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INVESTIGATIONS ON THE MECHANISMS OF SULFURIC

ACID LEACHING OF CHALCOPYRITE IN THE PRESENCE OF
HYDROGEN PEROXIDE
a b
P. A. Olubambi & J. H. Potgieter
a
Department of Chemical and Metallurgical Engineering , Tshwane University of
Technology , Pretoria, South Africa
b
School of Biology, Chemistry and Health Science, Manchester Metropolitan University ,
Manchester, UK
Published online: 01 Oct 2009.

To cite this article: P. A. Olubambi & J. H. Potgieter (2009) INVESTIGATIONS ON THE MECHANISMS OF SULFURIC ACID
LEACHING OF CHALCOPYRITE IN THE PRESENCE OF HYDROGEN PEROXIDE, Mineral Processing and Extractive Metallurgy
Review: An International Journal, 30:4, 327-345, DOI: 10.1080/08827500902958191

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 Mineral Processing & Extractive Metall. Rev., 30: 327–345, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 0882-7508 print/1547-7401 online
DOI: 10.1080/08827500902958191

INVESTIGATIONS ON THE MECHANISMS OF

SULFURIC ACID LEACHING OF CHALCOPYRITE
IN THE PRESENCE OF HYDROGEN PEROXIDE
Downloaded by [Tshwane University of Technology] at 22:22 18 March 2014

P. A. OLUBAMBI1 AND J. H. POTGIETER2

1
Department of Chemical and Metallurgical
Engineering, Tshwane University of Technology,
Pretoria, South Africa
2
School of Biology, Chemistry and Health Science,
Manchester Metropolitan University,
Manchester, UK

The sulfuric acid leaching behavior of chalcopyrite in the

presence of hydrogen peroxide was studied at 25◦ C using electro-
chemical techniques. The effects of increasing the concentra-
tions of hydrogen peroxide up to 3 M on chalcopyrite dissolution
were carried out in shake flasks prior to electrochemical studies.
Electrochemical investigations were carried out on particulates
electrode made from powdered chalcopyrite samples using poten-
tiodynamic and chronoamperometric techniques. Increasing the
concentrations of hydrogen peroxide considerably accelerated the
leaching of both copper and iron. Morphologies of the leached
residues examined by scanning electron microscope revealed
similar products on the surfaces of chalcopyrite for all the condi-
tions of leaching. A reduction in sizes of the particles, which
increase the porosity of the residues, was observed at increasing
concentrations of hydrogen peroxide. X-ray analysis revealed the
presence of elemental sulfur in the solid residues with increasing
crystallinity as the concentration of hydrogen peroxide increased.
Polarization curves showed that hydrogen peroxide raised the
dissolution potentials of chalcopyrite toward more noble values.

Address correspondence to P. A. Olubambi, Department of Chemical and Metal-

lurgical Engineering, Tshwane University of Technology, Private Mail Bag X680,
Pretoria, South Africa. E-mail: polubambi@yahoo.com
 328 P. A. OLUBAMBI AND J. H. POTGIETER

The addition of hydrogen peroxide also drastically increased the

dissolution currents, current densities, and dissolution rates, and
reduced the passivity of chalcopyrite. Increasing the concen-
tration of hydrogen peroxide and dissolution potential resulted
in a characteristic current increase/decrease behavior of the
ore. Higher dissolutions obtained at increased concentrations
of hydrogen peroxide were attributed to the porous agglom-
erate nature of the leached residues that did not passivate the
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chalcopyrite surface, but aided further dissolution through electron

transfer.

Keywords: chalcopyrite, electrochemical study, hydrogen peroxide,

sulfuric acid

INTRODUCTION
Hydrometallurgical processing has become an increasingly important
aspect in the recovery of base and precious metals from complex
sulfide ores. This is because it satisfies industrial requirements
in terms of technical effectiveness, flexibility, ease of operation,
cost-effectiveness, environmental friendliness, and the ability to be
expanded from a small scale. However, hydrometallurgical operations
do suffer some drawbacks, including low recovery of extracted metal,
difficulties in solid–liquid separation, and the effect of impurities
on the ease of purification. Another major problem confronting
hydrometallurgical processing of sulfide ore, especially chalcopyrite, is
low solubility in many leaching solutions. As a result of the diffi-
culty usually encountered in getting the desired metals into aqueous
solution, careful consideration must be given to selecting suitable
leaching reagents for the recovery of the constituent metals.
Among the several factors determining choice and effectiveness,
leaching reagents are usually assessed in terms of dissolution power,
price, and environmental friendliness. Several studies have been
reported on the effectiveness of different reagents for chalcopyrite
leaching. Halogen salts of chlorides and bromides (Stanley and Subra-
manian 1977), chlorine gas-saturated water (Ekinci et al. 1998), and
nitrogen dioxide (Frankiewicz and Lueders 1979a,b) have been used
for copper recovery from chalcopyrite. It should be noted, however,
that these reagents are, in general, very slow in the rate of metal
recovery, coupled with many problems associated with the removal
of iron and effective recovery of copper and zinc from the leach
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 329

