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Leaching of chalcopyrite with ferric ion. Part I:

General aspects

Article in Hydrometallurgy August 2008

DOI: 10.1016/j.hydromet.2008.04.015

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Leaching of chalcopyrite with ferric ion. Part I: General aspects

E.M. Crdoba a, J.A. Muoz b, M.L. Blzquez b, F. Gonzlez b, A. Ballester b,
a
Escuela de Ingeniera Metalrgica y Ciencia de los Materiales, Facultad de Ingenieras Fsico-Qumicas, Universidad Industrial de Santander, Bucaramanga, Colombia
b
Departamento de Ciencia de Materiales e Ingeniera Metalrgica, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, 28040 Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Available online 2 May 2008 This paper presents a review of the literature on chalcopyrite leaching with ferric sulphate in acid medium.
The effects of several parameters (ferric salt anion, oxidant concentration, pH and temperature) are examined
Keywords: and possible explanations are offered for the passivation of this sulphide during dissolution. The main
Chalcopyrite theories related with chalcopyrite passivation point to the formation of a diffusion layer surrounding the
Leaching
chalcopyrite during dissolution, consisting of: bimetallic sulphide, copper polysulphide with a decit of iron
Ferric iron
Mechanism
with respect to chalcopyrite, and elemental sulphur. Recent studies suggest that ferric ion plays two
important and opposite roles in this process: as a mineral oxidizing agent and as the agent responsible for
chalcopyrite passivation.
2008 Elsevier B.V. All rights reserved.

1. Introduction 2. Chalcopyrite crystal structure

Chalcopyrite, (CuFeS2), is the most abundant copper mineral in The chemical formula that best describes chalcopyrite is Cu+Fe3+S2 2
nature (Dutrizac, 1978) counting for about 70% of copper reserves in the (De Filippo et al., 1988; Boekema et al., 2004; Mikhlin et al., 2004). The
world (Rivadeneira, 2006). In metallurgical applications it is mainly crystal structure consists in a relatively simple tetragonal lattice, close
subjected to pyrometallurgical treatment after concentration by a o- to cubic (Betejtin, 1977; Sand et al., 2001), with each sulphur ion
tation process. Hydrometallurgy, as an alternative to pyrometallurgy, surrounded by four metal ions of copper and iron located on tetra-
presents important advantages such as the possibility of treating low- hedron angles and in a certain order in each plane (Fig. 1).
grade ores (increasingly more abundant in the case of copper) and easier In the rst and fth planes, corresponding to the lower and upper
control of waste, with the attendant benets to the environment. faces of the tetragonal prism, Fe ions are located at the square angles
At present, approximately 18% of world copper production is and Cu ions in the middle. In the third plane, at the prism centre, the
treated by hydrometallurgy (Bravo, 2006). The process involves static order is the reverse. In the second and fourth planes, two Cu ions bond
leaching in heaps followed by solvent extraction and electrolytic pre- two Fe ions, but there are iron ions underneath copper cations in the
cipitation of copper. Despite that, the only existing industrial pro- second plane, and vice versa in the fourth plane.
cesses for the treatment of chalcopyrite concentrates at present are
pyrometallurgical. Chalcopyrite is highly refractory under hydrome-
tallurgical conditions, due to surface transformations which render
products very stable under oxidizing conditions (Burkin, 1969). Never-
theless, different hydrometallurgical processes have been investigated
on both laboratory and pilot scales in attempts to implement these
technologies at industrial level.
Any proposal for an economically viable hydrometallurgical process
for the treatment of chalcopyrite should take into account basic studies
that elucidate the chemical and electrochemical aspects governing
leaching. This review presents information on the fundamental aspects
of chalcopyrite leaching and the problems associated with low copper
recoveries from this mineral.

Corresponding author. Tel.: +34 91 3944339; fax: +34 91 3944357.

E-mail address: ambape@quim.ucm.es (A. Ballester). Fig. 1. Chalcopyrite crystal lattice (Betejtin, 1977).

0304-386X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.04.015
 Author's personal copy
82 E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8187
Although chalcopyrite presents a crystal structure essentially charac-
terized by covalent metalsulphide bonds, its semiconducting properties
indicate that not all bonding electrons correspond to simple covalent
crystals (Forward and Warren, 1960).
