Electrochimica Acta 127 (2014) 7–19

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical dissolution of fresh and passivated chalcopyrite

electrodes. Effect of pyrite on the reduction of Fe3+ ions and transport
processes within the passive film
O.G. Olvera ∗ , L. Quiroz, D.G. Dixon, E. Asselin
Department of Materials Engineering, The University of British Columbia 309-6350 Stores Road, Vancouver, BC, V6 T 1Z4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The effect of pyrite (FeS2 ) on the electrochemical dissolution of fresh and passivated chalcopyrite (CuFeS2 )
Received 28 October 2013 electrodes has been studied. Current density values for the dissolution of CuFeS2 were calculated from EIS
Received in revised form 27 January 2014 measurements. FeS2 increased the dissolution rate of fresh and passivated CuFeS2 electrodes indicating
Accepted 31 January 2014
that the galvanic effect continued even after the electrode was chemically passivated. The dissolution
Available online 15 February 2014
rate of CuFeS2 decreased by a factor of 3 after the passivation treatment. Due to the low diffusion rates of
ions within the CuFeS2 passive film and due to an increase in the resistance to the transfer of electrons at
Keywords:
the electrode/film interface, the activity of FeS2 for the reduction of Fe3+ ions was also reduced by a factor
Chalcopyrite
Pyrite
of 2.3 even though FeS2 was not exposed to any chemical treatment. The results in this work indicate that
Galvanic effect the dissolution rate of the fresh CuFeS2 electrode was controlled by the reduction of Fe3+ ions whereas
EIS for the passivated CuFeS2 electrode the dissolution rate was controlled by diffusion within the passive
Passivating film. film.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Chalcopyrite (CuFeS2 ) is the most abundant copper sulphide
mineral accounting for nearly 70% of the known reserves in the
world [1]. Hydrometallurgical processes continue to attract interest
since they possess the ability to treat low tonnages of complex ores
containing high impurities. However, due to the slow dissolution
rates of CuFeS2 , hydrometallurgical processes have not yet found
widespread application. In spite of this, there have been a number
of processes developed for the leaching of CuFeS2 and other copper-
bearing minerals; several of these processes have been reviewed by
Baba et al. [2] and Dreisinger [3].
One of the latest developments in the chemical leaching of
chalcopyrite in sulphate media under atmospheric pressure is the
GalvanoxTM process. This process consists in the addition of pyrite
(FeS2 ) to the leach slurry in the presence of Fe3+ ions. FeS2 and
CuFeS2 are thought to form a galvanic couple where FeS2 acts as
an extended surface for the reduction of Fe3+ ions, increasing in
this way the rate of the anodic dissolution of CuFeS2 [4,5]. Fig. 1
shows a simple schematic representation of the reactions that are
thought to take place in the GalvanoxTM process. These reactions
∗ Corresponding author. Tel.: +1 604 827 5070.
E-mail addresses: oscar.olvera@ubc.ca, og.olvera@yahoo.com.mx (O.G. Olvera).
are represented by Eqs. 1–4; Eq. 1 represents the anodic dissolution
of CuFeS2 to yield cupric and ferrous ions, as well as an elemental
sulfur product layer that forms on the surface of the CuFeS2 parti-
cle. The second reaction (Eq. 2) comprises the reduction of Fe3+ ions
that are further regenerated by oxidizing Fe2+ ions with dissolved
O2 (Eq. 3). The overall reaction for the process is represented by Eq.
4.
CuFeS2 → Cu2+ + Fe2+ + 2S0 + 4e− (1)
4Fe3+ + 4e− → 4Fe2+ (2)
4Fe2+ + O2 + 4H+ → 4Fe3+ + 2H2 O (3)
CuFeS2 + 4Fe3+ → Cu2+ + 5Fe2+ + 2S0 (4)
The quality of FeS2 as a catalyst depends on its source and its cat-
alytic properties seem to be related to its silver content [6]. Nazari
et al. [7] showed that the catalytic properties of different sources of
FeS2 could be enhanced by pretreating them with small amounts
of silver. This effect was later suggested to be a consequence of a
decrease in the electrical resistivity of the sulfur product layer cov-
ering the CuFeS2 particles, thus facilitating the electrical contact
between CuFeS2 and FeS2 . A concomitant increase in the catalytic
properties of FeS2 for the reduction of Fe3+ ions was also postulated
[8].

