rest potential of the ferric reduction reaction, the rotation rate was observed to exert no
influence on the reaction rate since the reaction is electrochemically controlled. It was also
observed that increases in ferric concentration and temperature increased the rate of reduc-
tion of ferric ions on pyrite•
The kinetic expression for the reduction of ferric ions on pyrite is given by Eq. (22). It
was derived in a manner similar to that ofEq. (15). However, owing to the oxidative nature
of ferric ions one would expect that some dissolution of the pyrite cathode would occur.
The oxidation of pyrite by ferric ions was observed to be negligible. However, the kinetic
parameters for the cathodic process are expressed in terms of the overall process occurring
on the cathode:

, RT F "'~-A'-~
'Tc=vln| F?--
164-:-;-+ t
L. " t,~cto c
')] (22)

where:

"'......
E
4 .......... 1522 rpm
<I
E

C~

L
L

U 2
-O
o

I I I I I I I
0•00 o.2s o•so O.TS ~.o0 ~.2s ~.so ~.7s
ElecLrode PoLential vs SCE (VolEs) x 101

Fig. 7. The dependence of the rate of ferric reduction on pyrite, at high cathodic overpotentials, on electrode
rotation. Conditions: 298 K, 0.2 M F e 3+ , 0.5 M H +, scan rate 1 mV s -1.
366 P.R. Holmes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375

O~c r = charge transfer coefficient for the overall cathodic process;

io.cr = exchange current density for the overall cathodic process;
ilx = limiting current density for the overall cathodic process.

Formation of the copper-pyrite cell

The effect of the potential drop across the external load on the galvanic current between
copper and pyrite is shown in Fig. 8. The external load, or the cell voltage, is varied by the
potentiostat and represents the voltage drop between the mineral electrodes. The effect of
the concentration of ferric ions on the galvanic cell is shown in Fig. 8.
An increase in ferric concentration results in an increase in the galvanic potential of the
copper-pyrite couple. Fig. 9 illustrates that the relationship between the galvanic potential
and the concentration of ferric ions in the solution is linear. Two factors contribute to the
increase in galvanic potential with increasing ferric concentration. The first of these is the
variation in the anodic and cathodic rest or corrosion potentials associated with increases
in ferric concentration. The anodic and cathodic rest or corrosion potentials become more
positive with increasing concentration of ferric ions and hence the galvanic potential will
move to more positive values. The second contributing factor to the increase in galvanic
potential is the variation in the kinetic parameters of the anodic and cathodic half-reactions.
Increases in ferric concentration increase the exchange current density and limiting current
densities. The galvanic potential occurs where the currents at the anodic mineral and cathodic
mineral are equivalent. Hence, for the galvanic potential to shift in a positive direction, the
increases in ferric concentration must have a more pronounced effect on the rate of ferric
reduction than on the rate of copper dissolution.
Model prediction of galvanic interaction in the copper-pyrite cell
By substituting Eqs. (21) and (22) into Eq. (12) and assuming that the solution voltage
losses are negligible, one obtains Eq. (23) which is the mathematical model describing the
galvanic interaction between copper and pyrite:

4.00

""-, x x 0.1M Fe 3 +
I .. a ........ @ ........... e 0 . 2 6 1 Fe 3+
3.00 ...... ~ . '-.,,..~ + ............ + 0 . 3 P 1 Fe 3+

,~
2.00~ , ~ ~ "0..:: ....
.....~ . ,
.........
"-~
" " ~ - 4., "''.-,.
",s,.::: -~.
z~..................~ 0 . 6 M Fe 3+

0.00 "l I
0.00 -0,50 -I.00 -I,50 -2.00 -2.50 -3,00 -3.50 -4.00 "4.50

Cell VolLage (VolLs] x 101

Fig. 8. The effect of ferric concentration on the magnitude of galvanic interaction in the copper-pyrite couple.
Conditions: 298 K, 2003 rpm, 0.5 M H ÷.
 P.R. Holmes, F.K. Crundwell/ HydrometaUurgy39 (1995) 353-375 367

1.40 -
X

t ~ a
1.30 -

-- 1.20 "
rO

g
~,J 1.10 -
O
(3-

C 1.00 -
rg
> [3
ro

0.90 I I I I I I I I
0.00 0.75 I.SO 2.25 3.00 3.75 4.50 S.25 6.00

ConcenLraLion OF Fe 3+ (mol/l) x I01

Fig. 9. The dependence of galvanic potential on ferric concentration. Conditions: 298 K, 2003 rpm, 0.5 M H + .