liquors. Prasad and Pandey (1998) reviewed and compared the effec-
tiveness of sulfuric acid, hydrochloric acid, nitric acid, ferric chloride,
and ferrous sulfate for sulfide ore leaching and found that nitric
and hydrochloric acids were comparatively and respectively the most
effective. Since nitric acid and hydrochloric acid usually induce a
very corrosive environment, and thus require very expensive corrosion-
resistant equipment, their industrial applications are limited. A number
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of research articles have been focused on acid leaching of sulfide ores

in chloride and sulfate media (Al-Harahsheh et al. 2006; Buttinelli
et al. 1992; Carneiro and Leão 2007; Hirato et al. 1987; Hiroyoshi
et al. 2001; Liddicoat and Dreisinger 2007; Lundström et al. 2005;
Souza et al. 2007). Despite the effectiveness of these reagents, they
suffer the major drawbacks of high corrosiveness and difficulties in
solution recoverability.
In the search for suitable and sustainable alternative leaching
reagents, attention has been refocused on the use of easily available
and cheap reagents like sulfuric acid. Sulfuric acid has been used for
a very long time for sulfide ore leaching, and means for improving
its effectiveness have been investigated by various researchers (Abdel-
Aal 2000; Antonijevic and Bogdanovic 2002, 2004; Havlik et al.
2005; Hiroyoshi et al. 2002; Ivascan and Roman 1975; Koch and
Grasselly 1952; Momade and Momade 1999; Padilla et al. 2003,
2005). Although, sulfuric acid is not as effective as stronger acids
like nitric acid and hydrochloric acid (Copur 2001, 2002; Prasad and
Pandey 1998), it is preferred over all other leaching reagents in terms
of cost, environmental friendliness, fewer corrosion problems, and
ease of its regeneration during electrowinning (Biswas and Davenport
1980).
As a means of optimizing the effectiveness of sulfuric acid
leaching, the possibility exists for using suitable oxidizing agents to aid
its dissolution kinetics. The use of oxygen as an oxidant for sulfuric
acid pressure leaching of chalcopyrite has been investigated under
conditions of varying stirring speed, concentration of sulfuric acid,
temperature, and partial pressure of oxygen (Padilla et al. 2007), and
it was observed that the oxygen partial pressure controlled the selec-
tivity of chalcopyrite dissolution. Several investigations have also been
reported on oxidative dissolution using hydrogen peroxide to aid and
promote the leaching potential of sulfuric acid (Antonijevic et al. 1997;
Eary and Cathles 1983; Jiagang et al. 2002; Olubambi et al. 2006).
 330 P. A. OLUBAMBI AND J. H. POTGIETER

Besides the high oxidizing potentials of hydrogen peroxide, it is easier

to handle than gaseous oxidizers and requires no pressure equipment,
as is the case with gaseous oxidizers. Oxidative dissolution of sulfide
ore using hydrogen peroxide in conjunction with sulfuric acid has
proved to be very effective.
Studies reported by Antonijevic et al. (1997, 2004) on the disso-
lution kinetics of chalcopyrite by hydrogen peroxide in sulfuric acid
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showed that copper recoveries were greatly increased as the concentra-

tions of sulfuric acid and hydrogen peroxide increase. Adebayo et al.
(2003) studied the influence of temperature, stirring speed, concen-
trations of hydrogen peroxide and sulfuric acid, as well as particle
size on chalcopyrite dissolution and found that dissolution kinetics
followed a shrinking-core model, with surface chemical reaction as
the rate determining step. Despite the extent of these studies on
sulfuric acid leaching in conjunction with hydrogen peroxide, it was
observed that they were all centered on the dissolution kinetics, which
could not provide sufficient information for understanding mecha-
nisms of dissolution. Since the leaching of a sulfide ore occurs via
an electrochemical mechanism similar to corrosion, which involves
electrochemical and chemical reactions of the mineral with the
leaching solution, useful information for understanding the mechanism
of the dissolution process of sulfuric acid/hydrogen peroxide could
possibly be obtained using electrochemical techniques. Although some
related studies have been reported on the electrochemical behavior
of chalcopyrite in sulfuric acid (Arce and Gonzalez 2002; Elsherief
2002; Hiroyoshi et al. 2004; Lazaro et al. 1995; Nava and Gonzalez
2006), they were carried out without the addition of an oxidant.
Moreover, the electrochemical techniques employed could not suffi-
ciently explain the passivity behavior of chalcopyrite. In this study, the
mechanism of sulfuric acid leaching of chalcopyrite in the presence of
hydrogen peroxide was investigated using potentiodynamic polarization
and chronoamperonic techniques.

MATERIALS AND EXPERIMENTAL METHOD

Materials
Finely ground samples of chalcopyrite ore obtained from the Council
for Minerals Technology (MINTEK), South Africa, were used for
this study. Its mineralogical and elemental composition as revealed by
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 331

Table 1. Mineralogical and elemental composition of the ore

XRD analysis (% composition) ICP-OES analysis (% composition)

Chalcopyrite Pyrite Silica Cu Fe S

66 11 6.8 24 30 31
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X-ray diffraction (XRD) and inductively coupled plasma–optical

emission spectrometer (ICP-OES) analysis are shown in Table 1.