The substitution of copper and iron by other metal atoms in the
crystal lattice of natural chalcopyrites leads to the formation of n- and
p-type semiconductor structures. Fig. 2 shows a simplied energy band
diagram for n-type semiconductor chalcopyrite with an energy gap
around 0.6 eV (Torma, 1991). While the electronic character of the lower
part of the conduction band is given by Fe 3d orbitals, the upper part of
the valence band is given by Cu 3d and S 3p orbitals.
3. Chemical leaching of chalcopyrite with ferric ion
The leaching of copper from sulphide ore bodies occurs naturally,
releasing copper and iron. In ancient times, copper was recovered by
cementation with metal iron and iron in the form of ferrous sulphate
by evaporation of the solution. The rst reference to the application of
ferric acid sulphate solutions to the leaching of copper minerals is
dated 1752, at Ro Tinto (Huelva, Spain). At that time, mineral heaps
were irrigated with acid solutions and copper recovered by cementa-
tion with metal iron. Nevertheless, the development of chalcopyrite
leaching processes using ferric solutions has been limited, chiey
because the slow kinetics makes for an incomplete mineral attack.
More recently, most research on chalcopyrite dissolution has been
directed at elucidating reaction mechanisms and improving the leach-
ing rate with ferric sulphate.
3.1. Thermodynamics and stoichiometry of the chalcopyrite dissolution
The Pourbaix diagram for the CuFeS2H2O system (Fig. 3) (Garrels
and Christ, 1965) shows that the dissolution of chalcopyrite in acid
medium takes place through a solid transformation in different
intermediate sulphides (Cu5FeS4, CuS, Cu2S), increasingly richer in
copper (Biswas and Davenport, 1976). According to this diagram, a pH
lower than 4 and an oxidizing redox potential higher than +0.4 V is
required to dissolve copper from chalcopyrite. These conditions are
achieved using oxidizing agents, the most common being ferric ion as
a sulphate or chloride.
Chalcopyrite dissolves in the presence of ferric ion according to the
following reactions (Dutrizac and MacDonald, 1974):
CuFeS2 4Fe3 Cu2 5Fe2 2S- 1
CuFeS2 4Fe3 3O2 2H2 OCu2 5Fe2 2H2 SO4 2 These authors found that around 70% of the sulphur was oxidized
Several researchers have reported the stoichiometry of chalcopyrite
leaching. Chronologically, Traill and McClelland (1926) were the rst to
study the dissolution of chalcopyrite with concentrated ferric chloride
(70 g/L) at high temperature (95 C); they obtained a copper yield of 90%
Fig. 2. The energy band diagram for chalcopyrite (Torma, 1991).
Fig. 3. Pourbaix diagram for the CuFeS2H2O system at 25 C (Garrels and Christ 1965).
after 5 h of leaching and only 6070% of Fe, probably because it hydrolysed
and precipitated during the process. In that study, the recovery of ele-
mental sulphur was as low as 5%, conrming that the reaction is sto-
ichiometric (2). In 1933, Sullivan investigated dissolution of chalcopyrite
concentrates in both ferric chloride and ferric sulphate, concluding that
around 75% of chalcopyrite dissolves according to reaction (1) and the
remaining by reaction (2). The lower rate of sulphate formation was
attributed to the presence of dissolved oxygen more than to the action of
ferric ion. Ichikuni (1960) established that ferric sulphate dissolved chal-
copyrite according to reaction (1); he found only slight deviations of the
Cu/Fe molar ratio in solution during the initial stage of leaching with ferric
chloride and concluded that there was a preferential dissolution of Fe
from the chalcopyrite lattice. Dutrizac et al. (1969) studied the dissolution
process of chalcopyrite-sinterized discs in acid ferric sulphate. The sto-
ichiometry of chalcopyrite dissolution was described by reaction (1) and
the rate-controlling step was assumed to be the transport of ferric sul-
phate through a sulphur layer, in constant growth, surrounding the chal-
copyrite surface. Then, in 1971, Haver and Wong (1971) proposed a third
reaction to describe chalcopyrite dissolution with FeCl3:
CuFeS2 3FeCl3 FeCl3 CuCl 4FeCl2 2S- 3
to elemental sulphur and the remainder to sulphate, and they pro-
posed that copper was dissolved in the monovalent form (Cu+).
