Hydrometallurgy 63 (2002) 15 22

www.elsevier.com/locate/hydromet

The role of EH measurements in the interpretation of the kinetics

and mechanisms of the oxidation and leaching of sulphide minerals
Michael J. Nicol *, Isabel Lazaro
A.J. Parker Cooperative Research Center for Hydrometallurgy, Murdoch University, Perth, WA, Australia
Received 13 August 1999; received in revised form 4 June 2001; accepted 17 August 2001

Abstract

Measurements have been made of the potentials of pyrite, arsenopyrite and chalcopyrite rotating disk electrodes in acid
sulfate solutions containing iron(III) and iron(II). These potentials have been compared with those of a stationary platinum wire
and glassy carbon (pyrite) and platinum (arsenopyrite and chalcopyrite) ring electrodes. It has been demonstrated that the
potential measured in the bulk of the solution can only be approximated to that at the surface of the minerals under conditions of
relatively high concentrations of iron(II). A theoretical treatment of the mixed potential model has enabled the difference
between the bulk solution potential and the mineral potentials to be calculated from the electrochemical characteristics of the
reactions involved. These calculated differences have been compared with the experimental values. D 2002 Elsevier Science
B.V. All right reserved.

Keywords: EH measurements; Potentials; Sulphide minerals

1. Introduction pressures, while the role of the bacteria is largely

The oxidation of sulphide minerals such as pyrite,
arsenopyrite and chalcopyrite has received renewed
interest in recent years as a result of the rapid develop-
ment of bacterially assisted and pressure oxidation
processes. In the case of these processes, it is now
generally accepted that these reactions occur mainly
by way of an indirect mechanism in which the active
oxidant is iron(III). Re-oxidation of iron(II) by dis-
solved oxygen is enhanced at high temperatures and
* an inert electrode such as platinum in the bulk of a
Corresponding author. Mineral Science, Murdoch University,
South St., Murdoch, WA 6150, Australia. Tel.: +61-8-9360-6766;
fax: +61-8-9360-6343.
E-mail address: nicol@central.murdoch.edu.au (M.J. Nicol).
limited to one catalysing this re-oxidation reaction
under ambient conditions. A number of recent pub-
lications (Kametani and Aoki, 1985; Verbaan and
Crundwell, 1986; Dry and Bryson, 1988; Ralph et
al., 1997; May et al., 1997; Ruitenberg et al., 1999)
have focussed on the use of redox (or platinum elec-
trode) potentials as a monitor of the rate of reduction
of iron(III) and also as a means of controlling the rate
of oxidation of the mineral by controlling the redox
potential. It has been tacitly or inadvertently assumed
in these studies that the potential (the so-called EH) of
leach solution or pulp is identical to that experienced
by the oxidising mineral surface (mixed potential).
This has been pointed out in a previous but apparently