Leaching Experiments
Leaching experiments were initially carried out in 250 ml Erlenmeyer
flasks at room temperature to assess the amounts of copper and iron
leached. The flasks were placed in an incubator shaker to provide the
necessary stirring and to maintain a constant temperature of 25◦ C.
Analytical grade sulfuric acid (98 vol% H2 SO4 ), hydrogen peroxide (34
vol% H2 O2 ), and distilled water were used. Leaching experiments were
conducted in two stages: sulfuric acid leaching followed by sulfuric acid
leaching in conjunction with hydrogen peroxide.

Sulfuric Acid Leaching. Sulfuric acid solution (1.0 M, 200 ml) was
introduced into the reactor. At the desired temperature, 2 g of the
ore were added to the acid solution and the contents were stirred
at a constant speed of 160 rpm. Two milliliters of pregnant solution
were taken from the reactor every 60 minutes, filtered, and the filtrate
was analyzed for copper and total iron using atomic absorption
spectrometry (AAS).

Sulfuric Acid With Hydrogen Peroxide Leaching. These experi-

ments were conducted to determine the effect of hydrogen peroxide
concentration on the dissolution rates in sulfuric acid. Equal volumes
of 100 ml each of 1.0 M sulfuric acid and 1.0 M hydrogen peroxide were
introduced into the reactor vessel. At the reaction temperature, 2 g of
ore were added and the stirring speed was kept at 160 rpm. Samples
were drawn from the reactor every 60 minutes and filtered. The filtrate
was then subjected to elemental analysis. The procedure was repeated
for varying concentrations of hydrogen peroxide (2.0 M and 3.0 M).
 332 P. A. OLUBAMBI AND J. H. POTGIETER

XRD and SEM Analyses of the Residues

Leach residues were examined using scanning electron microscopy
(SEM) to assess the morphology of the product layers on the
chalcopyrite surface. Mineral phases within the residues were identified
by powdered X-ray diffractometry. The samples were first subjected to
X-ray scanning using the Philips PW 1830 X-ray diffractometer with a
copper anode. After X-ray scanning of the samples, mineral peaks were
Downloaded by [Tshwane University of Technology] at 22:22 18 March 2014

identified using X/Pert High Score Plus software. The background and
peak positions were identified, and based on the peak positions and
intensities, a search-match routine was performed.

Electrochemical Study
Electrochemical Cell and Electrodes. A 500 ml Pyrex glass electro-
chemical cell constructed for a conventional three-electrode system was
used for the electrochemical measurements. The counter electrodes
were made of graphite rods of 0.5 mm diameter, while silver/silver
chloride 3 M potassium chloride was used as the reference electrode.
The working electrode was a particulate electrode made from the
powdered sample. These electrodes were prepared similar to the
procedure described by Munoz et al. (1998) and Lu et al. (2000b).
A 0.7 g mass of the base conductor material (powdered graphite) was
mixed with 0.3 g of powdered sample and 0.6 ml silicon oil from Sigma
Aldrich and compressed under pressure using a carbon paste electrode
holder. Electrochemical tests were carried out using an Autolab poten-
tiostat (PGSTAT20 computer controlled) using the General Purpose,
Electrochemical Software (GPES, version 4.9).

Electrochemical Measurements. Electrochemical measurements

were carried out in four different solutions: 1 M sulfuric acid and
1 M sulfuric acid with three different concentrations of hydrogen
peroxide used for the leaching experiments. All the electrochemical
measurements were conducted at 25◦ C. The leaching medium with
the electrodes was placed on a thermostatically controlled heated
plate. Potentiodynamic polarization and potentiostatic current–time
experiments were used to study the electrochemical behavior of the
ore. For potentiodynamic polarization experiments, the potential was
scanned from 0 mV to 1200 mV at a scan rate of 2 mVs−1 . Before
potentiodynamic polarization measurements, the cell was left for about
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 333

10 min to stabilize the open-circuit potential (OCP) after immersion of

the working electrode in the electrolytes. Potentiostatic current–time
experiments were carried out at different dissolution potentials of
600 mV, 750 mV, and 900 mV.

RESULTS AND DISCUSSIONS

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Effects of Hydrogen Peroxide Concentration on Copper and

Iron Dissolution
The results of the dissolution in the shake flask carried out to asses
the amounts of copper and iron leached are presented in Figures 1
and 2. The results show that increasing the concentration of hydrogen
peroxide considerably accelerated the leaching of both copper and
iron. During sulfuric acid leaching without hydrogen peroxide addition,
very small amounts of copper were leached. Copper leaching rose from
4% within the first hour to a highest amount of 7% at the fifth hour of
leaching. However, when 1 M hydrogen peroxide solution was added,
copper leaching increased drastically from 46% during the first hour
of leaching to a highest amount of 52% in the sixth hour. In all the
concentrations of hydrogen peroxide studied, the highest copper disso-
lution of 87% was obtained at a hydrogen peroxide concentration of

Figure 1. Effects of hydrogen peroxide addition on copper dissolution.

 334 P. A. OLUBAMBI AND J. H. POTGIETER
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Figure 2. Effects of hydrogen peroxide addition on iron dissolution.

