Int. J. Miner. Process.

67 (2002) 17 – 28
www.elsevier.com/locate/ijminpro

A comparative study of electrochemical behavior

of chalcopyrite, chalcocite and bornite in sulfuric
acid solution
Elsa M. Arce a,*, Ignacio González b,1
a
Departamento de Ingenierı́a Metalúrgica, Instituto Politécnico Nacional-ESIQIE,
Apdo. Postal 75-876, C.P. 07300 Mexico, D.F., Mexico
b
Departamento de Quı́mica, Universidad Autónoma Metropolitana-Iztapalapa,
Apdo. Postal 55-534, C.P. 09340 Mexico, D.F., Mexico
Received 15 March 2001; received in revised form 5 October 2001; accepted 11 February 2002

Abstract

A comparative study of the electrochemical behavior of different copper sulfide minerals

(chalcopyrite, bornite and chalcocite) in sulfuric acid solutions was performed. Carbon paste
electrodes (CPE) containing mineral particles with nonconducting binder were used. The
comparative study shows that the chalcopyrite oxidation process does not produce covellite as
claimed by some authors. Chalcopyrite oxidation has been found to produce a nonstoichiometric
sulfide, Cun
1Fen
1S2n. On the other hand, it is apparent that bornite is not an intermediary species
formed in the chalcopyrite reduction; the reduction of chalcopyrite directly produces chalcocite.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: chalcopyrite; chalcocite; bornite; CPE; voltammetry

1. Introduction

The electrochemical behavior of sulfide and oxide minerals has been largely studied
(Peters, 1977; Kobayashi et al., 1990; McMillan et al., 1982). Metal sulfides have received
the most attention because they are recognized as valuable sources of nonferrous metal.
Koch (1975) has reviewed the electrochemistry of sulfide minerals and Shuey (1975) has

*
Corresponding author. Fax: +52-57-296000x55270.
E-mail addresses: earce@ipn.mx (E.M. Arce), igm@xanum.uam.mx (I. González).
1
Fax: +52-58-044666.

0301-7516/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 1 - 7 5 1 6 ( 0 2 ) 0 0 0 0 3 - 0
18 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28

reviewed the electronic properties of both oxide and sulfide minerals. Numerous electro-
chemical studies on copper sulfide minerals have been performed (Woods and Hope,
1999; Buckley and Woods, 1993; Tao et al., 1994; Brage et al., 1979; Koch and McIntyre,
1976), most of them aimed at understanding their behavior in different stages of mineral
processing, particularly in the leaching and flotation processes. These electrochemical
processes, which are determined by the electrochemical interactions on dissolution at the
electrode surface, are dependent on the composition and morphology of the mineral.
During these processes, the surface modification occurs with a heterogeneous composition
and morphology that depends on, among other factors, the applied potential, pH,
temperature, rate of the potential scan, type and concentration of sulfur-containing ions
and compounds, presence of different types of chemical active solid phases, compounds
influencing into the wetting properties of surface.
The dissolution of metal components from chalcopyrite (CuFeS2) is slow, even in
highly acidic solutions. Methods that are successful in leaching copper invariably dissolve
iron as well (Biegler and Swift, 1977). Many works have shown that the leaching
chalcopyrite process is inhibited by a layer of a thickening product formed, but there is
a disagreement on its nature and little is known about the electrochemistry involved in its
formation (Parker et al., 1981; Holliday and Richmond, 1990; Biegler and Horne, 1985).
Previous electrochemical studies have proposed the direct oxidation of chalcopyrite to
covellite, CuS (Eq. (1)).

