Hydrometallurgy 56 2000.

145155
www.elsevier.nlrlocaterhydromet

An electrochemical study of the effect of chloride

ions on the dissolution of chalcopyrite in acidic
solutions
Z.Y. Lu, M.I. Jeffrey ) , F. Lawson
Department of Chemical Engineering, Monash Uniersity, Clayton, Victoria 3168, Australia
Received 1 February 1999; received in revised form 3 December 1999; accepted 17 December 1999

Abstract

The electrochemical oxidation of a CuFeS 2 chalcopyrite. concentrate in a mixed chloride

sulfate electrolyte was studied using carbon paste electrodes. This technique was found to give
very reproducible results, and has the advantage that actual concentrate particles can be used in
place of large crystalline mineral samples. It will be demonstrated that during the initial stages of
leaching, the oxidation of chalcopyrite at low overpotentials is hindered by the formation of a
metal-deficient sulfide surface. When chloride ions are present, it will be shown by both transient-
and steady-state techniques that the oxidation of the mineral is significantly enhanced. These
results have also been found to be in very good agreement with those obtained by direct leaching
of the same concentrate. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Electrochemical oxidation; Chloride ions; Chalcopyrite

1. Introduction

Chalcopyrite CuFeS 2 . is the most abundant primary copper ore, and as a result, the
extractive metallurgy of copper is based largely on this mineral. Traditionally, the
copper has been recovered using pyrometallurgical processes such as flash smelting. In
recent years, there has been a push to develop alternative processes that do not produce
sulfur dioxide as a by-product. Sulfuric acid leaching is perhaps the simplest alternative

)
Corresponding author.
E-mail address: matthew.jeffrey@eng.monash.edu.au M.I. Jeffrey..

0304-386Xr00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 0 6 8 - 2
146 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155

to smelting, although this process has not been adopted commercially because of the
slow leaching kinetics and poor copper extraction at atmospheric pressure w1x.
The leaching of chalcopyrite is an electrochemical process involving the oxidation of
sulfide to sulfur, sulfate or other oxysulfur anions w1x. The overall electrochemical
reactions occurring during the oxidative leaching of chalcopyrite can be represented by
the half reactions:
CuFeS 2 Cu 2q
q Fe 3qq 2S q 5ey 1.

5Hqq
5
4
O 2 q 5ey 52 H O 2 2.
Thus, standard electrochemical techniques have been used to determine mechanistic
details of the leaching process. These studies have shown that the poor leaching kinetics
are a result of anodic passivation; one theory is that the passivation is caused by the
formation of an insulating layer of elemental sulfur on the chalcopyrite surface w2,3x.
Indeed, recent studies w4x have shown that sulfur is the major product formed in
long-term leaching; however, this does not necessarily imply that sulfur causes the
passivation during the initial stages of mineral oxidation.
Recently, it has been shown that other sulfides can be effectively leached using a
mixed sulfatechloride system w5,6x. The role of chloride ions is believed to limit the
extent of passivation by elemental sulfur w5,6x. The aim of the current study is to extend
this work by applying electrochemical techniques to investigate the initial oxidation and
passivation of chalcopyrite in acid solutions containing sulfate and chloride ions.

2. Experimental

An interesting aspect of the published electrochemical studies concerning chalcopy-

rite is an apparent lack of reproducibility. Lazaro et al. w2x have shown that this problem
can be overcome by the use of a carbon paste electrode CPE. in which a ground
mineral sample of chalcopyrite is mixed with carbon and a nonconductive binder to
form a paste. In the present study, the carbon paste was prepared from a copper
concentrate supplied by Mt. Isa Mines, Queensland, Australia. It is thus expected that
the electrochemical data would more accurately reflect on the processes that occur
during an industrial leaching process.
X-ray diffraction analysis of the copper concentrate showed that it contained mainly
chalcopyrite together with a small amount of quartz and pyrite. The concentrate as
received. was found to have a D50 of 15.1 mm, and this was used without further
grinding to prepare the carbon paste. The CPE consists of three components: electro-ac-
tive material chalcopyrite concentrate., carbon powder Metrohm EA 267. and Nujol
oil spectroscopic grade.. The concentrate was thoroughly mixed with carbon powder in
a ratio of 2CuFeS 2 :1C in an agate mortar and then wetted by adding 0.1 g of Nujol to
each 1 g of mixed powder. The homogeneous paste thus produced was pressed into the
cavity of a teflon cylinder, giving an active surface area of 0.2 cm2 . A schematic of the
electrode is shown in Fig. 1. One of the necessary features of the CPE holder is the
 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 147

Fig. 1. Schematic diagram showing the carbon paste electrode holder. 1. Stainless steel holder. 2. Teflon
coating. 3. Stainless steel screw press. 4. Carbon paste surface areas 0.2 cm2 ..