RT r/
E ...... - E c .... = --;--=In -i -L-c- - ~ c )l+....7.:ln(/j.~,/_t_VloaagZ
[ (23)
• ' acE | {/...~ OZaV \toaAJ
/i, cl~., +1

where V l o a d = the load of the galvanic circuit, i.e., the variation in the voltage across the
mineral-mineral contact;
The model equation is valid for a galvanic cell in which anodic and cathodic processes
occur on both the anode and cathode. In addition, the anodic process is controlled by the
rate of the electrochemical reaction and the cathodic process is controlled by both reaction
and mass transfer.
The cathodic corrosion potential, the anodic corrosion potential and the voltage applied
between the minerals were determined by experimental measurement. Potentiostatic exper-
iments were used to generate the polarisation data for the anodic and cathodic half-reactions.
The polarisation data for the dissolution of copper, were hereafter regressed upon with Eq.
(21 ) to determine the kinetic parameters associated with this reaction. Similarly, the polar-
isation data for the reduction of ferric ions on pyrite were regressed upon, with Eq. (22),

Table 2
Kinetic parameters used in the galvanic model equation

Parameters E~,,~ io' a' il'

(V) (Am -2) (Am -2)

Cu-FeS2 (anode) 0.073 104 0.94 -

Cu-FeS2 (cathode) 0.54 13 0.13 128
PbS-FeS2 (anode) 0.25 2 0.81 -
PbS-FeS2 (cathode) 0.57 16 0.17 97
368 P.R. Holmes, F.K. Crundwell / HydrometaUurgy 39 (1995) 353-375

I O Measured Cu-FeS 2
_ ~ -- PredicLed Cu'FeS2
4.00 I~ ~ O P1. . . . . . d PbS-FeS 2

,.,~.

¢.D 2.00 """,~

£)

>~ "G,, ""-. D

-o......... ---2
0

o.oo I I I I I I I
0.00 " 0.50 - 1.00 - 1.50 - 2.00 - 2.50 - 3.00 -3.50
Cell VolLege (Volts) x 101

Fig. 10. Model prediction of galvanic interaction in the copper-pyrite and galena-pyrite couples. Conditions: (i)
Cu-FeS2:318 K, 2003 rpm, 0.2 M F e 3÷, 0.5 M H + . (ii) PbS-FeS2:308 K, 1041 rpm, 0.2 M F e 3+, 0.5 M H ÷.

to obtain the kinetic parameters associated with this reaction. The kinetic parameters for the
dissolution of copper and reduction of ferric ions on pyrite are listed in Table 2.
The regressed kinetic parameters along with the cathodic corrosion potential, anodic
corrosion potential and voltage drop across the mineral-mineral contact were substituted
into the galvanic model, Eq. (23). From Eq. (23), the galvanic current, Ig, can be determined
as a function of the load of the galvanic cell, V~oad.This equation was solved numerically,
using a Regula-Falsi iteration technique. The comparison between the model prediction
and experimentally measured galvanic currents is illustrated in Fig. 10.
Fig. 10 illustrates the good correspondence between the experimentally measured gal-
vanic currents and those predicted by the galvanic model equation. The differences that are
present can probably be attributed to the geometry of the rotating ring-disc electrode which
results in the ferric concentration at the mineral discs being slightly different than the ferric
concentration at the rings.