CuFeS2 Z0:75CuS þ 0:25Cu2þ þ Fe2þ þ 1:25S þ 2:5e
ð1Þ

More recent studies (Price, 1981; Lázaro et al., 1995) proposed the formation of
previous nonstoichiometric sulfides in the chalcopyrite electrodes (Eq. (2)).

nCuFeS2 ZCu2þ þ Fe3þ þ Cun
1 Fen
1 S2n þ 5e
ð2Þ

There are important differences between both proposed mechanisms: the dissolved iron
leaves the mineral in its +2 or +3 oxidation state, the solid product layer contains sulfur
and covellite or only sulfur and the ratio of dissolved iron to dissolved copper is 4:1 or 1:1,
respectively.
The differences of the electrochemical reactions associated to the chalcopyrite oxida-
tion process could be associated to the different oxidation states of copper (i.e. Cu+, Cu2+)
in the chalcopyrite structure. This fact is a controversial matter in the literature (Dana and
Ford, 1986).
Other studies of hydrometallurgical processing of chalcopyrite have indicated the initial
transformation to bornite (Cu5FeS4) or to chalcocite (Cu2S) and these minerals are leached
more easily. Electrochemical studies have been performed in order to identify the steps
involved in chalcopyrite reduction (Biegler and Horne, 1985; Lázaro et al., 1995; Warren
et al., 1985). However, there are some discrepancies regarding the identification of these
steps. In this work, we performed a comparative study of the electrochemical behavior of
different copper minerals (chalcopyrite, bornite and chalcocite) in sulfuric acid solutions,
in order to contribute to a better understanding of the electrochemical conversion of copper
minerals.
 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28 19

2. Experimental

A total of 0.8 g of graphite (Aldrich, 99.99% purity) was pulverized together with
0.2 g of mineral (chalcopyrite, bornite or chalcocite) in an agate mortar. The resulting
powder was added with 0.8 ml of silicon oil (Aldrich) and this was mixed to form a
homogeneous paste. This paste was placed in a 7-cm-long, 0.4-cm-diameter plastic
tube provided with a plunger to eliminate the paste once it had reacted (approximately
0.5 cm); the surface was levelled with a glass spatula. Thus, the surface can be
renewed for each experiment. Electrical contact was achieved with a platinum wire
silver-soldered to a copper wire.
A 100-ml glass cell suitable for work under inert atmosphere was used in connection
with a device that allows the adaptation to a three-electrode system. The voltammetric
response was obtained with a PAR potentiostat (model 273A) coupled to a personal
computer. The working electrode was a carbon –mineral paste electrode; the reference was
a saturated calomel electrode while a graphite rod (Johnson Matthey, 99.99% purity) was
the counter electrode. Solutions of H2SO4, prepared with deionised water (Milli-Q quality),
were used as the electrolyte. Solutions were deaerated with nitrogen, and a nitrogen
atmosphere was maintained in the cell during the experiments. Prior to the electrochemical
study, the mineral –carbon paste electrode (CPE) was maintained in the electrolyte solution
for 10 min in order to obtain reproducible results. All the experiments were conducted at
298 K in sulfuric acid solutions, at a sweep rate potential, v, of 20 mV s
1.

3. Results and discussion

Chalcocite, covellite and bornite are sulfide minerals proposed as intermediates in the
electrochemical oxidation and reduction of chalcopyrite. For this reason, first we
performed an electrochemical study of these intermediates in order to make a better
identification of the electrochemical steps involved in the chalcopyrite redox processes.
Unfortunately, the covellite was not available for our research team, but it could be formed
by the chalcocite electrooxidation.
The electrochemical studies of these minerals have generally used solid mineral
electrodes. The voltammetric transformations between these sulfides have not been
sufficiently discussed since a systematic comparison of the mineral oxidation processes
using solid electrodes is troublesome because polishing makes surface reproducibility
difficult. A suitable alternative to solid electrodes for electrochemical studies are carbon
paste electrodes (CPE). In these electrodes, the mineral surface available for electro-
chemical studies is quite consistent (Cisneros-González et al., 1999; Gerlach and Kuzeci,
1983; Lázaro et al., 1995; Nicolás, 1997). Brage et al. (1979) performed an electro-
chemical characterization of mineral particles using an electrolyte binder (H2SO4) for the
preparation of the CPE. The chemical nature of this binder modifies the mineral surface in
the paste even before initiation of the voltammetric studies. Another alternative is the use
of nonconducting binder, as the silicon oil, which does not react with the mineral particles,
but the wetting properties of the mineral surface must be certainly modified. However, the
comparative study could be performed if the same binder is used for the preparation of all
20 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28

mineral – CPEs. The study of the modification of the wetting properties of the mineral
surfaces is out of the scope of this paper.

