Hydrometallurgy 71 (2004) 329 – 334

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Kinetics of chalcopyrite dissolution by

hydrogen peroxide in sulphuric acid
M.M. Antonijević a,*, Z.D. Janković b, M.D. Dimitrijević b
a
Technical Faculty Bor, University of Belgrade, P.O. Box 50 VJ 12, Serbia, 19210 Bor, Yugoslavia
b
Copper Institute, Zeleni bulevar 35, 19210 Bor, Yugoslavia
Received 26 July 2002; received in revised form 23 March 2003; accepted 24 March 2003

Abstract

The extraction of copper from a chalcopyrite concentrate by hydrogen peroxide in sulphuric acid solutions was studied. The
influence of various parameters was investigated in order to elucidate the kinetics of chalcopyrite dissolution. It was determined
that stirring speed had no effect on the rate of chalcopyrite dissolution, which suggested that reaction was not controlled by
liquid-phase diffusion. Dissolution curves were found to conform to the surface reaction controlled shrinking core model, i.e.,
1
(1
X)1/3 = kst. Both the magnitude of the activation energy of 60 kJ/mol and the linear relationship between the rate
constant and the inverse particle radius support the fact that dissolution is controlled by the surface reaction. Hydrogen peroxide
had great influence on the rate of chalcopyrite dissolution; a reaction order of unity was calculated with respect to the
concentration of this oxidant. Sulphuric acid also had influence on chalcopyrite dissolution, with a reaction order of 0.3 with
respect to the acid concentration being established.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Chalcopyrite dissolution; Kinetics; Acid

1. Introduction regulations concerning SO2 emissions into the atmo-

sphere have led to the development of hydrometallur-
Chalcopyrite, CuFeS2, along with bornite Cu3Fe3 gical methods of copper extraction as opposed to the
S5, covellite CuS and chalcocite Cu2S, belongs to the classic pyrometallurgical routes. Thus, at present, 15 –
economically most important sulphide copper miner- 20% of the total world copper production accounts for
als. Among the aforementioned minerals, chalcopyrite hydrometallurgical treatment. Hydrometallurgical
contains the least copper, only 34.5%; it is, however, treatment comprises leaching, extraction and electro-
the most important copper mineral because it is the winning. Leaching, as the first step in the sequence of
most abundant in the sulphide copper-bearing depos- operations, consists of extraction of copper from ore
its. The need for exploiting poor and complex ores into solution—dissolution, which is accompanied by
with a low copper content and increasingly stringent redox reactions. Dissolution of copper sulphides is
performed by the use of suitable reactants in the
* Corresponding author. Tel.: +381-3024555; fax: +381-
presence of oxidants (so-called oxidative leaching).
3021078. Numerous studies have been conducted to this end.
E-mail address: [email protected] (M.M. Antonijević). Chalcopyrite dissolution has been carried out most

0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-386X(03)00082-3
330 M.M. Antonijević et al. / Hydrometallurgy 71 (2004) 329–334