screw press that allows the paste to be compacted. For each measurement, a fresh
electrode surface was exposed by scraping a layer of paste out of the cavity and then
smoothing the surface with a spatula. The thickness of the paste for each measurement
was set at 3 mm and the electrode produced in this way had a resistance of less than 15
V.
Solutions were prepared using AR grade sulfuric acid and sodium chloride. In
addition, each solution contained 10y4 M Fe 3q and Cu2q, which kept the Fe 3q and
Cu2q ion concentrations in solution essentially constant during each experiment. The
solutions were thoroughly degassed by passing high-purity nitrogen through for 30 min
before and during each experiment. A saturated calomel electrode was used as the
reference electrode in the studies, and this was introduced via a Luggin capillary
extending to the center of the cell just below the end of the working electrode.. All
potentials are reported with respect to the SHE. A platinum wire was used as the counter
electrode. In the voltammetry experiments, a potential scan rate of 20 mV s y1 was
adopted in all cases.

3. Results and discussion

Cyclic voltammetry was used to study the electrochemical leaching behaviour of the
concentrate; shown in Fig. 2 are the voltammograms for 1 M sulfuric acid in the absence
of chloride ions. These experiments were performed using a stationary electrode. The
solid line represents the voltammogram when the potential scan is started in the anodic
148 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155

Fig. 2. Cyclic voltammogram showing the oxidation and reduction of chalcopyrite in 1 M sulfuric acid. The
solid line results when the scan is initiated in the positive anodic. direction, and the dashed line results when
the scan is initiated in the negative cathodic. direction. Experimental conditions: T s 208C, 0 M NaCl, 20 mV
sy1 .

direction, and the dashed line represents the cathodic direction. These voltammograms
were found to be similar to those obtained by using massive chalcopyrite mineral
samples w7,8x. This result is not surprising, as quartz and pyrite are essentially inert in
the potential region of interest w9x. It is clear from Fig. 2 that the voltammograms exhibit
four anodic and four cathodic peaks. These peaks are discussed in detail below.
According to Price and Warren w3x peak A1 at relatively lower anodic overpotentials.
is due to the partial oxidation of chalcopyrite, as shown in Eq. 3., where y ) x.

CuFeS 2 Cu 1yx Fe 1yy S 2yz q xCu

2q
q yFe 2qq zS q 2 x q y . ey 3.

This suggests that there is release of iron from the chalcopyrite lattice during anodic
dissolution. The structure Cu 1y x Fe1yy S 2yz is an intermediate product, which mixed
with sulfur, forms a passive electron conducting layer on the mineral surface. Parker et
al. w10x referred to the product as a polysulfide, which has semi-conducting properties. It
is worth noting that in terms of a charge balance, z must always equal x q y; otherwise,
SyII. would not be oxidised to S0..
Peaks C1 and C2 reflect the reduction of the products produced at peak A1;
otherwise, they would appear in the dashed voltammogram as well. The obvious
difference in the areas under the anodic peak A1 and cathodic peaks C1 and C2 indicate
that the reaction is not fully reversible. This observation is consistent with the results of
other investigators e.g. Lazaro et al. w2x.. Peak C3 corresponds to the reduction of the
remaining chalcopyrite to an intermediate copper sulfide phase such as talnakhite
Cu 9 Fe 8 S 16 . or bornite Cu 5 FeS 4 . Eqs. 4. and 5., respectively.. At potentials more
negative than peak C3, chalcocite is formed, and the iron is completely removed from
 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 149

the lattice, as shown in Eq. 6.. Other reactions that may occur at these negative
potentials are the reduction of Cu2q to copper metal, and the evolution of hydrogen.
Cu Fe S q Fe q 2H S
9CuFeS 2 q 4Hqq 2ey 2q
4.
5CuFeS q 12H q 4e Cu FeS q 4Fe q 6H S
9 8 16 2

q y 2q
5.
2CuFeS q 6H q 2e Cu S q 2Fe q 3H S
2 5 4 2

q y 2q
2 2 2 6.
When the potential sweep is reversed at y380 mV, it can be seen that there are three
anodic peaks: A2, A3 and A1X . Each of these peaks corresponds to the oxidation of
products produced during the cathodic sweep. Price and Warren w3x have suggested that
in the potential region of peaks A2 and A3, H 2 S is oxidised to elemental sulfur. In
addition, any copper metal that is formed in the cathodic sweep will be oxidised to Cu2q
in this potential region. Finally, the peak A1X is attributed to the oxidation of chalcocite
Cu 2 S. to non-stoichiometric sulfides Cu 2yx S. being deficient in copper w3x. Given that
the charge associated with peak A1X is almost the same as that for peaks C3 and C4, it is
likely that x will be close to 1, with covellite being formed as the main product.
Cu 2 S Cu 2yx S q xCu
2q
q 2 xey 7.