http://dx.doi.org/10.1016/j.electacta.2014.01.165
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
8 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19
Fig. 1. Schematic representation of the reactions taking place in the GalvanoxTM
process.
The improvement of hydrometallurgical processes is strongly
related to understanding the kinetics and mechanisms underlying
the dissolution of minerals. It has been recognized that the main
factors affecting the dissolution rate of CuFeS2 are the concentra-
tion of the oxidizing species, the redox potential of the solution and
the presence of a passivating layer [9–11].
Fe3+ ions are the most commonly applied oxidizing agent used
in CuFeS2 leaching [11 and references within]. It has been reported
that the leaching rate of CuFeS2 depends on Fe3+ ions when con-
centration is below 0.1 mol L−1 whereas at higher concentrations
no further increase in the dissolution rate is observed [12–14].
An explanation for this effect was given by Hirato et al. [15] who
calculated that the concentration of Fe3+ and FeHSO4 2+ increased
when total Fe concentration increased up to 0.1 mol L−1 whereas
for higher concentrations the predominant species was FeSO4 + .
This explanation flows from the fact that, according to Ashurst
and Hancock [16], the Fe3+ and FeHSO4 2+ species are outer-sphere
complexes while FeSO4 + is an inner-sphere complex where charge
transfer is retarded since it involves the breaking of the Fe3+ and
SO4 2− bond to form the FeSO4 outer-sphere complex. Thus only
FeHSO4 2+ and Fe3+ would act as the electroactive species [17].
With regards to the rate determining step in the dissolution
of CuFeS2 , Linge [18] demonstrated that pore diffusion through
the sulphur film did not limit the dissolution rate; instead it was
proposed that a solid diffusion process was the rate controlling
step. Similarly, Dutrizac [19] studied the dissolution of CuFeS2 in
ferric sulphate and ferric chloride media and found that leaching
rates were independent of acid concentration (for acid concentra-
tions lower than 1 mol L−1 ) and degree of agitation. More recently
Ghahremaninezhad et al. [20] showed that any contribution of
the Fe3+ reduction limiting current density could be neglected and
that the major contribution to the dissolution current of a CuFeS2
electrode came from charge transfer reactions; these authors also
suggested that the passive film was a better electronic conductor
than an ionic conductor and that the diffusion of atoms within the
passive film was the reason for the slow reduction of Fe3+ on the sur-
face of the electrode. There have also been several works reporting
that the kinetics of CuFeS2 leaching with Fe3+ occur under linear or
parabolic kinetic chemical control regimes, with activation ener-
gies ranging from 40 to 130 kJ mol−1 between 35 to 100 ◦ C both in
sulphate and chloride media [10,12,15,21–23].
As mentioned before, the presence of a passivating layer is
one of the main factors affecting the leaching rate of chalcopy-
rite. This passivating layer causes the mineral to leach at very
low rates, which is one of the main drawbacks of hydrometallur-
gical processes. In addition to this, the presence of a passivating
layer complicates the analysis of the kinetics and mechanisms
involved in the leaching of CuFeS2 . To date there are differ-
ent theories regarding the nature of the passive layer formed
during the leaching of the mineral and the nature and mecha-
nisms of formation have been the subject of several articles and
reviews [9,12,24–26]. The following passivating films have been
suggested: elemental sulfur in both porous and compact layers;
metal-deficient sulphides; polysulphides and, iron precipitates
such as jarosite, KFe3 (SO4 )2 (OH)6 , and ferrihydrite, Fe5 O3 (OH)9 .
Interestingly, regardless of the nature of this passive film, in a recent
work Rivera [27] observed that adding FeS2 to a CuFeS2 concentrate
that was showing signs of passivation increased the leaching rate
and overcame the passivation effects observed prior to its addition.
Similar results were observed when activated carbon was added to
an enargite (Cu3 AsS4 ) concentrate after having observed its passiv-
ation [28].
In the present work we have studied the effect of FeS2 on the
electrochemical dissolution of fresh and passivated CuFeS2 elec-
trodes. The dissolution current density values were determined
using electrochemical impedance spectroscopy (EIS). The effect of
the passive film on the dissolution rate of CuFeS2 was also quan-
tified. An experimental rate expression for the electrochemical
dissolution of fresh CuFeS2 electrodes was obtained and compared
against a theoretical model based on mixed potential theory. A sim-
ple kinetic analysis was conducted to determine the rate controlling
step on the dissolution of fresh and passivated CuFeS2 electrodes.
2. Experimental
2.1. Mineral characterization
The CuFeS2 sample used in this study was from the La Ranita
mine in Chihuahua, Mexico. The mineral sample was analyzed by X-
ray powder-diffraction (XRD) for quantitative phase analysis using
the Rietveld method and the International Centre for Diffraction
Database PDF-4 and Search-Match software by Bruker. The sample
was reduced to the optimum grain-size range for quantitative X-ray
analysis (<10 ␮m) by grinding under ethanol in a vibratory McCrone
Micronising Mill for 7 minutes. Step-scan XRD data were collected
over a range 3-80◦ 2␪ with CoK␣ radiation on a Bruker D8 Focus
Bragg-Brentano diffractometer equipped with an Fe monochroma-
tor foil, 0.6 mm (0.3◦ ) divergence slit, incident- and diffracted-beam
Soller slits and a LynxEye detector. The long fine-focus Co X-ray tube
was operated at 35 kV and 40 mA, using a take-off angle of 6◦ .
2.2. Electrochemical techniques
The dissolution of a CuFeS2 electrode was studied in a conven-
tional three electrode cell. A CuFeS2 electrode was used as working
electrode, a graphite rod as counter electrode and a saturated
calomel electrode (SCE, +0.24 V/SHE) as reference electrode. Most
experiments were performed at 25 ◦ C except for those performed
during the passivation of the electrode at 50 ◦ C. The working elec-
trode consisted of cubic-shaped CuFeS2 with an exposed surface of
1.9 cm2 . The CuFeS2 electrode was fixed to a copper wire using
silver-containing epoxy resin. The whole assembly was further
embedded in a high temperature non-conductive epoxy resin. Prior
to each electrochemical experiment the electrode was polished
with 1200 grit carbide paper. Electrodes were rinsed with deion-
ized water and acetone and left to dry. The polishing and acetone
rinsing steps were omitted for the experiments with the passivated
CuFeS2 electrode to avoid changes in the formed product layer.
The electrolyte used in the experiments was a 0.5 mol L−1
H2 SO4 (Fisher Scientific, 95 to 98%) aqueous solution prepared
with deionized water; FeSO4 ·7H2 O (Fisher Scientific, 100%) and
Fe2 (SO4 )3 ·5H2 O (Sigma Aldrich, 97%) were added in the desired
concentrations. Nitrogen gas was sparged 30 minutes before and
during the electrochemical experiments to remove dissolved
oxygen from the electrolyte. The measured pH of the solutions
used in this study was always in the range of 0.77–0.80.
 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19 9

Electrochemical experiments were performed with a PARSTAT 400

2273 potentiostat from Princeton Applied Research. Open circuit
potential (OCP) measurements were performed until the electrode 390
EM = 39.5log[Fe3+] + 435.7
potential stabilized with a change of no more than 1 mV in 10 min.
EIS measurements were conducted at the measured OCP, with 380
an a.c. amplitude of 5 mV in the frequency range of 10 kHz to 10
370

OCP vs SCE/mV
mHz; impedance was measured three times at each frequency to
decrease the contribution of experimental error when fitting the 360
experimental data; ZSimpWin v3.30 software was used to fit the
impedance data. 350
To evaluate the effect of FeS2 on the electrochemical behaviour
of CuFeS2 three different FeS2 particles denominated P1, P2 and 340
P3 were used, their corresponding weights were 124, 266 and
754 mg. The surface area for these particles could not be directly 330
measured by physisorption due to their very small size; however,
320
based on their respective masses an equivalent surface area was
calculated assuming particles were spherical (no correction factor 310 0 1 2
was introduced to account for roughness and irregularities). The 10 10 10
calculated areas for P1, P2 and P3 were 0.41, 0.68 and 1.37 cm2 ,
[Fe ]/mmol L-1
3+
respectively.
To conduct the electrochemical experiments the CuFeS2 elec- Fig. 2. Effect of Fe3+ concentration on the OCP of a fresh CuFeS2 electrode. T = 25 ◦ C;
trode was placed in the electrolyte with the mineral surface facing 0.5 mol L−1 H2 SO4 + 0.1 mol L−1 FeSO4 .
upwards, thereafter the FeS2 particle to be evaluated was fixed to
the tip of a plastic pipette and placed on top of the electrode. This
ensured that the electrical contact between the electrode and the
3.2. OCP measurements
corresponding FeS2 particle was constant during the experiments.

Before analyzing the effect of FeS2 on the electrochemical behav-

2.3. Passivation of the CuFeS2 electrode ior of CuFeS2 , a set of experiments to evaluate the effect of Fe3+
and Fe2+ ions on the measured potential and EIS spectra of the
The CuFeS2 electrode was passivated by immersing it in an aque- fresh CuFeS2 electrode was first conducted. The objective of these
ous solution of 0.5 mol L−1 H2 SO4 , 0.05 mol L−1 Fe2 (SO4 )3 ·5H2 O experiments was to ensure that the correct physical meaning was
and 0.1 mol L−1 FeSO4 ·7H2 O at 50 ◦ C for 96 h; N2 was bubbled dur- assigned to the charge transfer resistances present in the equivalent
ing this treatment. Before and after the passivating treatment, the electrical circuit used to model the experimental EIS data presented
CuFeS2 electrode was analyzed by scanning electron microscopy in further sections.
(SEM) and energy-dispersive X-ray spectroscopy (EDX) to see if Fig. 2 shows an increase of the measured potential with increas-
differences in morphology and chemical composition could be ing Fe3+ concentration. The semi-logarithmic plot led to a linear
observed. No appreciable differences could be observed, which sug- relationship between these two variables with a slope of 39.5 mV
gests that the thickness of the passive film was below 200 nm; since in the range of concentrations analyzed (1–100 mmol L−1 ). This
differences were not observed results have not been presented. value differed from the 79 mV slope value reported by Hirato et al.
[15] at 70 ◦ C when increasing the Fe3+ concentration from 0.01 to
2.4. Leaching of CuFeS2 1.0 mol L−1 ; the equivalent slope at 25 ◦ C for this value is 68.6 mV
which is 29.1 mV higher than the value obtained in this work. To
A leaching test was conducted to provide a point of comparison explain this difference we used mixed potential theory to derive an
for the CuFeS2 dissolution rates estimated using EIS. For this pur- analytical expression for the mixed potential (EM ). First, Eq. 5 states
pose, 1.0 g of the same CuFeS2 sample used for the electrodes was that the sum of the cathodic and anodic currents on the surface of
added to 150 mL of a solution of the same composition as in section the electrode must be zero:.
2.3. Before the test the sample was ground and sieved so that only
particles in the range 53 < dp < 106 ␮m were present in the leach ⎡  ⎤
EM − E 0 3+
slurry; an analytical expression was used to estimate the total area /Fe2+
AC kFe3+ [Fe3+ ] exp ⎣− ⎦
Fe
of the CuFeS2 exposed to the solution (∼190 cm2 g−1 ). The temper- ˇFe3+
ature was 25 ◦ C and N2 was bubbled during the entire experiment
to remove dissolved O2 from the solution. A magnetic stirrer was 
EM − E 0 3+
set at 400 rpm to mix the solution. The duration of the experiment Fe /Fe2+
= AA kFe2+ [Fe2+ ] exp
was 70 h and samples were taken at 4, 27, 48 and 70 h. The sam- ˇFe2+
ples were analyzed by X-ray fluorescence (XRF) using an acquisition 
time of 5 minutes per measurement to obtain an accurate value for 0
EM − ECuFeS
the concentration of Cu. +AA kCuFeS2 exp 2
(5)
ˇCuFeS2