5.2. The galena-pyrite galvanic couple

Reactions at the galena anode

Fig. 11 shows that the rate of the dissolution of galena is independent of the rate of
electrode rotation in sodium nitrate solutions. Paul et al. [8] proposed that the peak at
approximately 0.48 V vs. SCE corresponds to the oxidation of the sulphur film, which is
formed on the galena surface, to thiosulphate. The effect of temperature on the rate of
dissolution of galena was pronounced. The Arrhenius plot for this reaction is shown in Fig.
12. The apparent activation energy for the dissolution of galena was observed to be 72
kJ mol- 1 at an electrode potential of 0.45 V vs. SCE. The magnitude of the activation
energy confirms that the dissolution of galena is controlled by the rate of the reaction at the
electrode surface. Johnson et al. [ 9] observed an apparent activation energy of 52 kJ mol-
at an electrode potential of 0.38 V vs. SCE.
 P.R. Holmes, F.K. CrundweU / Hydrometallurgy 39 (1995) 353-375 369

E - - S61 rpm
L)
........... 801 rpm • /
16.0 -
............1 0 4 1 r'pm / /

09
C
12.0 - //i//-
8.00 -

L
(--

4.00 -

._u

C
<I
o.oo -0,30
I
-0.15
I
o.oo
i t--"3-
o.ws 0.30 o.4s
I o.6o
I
0.75

ElecLrode PoLenLial vs SCE (VolLs)

Fig. 11. The dependence of galena dissolution rate on the rate of electrode rotation. Conditions: 298 K, 0.6 M
NaNO 3, 0.5 M H + , scan rate 1 mV s -1.

Fig. 13 shows the effect of illumination on the rate of dissolution of galena. Koch [ 17]
proposed that illumination would not affect the dissolution of n and p-type pyrite, n-type
galena and n-type chalcopyrite, due to the small band gaps of these minerals. The results
obtained in this research contrast with the observations of Koch [17]. Paul et al. [8]
observed that the anodic current for galena dissolution increased by a factor of 3 to 7,
between electrode potentials of 0.20 and 0.35 V vs. SCE, when the surface of galena was
illuminated.
The effect of illumination is explained in terms of the band structure theory of semicon-
ductors as follows. The electronic structure of the galena electrode consists of the valence

E
tJ

~D
.o

E:3

O
L
i0_2 -

T3 8

~ ' I I I I I I I
0.30 0.31 0.31 0.32 0.32 0.33 0.33 0,34

TemperaLure " 1 (K - I) x 10 2

Fig. 12. Determination of the apparent activation energy for galena dissolution. Conditions: 0.6 M NaNO3, 0.5 M
H +, 1041 rpm, scan rate 1 m V s -~.
370 P.R. Hohnes, F.K. Crundwell / Hydrometallurgy 39 (1995) 353-375

od 1008~
E
<0 6

4
E

2
2
10-1 e •
a - Da
*
•. - ............. IlluminaLed
4 "

(_
u 22 "

10-2 s --
(9
"(:3
e
6
rl ...........I 1 I
<J: 4

0.00 0.80 1.60 2,40 3.20 4.00 4.80 5.60

OverpoLenLial (Volt, s) x lO 1

Fig. 13. Tafel plot of the effect of illuminationon the rateof galena dissolution. Conditions: 298 K, 0.6 M NaNO3,
0.5 M H ÷ , 1041 rpm, scan rate 1 mV s- ~.

band, associated with S 2 - anions, and the conduction band, associated with Pb 2÷ cations,
separated by the band gap (Fig. 14a). As the surface of galena is illuminated by light of
greater energy than the band gap, electrons are excited from the valence band into the
conduction band where they are transferred to the external circuit (Fig. 14b). Two positive
holes left in the valence band react with a sulphur anion to form sulphur on the surface of
the electrode, and, at the same time a lead ion moves from the lattice structure into the
solution (Fig. 14c). The two reactions are given by Eq. ( 2 4 ) and Eq. ( 2 5 ) , respectively:

SZa~i~e-I- 2h + --->S ° (24)

pl.,2+ _> 2+
Ulattice Pbaq. . . . . (25)

Paul et al. [ 8 ] observed that at electrode potentials between 0.25 and 0.35 V vs. SCE the
Tafel slopes varied between 46 and 84 m V decade- ]. Furthermore Tafel slopes of 88 to

Energ~ Ener9~ Ener9~

c o n d u c t i o n band p b 2+ pb 2+,
pb 2+ pb 2+ 2e ",i------~ Pb 2+ p b 2 + - i. p b 2+
aq

I light
band ~olution
I
9ap i /
I,/
1

S2 - S2" 2h ÷ 2h++ S2- ]S °

valence band
S2 - S2 - S2 "

a b c
Fig. 14. Stages in the dissolution of galena underillumination.
 P.R. Holmes, F.K. CrundweU / Hydrometallurgy 39 (1995) 353-375 371

O'4
E
~J

16.0 -

E
:7)

12.0 -

4.00 -

ooo I I I I I I I
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

ConcenLraLion Of" Fe 3+ (mol/I) x 101

Fig. 15. Determination of the diffusion coefficient for ferric reduction on pyrite. Conditions: 298 K, 1041 rpm,
0 . 5 M H ~.