0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All right reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 1 ) 0 0 2 0 6 - 7
16 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522
largely ignored review (Nicol, 1993). This concept
was, in fact, first published in Nicol et al. (1975) in
connection with an electrochemical model for the
leaching of uranium dioxide and has been the source
of several publications dealing with its application to
hydrometallurgy (Power and Ritchie, 1983; Li et al.,
1992). However, in many cases, this has been over-
looked in the interpretation of leaching reactions.
Although other authors have addressed the role of
EH and mixed potential, especially in flotation studies,
this has largely been limited to reactions in the bulk
solution and not at the mineral surface (Rand and
Woods, 1984; Ralston, 1991; Natarajan and Iwasaki,
1974).
In this study, the potentials of pyrite, arsenopyrite
and chalcopyrite electrodes have been measured at the
same time as that of a platinum electrode in acid
sulphate solutions containing iron(II) and iron(III).
This study has been further enhanced by measuring
the potential of a platinum ring electrode surrounding
disk electrodes of arsenopyrite and chalcopyrite and a
glassy carbon ring surrounding a pyrite electrode. A
theoretical basis for the measurements has been
developed and the predictions were compared to the
experimental measurements.
2. Experimental
Rotating ring disk electrodes and a platinum wire
were used for all the measurements. The rotating disk
(pyrite, arsenopyrite or chalcopyrite) component of the
ring disk electrodes was fabricated from pure natural
samples of the three minerals. The ring of the ring
disk electrodes was fabricated from platinum (arsen-
opyrite and chalcopyrite) and glassy carbon (pyrite).
The electrode dimensions and the calculated collection
efficiency (N) for each electrode are given in Table 1.
Before making any electrochemical measurements, the
surfaces of the ring and disk electrodes were prepared
Table 1
Ring disk electrode dimensions
RRDE r1 (mm) r2 (mm) r3 (mm)
Pyrite glassy carbon 2.35 2.5 3.5
Arsenopyrite platinum 2.5 2.675 3.675
Chalcopyrite platinum 3.5 3.7 4.7
by being ground on fine silicon carbide paper (grade
2400). In some instances, the electrodes were also
polished with 0.05 mm alumina paste followed by
ultrasonic cleaning.
Potentials were measured against mercury/mercu-
rous sulphate reference electrodes (0.64 V versus the
standard hydrogen electrode (SHE)) and are quoted on
the SHE scale. Solutions were prepared from labora-
tory reagent grade chemicals and distilled water, and
the pH was adjusted to 1.5 with sulphuric acid. All
experiments were carried out at 25 C with the
solutions exposed to the atmosphere.
Three different solutions were used in the experi-
ments.
(A) 10 g/L iron(III) as the sulphate. Residual
iron(II) in this solution was titrated by the addition
of a solution of permanganate until the potential of a
platinum electrode increased above 1.0 V versus the
SHE. The solutions used for each mineral therefore
had minor differences in the iron(II) content.
(B) 10 g/L iron(II) + 5 mg/L iron(II) as the sul-
phates.
(C) 5 g/L iron(III) + 5 g/L iron(II) as the sulphates.
Cyclic voltammograms were obtained using a PAR
Model 372 potentiostat and a Houston Instrument
Model 2000 X Y recorder system coupled to a con-
ventional three-electrode system. All voltammograms
were initiated in an anodic direction from a potential of
25 mV cathodic to the rest potential at a sweep rate of 2
mV/s. Experiments were conducted in a conventional
glass-jacketed three-electrode cell with the electrodes
rotated using the equipment assembled at Murdoch
University. The potential time transients were ob-
tained through a data acquisition card linked to a
personal computer operated using Labview software.
3. Results
3.1. Rest potential measurements
3.1.1. Pyrite
The potentials of a freshly polished pyrite rotating
disk electrode and a platinum wire electrode immersed
N in the same solution were followed as a function of
0.40 time after the immersion in all three solutions. Also
0.44 recorded was the potential of the glassy carbon ring
0.39 electrode which surrounded the pyrite disk. The
 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522
Fig. 1. Variation of the potentials with time for a rotating pyrite disk
electrode, a glassy carbon ring electrode and a stationary platinum
wire electrode in Solution (A) at 25 C.
results for solutions (A) and (B) are shown in Figs. 1
and 2. It is apparent that in the case of the solution
containing only iron(III), the mineral potential (Em) is
about 450 mV lower than the potential of the platinum
electrode (EH), while for solution (B), the difference
after 1 h is about 30 mV. The rotation speed of the
electrode was found to have a negligible effect on Em
and EH in these experiments. The ring potential was
found to take on values between Em and EH as
expected.
In the case of the solution containing equal con-
centrations of iron(III) and iron(II), the potentials (not
shown) were found to be identical within experimen-
tal error and did not vary with the rotation speed.
Fig. 2. Variation of the potentials with time for a rotating pyrite disk
electrode, a glassy carbon ring electrode and a stationary platinum
wire electrode in Solution (B) at 25 C.
17
Fig. 3. Variation of the potentials with time for a rotating
arsenopyrite disk electrode, a platinum ring electrode and a
stationary platinum wire electrode in Solution (A) at 25 C.
3.1.2. Arsenopyrite
In the case of arsenopyrite, the potential of a
platinum ring electrode was also monitored in addi-
tion to that of the mineral and a platinum wire
electrode as described above. The results for solutions
(A) and (B) are shown in Figs. 3 and 4 for a rotation
speed of 1000 rev/min. The results obtained at 100
rev/min were very similar with the mineral and ring
potentials initially being about 10 mV lower. As in the
case with pyrite, the difference EH
Em is significant
for both solutions. It should also be pointed out that
the ring potential increases as the mineral potential
decreases with time for both solutions.
In the case of solution (C), the potentials of all the
electrodes were within 3 mV of each other. Similar
potentials values for a stationary arsenopyrite elec-
trode in a solution of composition similar to (B) have
previously been reported (Zhang et al., 1996).
Fig. 4. Variation of the potentials with time for a rotating
arsenopyrite disk electrode, a platinum ring electrode and a
stationary platinum wire electrode in Solution (B) at 25 C.
18 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522