frequently in acid sulphate and chloride media in the and 0.063 – 0.080 mm). The experiments were carried
presence of iron(III) as an oxidant (Dutrizac, 1978, out with the 0.050 –0.063 mm fraction unless other-
1981; Havlı́k et al., 1995). wise stated.
In this paper, the dissolution, i.e., oxidation of The solution was investigated in a 500 mL glass
chalcopyrite was done with hydrogen peroxide in acid reactor equipped with a glass stirrer. The reactor was
sulphate solutions. The purpose was to study the filled with 250 mL of peroxide solution, which was
kinetics of chalcopyrite oxidation by hydrogen per- heated to the desired temperature. When the desired
oxide. Hydrogen peroxide was chosen because it is a temperature was attained, a charge of 0.500 g of
strong oxidant and the reaction kinetics should be chalcopyrite was added to the peroxide solution,
accelerated as chalcopyrite is the most refractory of stirring was started, and the temperature of the reac-
the copper sulphides. In addition, hydrogen peroxide tion mixture was then maintained constant. The frac-
is an environmentally safe reagent as, apart from tion of chalcopyrite was followed over time; at
water no other reaction products are generated during definite time intervals, six samples of 1 mL each were
oxidation of sulphide minerals. This fact along with taken for the determination of copper by AAS. The
high redox potential have caused hydrogen peroxide reaction residues after oxidation were washed with
to be studied as an oxidizing agent for the dissolution distilled water, dried and examined by X-ray diffrac-
of various mineral raw materials such as oxide uranif- tion analysis.
erous ores (Eary and Cathles, 1983; Hiskey 1980), a
gold-containing chalcopyrite concentrate (Deschenes
and Ghali, 1988) and a zinc –lead bulk concentrate 3. Results and discussion
(Vazarlis, 1987) as well as concentrates of sphalerite
(Baláž and Ebert, 1991) and pyrite (McKibben and 3.1. Effect of stirring speed
Barnes, 1986; Dimitrijević et al., 1996, 1999; Anto-
nijević et al., 1997). In order to examine the effect of stirring speed on
By means of electrochemical studies, hydrogen the rate of chalcopyrite oxidation, experiments were
peroxide was found to be produced as an intermediate carried out at various stirring speeds (without stirring,
during oxygen reduction. This fact points to the 300, 600 and 900 min
1) at 313 K in solutions
possibility of the existence of some analogies between containing 2.0 M H2O2 and 2.0 M H2SO4. The
chalcopyrite oxidation by hydrogen peroxide and its duration of each experiment was 180 min. The frac-
oxidation by molecular oxygen. Since chalcopyrite tion of chalcopyrite reacted was calculated on the
oxidation by hydrogen peroxide in aqueous solutions basis of the copper released into solution.
is rather slow and yet very important in the leaching of The data in Table 1 show that the rate of chalco-
sulphide ores as well as in their grinding and flotation, pyrite oxidation is independent of the stirring speed,
it would be of interest to ascertain this analogy,
provided that chalcopyrite dissolution by hydrogen
Table 1
peroxide is fast enough. This paper addresses this Effect of stirring speed on the fraction of chalcopyrite reacted
problem. (conditions: 2.0 M H2O2, 2.0 M H2SO4, 313 K)
Time Fraction of chalcopyrite reacted
(min) Stirring speed (min
1)
2. Experimental
No stirring 300 600 900

A chalcopyrite sample obtained by refloating chal- 0 0 0 0 0

10 0.049 0.047 0.051 0.047
copyrite concentrate from the Veliki Krivelj copper
20 0.089 0.099 0.087 0.095
mine (Bor, Yugoslavia) was used during this study. 30 0.126 0.116 0.120 0.115
The sample obtained assayed 34.33% Cu, 30.83% Fe 60 0.211 0.200 0.206 0.202
and 34.19% S. X-ray diffraction analysis revealed 90 0.276 0.288 0.284 0.288
only peaks for chalcopyrite. The sample was sieved 120 0.345 0.357 0.360 0.349
180 0.450 0.455 0.460 0.455
into three size fractions (0.040 – 0.050, 0.050 –0.063
 M.M. Antonijević et al. / Hydrometallurgy 71 (2004) 329–334 331

which points to the fact that the reaction is not

controlled by film diffusion. For this reason, all
subsequent experiments were carried out without
stirring that was used only to homogenize the solution
prior to sampling.
Different results were obtained during pyrite oxi-
dation by hydrogen peroxide in sulphuric acid. That is,
it was observed that stirring had a negative influence
on the oxidation of pyrite and a conclusion was drawn
that this influence is not caused by peroxide decom-
position at higher stirring speeds but probably by
better contact between pyrite particles and peroxide
in the absence of stirring (Antonijević et al., 1997).

3.2. Effect of temperature Fig. 2. The variation in 1
(1
X)1/3 with time at various
temperatures. Symbol as in Fig. 1.
The experiments were carried out in the 298 – 323
K temperature range in solutions containing 2.0 M
H2O2 and 2.0 M H2SO4. The results are given in Fig. plots of 1
(1
X)1/3 versus time. The rate constants
1. It can be seen that the dissolution curves become were calculated as slopes of the straight lines. By
parabolic with increasing temperature above 313 K. using these values, the Arrhenius diagram in Fig. 3
The reason for this retardation of the rate of chalco- was drawn, from which an activation energy of 60 kJ/
pyrite oxidation is a very rapid decomposition of mol was calculated.
H2O2 at elevated temperatures (Dimitrijević et al., The magnitude of the activation energy of 60 kJ/
1996). mol supports the proposed surface reaction shrinking
The dissolution curves in Fig. 1 were linearized by core model.
means of the surface reaction shrinking core model Similar values of activation energy were found for
(Sohn and Wadsworth, 1979): the chalcopyrite oxidation by ferric ions. Thus the
magnitude of the activation energy for chalcopyrite
1
ð1
X Þ1=3 ¼ ks t ð1Þ
oxidation by ferric chloride is between 40 and
where X is the fraction of pyrite reacted, ks is the
apparent rate constant and t is time. Fig. 2 shows the

