Minerals Engineering 15 (2002) 215223

www.elsevier.com/locate/mine

The inuence of cathodic reduction, Fe2 and Cu2 ions on the

electrochemical dissolution of chalcopyrite in acidic solution
A.E. Elsherief *

Electrometallurgy Laboratory, Central Metallurgical R&D Institute, CMRDI, PO Box 87, Helwan, Cairo, Egypt
Received 3 October 2001; accepted 12 November 2001

Abstract
The electrochemical behaviour of chalcopyrite has been studied in sulphuric acid solutions with the carbon paste electrode
technique. Cyclic voltammetry were performed and the eect of cathodic scan limit, Fe2 and Cu2 ion concentrations were fol-
lowed. The presence of Cu2 ions in solutions leads to an increase in both the oxidation and the reduction currents, but in either case
further increases in currents were observed when Fe2 ion was added in admixture to the electrolyte. Chalcocite was identied as a
product of reactions at extremely high cathodic potentials. The morphology and structure of the produced products after anodic or
cathodic treatments of chalcopyrite were examined by the scanning electron microscopy. 2002 Elsevier Science Ltd. All rights
reserved.

Keywords: Sulphide ores; Extractive metallurgy; Electrometallurgy; Leaching; Mineral processing

1. Introduction layer is depended on the electrolyte composition and the

As the world moves into the new millennium, the
need for copper is growing rather than shrinking. It is
one of humanitys most important metals. Chalcopyrite
is both the most abundant copper sulphide mineral and
the most refractory. It reacts extremely slow under
typical leaching conditions. Much of the recent work on
the hydrometallurgical processing of sulphide minerals
has focused on the electrochemistry of the substances
involved (Shuey, 1975; Biegler and Swift, 1979; Crun-
dwell, 1988; Osseo-Asare, 1992; Elsherief, 1994; Elsh-
erief et al., 1995). There has been substantial interest in
the oxidative electrodissolution of chalcopyrite. The
thermodynamics of dissolution process may be dis-
cussed on the basis of Eh pH diagrams (Bartlett et al.,
1986). From this it may be seen that chalcopyrite is
stable under neutral or slightly oxidizing conditions. At
a value of pH about zero, it is necessary to increase the
redox potential above +0.44 V vs. SHE in order to se-
cure dissolution of copper.
Biegler and Swift (1979) studied the electrochemistry
of the anodic dissolution of chalcopyrite in 1 M HCl and
in 1 M H2 SO4 . They observed that the sulphur product
*
Tel.: +20-501-0642; fax: +20-501-0639.
E-mail address: rucmrdi@rusys.eg.net (A.E. Elsherief).
0892-6875/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 8 9 2 - 6 8 7 5 ( 0 1 ) 0 0 2 0 8 - 4
electrode potential. The anodic oxidation of chalcopy-
rite led to the dissolution of copper and iron, and the
formation of elemental sulphur or sulphate ions. Baur
et al. (1974) and Linge (1976) observed the preferential
dissolution of iron during the oxidation of chalcopyrite,
and postulated the formation of a metal-decient sul-
phide layer, richer in copper than iron, on the electrode.
Anodic polarization studies on chalcopyrite electrodes
have revealed the existence of a passive region where the
current does not increase with increasing potential.
Warren et al. (1982) anodized chalcopyrite in acid sul-
phate media at 25 C and found that the passive region
occurred in the potential range 0.60.9 V (SHE). They
proposed that in the passive region chalcopyrite reacts
initially to form an intermediate defect structure,
Cu1x Fe1y S2z , termed S1 . The intermediate S1 decom-
poses further to form a second intermediate, CuSn ,
termed S2 . They proposed that S1 and S2 are bornite
Cu5 FeS4 and covellite (CuS), respectively.
The cathodic reduction of chalcopyrite has also been
investigated. Thermodynamic data, summarized in the
form of Eh pH diagrams (Bartlett et al., 1986), predict
that the reduction products of chalcopyrite in acid so-
lutions could include hydrogen sulphide and ferrous ion
together with the solid phases bornite, chalcocite and
elemental copper, formed in the order with decreasing
potential. Biegler and Constable (1976), using a slurry
216 A.E. Elsherief / Minerals Engineering 15 (2002) 215223