Fig. 5. Variation of the potentials with time for a rotating

chalcopyrite disk electrode, a platinum ring electrode and a
stationary platinum wire electrode in Solution (A) at 25 C.

3.1.3. Chalcopyrite
The results of the potential measurements obtained
with chalcopyrite are shown in Figs. 5 and 6 for Fig. 7. Linear sweep (2 mV/s) voltammograms for rotating (1000
solutions (A) and (B), respectively. The results are rev/min) disks of pyrite, arsenopyrite and chalcopyrite in Solution
similar to those observed for arsenopyrite with the (B).
difference EH
Em being significant although the
variation of the ring and disk potentials with time potential lies in the region of activation control. In
does not show the opposite trends noted in the case of all cases, the rotation speed seemed to have an effect
arsenopyrite. only on the ring potential for the arsenopyrite and
Once again, the potentials of all electrodes were
similar in the case of solution (C) with the disk
electrode being 8 mV lower than the ring and wire
electrodes.
As expected, no effect of rotation speed on the
mixed potentials of pyrite, arsenopyrite and chalco-
pyrite was observed, considering that the mixed

Fig. 6. Variation of the potentials with time for a rotating Fig. 8. Linear sweep (2 mV/s) voltammograms for rotating (1000
chalcopyrite disk electrode, a platinum ring electrode and a rev/min) disks of pyrite, arsenopyrite and chalcopyrite in Solution
stationary platinum wire electrode in Solution (B) at 25 C. (C).
 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522
chalcopyrite experiments. A slight increase in the
potential was observed for the ring in the chalcopyrite
experiment (Fig. 5). Meanwhile, a drop followed by
an increase in the potential is observed for the ring in
the arsenopyrite case (Fig. 3).
3.2. Linear sweep voltammograms
Linear sweep voltammograms obtained at each
mineral electrode in solutions (B) and (C) are given
in Figs. 7 and 8. The data obtained from these experi-
ments were used to estimate the electrochemical
kinetic parameters as described in Appendix A. Atten-
tion is drawn to the relatively low reactivity of the
chalcopyrite electrode for the iron(III)/iron(II) couple
in the sulfate solutions (Fig. 8).
4. Discussion
As illustrated qualitatively in a previous review
(Nicol, 1993), in the case of noble metal sulphides
such as those used in this study, a type(III) situation
prevails in which the mixed potential (Fig. 9), Em,
generally falls close to the equilibrium potential (EH)
of the iron(III)/iron(II) couple, provided that the
iron(II) concentration is not negligibly small. The
Fig. 9. Schematic current/potential curves for the mixed potential
model for the oxidation of a sulfide mineral by iron(III). The solid
curves refer to the iron(III)/iron(II) couple and the dotted curve to
the anodic oxidation of the mineral.
19
consequence is that the contribution of the anodic
current due to oxidation of the mineral, im (which is
proportional to the leaching rate), is small compared
to the exchange currents due to the iron couple at the
mixed potential which is located by the requirement
that at E = Em, ia + im =
ic where ia and ic are the
partial currents for the oxidation of iron(II) and the
reduction of iron(III), respectively. The mixed poten-
tial in these cases is often determined therefore by the
characteristics of the iron couple and not by the anodic
characteristics of the mineral and can be approximated
by the equilibrium potential or EH.
Thus, assuming that the oxidation of the mineral is
irreversible, i.e. the cathodic reduction of the mineral
can be ignored at the potentials encountered during
oxidation, one can treat the above situation in the
following way.
At the mixed potential (Em),
ia im
ic 1
and writing each of these currents in terms of the
Butler Volmer equation,
im km expbm Em 2
ia ka FeIIexpba Em 3