3. Results and discussion

3.1. Mineral characterization
The results of quantitative phase analysis of Rietveld refine-
ments revealed that the only crystalline phases in the mineral
electrodes were CuFeS2 (99.6 wt. %) and quartz (0.4 wt. %).
For the time being, and for the purposes of this analysis, the
values for the cathodic and anodic reaction surface areas will be
considered to be equal so that AC = AA = A. Eq. 5 can be further sim-
plified by grouping the reaction constants, ki , with the standard
redox potentials, E0 i , in the argument of the exponential terms so
that Eq. 6 is obtained. The latter expression was further rearranged
10 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19

470 430
460

450
420
OCP vs SCE/mV

440 P2 P3

OCP vs SCE/mV
430
410
420
P1
410
400
400 EM = -30.0log[Fe2+] + 370.3

390 0 1 2
10 10 10 390 No FeS2
[Fe ]/mmol L-1
2+
Fresh electrode
2+ ◦
Fig. 3. Effect of Fe concentration on the OCP of a fresh CuFeS2 electrode. T = 25 C; Passivated electrode
0.5 mol L−1 H2 SO4 + 0.05 mol L−1 Fe2 (SO4 )3 .
380
0 0.5 1 1.5
to yield Eq. 7:


 FeS2 surface area/cm2
 3+ EM  2+ EM
k Fe3+ [Fe ] exp − = k Fe2+ [Fe ] exp
ˇFe3+ ˇFe2+ Fig. 4. Effect of FeS2 equivalent area on the OCP of fresh and passivated CuFeS2

 electrodes. T = 25 ◦ C; 0.5 mol L−1 H2 SO4 , 0.05 mol L−1 Fe2 (SO4 )3 , 0.1 mol L−1 FeSO4 .
EM
+k CuFeS2 exp (6)
ˇCuFeS2 if the oxidation of Fe2+ ions was the only anodic reaction occur-
ring on the surface of the electrode. Therefore it can be suggested


 that the less negative slope obtained in this study was caused by
 3+  2+ 1 1
k Fe3+ [Fe ] = k Fe2+ [Fe ] exp EM + a low contribution of the oxidation of Fe2+ ions to the total anodic
ˇFe2+ ˇFe3+
current.


 Fig. 4 shows the effect of contacting different FeS2 particles with
1 1
+k CuFeS2 exp EM + (7) fresh and passivated CuFeS2 electrodes on their OCP. In the absence
ˇCuFeS2 ˇFe3+
of pyrite, the OCP measured with the fresh CuFeS2 electrode was
394 mV and it increased up to 424 mV when the largest particle
To derive an analytical expression for EM some assumptions are
used in this study (P3, 1.37 cm2 ) was contacted with the fresh
required. Although we recognize that it is not yet justifiable, for the
CuFeS2 electrode. After the electrode was passivated a decrease in
sake of the analysis, it will be assumed that the contribution of the
the OCP was observed from 394 to 385 mV in the absence of FeS2
oxidation of Fe2+ ions to the total anodic current is much lower than
and from 424 to 420 mV when P3 was in contact with the elec-
the contribution of the anodic dissolution of CuFeS2 ; under these
trode; this indicates that the effect of FeS2 on the electrochemical
circumstances Eq. 7 simplifies to:

properties of CuFeS2 persisted after the passivating treatment of
2.3RT k Fe3+ [Fe3+ ]
EM =   log
F ˛CuFeS2 + ˛Fe3+ k CuFeS2
When the charge transfer coefficients in Eq. 8 are the same
and equal to 0.5 then the semi-logarithmic plot of EM against
the concentration of Fe3+ ions yields a straight line with a slope
of 59 mV at 25 ◦ C, regardless of the values of the rate constants,
ki . The value obtained in Fig. 2 was 39.5 mV which implies that
the sum of the charge transfer coefficients is 1.5. Taking the
value obtained by Ghahremaninezhad et al. [20] for the cathodic
charge transfer coefficient, ˛Fe3+ = 0.5, then a value for the anodic
charge transfer coefficient ˛CuFeS2 = 1 would explain the lower slope
observed in Fig. 2, compared with the value reported by Hirato et al.
(1987).
The effect of Fe2+ concentration on the measured potential
(Fig. 3) was less clear because a linear relation was not observed
as in Fig. 2. This complication was partly because the number of
solutions analyzed was insufficient to conduct an adequate kinetic
study, which was considered to be beyond the limits of this work.
However a decrease in potential was observed with increasing
Fe2+ concentration; despite the limited experimental data shown in
Fig. 3 a linear fit with a slope of −30 mV was calculated; again, this
value was different than the −59 mV slope that would be expected
the electrode. Mehta and Murr [29] also reported an increase of
(8) 40 mV in the potential by connecting FeS2 and CuFeS2 electrodes
immersed in a 1 mol L−1 H2 SO4 solution. More recently, Majuste
et al. [30] observed similar increases when they evaluated the
effects of FeS2 inclusions on the electrochemical behavior of CuFeS2
electrodes; these authors observed an increase of 100 mV for an
electrode containing 42% FeS2 compared to a pure CuFeS2 electrode
in a 0.1 mol L−1 H2 SO4 , 0.05 mol L−1 Fe3+ solution.
3.3. Electrochemical Impedance Spectroscopy
Fig. 5 shows the impedance (a) and phase angle (b) Bode plots
measured with the fresh CuFeS2 electrode in solutions containing
different concentrations of Fe3+ . By visual inspection two different
electrochemical processes can be observed; the first, at frequencies
between 32 and 98 Hz, showed a shifting of the phase peak (Fig. 5b)
towards higher frequencies as Fe3+ concentration was increased.
The second electrochemical process was observed at frequencies
below 1 Hz. The electrochemical nature of these processes will be
discussed in further paragraphs.
The effect of Fe2+ on the impedance spectra of the fresh CuFeS2
electrode is presented in Fig. 6; as Fe2+ concentration was decreased
a shift from 120 to 50 and 32 Hz was observed in the phase peak
 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19 11

60
a) b)
3+
100 mM Fe 100 mM Fe3+
10 mM Fe3+ 50 10 mM Fe3+
3+
3 1 mM Fe 1 mM Fe3+
10
40

Phase angle/°
|Z|/Ω cm2

30

2
10
20

10

1
10 0
-2 0 2 4 -2 0 2 4
10 10 10 10 10 10 10 10
Frequency/Hz Frequency/Hz

Fig. 5. Effect of Fe3+ concentration on the impedance spectra of a fresh CuFeS2 electrode. T = 25 ◦ C; 0.1 mol L−1 FeSO4 , 0.5 mol L−1 H2 SO4 . a) Impedance modulus and b) Phase
angle.