Fig. 1. Effect of temperature on chalcopyrite dissolution. Fig. 3. Arrhenius plot of data presented in Fig. 2.
332 M.M. Antonijević et al. / Hydrometallurgy 71 (2004) 329–334

60 kJ/mol, whereas its value is somewhat higher

where ferric sulphate was used as an oxidant and is
around 60 – 80 kJ/mol (Dutrizac, 1981).
When chalcopyrite oxidation is compared with
pyrite oxidation studied in hydrogen peroxide and
sulphuric acid solutions (Antonijević et al., 1997) it
can be seen that the influence of temperature on the
dissolution kinetics is similar except for the fact
that the values of fraction of pyrite reacted are
higher by approximately 10%. In addition, a similar
magnitude of the activation energy was found for
the oxidation of pyrite by hydrogen peroxide in
sulphuric acid solutions (68 kJ/mol).
Fig. 5. Dependence of ks on 1/R.
3.3. Effect of particle size

The experiments were carried out with three 3.4. Effect of hydrogen peroxide concentration
particle sizes (0.040 – 0.050, 0.050 – 0.063 and
0.063 – 0.080 mm) at 313 K in solutions containing The experiments were carried out by varying
2.0 M H2O2 and 2.0 M H2SO4. The smaller the the initial H2O2 concentration in the 0.1– 5.0 M
particle size, the faster was chalcopyrite oxidation, range at 313 K in solutions containing 2.0 M
as can be seen in Fig. 4. Linearization of the H2SO4. Increasing the hydrogen peroxide concen-
kinetic curves was carried out by means of Eq. tration accelerated considerably chalcopyrite oxida-
(1). Values of the rate constants were plotted versus tion (Fig. 6).
the reciprocal of the particle radii, yielding a linear The oxidation curves were linearized by means of
relationship with a correlation coefficient of 0.997 Eq. (1) (Fig. 7), and rate constants were determined.
(Fig. 5). By constructing the plots of lnks versus ln[H2O2],
Linear dependence of the rate constant on the the reaction was found to be approximately first
inverse particle radius is another fact in favour of order with respect to H2O2 concentration (Fig. 8).
the proposed surface reaction shrinking core model.

Fig. 6. Effect of hydrogen peroxide concentration on chalcopyrite

Fig. 4. Effect of particle size on chalcopyrite oxidation. dissolution.
 M.M. Antonijević et al. / Hydrometallurgy 71 (2004) 329–334 333

This implies that, in addition to the dominant

leaching reaction:
2CuFeS2 þ 17H2 O2 þ 2Hþ

¼ 2Cu2þ þ 2Fe3þ þ SO2

4 þ 18H2 O ð2Þ
a small part of sulphide ion reports in the elemental
form:

2CuFeS2 þ 5H2 O2 þ 10Hþ

¼ 2Cu2þ þ 2Fe3þ þ S0 þ 10H2 O ð3Þ

Similar results were found for pyrite dissolution by

1/3
Fig. 7. Variation of 1
(1
X) with time for various hydrogen hydrogen peroxide in perchloric acid, where 3% of the
peroxide concentration. sulphide sulphur was oxidized to the elemental form
and the remainder to the sulphate ion (Dimitrijević et
Incidentally, a first-order reaction with respect to al., 1996).
hydrogen peroxide concentration was found also for
pyrite oxidation by this oxidant in sulphuric acid 3.5. Effect of sulphuric acid concentration
solutions (Antonijević et al., 1997).
XRD analysis of the solid residue, after chalcopy- The experiments were carried out in solutions
rite oxidation in a solution containing 0.5 M H2O2 containing different initial H2SO4 concentrations
and 2.0 M H2SO4 during which a chalcopyrite con- (0.1 – 5.0 M) at 313 K in solutions containing 2.0 M
version of 11.1% was attained, detected no solid H2O2. Increasing the sulphuric acid concentration
products. This could lead one to come to the conclu- resulted in accelerated chalcopyrite oxidation (Fig. 9).
sion that sulphate ion is the only product of sulphide However, at very high acid concentrations (3 –5
sulphur oxidation. However, XRD analysis of the M), this effect is not observed any longer, i.e.,
solid residue of the leaching experiment at 5.0 M approximately similar fractions of chalcopyrite
H2O2 and 2.0 M H2SO4, during which 55% of the reacted are obtained. Furthermore, at the lowest con-
chalcopyrite was dissolved, revealed small amount of centration investigated (0.1 M), the curve obtained
elemental sulphur.

Fig. 9. Effect of sulphuric acid concentration on chalcopyrite

Fig. 8. Determination of the reaction order with respect to [H2O2]. dissolution.
334 M.M. Antonijević et al. / Hydrometallurgy 71 (2004) 329–334

shows some deviation from the other curves. The rate-controlling step. Both the value of the
fractions reacted in the first 60 min are somewhat activation energy of 60 kJ/mol and the linear
higher, and a plateau is reached after 90 min that relationship between the rate constant and the
corresponds to the end of reaction. Perhaps the reac- reciprocal of the particle radius confirm the
tion is at the beginning more intense because of a postulated reaction model.
lower concentration of sulphuric acid that is the  Increasing the hydrogen peroxide concentration
stabilizer of hydrogen peroxide decomposition (Anto- accelerates considerably chalcopyrite oxidation.
nijević et al., 1997). Afterwards, due to chalcopyrite The oxidation rate is first order with respect to
oxidation, iron(III) is released. It can undergo hydro- hydrogen peroxide concentration.
lysis with formation of ferric hydroxide that can  Increasing the sulphuric acid concentration accel-
hinder contact between hydrogen peroxide and chal- erates chalcopyrite oxidation. The reaction order
copyrite. Owing to catalytic decomposition of hydro- with respect to sulphuric acid concentration is
gen peroxide, caused by ferric ions, ferric hydroxide, 0.3.
chalcopyrite particles etc., oxygen is generated that
can also hamper the contact of hydrogen peroxide
with chalcopyrite. Acknowledgements
After linearizing the oxidation curves and calculat-
ing rate constants, a reaction order of 0.3 with respect The authors wish to thank the Scientific Fund of
to sulphuric acid concentration (between 0.5 and 3 M the Republic of Serbia for financial support (Project
H2SO4) was determined from a lnks versus ln[H2SO4] No. 1622).
diagram.
During the study of the effect of sulphuric acid
concentration on pyrite oxidation by hydrogen perox- References
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0.36
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metallurgy 46, 71.
essential difference between chalcopyrite oxidation
Baláž, P., Ebert, I., 1991. Hydrometallurgy 27, 141.
and pyrite oxidation by hydrogen peroxide in sulphu- Deschenes, G., Ghali, E., 1988. Hydrometallurgy 20, 179.
ric acid solutions as regards to the effects examined in Dimitrijević, M., Antonijević, M.M., Janković, Z., 1996. Hydro-
this paper. metallurgy 42, 377.
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On the basis of the results of this study, the Havlı́k, T., Škrobian, M., Baláž, P., Kammel, R., 1995. Int. J. Miner.
following conclusions can be drawn: Process 43, 1.
Hiskey, J.B., 1980. Trans. Inst. Min. Metall. C89, 145.
McKibben, M.A., Barnes, H.L., 1986. Geochim. Cosmochim. Acta
 The rate of chalcopyrite oxidation by hydrogen 50, 1509.
peroxide in sulphuric acid is independent of Sohn, H.Y., Wadsworth, M.E., 1979. Rate Processes of Extractive
stirring speed, which indicates that the reaction is Metallurgy. Plenum, New York, p. 133.
not controlled by diffusion in the liquid phase. Vazarlis, H.G., 1987. Hydrometallurgy 19, 243.
 The oxidation kinetics follows a shrinking core
model with the surface chemical reaction as the