3 M in the fourth hour of leaching. Similar results and trends were

obtained for iron dissolution, although lower than copper leaching. The
greatest iron total dissolved was obtained in the third hour when 3 M
hydrogen peroxide solution was added.
The observed increase in dissolution resulting from increasing the
concentration of hydrogen peroxide may be due to the high oxidation
potential of hydrogen peroxide. This could have resulted in the partial
conversion of chalcopyrite to elemental sulfur and subsequently to
sulfate. According to Mahajan et al. (2007), chalcopyrite leaching by
hydrogen peroxide results in dissolution of copper and iron ions from
the chalcopyrite matrix according to Equation (1):

CuFeS2 → Cu2+ + Fe2+ + 2S0 + 4e−
(1)

During sulfuric acid leaching without the addition of hydrogen

peroxide, chalcopyrite dissolves slowly according to Equation (2):

CuFeS2 + 2H2 SO4 + O2 → CuSO4 + FeSO4 + 2S0 + 2H2 O
(2)

However, in the presence of hydrogen peroxide, chalcopyrite disso-

ciates rapidly according to Equation (3), while a small amount
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 335

of sulfide ions also occur in the elemental form, as expressed in

Equation (4) (Antonijevic et al. 2004):
2CuFeS2 + 17H2 O2 + 2H+ → 2Cu2+ + 2Fe3+ + 4SO2−
4 + 18H2 O (3)

2CuFeS2 + 5H2 O2 + 10H+ → 2Cu2+ + 2Fe3+ + 2S0 + 10H2 O
(4)

The increase in chalcopyrite dissolution in the presence of hydrogen
peroxide could be attributed to the fact that when hydrogen peroxide
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reacts with minerals, it decomposes to the hydroxyl anion (OH− )

and hydroxyl radical (HO∗ ; Lin and Luong 2004) according to
Equation (5):
H2 O2 → HO∗ + OH−
(5)
The reactive hydroxyl radical (HO∗ ) reacts with chalcopyrite to
form elemental sulfur (Equation (6)), which is oxidized to sulfate ions
(Equation (7)), and finally reacts with copper and iron ions to form an
aqueous solution of copper and ferrous sulfates (Equations (8) and (9)):
2HO∗ + 2S2− → 2S0 + H2 O + 0
5O2 (6)
+
2S0 + 3O2 + 2H2 O → 2SO2−
4 + 4H (7)
Cu2+ (aq) + SO2−
4 (aq) → CuSO4 (aq) (8)
Fe (aq) +
2+
SO2−
4 (aq) → FeSO4 (aq)
(9)
The amounts of copper and iron dissolved as presented in Figures 1
and 2 revealed an increase in metal dissolution up to a maximum value,
after which there was a general decrease. Although the amounts of
copper and iron dissolved during sulfuric acid leaching were generally
small as compared with hydrogen peroxide additions, it was obvious
that the rate of decrease in dissolution after the maximum value was
reached was not pronounced during sulfuric acid leaching alone as
compared with hydrogen peroxide addition. The decrease in disso-
lution after the maximum value was reached could be attributed to a
decrease in the leaching strength of the media with time. The decrease
in leaching strength was more pronounced as the concentration of
hydrogen peroxide increased, due to its possible decomposition to water
(Equation (10)), which could be greater at higher concentrations:
H2 O2 → H2 O + 0
5O2
(10)
The further decrease in dissolution after the maximum value was
reached could also be due to cupric and ferrous ions precipitating
 336 P. A. OLUBAMBI AND J. H. POTGIETER

from the leaching solution. Hiroyoshi et al. (2004) noted that the
presence of cupric and/or ferrous ions within the leaching system
causes activation (or depassivation) rather than passivation, and a lack
of these ions could lead to a high-resistance passive layer forming
on the chalcopyrite surface. The precipitated products could therefore
possibly hinder the transfer and transportation of both lixiviate to the
mineral’s surface and the solubilized species from the mineral’s surface
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to the leaching solution.

Analysis of Leached Residues

The micrographs of the scanning electron microscope analysis of
the residues are shown in Figure 3. The surface morphologies of
solid residues were very similar for all the conditions of leaching.
As observed in the SEM micrographs of the residues, the product
layers were distinctly crystalline and porous in nature. A similar obser-
vation was reported by Mahajan et al. (2007), where elemental sulfur
present on the surface of chalcopyrite residue was identified as discrete
crystalline particles instead of a coating or continuous film. As the

Figure 3. SEM micrographs of the residues after leaching in (A) 1 M sulfuric acid; (B) 1 M
sulfuric acid and 1 M hydrogen peroxide; (C) 1 M sulfuric acid and 2 M hydrogen peroxide;
(D) 1 M sulfuric acid and 3 M hydrogen peroxide. (Bar sizes 10 m.)
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 337

concentrations of hydrogen peroxide increased, particle size reduc-

tions were observed. This indicates that the fractions of ores that were
dissolved increased as concentrations of hydrogen peroxide increased.
X-ray analysis of the solid residues after chalcopyrite leaching in all
the media revealed the presence of no new solid product in the residues
of the sulfuric acid leaching without hydrogen peroxide addition. This
is probably due to the fact that sulfate ion might be the only product
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of sulfide sulfur oxidation (Antonijevic et al. 2004), which would have

occurred in aqueous form. XRD analysis of the residues of the leaching
in the presence of hydrogen peroxide, however, revealed traces of
elemental sulfur. Although the sulfur contents were not quantified,
qualitative analysis showed that elemental sulfur had more peaks, with
increasing peak intensities as the concentration of hydrogen peroxide
increased. This suggests that elemental sulfur formation could have
resulted from the decomposition reactions of chalcopyrite by hydrogen
peroxide, as shown in Equations (3) and (5).