electrode, found that the solid reduction products ran-

ged in composition from digenite to chalcocite with a
small amount of elemental copper. During the electro-
reduction of chalcopyrite, other workers have found
that H2 S gas evolves and Fe2 dissolves into the cath-
olyte, while several compounds were detected as reduc-
tion products, e.g., bornite, djurleite, digenite and others
(Warren et al., 1985; Lazaro et al., 1995).
The purpose of this study is to study the electro-
chemical behaviour of chalcopyrite using a carbon paste
electrode (CPE). Activation techniques through chang-
ing the chalcopyrite to chalcocite or other sulphides,
which are more susceptible to leaching than the original
CuFeS2 , are also reported.
The electrochemical investigations have been carried
out by performing cyclic voltammetry and potentiostatic
experiments. The eect of cathodic scan limit and the
presence of Fe2 and Cu2 ions have been examined as
well as the micrograph of chalcopyrite massive electrodes Fig. 1. Schematic illustration of the carbon paste electroactive elec-
leached under applied cathodic or anodic treatment. trode, CPEE.

Because of the shape of the electrode, the reaction

2. Experimental details
2.1. Materials
Natural samples of chalcopyrite were used in this
work. They were handpicked samples of high quality as
evidenced by X-ray diractions. XRF analysis reported
the following composition: Cu 35.49 wt%, Fe 28.78
wt%, S 25.32 wt%, CaO 0.62 wt% and Al2 O3
0:57 wt% (stoichiometric chalcopyrite composition:
Cu 34.62 wt%, Fe 30.42 wt%, and S 34.94 wt%).
All experiments were carried out using solutions
prepared from analytical grade reagents and distilled
water. Solutions of sulphuric acid diluted with distilled
water were used as electrolytes. To study the eect of
Fe2 and Cu2 ions on the electrochemical behaviour of
chalcopyrite, they were introduced into the electrolyte
by pipeting appropriate volumes of concentrated aque-
ous stock solutions prepared from their sulphate salts in
100 g l1 H2 SO4 .
2.2. Preparation of carbon paste electrodes
The CPE consisted of a carbon paste and 10% of the
nely ground chalcopyrite. A carbon paste was made by
mixing graphite powder and paran oil. The carbon
paste was lled and pressed into the open end of the
electrode. On top of this a homogenized layer 0.5 mm
thick of the electroactive paste was placed. A full de-
scription of the CPE has been given previously (Elsh-
erief, 1994). A J-type electrode was used; a schematic
diagram of the electrode is shown in Fig. 1. These
electrodes were shaped in such a way that their surfaces
were oriented toward the surface of the electrolyte.
products remained on the surface and did not fall o.
The geometrical area of the electrode surface was
0:2 cm2 . For each measurement, the electroactive sur-
face was always renewed.
2.3. Chalcopyrite massive electrode
A full description of the massive electrode was given
previously (Elsherief, 1994). A large sample of the
mineral was cut into a cubic shape, 5 mm length. It was
attached to a brass disc, insulated with a teon tube, by
means of graphite base conducting cement. Then it was
buried in epoxy resin leaving only one free face exposed
to the solution. Prior to each experiment, the electrode
surface was polished gently on grade p 1000 silicon
carbide paper under double distilled water.
2.4. Voltammetric studies
A conventional three-electrode cell was used with the
CPE of the tested mineral as the working electrode. A
graphite rod served as the counter electrode and a
mercury/mercurous sulphate reference electrode,
E 650 mV vs. standard hydrogen electrode (SHE), as
the reference electrode. The reference electrode was
placed in a Luggin capillary, which was placed just
above the surface of the working electrode. The tem-
perature was maintained at 20 C.
The voltammetric response was obtained from a Po-
tentioscan Pos 73, Wenking, coupled to a personal
computer. In each electrochemical experiment, the cyclic
voltammetry was initiated from the open circuit poten-
tial, OCP, with a sweep rate of 20 mV s1 unless oth-
erwise stated.
 A.E. Elsherief / Minerals Engineering 15 (2002) 215223
3. Results and discussion
3.1. Cyclic voltammetry
Cyclic voltammetry was used to study the electro-
chemical behaviour of chalcopyrite mineral. The vol-
tammograms in 100 g l1 sulphuric acid solutions are