for the first time constant when concentrations were 100, 10 and
1 mmol L−1 (Fig. 6b), respectively. The effect of decreasing Fe2+ con-
centration on the impedance modulus (Fig. 6a) was similar as that
observed for Fe3+ in Fig. 5a, where an increase of the impedance
was observed at frequencies below 1 Hz.
Fig. 7 presents the Bode plots for the fresh CuFeS2 electrode
in contact with the different FeS2 particles. As in Figs. 5 and 6,
two different time constants were observed in all experiments,
the first time constant was observed at about 120 Hz and the sec-
ond at 25 mHz. These time constants shifted to higher frequencies
when FeS2 was contacted with the CuFeS2 electrode. In regards to
the first time constant, the phase angle decreased from 56◦ in the
absence of FeS2 , to 51◦ when P1 and P2 were in contact with the
CuFeS2 electrode, and to 49◦ in the case of P3. The effect of FeS2
was more evident in the second time constant where the decrease
in the phase angle was more evident and went from 19◦ for the
electrode alone to 7◦ when P3 was in contact. In the case of the
moduli of the impedance, the effect of FeS2 could only be observed
for frequencies below 100 Hz where a decrease can be appreci-
ated as the area of the CuFeS2 particle used in the experiment
increased.
According to previous reports [5,8,30,31] the main effect of FeS2
consists in providing an extended surface area for the reduction
of the oxidant to take place, thereby increasing the dissolution
of CuFeS2 . From Figs. 5 to 7 it can be proposed that the changes
observed in the EIS spectra are mostly related to changes in the
rate of reduction of Fe3+ ions. According to the literature there is
also evidence that the mass transfer of Fe3+ to the electrode surface
has no influence on the dissolution of CuFeS2 [18,19]. To confirm
this, a magnetic stirrer was placed in the electrochemical cell and
rotated at 800 rpm. Fig. 8 shows that the results of the experiments
where the solution was stagnant and when it was agitated were
the same and it is safe to conclude that, under the conditions of
our experiments, there is no effect of mass transfer processes of
any soluble species present in the electrolyte on the dissolution of
CuFeS2 .

70
a) b)
2+
100 mM Fe 100 mM Fe2+
60
10 mM Fe2+ 10 mM Fe2+
2+
3 1 mM Fe 1 mM Fe2+
10
50
Phase angle/°
|Z|/Ω cm2

40

30
2
10

20

10

1
10 0
-2 0 2 4 -2 0 2 4
10 10 10 10 10 10 10 10
Frequency/Hz Frequency/Hz

Fig. 6. Effect of Fe2+ concentration on the impedance spectra of a fresh CuFeS2 electrode. T = 25 ◦ C; 0.05 mol L−1 Fe2 (SO4 )3 , 0.5 mol L−1 H2 SO4 . a) Impedance modulus and b)
Phase angle.
12 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19

a) 60
b)
No Pyrite
3
10 Pyrite 1
50 Pyrite 2
Pyrite 3
40

Phase angle/°
|Z|/Ω cm2

30
2
10
No Pyrite 20
Pyrite 1
Pyrite 2
Pyrite 3 10

1
10 -2 0 2 4
0 -2 0 2 4
10 10 10 10 10 10 10 10
Frequency/Hz Frequency/Hz

Fig. 7. Effect of FeS2 on the impedance spectra of a fresh CuFeS2 electrode. T = 25 ◦ C; 0.1 mol L−1 FeSO4 , 0.05 mol L−1 Fe2 (SO4 )3 , 0.5 mol L−1 H2 SO4 CuFeS2 electrode. a)
Impedance modulus and b) Phase angle.

1000 50 Table 1
Estimated parameters from the experimental results shown Figs. 5 and 6 by fitting
to equivalent circuit shown in Fig. 9.

40 Fe2+ , mmol L−1 100 100 100 10 1

Fe3+ , mmol L−1 1 10 100 100 100
100 0 RPM R ,  cm2 19 18 17 18 22
Phase angle/°

800 RPM 30 Q, ␮F sn-1 cm−2 74.6 78.4 27.7 49.3 64.5

|Z|/Ω cm2

n 0.87 0.85 0.86 0.90 0.88

RC , k cm2 18.3 7.5 2.1 3.4 4.1
RA ,  cm2 153 326 393 687 1065
20 Y0 , mF s0.5 cm−2 5.6 5.3 5.5 2.8 1.6
10 ␻0 , s−1 162.2 60.8 133.0 33.0 5.5
K 1.8 3.0 5.8 1.9 1.8
10 nD 0.41 0.48 0.56 0.38 0.48
␹2 × 105 6.3 6.5 7.7 16.2 79.5
Error in |Z|, % 0.8 0.8 0.9 1.3 2.8

0 0
-2 0 2 4
10 10 10 10 iii) Diffusion of ions in the solid side of the electrode-electrolyte
Frequency/Hz interface occurs in series with the anodic dissolution of CuFeS2
Fig. 8. Effect of stirring rate on the impedance spectra of a fresh CuFeS2 electrode.
T = 25 ◦ C; 0.05 mol L−1 Fe2 (SO4 )3 , 0.1 mol L−1 FeSO4 , 0.5 mol L−-1 H2 SO4 . The proposed circuit consists of a constant phase element (CPE)
to account for the presence of non-idealities in the capacitance of
the double layer in parallel with two faradaic resistances; the first
To fit the experimental data in Figs. 5–7 the equivalent electrical resistance, RC , corresponds to the cathodic reduction of Fe3+ ions
circuit shown in Fig. 9 was used. This equivalent circuit was derived whereas the second one, RA , corresponds to the anodic dissolution
based on the following assumptions: of the electrode and is in series with a diffusion impedance element,
ZD , to account for solid state diffusion processes. To model the dif-
i) The only cathodic reaction occurring is the reduction of Fe3+ fusion processes in the system a CPE-restricted diffusion element
ions was selected. This element was proposed by Bisquert et al. [32,33]
ii) Mass transfer of Fe3+ or any other soluble species does not to model diffusion layers where hindrance to mass transport can
affect the dissolution rate of CuFeS2 under the experimental be present at the boundaries. The expression for ZD is given by Eq.
conditions used in this study 9 and the physical meaning of Y0 , ␻0 and K is discussed in further
paragraphs.
⎡   ⎤
n ω0 ωn ω0
(jω) + 0
coth
1 ⎢ jω K jω ⎥
ZD = ⎣ ωn   ⎦ (9)
Y0 ω00.5 jω n ω0
K
0
ω0 + (jω) coth jω

The fitted parameters obtained from the experimental data

shown in Figs. 5 and 6 are summarized in Table 1; fitted param-
eters from Fig. 7 are reported in Table 2. The comparison between
the discrete points and the continuous lines in Figs. 5–7 as well as
Fig. 9. Equivalent circuit used to fit experimental impedance spectra obtained with the low values of ␹2 indicate agreement between the model and
fresh and passivated CuFeS2 electrodes. the experiments.
 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19 13

Table 2
Estimated parameters from the experimental results for the fresh and passivated CuFeS2 electrodes shown in Figs. 7 and 12 by fitting to equivalent circuit shown in Fig. 9.