Dutrizac (1989) established that during chalcopyrite leaching with
ferric sulphate at 95 C the sulphide sulphur was practically all oxidized
to S (94%). More recently, in 1995, Hackl et al. (1995) found that during
leaching of chalcopyrite with ferric sulphate at high temperature and an
oxygen pressure of 0.69 MPa, the oxidation of sulphide sulphur to
sulphate increased from 28 to 100% when the temperature rose from 110
to 200 C. This was associated with an increase in oxygen consumption.
These results indicate that although both reactions (1) and (2)
can take place during the leaching of chalcopyrite, the formation of
sulphate is limited by the availability of oxygen in the leaching
medium.
Nevertheless, recent studies have demonstrated that chalcopyrite
transforms into intermediate phases and so reactions (1) and (2) must be
considered as overall reactions of the chalcopyrite dissolution process.
3.2. Effect of ferric salt anion
Sullivan concluded that ferric chloride is a better chalcopyrite
leaching agent than ferric sulphate and that the effect was more
 Author's personal copy
E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8187
Fig. 4. Inuence of pH on chalcopyrite leaching at 68 C and 0.5% PD (100 mL of leaching
solution and 0.5 g of mineral).
marked at high temperatures. Dutrizac et al. (1969) found that, in a
temperature range between 50 and 100 C, the chalcopyrite leaching
rate was linear in chloride medium and parabolic in sulphate medium.
Two years later, Dutrizac and MacDonald demonstrated that the
addition of chloride ion sped up chalcopyrite dissolution with ferric
sulphate at temperatures higher than 50 C (Dutrizac and MacDonald,
1971). At lower temperatures there was no effect. Majima et al. (1985)
established that the chalcopyrite leaching rate was approximately one
order of magnitude lower with ferric sulphate than with ferric
chloride. This agrees with the observation made by these authors
that the elemental sulphur formed during leaching was more porous
with ferric chloride than with ferric sulphate.
These researches support the idea that ferric chloride has greater
oxidizing power than ferric sulphate during chalcopyrite leaching.
However, several factors restrict the application of ferric chloride on
an industrial scale, such as:
- The afnity of this ion towards many elements complicates the
process of separating copper from the solution.
- Chloride solutions are extremely corrosive.
- Hydrochloric acid is more expensive than sulphuric acid.
The last factor is of prime importance since pyrometallurgical ex-
traction of copper from chalcopyrite, as in other industries, entails the
recovery of large amounts of SO2 to achieve sulphuric acid production at
very low cost.
3.3. Effect of ferric ion concentration
Different researchers have pointed out that the chalcopyrite
dissolution rate is strongly affected by ferric ion concentration, but
only at low concentrations. At high concentrations, the effect is neg-
ligible. Sullivan (1933), Linge (1976), Dutrizac et al. (1969), Muoz
et al. (1979) and Kametani and Aoki (1985), among others, found no
clear kinetic effect when the ferric ion concentration exceeded 0.01 M.
A few authors have observed a relationship of dependence between
chalcopyrite dissolution rate and ferric ion concentration. Hirato et al.
(1987) found that chalcopyrite dissolution improved when the con-
centration of ferric sulphate was increased from 0.001 to 0.1 M. These
Table 1
Effect of temperature on the kinetics during the chalcopyrite leaching with ferric ion
Medium Temperature (C) Activation energy (kJ/mol)
Ferric sulphate 5094 71
6090 84
5078 88
3568 130.7
Ferric chloride 6090 60
5584 69
50100 47
83
authors estimated that the concentration of Fe3+ and FeHSO2+ 4 ionic
species increased when the total iron concentration increased, up to a
limiting value of 0.1 M. Above this value, the most important species
was FeSO+4. They concluded that the Fe3+ and FeHSO2+ 4 ionic species are
responsible for chalcopyrite dissolution in sulphate medium.
3.4. Effect of pH
pH also affects chalcopyrite dissolution. According to Dutrizac et al.