shown in Figs. 2 and 3.
Fig. 2 represents the voltammogram when the po-
tential scan is started in the anodic direction. The
starting potential is the open circuit potential (OCP),
)440 mV. During the excursion to positive potentials,
the current does not increase between the OCP and 400
mV. As the scan proceeds towards more positive po-
tentials an anodic peak A1 appears at 550 mV. Peak A1
is a result of passivation of the mineral surface. Ac-
cording to Price and Warren (1986) the peak A1 corre-
sponds to the partial oxidation of the mineral to mixed
sulphides, as shown in the following reaction:
Fig. 2. Cyclic voltammograms of chalcopyrite-CPE in 100 g l1
H2 SO4 , started positive with dierent cathodic scan limit: (1) )500 mV;
(2) )1000 mV and (3) )1250 mV, at 20 C, 20 mV s1 .
Fig. 3. Cyclic voltammograms of chalcopyrite-CPE in 100 g l1
H2 SO4 , started negative with dierent cathodic scan limit: (1) )1000
mV and (2) )1250 mV, at 20 C, 20 mV s1 .
217
CuFeS2 Cu1x Fe1y S2z xCu2 yFe2 zS
2x ye 1
The Cu1x Fe1y S2z , an intermediate product, and the
sulphur form a passive electron-conducting layer on
the mineral surface. Parker et al. (1981) referred to the
product as a polysulphide, which has semi-conducting
properties.
On reversing the scan direction after peak A1, the
current returns to zero and then increases in the ca-
thodic direction where a poorly dened cathodic peak
C1 is developed at )30 mV. On going further on the
cathodic direction, a well-dened cathodic peak C2 is
observed at )275 mV, Fig. 2, curve 1. The prewave peak
C1 reects the reduction of the products produced at
peak A1. The obvious dierence in the areas under the
anodic peak A1 and cathodic prewave peak C1 indicate
that the reaction is not fully reversible. This is likely due
to dissolution of the product formed during the anodic
sweep. This observation is consistent with the results of
other investigators (Parker et al., 1981; Lazaro et al.,
1995; Lu et al., 2000). Peak C2 corresponds to the re-
duction of the remaining chalcopyrite to an intermediate
copper sulphide phase such as talnakhite Cu9 Fe8 S16 or
bornite Cu5 FeS4 , respectively, as shown in the fol-
lowing equations (Warren et al., 1985; Kuzeci and
Kammel, 1988; Lu et al., 2000):
9CuFeS2 4H 2e Cu9 Fe8 S16 Fe2 2H2 S
2
2
5CuFeS2 12H 4e Cu5 FeS4 4Fe 6H2 S
3
If the cathodic limit is extended to )1000 mV, curve 2 in
Fig. 2, another well-dened cathodic peak C3 is devel-
oped at )700 mV, which is assigned to the formation of
chalcocite at potentials more negative than peak C2, and
iron is completely removed from the chalcopyrite lattice,
as shown in reaction (4) (Warren et al., 1985; Price and
Warren, 1986; Lu et al., 2000):
2CuFeS2 6H 2e Cu2 S 2Fe2 3H2 S 4
The conversion of CuFeS2 to Cu5 FeS4 prior to the
formation of CuS2 is expected as indicated by the Eh pH
earlier diagrams (Bartlett et al., 1986). Other reactions
that may occur at these negative potentials are the re-
duction of Cu2 to copper metal (Kuzeci and Kammel,
1988).
When the reduction limit is made more cathodic,
)1250 mV, curve 3 in Fig. 2, a complete reduction to
chalcocite occurs. The reduction process occurs in par-
allel with the hydrogen evolution. Formation of copper
is predicted at such suciently cathodic potentials,
according to (Bartlett et al., 1986):
CuFeS2 4H 2e Cu Fe2 2H2 S 5
218 A.E. Elsherief / Minerals Engineering 15 (2002) 215223
2Cu2 S 4H 4e 4Cu 2H2 S 6 the corresponding reduction products are deposited on
The positive return scan curves after reversing the po-
tential sweep at the aforementioned cathodic limits of
)500, )1000 and )1250 mV were recorded. When the
potential sweep is reversed at )500 mV, curve 1 in Fig.
2, the products of cathodic reduction resting at the
surface are oxidized, and an anodic peak A2 appears on
the anodic scan at )70 mV. This peak corresponds to
the oxidation products produced during the cathodic
sweep. It reects the oxidation of the formed bornite on
the surface according to the reaction (Kuzeci and
Kammel, 1988):
Cu5 FeS4 xCu2 Cu5x FeS4 2xe 7 C2 and C3 appear as the potential progresses towards
The shape of peak A2 could imply several electro-
chemical reactions. Then at a more positive potential,
peak A10 is developed. The peak A10 , that overlaps with
the rst oxidation A1, is attributed to the oxidation of
the non-stoichiometric sulphides being decient in cop-