3.1. Voltammetric study of chalcocite

Fig. 1 shows two typical voltammograms obtained for chalcocite –CPE (weight ratio of
20:80 wt.%), in 1 M H2SO4 at a sweep rate potential of 20 mV s
1. The scan potential was
initiated from the open circuit potential, Ei = 0 =0.15 V/SCE, in the positive- and negative-
going directions (Fig. 1a,b), respectively. A more detailed study of the chalcocite
electrochemical behavior had been previously reported (Arce and González, submitted
for publication). When the scan potential was initiated in positive direction, an anodic
peak, a1, appeared. When the scan potential was inverted, two cathodic peaks, c1 and c2,
were observed. These peaks can be associated with the reduction of the oxidation products
formed in a1. From the comparison of these voltammograms, it is possible to establish
that, when the scan potential is initiated in negative direction (Fig. 1b), a very small
reduction process is observed, indicating that the chalcocite presents small quantities of
chemical oxidation products on its surface formed during the chalcocite manipulation. At
more negative potential, a reduction process associated with chalcocite is observed (c3).

Fig. 1. Typical cyclic voltammograms obtained with chalcocite – CPE (20 wt.%, using silicon oil binder) in a 1 M
H2SO4 solution, at v = 20 mV s
1. The scan potential was initiated in different direction from open circuit
potential (EOCP = 0.15 V/SCE): (a) positive direction; (b) negative direction. The arrows indicate the scan potential
direction.
 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28 21

From our previous report (Arce and González, submitted for publication) and in
accordance with other reports (Holliday and Richmond, 1990; Biegler and Horne,
1985), it was possible to deconvolute the oxidation processes associated with the peak
a1. A study of the effect of the positive scan switching potential on the voltammetric
response was performed in order to deconvolute the different processes associated with the
peak a1 (Fig. 2). A more detailed description of this study has been reported previously
(Arce and González, submitted for publication). Here, the principal transformations of
chalcocite are discussed.
The initial oxidation of chalcocite forms djurleite (Eq. (3)).

Cu2 S Z Cu1:92 S þ 0:08Cu2þ þ 0:16e
ð3Þ

The formation of djurleite occurs by redox reaction due to the presence of oxygen during
the mineral – CPE preparation (Brage et al., 1979) or when the scan potential is initiated in
positive direction for E+kV0.200 V vs. SCE (Fig. 2a). The small current associated to the
peak c4 is possibly related to the reduction process of the oxidation products (e.g. Cu1.92S)
formed on the chalcocite surface during the electrode preparation (Fig. 1b).
When the oxidation of chalcocite were performed for 0.200 V E + k <0.350 V vs. SCE
(Fig. 2b), digenite could be formed onto chalcocite surface (Eq. (4)).

Cu1:92 S Z Cu1:60 S þ 0:32Cu2þ þ 0:64e
ð4Þ

The cathodic peak c1 is associated to the digenite reduction.
When the oxidation of chalcocite is performed for E+kz0.350 V vs. SCE (Fig. 2c,d),
the blue-remaining covellite (Cu1.40
1.36S) and covellite (CuS) were formed.

Cu1:60 S Z CuS þ 0:60Cu2þ þ 1:20e
ð5Þ

The reduction processes associated to blue-remaining covellite and covellite formed
during the direct scan potential, E+kz0.350 V vs. SCE are related with the shoulder c2Vand
with the peak c2, respectively. The shoulder c2V diminish as E+k is more positive,
indicating the total conversion of chalcocite to covellite.
The peak potential associated to the peak c2 (Epc2=
0.300 V vs. SCE) corresponds to
the covellite reduction (Eq. (6)).