ic kc FeIIIexp
bc Em 4
where km, ka and kc are the electrochemical rate
constants and bm, ba and bc are the parameters defined
by the relationship bi = aiF/RT where a is the so-called
transfer coefficient which is generally close to 0.5 and
the other terms have their usual significance. Em is the
potential with respect to some reference electrode and
the values of k will depend on the choice of this
reference potential.
These expressions can be substituted in Eq. (1) and
the resulting equation can be solved for Em. An ana-
lytical solution is only possible for bm = ba = bc = b.
This is reasonable given that the transfer coefficients
are often close to 0.5.
For this case, it can be shown that
1 kc 1 FeIII
Em ln ln : 5
2b ka 2b km =ka FeII
20 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522

The equilibrium potential (EH) for the iron(III)/
iron(II) couple can be derived in the same term by
setting ia =
ic for E = EH and solving for EH as
above,
1 kc 1 FeIII
EH ln ln ; 6
2b ka 2b FeII
which, as expected, has the same form as the Nernst
equation with Eo = 1/2bln(kc/ka).
Thus, one can write:
 
1 km
EH
Em ln 1 ; 7 lutions containing very low concentrations of iron(II),
2b ka FeII
which shows that, as expected, EH will be greater than
Em and that for ka[Fe(II)] H km, EHEm and therefore
defines the conditions under which the assumption
discussed above will be valid. On the other hand, for
very low concentrations of Fe(II) and/or km H ka, the
above relationship simplifies to:
EH
Em 1=2b ln1=FeII 1=2b lnkm =ka :
In all such cases, it should be remembered that the
concentrations referred to in the above expressions are
those at the mineral surface and that these values can
differ substantially from the bulk values which are
reflected in the value measured as EH. This is partic-
ularly true for the concentration of Fe(II), which can
be significantly higher at the mineral surface where it
is produced by the reduction of Fe(III), and in the case
of these minerals, also by anodic oxidation of the
mineral. It is for this reason that the potential of the
ring electrode is important as an experimental indica-
tor of the value of EH in the region close to the disk
electrode.
The table below summarizes the various potential
measurements taken after 1 h for the various minerals.
It is apparent that, as predicted, the potential of the
mineral surface is almost identical to that of the bulk
solution (as measured by EH) and to that of the ring
electrode only for solutions containing appreciable
concentrations of iron(II). On the other hand, for so-
the difference EH
Em can be as much as 0.5 V for all
minerals. The variation shown for the potential of
solution (A) is due mainly to the variation in the amount
of permanganate added to reduce the Fe(II) content in
each case. It should be noted that the ring electrode
potential lies, as expected, between EH and Em. The last
two columns in Table 2 compare the experimental
values of the difference ER
Em with those that have
been estimated using Eq. (7) above as outlined in
Appendix A. The results are surprisingly close, con-
8 sidering the approximations inherent in the treatment
and the experimental data and lend a degree of quanti-
tative credence to previous qualitative observations and
interpretations.
The lower predicted differences in the case of the
oxidised solutions with chalcopyrite and arsenopyrite
are probably due to the fact that the mineral surfaces
undergo changes leading to partial passivation under
oxidising conditions. This is apparent in, for example,
the mineral and ring potential profiles as shown in
Figs. 3 and 4 for arsenopyrite. Thus, the increase in