per (Kuzeci and Kammel, 1988; Lu et al., 2000).
Whereas, if the potential sweep is inverted at )1000
mV, curve 2, poorly dened anodic peaks A4 and A3
appear on the anodic scan between )620 and )400 mV.
They reect the oxidation of the formed Cu2 S and H2 S
to elemental sulphur, respectively, according to (Warren
et al., 1985; Price and Warren, 1986; Kuzeci and Kam-
mel, 1988; Lu et al., 2000):
Cu2 S Cu2x S xCu2 2xe 8 If the cathodic limit potential is increased to )1250
0 
H2 S S 2H 2e 9
The oxidation potential region associated with oxidation
of Cu2 S and H2 S appears poorly dened in the vol-
tammogram. Peak A2 shifts slightly towards less posi-
tive potential. It is related also to the reverse oxidation
of electrodeposited copper.
On reversing the sweep potential at )1250 mV, curve
3, the aforementioned anodic peaks are clearly observed.
Peak A2 is enlarged and cover the potential range from
)150 to 0 mV, and the peaks A3 and A4 are clearly
observed. Most characteristic is the appearance of the
anodic peak A5 at )860 mV, which is probably due to
the formation of Cu2 S through the anodic reaction of
deposited copper and H2 S (Lu et al., 2000):
2Cu H2 S Cu2 S 2H 2e 10
A5 only appears when the cathodic limit is greater than
the potential range of peak C3.
Fig. 2 shows the dependence of the anodic current
prole on the negative potential limit. It is clearly
observed that the height of the anodic current peak and
the corresponding peaks potential depend on the
cathodic limit of the potential excursion. The anodic
current during the positive return scan increases with the
increase of the cathodic scan limit. The increase of the
peak height on the anodic scan in this system means that
the surface.
Fig. 3 depicts the voltammetric response obtained
when the potential is initially scanned cathodically.
Curve 1 represents the voltammogram when the ca-
thodic scan limit is )1000 mV and curve 2 represents the
cathodic scan limit )1250 mV. The cathodic current
peak C1 becomes much smaller as compared with Fig. 2.
This corresponds perhaps to slight deviations in stoi-
chiometry in the freshly prepared natural chalcopyrite
electrode. The potential region associated with the
bornite to chalcocite transition appears poorly dened
in the voltammogram, where ill-dened cathodic peaks
the cathodic direction in the rst cycle. This may be
attributed to the absence of the oxidation products of
chalcopyrite formed during the started positive scan as
seen in Fig. 2. Also, it may be due to the formation of
some passive lm on chalcopyrite surface produced
chemically before starting the run and electrochemically
at such lower potentials (Warren et al., 1982). On the
return scan, poorly dened anodic peaks are obtained,
whereas, the anodic peak A10 markedly appears. As the
scan in Fig. 3, curve 1 is continued the cathodic current
is increased during the second cathodic cycle. This is
likely due to the oxidation of the more refractory chal-
copyrite. The oxidation products, intermediate phases,
may inuence the shape of the dissolution curves.
mV, Fig. 3, curve 2, there is a new cathodic current
contribution. The reduction at such higher potential,
which may be partially due to the evolution of hydrogen
at the electrode surface, allows the cathodic products to
be monitored during the subsequent anodic sweep. On
the reverse anodic scan the anodic peaks are markedly
developed during the positive-going potential scan. The
predicted oxidation peaks A5, A4, A3 and A2 appear at
)850, )450, )200 and )60 mV, respectively, indicating
that most of the chalcopyrite has been reduced to
chalcocite.
3.2. Eect of ferrous ion and cupric ion concentrations
3.2.1. Eect of Fe2
When chalcopyrite is leached, Fe2 is produced as
one of the reaction products. Therefore, it is important
to study the eect of Fe2 ions on the leaching process.
Cyclic voltammograms for the chalcopyrite-CPE in the
presence and absence of dierent concentrations of fer-
rous ion, (015 g l1 ), in 100 g l0  1 H2 SO4 solutions
are shown in Fig. 4.
On addition of Fe2 ions the OCP is shifted to more
positive potentials and the current increases in the pas-
sive region. This may be attributed to an additional
oxidation reaction of ferrous to ferric ions at the chal-
copyrite surface. On going further towards the anodic
 A.E. Elsherief / Minerals Engineering 15 (2002) 215223 219