I 13 mV decade ~ were observed at electrode potentials between 0.35 and 0.45 V vs. SCE.
Paramguru et al. [ 18] observed Tafel slopes of 120 mV decade -~. The Tafel slopes,
obtained in this study, for the dissolution of galena in sodium nitrate solution ranged from
75 to 130 mV decade- ~ between electrode potentials of 0.25 and 0.40 V vs. SCE. A
comparison of the exchange current densities cannot be made due to the use of a different
solution in this study.
The rate of galena dissolution in ferric nitrate solutions increased as the temperature was
increased. Owing to the small amount of ferric that was reduced on the galena electrode
and the surface and lattice effects associated with the galena electrode, the exact amount of
ferric reduced was difficult to determine. The kinetic model describing the rate of dissolution
of galena in ferric nitrate solutions is given by Eq. (21).

Reactions at the pyrite cathode

The rate of reduction of ferric ions on pyrite was observed to increase with increases in
ferric concentration, rate of electrode rotation and temperature. The increase in the limiting
current density with increasing'concentration of ferric ions is shown in Fig. 15. The slope
of this curve decreases with increasing ferric ion concentration. This suggests that the
diffusion coefficient is dependent on the concentration of ferric ions. Madsen [ 19] observed
a similar phenomenon when measuring the diffusion coefficients of ferric ions in sulphate
solutions by derivative chronoamperometry. The diffusion coefficient for ferric ion in 0.2
M ferric was determined to be 5.18 X 10-6 cm 2 s - l , which compares favourably to the
value of 5.30 x 10-6 cm 2 S- 1 obtained by Madsen [ 19 ] in 0.226 M ferric solution. The rate
of ferric reduction on pyrite is described by Eq. (22).

Formation of the galena-pyrite cell

The galvanic potential of the galena-pyrite galvanic couple in this study occurred at
electrode potentials of approximately 0.30 V vs. SCE. The only significant reactions in the
couple are therefore the anodic dissolution of galena and the reduction of ferric ions on
372 P.R. Hohnes,F.K. Crundwell/ Hydrometallurgy39 (1995)353-375

~ 3"2°t o o 1282 rpm

~:~.... ~ ............"1763 rpm
c 2.40-'- ",.~. ~,

(.D 1,60 -
u

>D 0.80-
~~,.,,.,~..

0.00 I I I I ~ o I ..........~1 I
0.00 -0.50 -L00 "1.50 -2.00 -2.50 °3.00 -3.50 - 4,00
Celt VolLage (Volts3 >< 101

Fig. 16. The effectof the rate of electroderotationon the magnitudeof galvanicinteractionin the galena--pyrite
couple. Conditions:298 K, 0.2 M Fe3÷, 0.5 M H÷.

galena and pyrite. If a larger pyrite electrode or a more noble cathode is used so that the
galvanic potential moves into the region where the oxidation of the sulphur film and the
passivation of the galena surface are important reactions, these reactions will then play an
important role in the action of the galvanic couple. Fig. 16 illustrates the effect of the rate
of electrode rotation on galvanic current. At low cell voltages, which correspond to high
cathodic overpotentials, the galvanic current is increased by a factor of 1.34 as the rotation
rate is increased from 1282 to 1763 rpm. At high cell voltages, which correspond to electrode
potentials near the rest potential, the effect of rotation becomes less pronounced. However,
one would expect this effect to disappear at high cell voltages since the reactions occurring
in the galvanic couple are both electrochemically controlled.
Illuminating the surface of the galena-pyrite couple increases the galvanic current of the
cell. The illumination effect is known to effect the dissolution rate of galena, as discussed
previously. Mishra and Osseo-Asare [ 20] note that illumination increases the anodic dis-
solution rate of n-type pyrite. It may therefore be possible, owing to the semiconducting
properties of pyrite, that illumination influences the rate at which ferric ions are reduced on
pyrite as well as the anodic dissolution of galena.