(1969), the acid prevents hydrolysis and precipitation of ferric salts,
since proton attack is negligible. Some researchers (Lu et al., 2000;
Antonijevi and Bogdanovi, 2004) have reported poor results for
chalcopyrite dissolution at low pH (b1.0). The rst authors reported
that the precipitation of ferric ion as jarosite is possible even at pH 0.9,
which shows how readily ferric salts hydrolyse. Antonijevi and
Bogdanovi found that at pH lower than 0.5, the chalcopyrite surface
lacks iron and this provokes its passivation. Our results (Fig. 4) show
that, in a pH range of 0.5 to 2.0, although increased pH favours
hydrolysis and precipitation of the oxidant, dissolution of chalcopyrite
with ferric sulphate diminishes with decreasing pH. This is under-
standable if we consider the speciation diagrams for Fe(III) in sulphate
medium. These show that the species responsible for oxidation of the
chalcopyrite is not Fe3+ proper, but probably Fe(SO4)2, since that is the
only species to show an increase of concentration in the given pH
range.
3.5. Effect of temperature
Table 1 shows the values of activation energy reported by different
researchers during chalcopyrite leaching with ferric ion. It also indi-
cates the kinetic control proposed in each study.
The high values of activation energy found by different authors
demonstrate the need for high temperatures in order to break down
bonds in the chalcopyrite crystal lattice. Our results (Fig. 5) show that
the effect of temperature on chalcopyrite chemical leaching is very
pronounced in the range between 35 and 68 C. In that range, copper
extraction increased from b3% to N80% after 13 days of leaching and an
activation energy of 130.7 kJ/mol was determined, which is appreci-
ably higher than that reported by other researchers (7188 kJ/mol) in
the range of temperature between 50 and 94 C using a sulphate
medium (Table 1). Thus, the differences observed are presumably due
to the different range of temperature tested.
These results agree with the theoretical analysis of Hiskey (1993)
who concluded that due to n-type semiconduction of chalcopyrite, the
transport of electrons through vacancies is minimum. The rst stage in
chalcopyrite oxidation, consumes vacants, which favours the transport
of electrons through the crystal lattice. Therefore, the heat consumed
in the displacement of ions from the bulk to the surface eliminates
vacancies at the surface and promotes the transport of electrons. This
means chemical mechanisms control chalcopyrite dissolution; how-
ever, as noted earlier, diffusion of the oxidant is also very important in
this process.
We would note that there are clear differences when using one or
other type of medium (sulphate or chloride). The activation energies
Kinetic control Bibliographic reference
Parabolic kinetics Diffusion control Dutrizac et al., 1969
Parabolic kinetics Electrochemical control Muoz et al., 1979
Parabolic-linear kinetics Chemical control Hirato et al., 1987
Parabolic-linear kinetics Chemical control Crdoba et al., in press
Linear kinetics Electrochemical control Hirato et al., 1986
Linear kinetics Electrochemical control Majima et al., 1985
Linear kinetics Diffusion control Dutrizac, 1978
 Author's personal copy
84 E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8187
Fig. 5. Inuence of temperature on chalcopyrite leaching.
are higher in sulphate than in chloride medium, which is consistent
with the lower oxidizing power of ferric sulphate (Section 3.2).
4. Passivation of chalcopyrite during leaching with ferric ion
After almost a century of research into the mechanisms of chal-
copyrite dissolution in ferric medium, there is consensus with respect
to the formation of a passivating layer on the surface which slows
down the oxidation reaction. But in spite of that, the nature of this lm
is still unknown, although it has been postulated that it must have low
porosity and/or be a bad electric conductor. Following is an account of
the principal theories on this topic.
In 1969, Burkin (1969) established that the diffusion lm sur-
rounding the chalcopyrite during leaching with Fe3+ formed by a
bimetallic sulphide with chemical and structural properties different
from the original raw material, but with the same semiconducting
properties. These intermediate products are the result of solid state
transformations that favour solubilization of cations from the crystal
lattice at different rates. Therefore, the model implies that the reaction
takes place preferentially at the interface, within the thickness of a
reaction front.
Later, Ammou-Chokroum et al. (1977) suggested that the rate of the
dissolution process is controlled by the formation and evolution of a
compact diffusion layer of a low-solubility copper polysulphide, less
reactive than the original chalcopyrite and with less iron. The thickness
of this lm is the result of two opposite reactions (Fig. 6): 1) formation
of a passive layer, Cp, because solid state diffusion is slower in copper
than in iron, which obeys a parabolic law; and 2) linear dissolution of
the passive layer, producing an outer lm of porous sulphur with no
controlling effect.