Fig. 4. Cyclic voltammograms of chalcopyrite-CPE in 100 g l1 Fig. 5. Cyclic voltammograms of chalcopyrite-CPE, started positive,
H2 SO4 , in the presence of dierent concentrations of Fe2 : (1) 0 g l1 ; in 100 g l1 H2 SO4 , in the presence of dierent concentrations of
(2) 5 g l1 ; (3) 10 g l1 and (4) 15 g l1 , at 20 C, 20 mV s1 . Cu2 : (1) 0 g l1 ; (2) 2 g l1 ; (3) 4 g l1 and (4) 8 g l1 , at 20 C,
20 mV s1 .

direction, the current increases signicantly as Fe2  is

increased up to 100 g l1 at A1, Fig. 4, curve 3. It is
clearly observed that addition of Fe2 drastically in-
creases current upon anodic polarization, which is
probably due to the competing oxidation of Fe2 to
Fe3 . This result conrms the electron conductivity
character of surface products formed (Warren et al.,
1985; Price and Warren, 1986; Kuzeci and Kammel,
1988; Lazaro et al., 1995; Lu et al., 2000). A decrease or
no increase in current is observed upon further additions
of Fe2 , Fig. 4, curve 4.
Addition of Fe2 ions increases current upon ca-
thodic polarization. The observed increase of the current
is directly related to the initial Fe2 concentration. This
indicates that the back reaction is negligible for reac-
tions (2)(5). Ferrous ions act as a reductant, which
enhance the formation of intermediate CuS2 that is more
amenable to oxidation than chalcopyrite as it is ob- Fig. 6. Cyclic voltammograms of chalcopyrite-CPE, started negative,
in 100 g l1 H2 SO4 , in the presence of dierent concentrations of
served on the return positive scan. It has been observed
Cu2 : (1) 0 g l1 ; (2) 1 g l1 ; (3) 2 g l1 and (4) 4 g l1 , at 20 C,
that ferrous ions enhanced chalcopyrite leaching rates 20 mV s1 .
(Hiroyoshi et al., 1997, 2000).

3.2.2. Eect of Cu2

Cupric ions are released from chalcopyrite together
with ferrous ions during the leaching. Therefore, the
eect of cupric ions on the cyclic voltammograms was
also examined and the results are shown in Figs. 5 and 6
for additions of copper from 1 to 9 g l1 .
The potential is initially scanned anodic, as seen in
Fig. 5. It is clear that the addition of a relatively small
amount of cupric ion, 2 g l1 , causes a signicant in-
crease in current during the anodic and the cathodic
sweep. The response current in the passive region is
slightly increased. With the addition of Cu2 ions, the
anodic current peak A1 is increased and remains higher
than observed with no addition of Cu2 . C2 and C3 are
increased with the increase of cupric ion concentrations
in the electrolyte up to 4 g l1 Cu2 , curve 3. Upon
further increase of cupric ions in the electrolyte, C2 and
C3 are greatly increased and merge together where three
peaks are registered in place of them, curve 4. The re-
verse scan shows that the possible reaction products
have been clearly detected as oxidation products during
the return anodic sweep at A4, A3 and A2 in the order
of increasing potentials in anodic direction, respectively.
The potentials of these three peaks are moved in the
anodic direction and an increase in dissolution current
eciency of sulphides when Cu2 is added to the elec-
trolyte is obtained.
Further details related to the CVs prole are recorded
during the started negative going excursion and shown
220 A.E. Elsherief / Minerals Engineering 15 (2002) 215223