Electrochemical Behavior of Chalcopyrite Dissolution

Polarization curves showing characteristic electrochemical behavior of
chalcopyrite during leaching in sulfuric acid and in various concen-
trations of hydrogen peroxide addition are shown in Figure 5. It
was observed that hydrogen peroxide raised the dissolution potentials
of chalcopyrite toward more noble values. Hydrogen peroxide shifted
the dissolution potential from 236 mV during sulfuric acid leaching
to 354 mV, 450 mV, and 460 mV, respectively, when 1 M, 2 M, and
3 M hydrogen peroxide was added. Hydrogen peroxide was observed
to drastically increase the dissolution currents, current densities, and
dissolution rates. The dissolution current gradually increased from
3
86 × 10−6 A to 4
99 × 10−6 A when 1 M hydrogen peroxide was
added, and increased to 1
67 × 10−5 A and 4
27 × 10−5 A, respectively,
when the concentration of hydrogen peroxide was increased at 2 M and
3 M. Similarly, the dissolution current density initially increased from
1
96 × 10−5 Acm−2 to 2
53 × 10−5 Acm−2 when 1 M hydrogen peroxide
was added, and later increased to 8
52 × 10−5 Acm−2 and 2
17 ×
10−4 Acm−2 , respectively, at 2 M and 3 M hydrogen peroxide additions.
The polarization curves also revealed that passivity of chalcopyrite
decreased as concentrations of hydrogen peroxide increased. It was
observed that, at 650 mV, the dissolution current decreased drasti-
cally within the passivity range during sulfuric acid leaching before
 338 P. A. OLUBAMBI AND J. H. POTGIETER
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Figure 4. Current–time curves showing the behavior of chalcopyrite dissolution at a

fixed potential of 600 mV in sulfuric acid and in various concentrations of hydrogen
peroxide.

it increased again at 800 mV. On the other hand, corrosion currents

increased steadily when hydrogen peroxide was added.
The electrochemical behavior of chalcopyrite observed in this work
can be explained based on the results of this study and similar studies
already reported in the literature. At lower potentials, where dissolution
current density is lower, Antonijevic and Bogdanovic (2004) suggested
that the chalcopyrite surface could be passivated. According to Lu
et al. (2000a,b), during initial leaching stages, chalcopyrite oxidation
at low overpotential is slowed by the formation of the sulfide surface
with low-grade metal, where oxidation of this mineral is developed by
a partial reaction, as represented by Equation (11), and y > x:
CuFeS2 → Cu1−x Fe1−y S2−z + xCu2+ + yFe2+ + zS0 + 2(x − y)e−

At increased potential where dissolution rate could possibly be
controlled by the rate of passive layer decomposition, Nava and
Gonzalez (2006) observed that the passive product can decompose to
form porous layers of nonstoichiometric polysulfide (Cu1−x Fe1−y S2−z ),
thereby allowing diffusional transport of charged species and disso-
lution of the mineral. It was suggested by Hiroyoshi et al. (2004)
that higher currents at lower potentials could result from the rapid
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 339

oxidation of the intermediate Cu2 S formed from chalcopyrite in the

presence of cupric and ferrous ions. From the polarization curves
shown in Figure 5, it can be seen that, as the potential increases, the
exchange of current also increases within the active dissolution region.
The initial dissolution of iron could thereby give rise to the disap-
pearance of iron from the crystal lattice of chalcopyrite, which may
promote the formation of unstable covellite as a result of the breaking
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of the Fe–S bond within the chalcopyrite lattice during dissolution. The
electropositive Fe2+ will thus be released into solution, while the Cu2+
will remain after the initial step as a result of the breaking of the Cu–S
bond. The unstable covellite formed could thus decompose to Cu2+
and promote complete dissolution of the chalcopyrite, as suggested by
Hiroyoshi et al. (2004).
Chalcopyrite oxidation observed during active dissolution was
suggested to be due to the presence of cupric and ferrous ions
(Elsherief 2002; Hiroyoshi et al. 2004; Nava and Gonzalez 2006).
On the other hand, its passivation could result from the presence
of several products including covellite, chalcocite, and sulfur (Arce
and Gonzalez 2002; Hackl et al. 1995; Klauber et al. 2001; Nava
and Gonzalez 2006). This observation was corroborated by the high
amounts of both copper and iron dissolved within the first 60 min
of dissolution in all the leaching media (Figures 1 and 2), which
could have resulted in the increased anodic currents. Elsherief (2002)
and Hiroyoshi et al. (2004) attributed the initial increase in the
anodic current that facilitated chalcopyrite dissolution observed during
active dissolution to the presence and coexistence of both cupric and
ferrous ions (Equation (1)) within the system. According to Nava and
Gonzalez (2006), the initial dissolution could occur when the nonstoi-
chiometric polysulfide (Cu1−x Fe1−y S2−z ) is formed.
The behavior of chalcopyrite observed within the passivity range
can be explained from a sulfur formation viewpoint. According to the
results of the X-ray analysis, elemental sulfur was the major product
formed on the surface of the solid residues after chalcopyrite leaching
in all the media. This is similar to the observation by Klauber et al.
(2001) that elemental sulfur, which can form a passive layer on the
chalcopyrite surface, is probably responsible for the passivation of
the chalcopyrite surface. Passivation could start when the amounts
of copper and iron on the surfaces of the chalcopyrite become very
minimal. According to Hiroyoshi et al. (2004), when the coexistence of
 340 P. A. OLUBAMBI AND J. H. POTGIETER