Fresh CuFeS2 electrodes Passivated CuFeS2 electrodes

No FeS2 P1 P2 P3 No FeS2 P1 P2 P3

R ,  cm2 17 18 17 17 41 38 38 39
Q, ␮F sn-1 cm−2 27.7 29.2 29.8 30.4 76.1 35.9 37.7 84.3
nCPE 0.86 0.85 0.85 0.85 0.75 0.83 0.83 0.73
RC ,  cm2 2148 943 642 432 6405 3885 3109 1065
RA ,  cm2 393 399 433 411 126 187 200 61
Y0 , mF s0.5 cm−2 5.4 6.8 6.8 6.1 1.4 2.22 2.2 1.3
␻0 , s−1 133 81 119 107 101 96 101 85
K 5.8 5.7 5.2 7.0 179 237 277 238
nD 0.56 0.60 0.54 0.58 0.64 0.73 0.73 0.65
␹2 × 105 7.7 9.6 13.5 4.8 25.6 4.0 5.1 3.3
Error in |Z|, % 0.9 1.0 1.2 0.7 1.6 0.6 0.7 0.6

meaning is as follows. Y0 can be regarded as the inverse of a War-

3+
burg constant, ␴; ␻0 is a characteristic frequency that depends on
R , effect of Fe
C
RA , effect of Fe
3+ the chemical diffusion coefficient, D, and the thickness of the diffu-
10
4
R , effect of Fe2+ sion layer, L (Eq. 10). K is a dimensionless parameter associated with
C 2+
R , effect of Fe
A the CPE that is used to model the impedance at the film/electrolyte
interface. Values of K « 1 are indicative of a totally blocking bound-
ary while values of K » 1 correspond to a boundary where the excess
RC, RA/Ω cm2

concentration is immediately absorbed [33]. Finally, nD is the CPE

exponent used in ZD to model the boundary dividing the diffusion
layer and the electrolyte.
3
10
ω0 = D/L2 (10)

Previous studies by Biegler and Horne [40] and Ghahrema-

2 be a more appropriate choice as opposed to the use of a Warburg
10 0
10 10
1
10
2 impedance.
[Fe2+], [Fe3+]/mmol L-1
Fig. 10. Effect of Fe3+ and Fe2+ concentration on RC and RA . Circle and square markers
correspond to the effect of Fe3+ while keeping Fe2+ concentration at 100 mmol L−1 .
Diamond and inverted triangle markers correspond to the effect of Fe2+ while keep-
ing Fe3+ concentration at 100 mmol L−1 .
The estimated values for the CPE exponent value, n, ranged from
0.85 to 0.90 in all cases, indicating that this element corresponds to
a capacitor exhibiting frequency dispersion. Such dispersive behav-
ior has been attributed to the distribution of physical properties
[34], surface disorder, roughness and inhomogeneities [35–38].
Table 1 shows a decrease in the value of the pre-exponential factor,
Q, of the CPE as the concentration of Fe3+ and Fe2+ increased; this
change was caused by a decrease in the dielectric constant of the
electrolyte in the double layer [20,39].
As Fe3+ concentration increased from 1 to 100 mmol L−1 RC
decreased from 18.3 to 2.1 k cm2 . Increasing Fe2+ concentration
from 1 to 100 mmol L−1 only led to a decrease of RC from 4.1 to 2.1
k cm2 . Fig. 10 shows an exponential decrease of RC with increas-
ing Fe3+ and a lower dependence on Fe2+ concentration. The effect
of Fe3+ concentration on RA was different than on RC and an increase
from 153 to 393  cm2 was observed when Fe3+ concentration
was increased from 1 to 100 mmol L−1 ; however, as with RC , RA
also increased with decreasing Fe2+ concentration. The fact that
RC decreased and RA increased with increasing Fe3+ concentration
indicates that RC and RA corresponded to the reduction of Fe3+ ions
(Eq.2) and to the anodic dissolution of CuFeS2 (Eq. 1), respectively.
Although the primary objective of these experiments was to
help with the assignment of physically-correct RC and RA it also
seems relevant to discuss the significance of the effect of Fe3+ and
Fe2+ concentrations on the parameters of the diffusion impedance
element used in the equivalent circuit shown in Fig. 9. The physical
ninezhad et al. [26] have reported the presence of a thin film on
freshly prepared CuFeS2 electrodes. Therefore, the use of the diffu-
sion impedance model proposed by Bisquert et al. [32,33] seems to
The value of Y0 only increased 4% when Fe3+ concentration
decreased from 100 to 1 mmol L−1 and it can be considered to have
remained constant. In regards to ␻0 no clear relation with the con-
centration of Fe3+ species could be observed while the value of K
decreased with decreasing Fe3+ concentration. This decrease sug-
gests that the film/electrolyte interface becomes more blocking or
resistive to the transfer of cations from the film to the solution; this
behavior could have been caused by the decrease of the concentra-
tion of electron acceptor species (Fe3+ ions) in the electrolyte and
a consequent decrease on the cathodic current density. Since both
the anodic and cathodic processes have to occur at the same rate
(Eq. 6) a decrease of the cathodic current should be accompanied
by a decrease of the anodic dissolution of the electrode and, con-
sequently, of the diffusion of cations within the film layer, hence
explaining the decrease of K as Fe3+ concentration was decreased.
When Fe2+ concentration was decreased from 100 to
1 mmol L−1 , the values of Y0 decreased from 5.4 to 1.6 mF s0.5 cm−2 ,
indicating an increase in the resistance to the diffusion of cations
within the thin layer on the surface of the electrode. In addition to
this, both the values of ␻0 and K also decreased with decreasing Fe2+
concentration. Since Fe3+ concentration was kept constant for these
experiments the explanation for this behavior should be different
from the explanation given in the previous paragraph. The values of
K indicate that the dissolution of ions within the film becomes more
resistive as Fe2+ concentration decreased; however, the decrease
in the characteristic frequency suggests that the thickness of the
diffusion film increased with decreasing Fe2+ concentration which
results in a more positive solution potential. These three indicators
(decrease on Y0 , ␻0 and K) suggest that the thickness of the film
increased with increasing the mixed potential of the electrode.
In order to calculate the numerical values of the thickness of the
film layer the value of the self-diffusion coefficients of Cu2+ and Fe2+
in CuFeS2 would be required to estimate the diffusion coefficient
14 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19

0.45 RC , indicating that the main effect of FeS2 on the fresh CuFeS2
electrode was to decrease the charge transfer resistance for the
0.40 reduction of Fe3+ ions. On the other hand, RA changed only within
a small range with an average value of 409  cm2 and a relative
0.35
standard deviation of 4.3% suggesting that there was no effect of
0.30 FeS2 on the charge transfer resistance for the anodic dissolution of
the electrode. Q only increased 10% when the largest FeS2 particle
(P3, 1.37 cm2 ) was contacted with the fresh CuFeS2 electrode while
ω -0.5/s 0.5