Model prediction of galvanic interaction in the galena-pyrite cell

Eq. (23) was used to predict the galvanic currents in the galena-pyrite couple. The kinetic
parameters, for the anodic dissolution of galena and the reduction of ferric ions on pyrite,
used in the galvanic model equation to obtain the predicted galvanic currents illustrated in
Fig. 10, are listed in Table 2. Fig. 10 illustrates the excellent correspondence between the
experimentally measured galvanic currents and those predicted by the galvanic model
equation. The minor differences that are present can probably be attributed to the surface
and lattice effects inherent in the mineral electrodes. These surface and lattice effects lead
to variations in the kinetic parameters ( [21-26] ).
 P.R. Holmes, F.K. CrundweU / Hydrometallurgy 39 (1995) 353-375 373

6. Conclusions

A review of the literature revealed that galvanic interactions between sulphide minerals
are generally described qualitatively. The magnitude of the galvanic interaction is generally
related to the difference bbetween the cathodic and anodic rest potentials. This is an approx-
imation since the kinetic parameters of the anodic and cathodic reactions are an important
criterion in determining magnitudes of galvanic interaction. Description of galvanic inter-
action which have included kinetic parameters are specific to a certain couple and/or have
not been experimentally verified.
A voltage balance over a galvanic couple provides an excellent basis for describing
galvanic interaction quantitatively. The voltage balance incorporates the anodic and cathodic
rest or corrosion potentials, kinetic aspects of the anodic and cathodic half-reactions, voltage
characteristics of the mineral-mineral contact and the voltage loss across the solution. The
kinetic characteristics of the anodic and cathodic half-reactions were determined by poten-
tiostatic measurements with a three-electrode cell. The kinetic parameters associated with
each half-reaction were determined by regressing the polarisation data with the Butler-
Volmer equation or the combined Butler-Volmer and diffusion equation. The use of a
potentiostat, during the characterisation of the galvanic couples, allowed a ready study of
the effect of mineral-mineral contact on galvanic interaction. The construction of the
galvanic couples as rotating ring-disc electrodes has proved to be a practical method, by
eliminating solution voltage losses, of studying galvanic interactions between minerals.
Two galvanic couples, copper-pyrite and galena-pyrite, were studied. At the galvanic
potential in the copper-pyrite couple the anodic dissolution of copper is an electrochemically
controlled reaction while the reduction of ferric ions on the pyrite cathode was observed to
be controlled by electrochemical and mass transfer processes. At the galvanic potential in
the galena-pyrite couple the anodic dissolution of galena was observed to be an electro-
chemically controlled reaction while the reduction of ferric ions on pyrite was controlled
by electrochemical and mass transfer processes. The kinetic parameters obtained during the
study of the anodic dissolution of copper in sodium sulphate solutions and the anodic
dissolution of galena in sodium nitrate solutions are in excellent agreement with those
obtained by other researchers.
Illumination of the galena-pyrite electrode surface resulted in an increase in galvanic
current. The effect is due to the excitation of electrons from the valence band to the
conduction band in n-type galena. From these observations it is concluded that the semi-
conducting properties of sulphide minerals strongly influence the magnitude of galvanic
interaction.
There is a very good correspondence between the experimentally measured galvanic
currents and those predicted by the galvanic model equation.

Acknowledgements

The authors would like to thank the Council for Mineral Technology (MINTEK), the
Foundation for Research and Development (FRD) and the University of the Witwatersrand
for financing this research.
374 P.R. Holmes, F.K. Crundwell / Hydrometallurgy 39 (1995)353-375

Appendix A. Nomenclature

ct charge transfer coefficient -

A electrode surface area m2
d i f f u s i o n film t h i c k n e s s m
D diffusion coefficient m2/s
E potential versus reference electrode V
F Faraday's constant C/mol
I current A
i current density A/m 2
il limiting current density A/m 2
io exchange current density A/m 2
77 overpotential V
R u n i v e r s a l gas c o n s t a n t J K- ~mol-
R' resistance
T temperature K
V potential difference V

Subscripts
a anode
c cathode
cor corrosion
e equilibrium/rest
g galvanic

References

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