cupric and ferrous ions becomes limiting, especially in the absence of

Cu2 S, an elemental sulfur layer grows on chalcopyrite due to the direct
oxidation of chalcopyrite, and the layer acts as a passive layer.
The increase in dissolution potential observed at increasing
hydrogen peroxide concentration in this study can probably be
attributed to instantaneous elemental sulfur formation. The elemental
sulfur formed could have created a passive layer on the chalcopyrite
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surface, thereby decreasing the initial reactivity of the ore. This can
also be due to the initial decomposition of hydrogen peroxide to
hydroxyl anion (OH− ) and hydroxyl radical (HO∗ ) when in contact
with chalcopyrite, as represented in Equation (5). An increase in the
dissolution as the hydrogen peroxide concentration increases could be
the result of the reactive nature of the hydroxyl radical (HO∗ ), which
could have accelerated the dissolution process. This increase could also
be attributed to the fast oxidation of the elemental sulfur to soluble
and conductive sulfates.
The pseudopassive behavior of chalcopyrite during leaching in the
presence of hydrogen peroxide (especially with 2 M and 3 M additions)
could be an indication that there is continual decomposition of the
passive elemental sulfur layer within the potential ranges studied in this
work. This might be due to oxidation of the elemental sulfur to sulfates
within these high potential ranges. The porous and crystalline nature of
the product layers of the residues could be an indication that they did
not form a protective and continuous coating that could prevent disso-
lution. The porous nature of the precipitates, which could also allow
open spaces between separate sulfur crystals, would thus keep the mineral
surface continually exposed to lixiviate and thereby permit the leaching to
continue. This could indicate that these permeable layers allow exchange
of ions and electrons at the solid–liquid interface to take place.
The chronoamperometric behavior of chalcopyrite in the presence
and absence of hydrogen peroxide under applied potentials of 600 mV,
750 mV, and 900 mV from three major zones in the passive regions
on the polarization curves are shown in Figures 4–7. Polarization
currents were found to increase with increasing applied potentials. The
chronoamperometric curves for leaching in hydrogen peroxide medium
displayed high dissolution, as revealed by the high corrosion currents
and the fluctuating current increase/decrease behavior. The character-
istic current increase/decrease behavior was very obvious as concen-
trations of hydrogen peroxide increased and at increased dissolution
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 341
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Figure 5. Potentiodynamic polarization curves showing electrochemical behavior of

chalcopyrite in sulfuric acid and in various concentrations of hydrogen peroxide.

Figure 6. Current–time curves showing the behavior of chalcopyrite dissolution at a

fixed potential of 750 mV in sulfuric acid and in various concentrations of hydrogen
peroxide.
 342 P. A. OLUBAMBI AND J. H. POTGIETER
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Figure 7. Current–time curves showing the behavior of chalcopyrite dissolution at a fixed

potential of 900 mV in sulfuric acid and in various concentrations of hydrogen peroxide.

potentials. This fluctuating current behavior can be attributed to

the simultaneous formation of elemental sulfur and its subsequent
oxidation to sulfate ions. A decrease in corrosion current might
result from the formation of elemental sulfur, which passivated the
chalcopyrite surface, while its further oxidation to sulfate ions may
result in a corresponding increase in the dissolution current. Higher
dissolution currents at increased concentrations of hydrogen peroxide
can be attributed to the crystalline agglomerate of the leached residues,
which would not have passivated the chalcopyrite surface.

CONCLUSION
Hydrogen peroxide accelerated the formation of elemental sulfur, which
probably passivated the chalcopyrite surface and thus reduced its initial
reactivity. Oxidation of the elemental sulfur to sulfates by hydrogen
peroxide accelerated chalcopyrite dissolution. The increase in the
porous and crystalline nature of the residues with increasing hydrogen
peroxide concentrations reduced the passive nature of chalcopyrite
and promoted dissolution. The presence of hydrogen peroxide can
be concluded to accelerate chalcopyrite leaching through the porous
and permeable nature of the dissolution products. The shape of the
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 343

current–time curves indicates that the controlling factor for the kinetics
in the presence of hydrogen peroxide is electron transfer.