in Fig. 6. It is observed that C3 is greatly increased with

the addition of cupric ions. The positive return scan
curve shows that the three aforementioned peaks, A4,
A3 and A2, are replaced with one peak. This peak grows
with the increase of Cu2 ion concentration in solutions.
In this case, it is possible to establish that this peak in-
volves both the oxidation process of the reduction
products obtained in C3 and the oxidation of copper
metal. Peak A10 is also increased, forming a plateau and
levelled o at higher current values.
Chalcopyrite reduction has been carried out in the
presence of cupric ion as described by the following
reactions (Nicol, 1975; Warren et al., 1985; Kuzeci and
Kammel, 1988): Fig. 7. Cyclic voltammograms of chalcopyrite-CPE started positive,
in: (1) 100 g l1 H2 SO4 ; (2) 1 2 g l1 Cu2 10 g l1 Fe2 ions, at
2CuFeS2 3Cu2 4e Cu5 FeS4 Fe2 11 20 C, 20 mV s1 .
2  2
CuFeS2 3Cu 4e 2Cu2 S Fe 12
Also the reduction of Cu2 to copper metal occurs at
this potential region, and any copper formed initially
will immediately reduce the chalcopyrite through the
galvanic reaction (Biegler and Constable, 1976):
CuFeS2 2H Cu0 Cu2 S H2 S Fe2 13
The main product as evidenced from the enhanced C3
peak in Fig. 6 is Cu2 S. Warren et al. (1985) found that
the actual product of reduction was found to be djurleite
Cu1:96 S, for stoichiometric simplicity chalcocite is indi-
cated. The presence of Cu2 leads to an increase in the
reduction current.
It has been reported consistently, and observed in the
present study, that increasing concentrations of cupric ion
Fig. 8. Cyclic voltammograms of chalcopyrite-CPE started negative,
results in a corresponding increase in the leaching rates of in 100 g l1 H2 SO4 , in the presence of a mixture of 2 g l1 Cu2
chalcopyrite (Nicol, 1975; Biegler and Constable, 1976). 10 g l1 Fe2 ions, at 20 C, 20 mV s1 .
Further increases in current are observed when Fe2 is
added together with Cu2 to the electrolyte. Figs. 7 and 8,
show typical voltammograms obtained in the positive and scan direction, the anodic peaks are considerably higher
negative directions, respectively, for chalcopyrite-CPE in than the analogous peaks obtained in base sulphuric
100 g l1 H2 SO4 solutions in the presence of 2 g l1 Cu2 acid solutions and they moved in the positive direction.
and 10 g l1 Fe2 .
When the scan potential is initiated in the positive 3.3. Characterization of the formed products
direction, Fig. 7, both of the anodic and cathodic cur-
rents are greatly enhanced. The anodic peak A1 is In order to characterize the compounds formed dur-
strongly shifted in the cathodic direction, while the ca- ing electrolysis on the mineral surface, the voltammetric
thodic peaks C2 and C3 are moved in the anodic di- behaviour of the chalcopyrite was subsequently studied
rection. Both of anodic and cathodic reactions are after anodic and cathodic treatments.
depolarized. Potentiostatic experiments were performed at 550 and
When the scan is initiated in the negative direction, )900 mV. These values were chosen since they fall in the
Fig. 8, the reduction processes are greatly enhanced and region where peaks A1 and C3 were developed, respec-
the cathodic peaks C1, C2 and C3 are strongly moved in tively. Constant potential experiments provided the
the less negative directions. The reductant products have current as a function of time and are presented in Fig.
less hydrogen overvoltage, where hydrogen evolution 9(a). On application of the cathodic polarizing potential,
sets in at less negative potentials. The presence of Cu2 )900 mV, the current immediately jumps in the cathodic
and Fe2 in the electrolyte has a pronounced eect on direction forming a sharp small peak before it becomes
the evolution of hydrogen. This eect should increase steady and remains almost constant at about 17 lA
the rate of reduction of chalcopyrite. On changing the after 30 s, curve 1 in Fig. 9(a).
 A.E. Elsherief / Minerals Engineering 15 (2002) 215223
Fig. 9. (a) Currenttime curves representing the: (1) reduction at )900 mV, and (2) oxidation at 550 mV, of chalcopyrite-CPE in 100 g l1 H2 SO4 , at
20 C. (b) Cyclic voltammograms of chalcopyrite-CPEs that result after potentiostatic treatments: (1) reduction at )900 mV, and (2) oxidation at 550
mV, in 100 g l1 H2 SO4 , at 20 C, 20 mV s1 .
Fig. 9(b), curve 1, depicts the voltammetric response
obtained for the potentiostatically assisted chalcopyrite.
After applying the cathodic constant potential, )900 mV
for 5 min, the scan potential is initiated from )1000 mV
in the positive direction. The potential sweep towards
the positive potential side presents three well-dened
and merged peaks A4, A3 and A2 at the region potential
from )450 to 0 mV, respectively. In this case, it is pos-
sible to establish that these peaks involve the oxidation
processes of the reduction products obtained during the
potentiostatic reduction process. They are likely due to
the already formed chalcocite when the potential is
moved rapidly in the negative direction upon applying
the cathodic constant potential )900 mV. These peaks
are similar to those described on curve 2 in Fig. 8. The
voltammogram in Fig. 9(b) shows that the nal state of
chalcopyrite is similar to that obtained by means of
cathodic reduction in the presence of Cu2 and Fe2 ions
in solution.
Anodic polarization of chalcopyrite-CPE was carried
out at constant anodic potential equal to 550 mV. The
results are given on curve 2 in Fig. 9(a). The application
of a positive potential pulse produces an anodic current
response due to the oxidation of the electrode. This
current subsequently decays with time to a steady-state
value. A steady-state passive current is obtained after 2
min.
Fig. 9(b), curve 2, taken after anodic polarization at
550 mV for 5 min, shows peculiarities; the cathodic
processes are greatly observed. The peaks C1, C2 and C3
are considerably higher than the analogous ones of Fig.
3, and they are moved in the negative direction. This shift
in the active direction suggests that after anodic treat-
ment of chalcopyrite there is an increase in reduction
rate. The denition of the negative-going potential CV
prole is improved by running the CV with an electrode,
which has been previously anodically polarized, and vice
221
versa. This indicates that the cathodic treatment of the
anodically polarized chalcopyrite electrode permits the
reactivation of the anode surface.
3.4. Morphology of the reaction products
The morphology of the reaction product was deter-
mined on a polished surface of massive chalcopyrite
mineral after the anodic and cathodic treatments at 550
and )900 mV, respectively. The leaching samples were
thoroughly water-washed and air-dried at room tem-
perature before inspection under SEM.
After 1 h of anodic leaching at 20 C in 100 g l1
H2 SO4 solutions at 550 mV, the scanning electron mi-
crographs show that the chalcopyrite surface have an
etched appearance. As is clear in Fig. 10(a), the surface
is roughened by leaching and this nding indicates an
increase in the eective reaction surface area. On the
other hand, particles of elemental sulphur appear in the
leached regions, which cause a decrease of the amount
of active sites. Fig. 10(b), shows that many sulphur
particles occur preferentially around edges. The SEM
indicates that the elemental sulphur product formed on
the surface of chalcopyrite during dissolution exhibits
dumbly structure and it is non-protective.
When the chalcopyrite massive electrode was cathod-
ically leached at 20 C in 100 g l1 H2 SO4 solutions at
)900 mV, the surface shows great evidence of attack and
most of the surface is covered with cracked layer. An in-
dication of the physical structure and mode of formation
of the solid reduction product is given in Fig. 11(a), which
shows crack and ssures during electrolysis. This texture
is caused by the change in molar volume as chalcopyrite
transforms to chalcocite and copper decient sulphide
CuS. The details of the surface morphology are shown in a
highly magnied photograph, Fig. 11(b), which shows
colloidal, cracked surface and corrosion pits.
222 A.E. Elsherief / Minerals Engineering 15 (2002) 215223