2CuS þ 2Hþ þ 2e Z Cu2 S þ H2 S ð6Þ

Note that reaction (6) is not exactly the reverse of reaction (1). However, the stoichiometry
of both reactions is the same (electrons involved are the same).
The electrochemical reaction associated with the peaks a2, a3 and a4 (Fig. 1b) are
described in our previous paper (Arce and González, submitted for publication), for the
present analysis is not necessary to be considered.

3.2. Voltammetric study of bornite

Figs. 3 and 4 show typical voltammograms obtained for bornite – CPE in 1 M H2SO4.
The scan potential was initiated in the positive (Fig. 3) and negative directions (Fig. 4),
starting from the open circuit potential (Ei = 0 = 0.172 V/SCE).
 22
E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28
Fig. 2. Effect of positive scan switching potential (E+k) on the voltammetric responses of chalcocite – CPE (20 wt.%, using silicon oil binder) in a 1 M H2SO4 solution at
v = 20 mV s
1. The scan potential was initiated in the positive direction from open circuit potential (Ei = 0). The scan potential was inverted at different potentials, E+k:
(a) +0.200, (b) +0.300 (c) +0.350, and (d) +0.450 V/SCE.
 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28 23

Fig. 3. Typical cyclic voltammogram obtained with bornite – CPE (20 wt.%, using silicon oil binder) in a 1 M
H2SO4 solution, at v = 20 mV s
1. The scan potential was initiated in positive direction from EOCP = 0.172 V/SCE.
The arrows indicate the scan potential direction.

The comparison of the voltammograms in Figs. 3 and 4 allows the establishment of the
cathodic peaks m2 and m1, corresponding to the reduction processes of the products
formed during the bornite oxidation, peak n1. The potential peaks m2 and m1 appear at the
same values as those associated with the reduction processes of covellite (Fig. 1a, peaks c2
and c1); thus, the broad anodic peak n1 could be associated with the transformation of
bornite to covellite. The influence of E+k over the anodic peak m1 (Fig. 5) allows to
propose that this transformation involves, at least, one nonstoichiometric product accord-
ing to the following reactions:
0.250<E+k<0.350 V vs. SCE:

Cu5 FeS4 ZCu5
x FeS4 þ xCu2þ þ 2xe
ð7Þ

in accordance with a previous study (Price and Chilton, 1980).

E+k > 0.350 V vs. SCE

Cu5
x FeS4 þ 6Hþ ZCuS þ ð4
xÞCu2þ þ 3H2 S þ Fe3þ þ ð5
xÞe
ð8Þ

This equation proposes the formation of covellite, Cu2+ and Fe3+. However, other authors
(Price and Chilton, 1980) have proposed the direct oxidation of chalcocite to Cu2+, Fe3+
24 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28

Fig. 4. Typical cyclic voltammogram obtained with bornite – CPE (20 wt.%, using silicon oil binder) in a 1 M
H2SO4 solution, at v = 20 mV s
1. The scan potential was initiated in negative direction from EOCP = 0.172 V/
SCE. The arrows indicate the scan potential direction.

and S0. Eq. (8) was proposed because in the reverse scan, it is observed that the peaks
associated to the reduction of covellite (peaks m1 and m2; Figs. 3 and 4).
The cathodic peak m3 could be associated with the reduction process of the oxidation
product formed on the bornite surface during the electrode preparation. Once this process
is carried out, the bornite oxidation is improved (Fig. 4, peak n1).
A deeper electrochemical study of bornite has been reported elsewhere (Bahena, 2001).