0.25
the value of n remained constant, indicating that the properties of
0

0.20
0.15
0.10
0.05
0 FeS2 particles with the fresh CuFeS2 electrode; however, despite
300 350 400
OCP vs SCE/mV
Fig. 11. Effect of OCP on the characteristic frequency, ␻0 , for the fresh CuFeS2 elec-
trode.
to be used in Eq. 10. Different authors have reported the diffusion
coefficient for chalcopyrite using different techniques [41,42], but
differences in orders of magnitude were found when they were
compared. However, from Eq. 10 it is recognized that the thickness
of the film layer, L, is proportional to ␻0 −0.5 , regardless of the value
of D. Fig. 11 shows a plot of ␻0 −0.5 against the measured OCP for
the different concentrations of Fe3+ and Fe2+ reported in Table 1.
Results suggest that the thickness of the film is almost constant for
potentials lower than 394 mV vs SCE. Increasing the ratio Fe3+ :Fe2+
led to an increase in the mixed potential of the electrode and appar-
ently also to an increase in the thickness of the film. It is important
to consider that the model proposed by Bisquert et al. [32] is limited
in that it considers that the transport of species occurs only by
diffusion. Therefore, if there is a contribution of migration to the
transport of cations within the film, the calculation of the thickness
of the diffusion layer would be affected. Thus these calculations
should be accompanied by surface characterization techniques to
confirm their validity.
The fitted parameters for the curves shown in Fig. 7 have been
summarized in Table 2. The parameter that was most affected
when FeS2 particles contacted the fresh CuFeS2 electrode was
the double layer where almost unaffected by the presence of FeS2 .
As for the parameters related to the diffusion of cations in the
electrode, Y0 increased with the presence of FeS2 but did not seem
to keep a direct relation with the size of the particles evaluated;
the same can be said of K as it decreased with the particles P1 and
P2 but then increased when P3 was used in the experiment. The
characteristic frequency, ␻0 , also decreased when contacting the
450
the changes in the value of ␻0 and regardless of the value of the
diffusion coefficient used in Eq. 9 the calculated values for the
diffusion layer thickness, L, would only change within a small
range (relative standard deviation of 11%). This result is expected
as there does not seem to be a reason for which contacting the FeS2
particles with the electrode would affect the values of ␻0 and L.
Fig. 12 shows the effect of FeS2 on the passivated CuFeS2 elec-
trode. The passivated electrodes showed a shift in the phase peaks
towards lower frequencies compared to the fresh electrodes; in the
case of the first time constant the shift in the phase peak happened
from 120 Hz to about 10 Hz whereas for the lower frequency time
constant the shift in the peak phase was observed from 25 mHz
to frequencies below 3 mHz. Otherwise, FeS2 had a similar effect
to that observed for the fresh CuFeS2 electrode in Fig. 7a where a
decrease in the impedance modulus was observed, particularly at
frequencies lower than 1 Hz. In addition to this, it is worth noticing
that the modulus of the impedance at 10 kHz increased from 17 to
37  cm2 .
The equivalent circuit shown in Fig. 9 already considers the dif-
fusion of species within a film layer and therefore was also used to
model the experimental data shown in Fig. 12. The fitted parame-
ters have also been summarized in Table 2.
Before discussing the effect of FeS2 on the passivated CuFeS2
electrode it is worth commenting on the differences observed with
the fresh electrode. The first difference was observed in the value
of the ohmic resistance, R , which increased by a factor of 2.4 after

a) b) 60
No Pyrite
3
10 Pyrite 1
50 Pyrite 2
Pyrite 3
40
Phase angle/°
|Z|/Ω cm2

30
2
10
No Pyrite
Pyrite 1 20
Pyrite 2
Pyrite 3 10

1
10 -2 0 2 4
0 -2 0 2 4
10 10 10 10 10 10 10 10
Frequency/Hz Frequency/Hz

Fig. 12. Effect of FeS2 on the impedance spectra of a passivated CuFeS2 electrode. T = 25 ◦ C; 0.05 mol L−1 Fe2 (SO4 )3 , 0.1 mol L−1 FeSO4 , 0.5 mol L−1 H2 SO4 . a) Impedance
modulus and b) Phase angle.
 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19
Fig. 13. Variation of ohmic resistance during the passivating procedure.
the passivating treatment. This apparent increase can be attributed
to an increase of the transfer of electrons at the electrode/film
interface as a consequence of the chemical treatment to which
the electrode was exposed. Armstrong and Edmondson [43] pro-
posed that the impedance of the electrode-film interface could be
described by a capacitor (Cf ) in parallel with two charge transfer
resistances, each associated with the transfer of electrons (Re ) and
to the transfer of cations (RC2 ) from the electrode to the film. It is
usually assumed that the resistance to the transfer of electrons is
much lower than the resistance to the movement of cations (Re «
RC2 ) and that the capacitance associated with the film-electrode
interface, Cf , is due to the space charge layer within the passive
film. Under these circumstances, the time constant associated with
the Re Cf circuit is larger than the frequencies analyzed in this work
and could not be resolved (1/Re Cf » ␻) [44]. Therefore an appar-
ent increase in the ohmic resistance (R ) would be expected in the
presence of the passive film. To calculate the value of the charge
transfer resistance of electrons at the electrode/passive film inter-
face, an average value for R was taken from values reported in
Table 2 (17  cm2 ) before the passivating treatment. This gave a
value of 24  cm2 for Re which was nearly constant in the presence
of different FeS2 particles.
The effect of the passive film can also be observed in Fig. 13
where the values of R have been plotted against the time dur-
ing which the electrode was immersed in solution at 50 ◦ C for the
passivating treatment. During the first 7 h of the experiment, R
reached a minimum value and thereafter kept increasing almost
linearly with time up to 94 h when the experiment was stopped. A
possible explanation for this is that the film originally present on
the surface of the electrode dissolves or changes in nature with a
consequent decrease on the resistance to the transfer of electrons
from the electrode to the film; thereafter a different film is formed
on the surface of the electrode with a consequent increase on the
resistance to the transfer of electrons and on the apparent ohmic
resistance, R .
Results in Table 2 also show that in the absence of FeS2 , RC
increased by a factor of 3 after the passivating treatment whereas
the anodic charge transfer resistance, RA , actually decreased by
a factor of 3.1. The parameters Y0 , K and ␻0 were also affected;
Y0 and ␻0 decreased while K increased by a factor of 31, being
the most affected parameter after the passivating treatment. The
change observed in Y0 indicates an increase in the resistance to the
diffusion of cations within the film. The substantial increase of K
indicates that despite the increase in Y0 , the transfer of species at
15
18
16
14
12
Dissolved Cu/mg
10
0
0 20 40 60 80
Time/h
Fig. 14. Extracted copper with time during the leaching of CuFeS2 . T = 25 ◦ C;
0.05 mol L−1 Fe2 (SO4 )3 , 0.1 mol L−1 FeSO4 , 0.5 mol L−1 H2 SO4 , 400 rpm.
the film/solution interface is not as hindered as in the case of the
fresh electrode, which was an unexpected result and suggests that
the transport of cations is limited within the film but not at the
film/solution interface.
When FeS2 was placed in contact with the passivated electrode
the value of RC decreased by a factor of 6 indicating that FeS2 contin-
ued to have a positive effect on the dissolution rate of the passivated
CuFeS2 electrode after it was passivated. The effect of FeS2 on RA
in the passivated electrode was different depending on the FeS2
particle and no direct relationship between the area of the FeS2
particles and the variation of RA could be observed. Given the val-
ues estimated for the fresh electrode in contact with the different
FeS2 particles, it is very likely that FeS2 had no actual effect on the
value of RA in the case of the passivated electrode. Similarly, the
values of Y0 , ␻0 and nD did not seem to have been modified by the
presence of FeS2 despite the variations observed. As for the val-
ues of K, these increased with FeS2 particles being contacted with
the passivated electrode although, once again, no relation could be
observed between this parameter and the size of the FeS2 particles
evaluated.
3.4. Leaching of CuFeS2
Fig. 14 shows the Cu extraction curve for the dissolution of
CuFeS2 . Since the leaching rate seemed to have decreased with time
the dissolution rate was calculated based on the first four hours of
the experiment. This time interval is most in agreement with the
rates calculated by the EIS experiments as they lasted less than
one hour each. The calculated value for the dissolution rate was
928 ␮gCu h−1 g−1 which, based on the stoichiometry given in Eq. 1,
corresponds to a current density of 8.2 ␮A cm−2 .
4. Discussion
According to the equivalent circuits shown in Fig. 9, the anodic
dissolution of CuFeS2 occurs in series with a diffusion process asso-
ciated with the migration of Cu2+ and Fe2+ cations [45] from the
solid to the solution in the case of fresh electrodes or through a
metal deficient film in the case of the passivated electrodes [20,45].
16 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19

Table 3
Calculated dissolution current densities at different experimental conditions. Fresh electrode
60
3+
[Fe ], mmol L −1 2+
[Fe ] mmol L −1
Electrode FeS2 jdissol , ␮A cm−2 Pass ivated electrode
condition
50
1 100 Fresh No 1.4
jdissol = 34.8APy + 13.3
10 100 Fresh No 3.4
100 100 Fresh No 12.0

jdissol/μA cm-2
40
100 1 Fresh No 6.2
100 10 Fresh No 7.6
100 100 Fresh P1 27.2 30
100 100 Fresh P2 40.0
100 100 Fresh P3 59.5
100 100 Passivated No 4.0 20
100 100 Passivated P1 6.6
100 100 Passivated P2 8.3
100 100 Passivated P3 24.1
10
jdissol = 15.0APy + 1.52