In 1979, Muoz et al. (1979) postulated that the limiting step in
chalcopyrite dissolution with ferric ion is the transport of electrons,
necessary to reduce the ferric ion in the solidliquid interface, through
an insulating lm of elemental sulphur (Fig. 7). According to this
Fig. 6. Model of chalcopyrite oxidation by Fe3+ with formation of an inner layer of
polysulphide (Cp) and outer layer of porous sulphur (after Ammou-Chokroum et al., 1977).
Fig. 7. Model of chalcopyrite oxidation by Fe3+ with formation of a low porous layer of
elemental sulphur (after Muoz et al., 1979).
model, the elemental sulphur affects both anodic and cathodic semi-
reactions, limiting the overall redox reaction of chalcopyrite dissolu-
tion. This model has been ratied by Dutrizac (1989) and Majima et al.
(1985).
In 1995, Hackl et al. (1995) proposed a model mixture of chemical
and diffusion control to explain the leaching and passivation of chal-
copyrite in sulphate medium. This model complements the model of
Ammou-Chokroum et al. (1977). Initially, iron dissolves preferentially to
copper forming an intermediate disulphide phase, Cu1 xFe1 yS2, where
y NN x and x +y 1:
CuFeS2 Cu1x Fe1y S2 xCu2 yFe2 2x ye ; yNNx; x y1 4
In the second stage:
Cu1x Fe1y S2 Cu1xz S2 zCu2 1yFe2 2z 1ye 5
which is slower than the previous stage, the disulphide dissolves to
form a copper polysulphide, Cu1 x zS2 or CuSn, where n = 2/(1 x z).
This polysulphide is probably responsible for chalcopyrite passivation.
Thus, the rate-controlling step consists of a very slow decomposition
of copper polysulphide to cupric ions and porous elemental sulphur,
with no effect on chalcopyrite passivation:
Cu1xz S2 1xzCu2 2S- 21xze 6
This model greatly depends on temperature, since the polysul-
phide dissolution rate increases with temperature. Chalcopyrite pas-
sivation does not occur at 200 C.
In a recent work, Hiroyoshi et al. (2001) studied the effect of ferrous
ion on chalcopyrite oxidation with ferric ions in sulphuric acid and in the
absence of oxygen. They discovered that in the presence of high con-
centrations of cupric ion, the ferrous ion has a very positive effect on
copper extraction and the kinetics were controlled by the ratio of Fe3+/
Fe2+ concentrations or by the redox potential of the solution. However,
the ferrous ion adversely affected chalcopyrite oxidation at low cupric
ion concentrations. To account for these results, they proposed a re-
action model involving incomplete reduction of chalcopyrite, according
to the following reaction:
CuFeS2 3Cu2 3Fe2 2Cu2 S 4Fe3 7
This reaction is followed by oxidation of Cu2S (more sensitive to
leaching than chalcopyrite) by ferric ion:
Cu2 S 4Fe3 2Cu2 S- 4Fe2 8
The two reactions (7) and (8) give the overall reaction (1), which
traditionally describes the leaching of chalcopyrite in ferric medium.
According to this model, the rate-controlling step is the initial
reduction of chalcopyrite. This only happens when the redox potential
of the solution is below a critical value, which in turn is a function of
the concentration of ferrous and cupric ions.
 Author's personal copy
E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8187
Nicol and Lazaro (2003) propose a different mechanism to
explain the chalcopyrite dissolution at low redox potentials. At
potentials lower than 0.4 V, chalcopyrite could be reduced by proton
attack:
CuFeS2 4H Cu2 Fe2 2H2 S 9
The next step would be the oxidation of hydrogen sulphide by
ferric ions:
2H2 S 4Fe3 2S- 4Fe2 4H 10
The overall reaction of this mechanism is again reaction (1).
In this model, the rate-controlling step is electrochemical. The rate
of reaction (10) decreases when the redox potential of the chalcopyrite
surface increases from 0.5 to 0.7 V.