REFERENCES
Abdel-Aal, E. A., 2000, ‘‘Kinetics of sulfuric acid leaching of low grade zinc
silicate ore.’’ Hydrometallurgy, 55, pp. 247–254.
Adebayo, A. O., Ipinmoroti, K. O., and Ajayi, O. O., 2003, ‘‘Dissolution kinetics
Downloaded by [Tshwane University of Technology] at 22:22 18 March 2014

of chalcopyrite with hydrogen peroxide in sulphuric acid medium.’’ Chemical

and Biochemical Engineering Quarterly, 17, pp. 213–218.
Al-Harahsheh, M., Kingman, S., and Bradshaw, S., 2006, ‘‘Scale-up possibil-
ities for microwave leaching of chalcopyrite in ferric sulphate.’’ Interna-
tional Journal of Mineral Processing, 80, pp. 198–204.
Antonijevic, M. M. and Bogdanovic, G. D., 2002, ‘‘Leaching of chalcopyrite
ore with sulphuric acid solution. 34th IOC on Mining and Metallurgy,
Bor Lake, Yugoslavia, Technical Faculty Bor, pp. 373–379.
Antonijevic, M. M. and Bogdanovic, G. D., 2004, ‘‘Investigation of the
leaching of chalcopyritic ore in acidic solutions.’’ Hydrometallurgy, 73,
pp. 245–256.
Antonijevic, M. M., Dimitrijevic, M., and Jankovic, Z. 1997, ‘‘Leaching of
pyrite with hydrogen peroxide in sulphuric acid.’’ Hydrometallurgy, 46,
pp. 71–83.
Antonijevic, M. M., Jankovic, Z. D., and Dimitrijevic, M. D., 2004, ‘‘Kinetics
of chalcopyrite dissolution by hydrogen peroxide in sulphuric acid.’’
Hydrometallurgy, 71, pp. 329–334.
Arce, E. M. and Gonzalez, I., 2002, ‘‘A comparative study of electrochemical
behavior of chalcopyrite, chalcocite and bornite in sulfuric acid solution.’’
International Journal of Minerals Processing, 67, pp. 17–28.
Biswas, A. K. and Davenport, W. G., 1980, Extractive Metallurgical of Copper,
Oxford, Pergamon Press, pp. 263–269.
Buttinelli, D., Lavecchia, R., Pochetti, F., Geveci, A., Guresin, N., and
Topkaya, Y., 1992, ‘‘Leaching by ferric sulphate of raw and concentrated
copper-zinc complex sulphide ores.’’ International Journal of Mineral
Processing, 36, pp. 245–257.
Carneiro, M. F. C. and Leão, V. A., 2007, ‘‘The role of sodium chloride on
surface properties of chalcopyrite leached with ferric sulphate.’’ Hydromet-
allurgy, 87, pp. 73–82.
Copur, M., 2001, ‘‘Solubility of ZnS concentrate containing pyrite and
chalcopyrite in HNO3 solutions.’’ Chemical and Biochemical Engineering
Quarterly, 15, pp. 181–184.
Copur, M., 2002, ‘‘An optimization study of dissolution of Zn and Cu in ZnS
concentrate with HNO3 solutions.’’ Chemical and Biochemical Engineering
Quarterly, 16, pp. 191–197.
Eary, L. E. and Cathles, L. M., 1983, ‘‘The kinetics of uranium dioxide disso-
lution in acidic hydrogen peroxide solutions.’’ Metallurgical Transactions,
14B, pp. 10, 325.
 344 P. A. OLUBAMBI AND J. H. POTGIETER

Ekinci, Z., Colak, S., Cakici, A., and Sarac, H., 1998, ‘‘Leaching kinetics of
sphalerite with pyrite in chlorine saturated water.’’ Minerals Engineering,
11, pp. 279–283.
Elsherief, A. E., 2002, ‘‘The influence of cathodic reduction, Fe2+ and
Cu2+ ions on the electrochemical dissolution of chalcopyrite in acidic
solution.’’ Minerals Engineering, 15, pp. 215–223.
Frankiewicz, T. C. and Lueders, R. E., 1979a, ‘‘Copper leaching employing
nitrogen dioxide as oxidant.’’ U.S. Patent 4, 132, 758.
Downloaded by [Tshwane University of Technology] at 22:22 18 March 2014