The dissolution current density of CuFeS2 at mixed potential con- 0

ditions is given by Eq. 11 (see also Eqs.5–7):
jdissol (EM ) = jA = −jFe3+
where jdissol is the dissolution current density of the CuFeS2 elec-
trode, jA the anodic dissolution of the electrode and jFe3+ , the Fe3+
ion reduction current density. Hence, by knowing jFe3+ or jA the
dissolution rate of the electrode can be determined. The anodic
dissolution of CuFeS2 , jA , occurs in series with a diffusion process
(Fig. 9), which depends on the frequency of analysis in the EIS
experiment. On the other hand, as shown in Fig. 8, the transport of
Fe3+ ions from the solution to the surface of the electrode does not
affect the electrochemical dissolution of CuFeS2 , thereby allowing
the direct determination of the dissolution current density (jdissol )
from the cathodic charge transfer resistance (RC ) via Eq. 12 [46].
The calculated dissolution current density values are summarized
in Table 3.
RT
jdissol (EM ) = −jFe3+ =
nFRC
Table 3 shows an increase in the rate of dissolution of CuFeS2
with increasing Fe3+ concentration and increasing FeS2 surface
area. Values ranging from 1.4 to 12.0 ␮A cm−2 were observed in
the absence of FeS2 in the range of Fe3+ and Fe2+ concentrations
analyzed in this work. The value calculated from the leaching exper-
iment was 8.2 ␮A cm−2 and is in very close agreement with the
value obtained from EIS experiments (12.0 ␮A cm−2 ); therefore,
the results shown in Table 3 can be considered as representative
of the dissolution rate of the electrode under different experimen-
tal conditions. Nevertheless we consider that a more systematic
study wherein a determination of the conditions under which the
use of electrochemical techniques is valid for the measurement of
dissolution rates should be conducted.
In the presence of FeS2 a dissolution current density of
59.5 ␮A cm−2 was obtained for the particle P3, with an area of 1.37
cm2 . This value represents an increase by a factor of 5 in compar-
ison to the value obtained in the absence of FeS2 . Majuste et al.
[30] obtained a value of 8.0 ␮A cm−2 with a CuFeS2 electrode when
Fe3+ concentration was 0.01 mol L−1 in a 0.1 mol L−1 H2 SO4 aque-
ous solution; this value matches well with the value obtained in
this work under similar conditions (0.5 mol L−1 H2 SO4 , 0.01 mol L−1
Fe3+ and 0.1 mol L−1 Fe2+ ); these authors also reported an increase
by a factor of 2.2 for a CuFeS2 electrode containing 42% FeS2 present
as inclusions in the surface of the electrode. You et al. [31] reported
a value of 5 ␮A cm−2 for a CuFeS2 electrode in contact with FeS2 in
a 0.01 mol L−1 Fe3+ and pH = 3.8 solution whereas Abraitis et al. [47]
reported values of 0.5 and 9.0 ␮A cm−2 in the absence and presence
of FeS2 , respectively, in a pH = 2.5 HCl solution.
The effect of the chemical passivation treatment on the dissolu-
tion current density can also be observed in Table 3. Although the
0 0.5 1 1.5
FeS2 surface area/cm2
(11)
Fig. 15. Effect of FeS2 surface on the dissolution current density of the fresh
and passivated CuFeS2 electrodes. T = 25 ◦ C; 0.5 mol L−1 H2 SO4 , 0.1 mol L−1 FeSO4 ,
0.05 mol L−1 Fe2 (SO4 )3 .
dissolution rate of the passivated electrode decreased by a factor of
3 in the absence of FeS2 , the effect of FeS2 on the dissolution rate of
the passivated electrode continued after the chemical treatment.
Fig. 15 shows the dissolution current densities plotted against the
surface area of the FeS2 particles for both fresh and passivated elec-
trodes. In both systems a linear increase of the dissolution rate
was observed with increasing pyrite particle size. From the results
shown in Table 3 and Fig. 15 the following observations are note-
worthy:
i) The galvanic effect between FeS2 and CuFeS2 persisted after
(12)
the passivating treatment. This result suggests that the passive
film has semiconducting properties as shown by Ghahrema-
ninezhad et al. [26] and does not prevent electron transfer
between both minerals.
ii) FeS2 was 2.6 and 9.9 times more active than fresh and passi-
vated CuFeS2 electrodes, respectively, for the reduction of Fe3+
ions.
iii) There was a change in the slope of the fitted curves in Fig. 15.
A decrease in the dissolution rate of CuFeS2 was expected in
the absence of FeS2 , however FeS2 particles were not subjected
to any chemical treatment and the same rate would have been
expected (34.8 ␮A cm−2 Py ) even after the CuFeS2 electrode was
passivated, given that the galvanic effect between the two min-
erals remained. This apparent decrease in the activity of FeS2
for the reduction of Fe3+ suggests a change in the rate deter-
mining step in the dissolution of CuFeS2 once the passive film
is formed.
Fig. 16 shows the effect of Fe3+ and Fe2+ concentrations on the
dissolution current density of CuFeS2 . This logarithmic plot shows
a linear increase of the dissolution current density with increas-
ing Fe3+ concentration; the linear fit gave an exponent of 0.46 for
the dependence of the dissolution current density on the concen-
tration of Fe3+ . The slope of the experimental points where Fe2+
concentration was varied gave an exponent of 0.14, indicating a
weaker dependence of the dissolution rate on the concentration of
Fe2+ . As it was previously mentioned, in order to get a more accu-
rate kinetic expression more experimental points are required; the
equations presented in Fig. 16 are limited, yet they provide valuable
information. The dissolution kinetics of different metal sulfides can
be represented by Butler-Volmer type rate equations [30,48,49]. To
 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19
Effect of Fe3+
Effect of Fe2+
1
10 jdissol = 15.9[Fe2+]0.14
jdissol/μA cm-2
jdissol = 32.3[Fe3+]0.46
0
10 0 1 2
10 10
[Fe ],[Fe2+]/mmol L-1
3+
Fig. 16. Effect of Fe3+ and Fe2+ concentration on the dissolution current density of
the fresh CuFeS2 electrode. Black circle markers correspond to the effect of Fe3+
while keeping Fe2+ concentration at 100 mmol L−1 . Blue square markers correspond
to the effect of Fe2+ while keeping Fe3+ concentration at 100 mmol L−1 .
derive a simple kinetic expression of the dissolution current density
using mixed potential theory Eq. 7 can be taken as starting point.
For simplicity, and to be able to derive an explicit expression, it will
be assumed that the charge transfer coefficient for the reduction of
Fe3+ ions and for both anodic reactions is the same and equal to 0.5.
By solving for EM and substituting in the kinetic expression for the
reduction of Fe3+ ions, jFe3+ , Eq. 13 is obtained:
    12
kFe3+ Fe3+
jdissol = kCuFeS2  
kCuFeS2 + kFe2+ Fe2+
A comparison of the equations presented in Fig. 16 and Eq.
13 indicates agreement between the theoretical electrochemical
model and the experimentally fitted equations; the electrochemi-
cal model predicts a reaction order of 0.5 while the fitted value was
0.46. On the other hand, Eq. 13 predicts a reaction order of −0.5
with respect to the concentration of Fe2+ but the fitted value was
0.14; if the product kFe2+ [Fe2+ ] in Eq. 13 is smaller than kCuFeS2 then
the expected exponent should be close to zero. This indicates that
under the present experimental conditions the anodic dissolution
of CuFeS2 occurs at higher rates than the oxidation of Fe2+ , and that
the current densities reported in this work indeed correspond to
the dissolution of the electrode, which was further confirmed by
the leaching experiment. With these considerations a rate expres-
sion can be used to approximate the dissolution current density of
the CuFeS2 electrode:
 A   0.5
jdissol ≈ 32.3 Fe3+
cm2
Expressions similar to Eq. 14 have been reported in the liter-
ature. In a recent review, Li et al. [11] reported reaction orders
for the dissolution of CuFeS2 with respect to Fe3+ ranging from
0.12–1.0 depending on the leaching media and temperature used
by different authors. Although Eq. 14 describes the dissolution of
CuFeS2 appropriately for the conditions used in this work and in the