Various different studies on chalcopyrite leaching with ferric ion
accept the theory that there is a diffusion barrier between the
leaching solution and the chalcopyrite that slows down the disso-
lution rate. However, the nature of this barrier is still in debate since
the mechanism of chalcopyrite dissolution by Fe3+ has not yet been
elucidated.
Crdoba (2005) reports clear evidence that chalcopyrite passiva-
tion is related to high redox potentials or high Fe3+/Fe2+ ratios. Ferric/
ferrous sulphate leaching solutions tend quickly to reach a chemical
equilibrium where activities of both ions are equal. This is associated
with a critical potential of approximately 450 mV vs Ag/AgCl. Then,
when the initial redox potential is very high, that tendency to equil-
ibrium favours rapid precipitation of ferric ion as jarosite (Fig. 8) and
consequently chalcopyrite passivation.
The evidence cited above suggests that passivation of chalcopyr-
ite during leaching is chiey the result of hydrolysis and precipita-
tion of Fe3+ rather than partial transformation of the chalcopyrite
surface.
5. Silver-catalyzed chalcopyrite leaching
A way to improve the chalcopyrite dissolution rate is by adding
Ag+.
In 1976, Pawlek (1976) studied the effect of Ag+ on the leaching of
chalcopyrite at 110 C and 100 kPa. After 30 min, chalcopyrite dis-
solution was complete in the presence of silver compared with 40%
copper dissolution in the absence of silver. In 1979, Miller and
Portillo (1979) proposed a model to interpret the catalytic effect of
silver ions in the leaching of chalcopyrite with sulphuric acid/ferric
sulphate solutions. The authors suggested that in the absence of
silver ions, a dense elemental sulphur layer forms on the mineral
surface, acting as a diffusion barrier and delaying the oxidative
leaching of chalcopyrite with ferric ions. Conversely, in the presence
Fig. 8. SEM micrograph of a leaching residue at EInitial = 600 mV.
85
Fig. 9. Electrochemical characterization of a massive chalcopyrite electrode at 35 C:
a) anodic polarization and b) cyclic voltammetry.
of silver ions the leaching of chalcopyrite takes place according to
the following reactions:
CuFeS2 4Ag Cu2 Fe2 2Ag2 S 11
Ag2 S 2Fe3 2Ag 2Fe2 S- 12
The rate of copper extraction is faster in the presence of silver
ions since the product layer is formed by a mixture of sulphur and
Ag2S, which is porous and does not exert a barrier effect on the
chalcopyrite dissolution. Price and Warren (1986) reported that the
elemental sulphur obtained under silver catalytic conditions, besides
being more porous, presented higher electrical conductivity and
hence facilitated the transport of electrons through the chalcopyrite
surface.
The model proposed by Miller and Portillo has since been con-
rmed by Burkin (1982) and Price and Warren (1986), who detected
the formation of silver sulphide on the chalcopyrite surface.
At the same time, some authors (Burkin, 1982) have pointed out
that silver can substitute copper in the crystal lattice of copper sul-
phides, given the chemical similarities between copper and silver.
With an excess of Ag, the reaction product on the mineral surface
could contain silver and silver sulphate. This is undesirable because of
the amount of silver that may be consumed and lost before the ob-
jective is achieved i.e., to diminish the formation of elemental
sulphur on the chalcopyrite surface. An excess of silver can also fa-
cilitate the sequestering of silver by jarosite (Carranza et al., 1997;
Bolorunduro et al., 2003).
The formation of silver jarosite may be represented by reaction:
Ag 3Fe3 2SO2
4 6H2 OAgFe3 SO4 2 OH6 6H
13
6. Electrochemical characterization and passivation of chalcopyrite
Fig 9a and b shows the electrochemical behaviour of an electrode
of massive chalcopyrite at 35 C.
It is accepted that during anodic polarization of chalcopyrite from
its rest potential, there are normally two different electrochemical
responses (Biegler and Horne, 1985; Warren et al., 1985; Price and
Warren, 1986; Gmez et al., 1996). The rst peak, between the rest
potential and approximately +740 mV vs. Ag/AgCl, corresponds to the
passive zone or prewave, and the second peak, at higher potentials, is
known as the transpassive zone.