Table 2
Summary of the various potentials after 1 h at 1000 rev/min
Mineral Solution EH (V) Em (V) EH
Em (V) ER (V) ER
Em (V)
Observed Calculated
FeS2 (A) 1.280 0.860 0.460 1.065 0.205 0.216
(B) 0.860 0.829 0.035 0.852 0.023 0.020
(C) 0.653 0.653 0 0.653 0 0
CuFeS2 (A) 1.325 0.805 0.520 1.230 0.425 0.305
(B) 0.840 0.755 0.085 0.830 0.075 0.064
(C) 0.668 0.660 0.008 0.668 0.008 0.001
FeAsS (A) 1.340 0.730 0.610 1.100 0.370 0.331
(B) 0.865 0.715 0.150 0.860 0.145 0.093
(C) 0.668 0.667 0.001 0.668 0.001 0.001
 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522
the ring potential is due to a decreasing rate of
production of iron(II) at the disk, thus increasing the
iron(III)/iron(II) ratio, and therefore, the potential at
the ring. More detailed ring disk electrode studies of
this phenomenon at chalcopyrite and arsenopyrite
electrodes will be published at a later date.
It should be emphasised that in a well-agitated
suspension of mineral particles, the bulk EH will be
closer to that observed at the ring than to the bulk EH
measured in our experiments. Thus, if the mass transfer
coefficient (which varies with the particle size) at a
suspended mineral particle is the same as that at a disk
rotating at 1000 rev/min (which is of the order of
5 10
3 cm/s), then ER
EH (surface) of a suspended solution (B) is also negligible. Both of these assump-
mineral particle. However, it does not follow that EH
(surface) = EH (bulk), which has often been assumed
from the apparent independence of an EH (bulk) profile
on the degree of agitation of a suspension since it is
well-known that the mass transport to the suspended
particles does not significantly increase with increasing
agitation beyond the point of suspension.
It should be clear from above that it is not possible
to accurately estimate the solution potential close to a
mineral surface from the value of the bulk EH. It is
therefore not surprising that previously published
attempts to fit the rate of leaching of pyrite and
arsenopyrite to a Butler Volmer expression using
bulk EH values were met with little success. Finally,
the results of the so-called EH-stat experiments, in
which the bulk EH is controlled by the electrochemical
or chemical oxidation of iron(II), should be used with
caution if used to derive mechanistic information.
Acknowledgements
I.L. acknowledges the research scholarship awarded
by CONACyT-SEP and the research funding from the
A.J. Parker Cooperative Research Center for Hydro-
metallurgy.
Appendix A
The derivation of the relevant kinetic parameters
km and ka is simplified considerably if the potential Em
in Eqs. (2) (4) is measured relative to that for the
equilibrium potential Ee of the Fe(III)/Fe(II) couple in
21
solution (C), i.e. equimolar concentrations of 0.090
mol/L.
Thus, the values of km for each of the minerals can
be obtained from the extrapolated intercept of the
linear Tafel plot of ln(im) versus Em
Ee for high
overpotentials using the data in Fig. 7. This value has
the dimensions of a current density and is proportional
to the predicted rate of dissolution of the mineral at a
mixed potential of Ee. This method assumes that the
potentials chosen are not close to the equilibrium
potential for the anodic oxidation of the mineral and
that the contribution to the total current from the
anodic oxidation of the small amounts of Fe(II) in
tions are well justified in the case of all three minerals.
Estimates of ka can be obtained from the data in
Fig. 8, which shows the current/potential character-
istics of the Fe(III)/Fe(II) couple in solution (C).
Assuming that the contribution of the anodic current
due to the oxidation of the mineral is negligible at this
potential, one can write for the net current at potentials
close to Ee,
i ia ic ka FeIIexpfba Em
Ee g