Frankiewicz, T. C. and Lueders, R. E., 1979b, ‘‘High slurry density mineral

leaching using nitrogen dioxide.’’ U.S. Patent 4, 144, 310.
Hackl, R. P., Dreisinger, D. B., Peres, E., and King, J. A., 1995, ‘‘Passivation
of chalcopyrite during oxidative leaching in sulfate media.’’ Hydrometal-
lurgy, 39, pp. 25–48.
Havlik, T., Turzakova, M., Stopic, S., and Friedrich, B., 2005, ‘‘Atmospheric
leaching of EAF dust with diluted sulphuric acid.’’ Hydrometallurgy, 77,
pp. 41–50.
Hirato, T., Majima, H., and Awakura, Y., 1987, ‘‘The leaching of chalcopyrite
with cupric chloride.’’ Metallurgical Transactions B, Process Metallurgy, 18,
pp. 31–39.
Hiroyoshi, N., Arai, M., Miki, H., Tsunekawa, M., and Hirajima, T., 2002, ‘‘A
new reaction model for the catalytic effect of silver ions on chalcopyrite
leaching in sulfuric acid solutions.’’ Hydrometallurgy, 63, pp. 257–267.
Hiroyoshi, N., Kuroiwa, S., Miki, H., Tsunekawa, M., and Hirajima, T., 2004,
‘‘Synergistic effect of cupric and ferrous ions on active-passive behavior
in anodic dissolution of chalcopyrite in sulfuric acid solutions.’’ Hydromet-
allurgy, 74, pp. 103–116.
Hiroyoshi, N., Miki, H., Hirajima, T., and Tsunekawa, M., 2001,
‘‘Enhancement of chalcopyrite leaching by ferrous ions in acidic ferric
sulfate solutions.’’ Hydrometallurgy, 60, pp. 185–197.
Ivascan, S. and Roman, O., 1975, ‘‘Nickel recovery from spent catalyst.’’
Buletinul Institutului Politehnic din IasCi, SectCia II, 21, pp. 47–51.
Jiagang, T., Yang, Y., Zhang, B., and Huang, Z., 2002, ‘‘Kinetics of silver
leaching from manganese-silver associated ores in sulfuric acid solution
in the presence of hydrogen peroxide.’’ Metallurgical and Materials Trans-
actions, 33B, pp. 813–816.
Klauber, C., Parker, S., Bronswijk, W., and Watling, H., 2001, ‘‘Sulphur speci-
ation of leached chalcopyrite surfaces as determined by X-ray photo-
electron spectroscopy.’’ International Journal of Minerals Processing, 62,
pp. 65–94.
Koch, S. and Grasselly, G., 1952. ‘‘Data on the oxidation of sulfide ore
deposits.’’ Acta Mineralogica-Petrographica, Szeged, 6, pp. 23–29.
Lazaro, I., Martinez-Medina, N., Rodriguez, I., Arce, E., and Gonzalez, I.,
1995, ‘‘The use of carbon paste electrodes with non-conducting binder
for the study of minerals: chalcopyrite.’’ Hydrometallurgy, 38, pp. 277–287.
Liddicoat, J. and Dreisinger, D., 2007. ‘‘Chloride leaching of chalcopyrite.’’
Hydrometallurgy, 89, pp. 323–331.
 THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 345

Lu, Z. Y., Jeffrey, M. I., and Lawson, F., 2000a. ‘‘The effect of chloride ions
on the dissolution of chalcopyrite in acidic solutions.’’ Hydrometallurgy,
56, pp. 189–202.
Lu, Z. Y., Jeffrey, M. I., and Lawson, F., 2000b. ‘‘An electrochemical study
of the effect of chloride ions on the dissolution of chalcopyrite in acidic
solutions.’’ Hydrometallurgy, 56, pp. 145–155.
Lundström, M., Aromaa, J., Forsén, O., Hyvärinen, O., and Barker, M. H.,
2005, ‘‘Leaching of chalcopyrite in cupric chloride solution.’’ Hydromet-
Downloaded by [Tshwane University of Technology] at 22:22 18 March 2014

allurgy, 77, pp. 89–95.

Mahajan, V., Misra, M., Zhong, K., and Fuerstenau, M. C., 2007, ‘‘Enhanced
leaching of copper from chalcopyrite in hydrogen peroxide–glycol
system.’’ Minerals Engineering, 20, pp. 670–674.
Momade, F. W. Y. and Momade, Z. G., 1999, ‘‘A study of the kinetics of
reductive leaching of manganese oxide ore in aqueous methanol–sulphuric
acid medium.’’ Hydrometallurgy, 54(1), pp. 25–39.
Munoz, J. A., Gomez, C., Ballester, A., Blazquez, M. L., and Gonzalez,
F., 1998, ‘‘Electrochemical behaviour of chalcopyrite in the presence of
silver and Sulfolobus bacteria.’’ Journal of Applied Electrochemistry, 28,
pp. 49–56.
Nava, D. and Gonzalez, I., 2006, ‘‘Electrochemical characterization of
chemical species formed during the electrochemical treatment of
chalcopyrite in sulfuric acid.’’ Electrochimica Acta, 51, pp. 5295–5303.
Olubambi, P. A., Borode, J. O., and Ndlovu, S., 2006, ‘‘Sulphuric acid
leaching of zinc and copper from Nigerian complex sulphide ore in the
presence of hydrogen peroxide.’’ Journal of the South African Institute of
Mining and Metallurgy, 106, pp. 765–770.
Padilla, R., Girón, D., and Ruiz, M. C., 2005, ‘‘Leaching of enargite in
H2 SO4 –NaCl–O2 media.’’ Hydrometallurgy, 80, pp. 272–279.
Padilla, R., Vega, D., and Ruiz, M. C., 2007, ‘‘Pressure leaching of
sulfidized chalcopyrite in sulfuric acid–oxygen media.’’ Hydrometallurgy,
86, pp. 80–88.
Padilla, D., Zambrano, P., and Ruiz, M. C., 2003, ‘‘Leaching of sulfidized
chalcopyrite with H2 SO4 –NaCl–O2 .’’ Metallurgical and Materials Trans-
action, 34B, pp. 153–159.
Prasad, S. and Pandey, B. D., 1998, ‘‘Alternative process for treatment of
chalcopyrite—a review.’’ Minerals Engineering, 11, pp. 763–781.
Souza, A. D., Pina, P. S., Leão, V. A., Silva, C. A., and Siqueira, P. F.,
2007, ‘‘The leaching kinetics of a zinc sulphide concentrate in acid ferric
sulphate.’’ Hydrometallurgy, 89, pp. 72–81.
Stanley, R. W. and Subramanian, K. N., 1977, ‘‘Recovering copper from
concentrates with insoluble sulfate forming leach.’’ U.S. Patent 4, 039,
406.

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