absence of FeS2 , it does possess limitations. For example, further
17
Fig. 17. Resistance to the diffusion of cations within the passive film in fresh and
passivated CuFeS2 electrodes in contact with different FeS2 particles.
10
work would be required to obtain a more detailed rate expression
to account for other factors such as pH and temperature.
Figs. 15 and 16 show that the dissolution of CuFeS2 was strongly
affected by the concentration of Fe3+ and by the presence of FeS2 .
This suggests that in the case of fresh electrodes the rate controlling
reaction is the reduction of Fe3+ ions and not the anodic dissolution
of chalcopyrite. If the limiting step in the dissolution of the fresh
electrode was the transport of ions within the passive film a weaker
or no dependence of the dissolution rate of CuFeS2 with respect to
Fe3+ concentration would have been observed. Following the same
reasoning it can also be said that even in the presence of FeS2 the
dissolution of CuFeS2 is controlled by the reduction of Fe3+ ions.
Therefore, before the passive film forms on the CuFeS2 surface, the
diffusion rate of ions from the solid to the solution has to be large
compared to the reduction of Fe3+ ions.
(13)
These findings agree with previous studies by Nazari et al. [8],
who suggested that the slow charge transfer process in the reduc-
tion of Fe3+ ions was the rate determining step in the dissolution
of un-passivated CuFeS2 , while in the presence of FeS2 this rate
increased due to the availability of an additional reaction surface.
If the transport of electrons or ions from the solid to the solution
was the slowest step in the dissolution of CuFeS2 no change in the
dissolution rate of CuFeS2 would be observed by increasing Fe3+
concentration or by contacting the electrode with the different FeS2
particles.
A different scenario was observed for the experiments con-
ducted with the passivated electrode. For this system a decrease
in the dissolution current density (vs. the fresh electrodes) was
observed both in the presence and absence of FeS2 ; an apparent
increase in the ohmic resistance was also observed, which cor-
responded to the resistance to the transport at the electrode/film
interface. To analyze the effect of the passivating treatment on the
diffusion within the passive film a diffusion resistance was defined
(14) in Eq. 15 [32,33]:
 −1
RD = Y0 ω00.5 (15)
The calculated values for RD are presented in Fig. 17. Although no
clear effect of FeS2 could be observed for this parameter, it is clear
that the passivating treatment increased the resistance to the dif-
fusion of cations within the passive film; in the experiments where
FeS2 was absent the value of RD increased by a factor of 4.3. These
results, and the apparent increase in the ohmic resistance, indicate
18 O.G. Olvera et al. / Electrochimica Acta 127 (2014) 7–19
that after the passivating treatment the increase in the diffusion of
ions within the passive film and the increase in the resistance to
electron transfer at the electrode/film interface are the causes for
the decrease in the dissolution rate of the CuFeS2 electrode after the
passivating treatment. On the other hand, according to the increase
in the values of K after the passivating treatment, it would seem that
the transfer of cations at the film/solution interface does not play a
key role on the dissolution rate of the electrode.
Ghahremaninezhad et al. [20] recently suggested that the reduc-
tion of Fe3+ ions on the surface of an electrochemically passivated
CuFeS2 electrode was fast and that the slow kinetics of this reaction
was due to the slow diffusion of Fe atoms through the passive film.
The results shown in this work agree with their conclusions.
Finally, Nazari et al. [8] observed that in the presence of silver-
modified FeS2 a small fraction of the silver dissolved and formed
silver sulfide in the passive film of CuFeS2 ; this increased the con-
ductivity of the passive film and allowed the transfer of electrons
from CuFeS2 to FeS2 thus avoiding passivation over several hours
of leaching. In view of the recent findings it is possible that the
presence of silver ions may also have enhanced the flux of cation
vacancies within the passive film. According to the point defect
model for passive films [50], an increase in the rate of diffusion
of cations within the passive film could cause an accumulation of
cation vacancies at the electrode/film interface; depending on the
relative rates of cation transfer at the electrode/film interface and
the rate of vacancy transport within the film, the excess vacancies
will condense and cause local detachment of the film. Once the
vacancy condensate has grown to a critical size, the stress in the
film will induce structural instability with the possible rupture of
the film and formation of a pit where rapid localized attack of the
mineral can occur.
Therefore, in addition to offering an additional surface for the
reduction of Fe3+ ions it seems that FeS2 may also enhance the
dissolution of CuFeS2 by increasing the rate of diffusion of cations
within the passive film and, under certain conditions, contribute to
the detachment of this film from the CuFeS2 particles. This would be
consistent with the observations made by Nazari et al. [8] where no
passive behavior was observed during the leaching of CuFeS2 in the
presence of silver-enhanced FeS2 , and would also help to explain
the results reported by Rivera [27] who observed that the addi-
tion of FeS2 to a copper concentrate after 24 h of leaching, that was
showing signs of passivation, resulted in an increase in the leaching
rate with complete copper extraction after 19 h in the presence of
FeS2 .
5. Conclusions
In this work the electrochemical dissolution of fresh and passi-
vated CuFeS2 electrodes has been studied. The rate of dissolution
of the fresh electrode increased with Fe3+ concentration and with
FeS2 but decreased by a factor of 3 after the passivating treatment.
On the other hand, dissolution rates of fresh and passivated elec-
trodes increased by factors of up to 5 and 6, respectively, when a
FeS2 particle (1.37 cm2 ) was contacted with the CuFeS2 electrode.
The catalytic effect of FeS2 continued after the passivating treat-
ment of the electrode indicating that the passive film allows the
transport of electrons between the passivated electrode and the
FeS2 particles.
The anodic dissolution parameters RA and those associated to ZD
were almost unaffected neither by Fe3+ concentration nor with con-
tact with FeS2 , while RC changed considerably with those variables
as well as with the passivation treatment. These results indicated
that the rate determining step in the electrochemical dissolution of
a fresh CuFeS2 electrode is the reduction of Fe3+ ions, even in the
presence of FeS2 .
On the contrary, the lower effect of FeS2 on the dissolution cur-
rent density of the passivated CuFeS2 electrode suggested that the
reduction of Fe3+ ions is not the rate controlling step on passi-
vated CuFeS2 . The increase in the resistances to the diffusion of
cations within the passive film and to the transfer of electrons at
the electrode/film interface seems to be responsible for the low
dissolution current densities observed after the passivating treat-
ment. Nonetheless, FeS2 still increased the dissolution rate of the
passivated electrode by increasing the reduction of Fe3+ ions.
Acknowledgements
The authors wish to acknowledge generous financial support
from Xstrata Process Support, SNC Lavalin, and the Natural Sciences
and Engineering Research Council of Canada (NSERC). We are also
appreciative of the Electron Microbeam and X-Ray Diffraction Facil-
ity in the Department of Earth, Ocean and Atmospheric Sciences at
UBC for the technical support provided for the QXRD analysis. The
authors also wish to acknowledge the reviewers for their valuable
comments and suggestions.
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