kc FeIIIexpf
bc Em
Ee g
and for [Fe(III)]=[Fe(II)]=[Fe] and ba = bc = b, it fol-
lows that ka = kc = k, and one can write,
i kFefexpfbEm
Ee g expf
bEm
Ee gg:
For potentials close to Ee, Em
Ee K1/b, and the
above relationship reduces to the well-known low-
field approximation to the Butler Volmer equation,
i 2kFebEm
Ee
from which k can be obtained by assuming b = 19.5
V
1. This is equivalent to assuming a transfer coef-
ficient of 0.5 for the Fe(III)/Fe(II) couple at the
mineral surfaces.
Finally, the only other required quantity in Eq. (7)
is the concentration of Fe(II) at the surface of the
mineral. This is estimated by using the ring electrode
potential as an indicator of the Fe(III)/Fe(II) ratio at
the mineral disk surface and is calculated from the
Nernst equation with E o = Ee.
22 M.J. Nicol, I. Lazaro / Hydrometallurgy 63 (2002) 1522
References
Dry, M.J., Bryson, A.W., 1988. Prediction of redox potential in con-
centrated iron sulphate solutions. Hydrometallurgy 21, 59 72.
Kametani, H., Aoki, A., 1985. Effect of suspension potential on the
oxidation rate of copper concentrate in a sulfuric acid solution.
Metall. Trans. 16B, 695 705.
Li, J., Zhong, T.K., Wadsworth, M.E., 1992. Application of mixed
potential theory in hydrometallurgy. Hydrometallurgy 29, 47 60.
May, N., Ralph, D.E., Hansford, G.S., 1997. Dynamic redox poten-
tial measurements for determining the ferric leach kinetics of
pyrite. Miner. Eng. 10 (11), 1279 1290.
Natarajan, K.A., Iwasaki, I., 1974. Eh measurements in hydrome-
tallurgical systems. Miner. Sci. Eng. 6, 35 44.
Nicol, M.J., 1993. In: Hiskey, J.B., Warren, G.W. (Eds.), The Role
of Electrochemistry in Hydrometallurgy, Hydrometallurgy Fun-
damentals, Technology and Innovation. The Metallurgical Soci-
ety, Littleton, CO, pp. 43 62.
Nicol, M.J., Needes, C.R.S., Finkelstein, N.P., 1975. Electrochem-
ical model for the leaching of uranium dioxide: 1. Acid media.
In: Burkin, A.R. (Ed.), Leaching and Reduction in Metallurgy.
The Institution of Mining and Metallurgy, London, pp. 1 11.
Power, G.P., Ritchie, I.M., 1983. Experimental illustrations of an
important concept in practical electrochemistry. J. Chem. Educ.
60, 1022 1025.
Ralph, D.E., May, N., Hansford, G.S., 1997. An electrochemical
step in bioleaching biomine. Conference Proceedings of IBS-
BIOMINE, QP3.1 QP3.10, AMF, Sydney, Australia.
Ralston, J., 1991. Eh and its consequences in sulphide mineral
flotation. Miner. Eng. 4, 859 878.
Rand, D.A.J., Woods, R., 1984. Eh measurements in sulphide min-
eral slurries. Int. J. Miner. Process. 13, 29 42.
Ruitenberg, R., Hansford, G.S., Reuter, M.A., Breed, A.W., 1999.
The ferric leaching kinetics of arsenopyrite. Hydrometallurgy
52, 37 53.
Verbaan, B., Crundwell, F.K., 1986. An electrochemical model for
the leaching of a sphalerite concentrate. Hydrometallurgy 16,
345 359.
Zhang, Y.Z., Zhao, T.C., Lu, Y.Y., 1996. Oxidation mechanism of
arsenopyrite in acidic ferric sulphate media in the absence and
presence of bacteria T. ferrooxidans. In: Warren, G.W. (Ed.),
EPD Conference Proceedings. The Minerals, Metals and Mate-
rials Society, Warrendale, PA, Anaheim, California, pp. 429
442.