3.3. Voltammetric study of chalcopyrite

Figs. 6 and 7 show typical voltammograms obtained for a chalcopyrite –CPE electrode
in 2 M H2SO4. The scan potential was initiated from the open circuit potential
(Ei = 0 =0.200 V/SCE) in the positive- (Fig. 6) or negative-going direction (Fig. 7), at a
sweep rate potential of 30 mV s
1. These voltammetric curves have been previously
reported. It is important to note that the experimental conditions used for the chalcopyrite –
CPE electrochemical characterization (electrolytic composition and sweep rate perturba-
tion) are slightly different to that used for chalcocite and bornite –CPE studies. These
differences are not important in making a comparison between the electrochemical
behavior of the different minerals used in this work. Fig. 6 shows the effect of the
cathodic scan switching potential (E
k) in the oxidation process ( y1). The scan begins in
the positive direction. The peak y1 represents a quasi-reversible transformation of
 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28
Fig. 5. Effect of positive scan switching potential (E+k) on the voltammetric responses of bornite – CPE (20 wt.%, using silicon oil binder) in a 1 M H2SO4 solution at v=20
mV s
1. The scan potential was initiated in the positive direction from open circuit potential (Ei = 0). The scan potential was inverted at different potentials, E+k: (a) +0.300,
(b) +0.350 (c) +0.400, and (d) +0.550 V/SCE.

25
26 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28

Fig. 6. Typical cyclic voltammograms obtained with chalcopyrite – CPE (20 wt.%, using silicon oil binder) in a 2
M H2SO4 solution, at v = 30 mV s
1. The scan potential was initiated in positive direction from EOCP = 0.2 V/SCE
until E+k = 0.7 V/SCE, then the scan potential was reversed until different E
k and the scan potential was again
reversed and stopped to E+k = 0.7 V/SCE. The figure shows two consecutive voltammetric cycles. One arrow
corresponds to the first cycle voltammogram and two arrows correspond to the second cycle (Lázaro et al., 1995).

chalcopyrite. The charge involved in the anodic process associated with the y1 peak is
practically recovered in the reduction process x1. The reduction processes associated with
x2 and x3 peaks seems to be independent of the previous oxidation – reduction processes of
chalcopyrite ( y1
x1). Another deep study of chalcopyrite has been previously reported
(Lázaro et al., 1995).
The comparison of Figs. 6 and 7 allows to propose that the chalcopyrite oxidation (peak
y1) forms an intermediate chemical species reduced in reversible way in the peak x1. This
behavior is typical for a nonstoichiometric iron surface (Lázaro et al., 1995; Price and
Warren, 1986). This process is described by:

CuFeS2 ZCu1
x Fe1
y S2
z þ xCu2þ þ yFe2þ þ zS0 þ 2ðx
yÞe
ð9Þ

The absence of cathodic peak associated with the covellite reduction in the voltammogram
of chalcopyrite oxidation – reduction (Fig. 6) confirms that the chalcopyrite oxidation
forms only Cu1
xFe1
yS2
z, instead of covellite as many authors had claimed (Parker et
al., 1981; Holliday and Richmond, 1990; Biegler and Horne, 1985).
The chalcopyrite reduction occurs via x2 and x3 peaks (Fig. 7). The final product
formed after peak x3 presents a broad oxidation peak, y2. This y2 peak presents the same
 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28 27

Fig. 7. Typical cyclic voltammogram obtained with chalcopyrite – CPE (20 wt.%, using silicon oil binder) in a 2
M H2SO4 solution, at v = 30 mV s
1. The scan potential was initiated in negative direction. The arrows indicate
the scan potential direction (Lázaro et al., 1995).

electrochemical behavior associated with the chalcocite oxidation (see Fig. 1a). This
behavior confirms the direct formation of chalcocite from the chalcopyrite reduction while
it was seen that no bornite is formed as intermediate.

4. Conclusions

The comparison of voltammetric behavior of chalcocite, bornite and chalcopyrite

allows the establishment of the steps involved in the chalcopyrite oxidation. The oxidation
process of chalcopyrite does not produce covellite, as some authors have claimed, since no
reduction of this species is observed on the reverse potential scan from voltammetric
chalcopyrite oxidation (Fig. 6). On the other hand, the reversible process obtained in the
chalcopyrite oxidation (Fig. 6) could be associated with the formation of nonstoichio-
metric sulfides, Cun
1Fen
1S2n. Bornite is not the intermediary species formed during the
chalcopyrite reduction. The product of this reduction is chalcocite.
28 E.M. Arce, I. González / Int. J. Miner. Process. 67 (2002) 17–28

Acknowledgements

This work was financially supported by DEPI-IPN. The authors are recipients of the
COFAA-IPN and SNI fellowships.

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