In the passive zone, the chalcopyrite surface transforms into a
copper-rich sulphide (CuS) and S because of the preferential dis-
solution of iron from chalcopyrite. The formation of covellite in this
zone has been justied by reaction (14) (Jones and Peters, 1976),
reaction (15) (Biegler and Swift, 1979; Biegler and Horne, 1985) or by
the transformation of chalcopyrite in an intermediate phase (bornite)
 Author's personal copy
86 E.M. Crdoba et al. / Hydrometallurgy 93 (2008) 8187
(reaction (16)) followed by oxidation to non-stoichiometric covellite
(reaction (17)) (Warren et al., 1985):
CuFeS2 2H2 O1=2CuS 1=2CuSO4 Fe2 S- 4H 6e 14
CuFeS2 0:75CuS 0:25Cu2 Fe2 1:25S- 2:5e 15
CuFeS2 Cu1x Fe1y S2z xCu2 yFe2 zS- 2x ye 16
Cu1x Fe1y S2z 2zCuSnonstoichiom: 1yCu2 1yFe2 21ye ; the ferric concentration is high.
where yNx
Whether or not the reactions by which CuS is formed are sto-
ichiometric, the different authors agree that this copper sulphide is
responsible for chalcopyrite passivation during oxidative dissolution.
In the transpassive zone, the passive layer breaks down and mas-
sive chalcopyrite dissolution takes place through reactions (18) and
(19) (Ammou-Chokroum et al., 1981; Yin et al., 1995, Gmez et al.,
1996) or through reaction (20):
CuFeS2 Cu2 Fe3 2S- 5e 18
CuFeS2 8H2 OCu2 Fe3 2SO2
4 16H 17e
CuFeS2 2H2 OCu2 Fe2 3=2S- 1=2H2 SO4 3H 7e 20 Antonijevi, M.M., Bogdanovi, G.D., 2004. Investigation of the leaching of chalcopyrite
In the anodic polarization curve (Fig. 9a), starting from the rest
potential (+230 mV), the two mentioned zones are clearly appreciable.
The passivation zone, with two electrochemical responses, A1 and A2,
indicates that chalcopyrite dissolves in this low-potential zone through
reactions (16) and (17).
In the cathodic branch (Fig. 9b), when the scan direction shifts
at + 800 mV, current density drops sharply to zero and practically
remains there over a wide range of potentials. Finally, from 150
to 500 mV, there is a large cathodic response (peak C). It is in this
zone that the reduction of chalcopyrite and covellite takes place,
through the following reactions:
2CuFeS2 6H 2e Cu2 S 2Fe2 3H2 S 21
2CuS 2H 2e Cu2 S H2 S 22
When the scan direction shifts to anodic values, the current
density again increases, showing two new anodic electrochemical
responses at approximately +310 mV (D) and +570 mV (E). According
to Biegler and Horne (1985), peak D reects the oxidation of reduction
products formed during the cathodic scan, Cu2S or non-stoichiometric
sulphides such as Cu8S5, Cu7S4, etc., as follows:
Cu2 SCuS Cu2 2e 23
Finally, the anodic peak E may be associated with the prewave
reaction (passive zone at low potential, peak A) of chalcopyrite
oxidation to CuS and S (reactions (14) to (17)). This peak could further
be related to the oxidation reaction of ferrous ion:
Fe2 Fe3 e 24
and later precipitation of the ferric ion as proposed by Tshilombo and
Dixon (2003). These authors observed the formation of ferric hydroxides
during the electrochemical oxidation of chalcopyrite at high potential
and temperature and concluded that they are formed by chemical pre-
cipitation of ferric ion generated by oxidation of ferrous ion.
7. Conclusions
While the refractoriness of chalcopyrite to chemical attack is very
much a matter of debate, it is unanimously agreed that the leaching
conditions must be oxidizing. The presence of ferric ion always plays a
central role since it is a by-product of chalcopyrite dissolution irres-
pective of the leaching conditions tested. The presence of ferric iron in
solution affects the process in two ways:
It favours leaching of the mineral when the ferric concentration is
suitable.
It causes passivation of the mineral surface and protects it from
attack through the formation of intermediate compounds when
17
At the same time, the ferrous ion plays an important role in this
process by balancing the composition of the leaching solution and
delaying the precipitation of ferric ion as jarosite, its nucleation on the
mineral surface, and ultimately passivation of the sulphide.
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