Fig. 10. The SEM after the chalcopyrite massive electrode was polarized at 550 mV for 1 h, in 100 g l1 H2 SO4 , at 20 C: (a) 2000 ; (b) 2000 .

Fig. 11. The SEM after the chalcopyrite massive electrode was polarized at )900 mV for 1 h, in 100 g l1 H2 SO4 , at 20 C: (a) 350 ; (b) 2000 .

4. Conclusion anodically polarized chalcopyrite permits the reactiva-

Chalcopyrite is the most dicult of the copper sulp-
hides to treat by hydrometallurgical route. The anodic
dissolution of chalcopyrite led to the formation of a
metal-decient copper-rich polysulphide which passi-
vates the electrode surface. The voltammetric response
depended on the initial scan direction and the starting
potential. Addition of Fe2 causes up to tenfold en-
hancement in the dissolution rate. The presence of Cu2
leads to a high increase in the reduction current. The
presence of Cu2 and Fe2 in solution signicantly en-
hances oxidation and reduction processes of chalcopy-
rite that are all signicantly depolarized, and hydrogen
evolution commences at much lower cathodic poten-
tials. Chalcopyrite can be electrolytically reduced to
iron-free copper sulphides, with a small proportion of
element copper at extremely high cathodic potentials.
According to the cyclic voltammograms of CuFeS2 that
has been anodically polarized, it can be inferred that the
electrode could become active at high cathodic poten-
tials. The results revealed that cathodic treatment of the
tion of the anode surface, where chalcocite is formed,
which is more susceptible to leaching than chalcopyrite
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