3.1. Passiation of chalcopyrite

The atmospheric leaching of chalcopyrite in mixed chloridersulfate is mainly

concerned with the oxidation of chalcopyrite at low overpotentials. It is should be clear
that in Fig. 2, peak A1 is a result of passivation of the mineral surface. Indeed, if the
potential is held in the range of 450900 mV; the current drops to low values very
quickly see Fig. 7.. After such an experiment, the chalcopyrite was dipped in CS 2 and
replaced in solution under potentiostatic control, and it was observed that the mineral
was still passive. Obviously, the CS 2 does not remove the passive film from the
chalcopyrite surface. It is thus believed that the passive nature of the mineral is a result
of the surface becoming metal-deficient, as shown in Eq. 3. and suggested by others
w11x. It has also been proposed that the passivation is a result of the formation of
elemental sulfur w2,3x; if this were the case, then the sulfur would be dissolved by the
CS 2 wash, and the mineral would be active upon re-immersion in solution.
The passivation process was further examined by allowing the mineral to rest at its
open circuit potential after the surface had been oxidised at 800 mV for 120 s. For
galena, it has been shown that after oxidation, surface relaxation occurs, with lead
diffusing from the bulk of the mineral to the metal-deficient surface w12x. Similar results
have been observed here for chalcopyrite; when a potential of 800 mV is reapplied, the
observed current depends on the time the electrode was at open circuit potential, as
shown in Fig. 3. This provides further evidence that the passivation of the chalcopyrite
is due to the formation of a metal-deficient surface layer, and not the formation of
elemental sulfur. When the mineral is allowed to relax for longer periods, more copper
and iron can diffuse from the bulk mineral to the surface, hence, the re-oxidation of the
chalcopyrite occurs at a much more rapid rate.
150 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155

Fig. 3. Currenttime curves representing the re-oxidation of chalcopyrite at a fixed potential of 800 mV. Prior
to each experiment, the mineral was oxidised at 800 mV for 120 s and then allowed to relax for the specified
time. Experimental conditions: T s 208C, 1 M H 2 SO4 , 20 mV sy1 .

3.2. Electrochemistry of chalcopyrite in the presence of chloride

Cyclic voltammograms for the chalcopyrite concentrate in the presence and absence
of 0.5 M sodium chloride are shown in Fig. 4. It is clear from this graph that chloride
ions have a substantial effect on the electrochemical behaviour of the sulfide. In
particular, the anodic peak A1 is twice as great in the presence of chloride ions. It is also
evident from Fig. 4 that peaks C3 and C4 the reduction of chalcopyrite to chalcocite via

Fig. 4. Voltammograms representing the effect of NaCl on the oxidationrreduction of chalcopyrite. Experi-
mental conditions: T s 208C, 1 M H 2 SO4 , 20 mV sy1 .
 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 151

talnakhite andror bornite. are larger in the presence of chloride ions. Obviously,
chloride ions enhance the oxidation and reduction of chalcopyrite; such a result is
consistent with chloride affecting the surface state of the Cu 1y x Fe1yy S 2yz formed
during the positive potential scan. It has been observed that the porosity of the sulfur
formed after a long period of leaching is affected by chloride w4x; however, the role of
chloride appears to differ here since sulfur is not the dominant product. At this stage, the
mechanism by which chloride initially enhances the oxidation of chalcopyrite remains
unresolved.
Since this project is mainly concerned with the leaching of chalcopyrite in the
presence of chloride ions, it was decided to concentrate on the potential region of the
anodic peak A1. Fig. 5 shows the voltammograms that result when the anodic and
cathodic limits are lowered. Also shown is the complete voltammogram for comparison.
The most obvious feature of these curves is that when the potential scan is reversed at
100 mV, the peak A1X is much smaller than peak A1. This confirms that the passive
nature of the oxidised surface persists during the second potential cycle. Such a result is
hardly surprising, as the surface has had little time to relax the scan rate is 20 mV sy1 .
prior to re-oxidation.
Fig. 6 shows the voltammograms representing the oxidation of chalcopyrite in the
presence of chloride ions at 208C and 708C. It is immediately clear that at 708C, the
oxidation reaction is far more rapid than that at 208C. This indicates that the passive film
is much less protective at elevated temperatures, and so one expects that at higher
temperatures, chalcopyrite will leach more rapidly. Such a result is consistent with
results of direct leaching experiments, which showed that copper extraction increased
with temperature up to 858C in direct leaching experiments involving the use of oxygen
as the oxidant, as the temperature is increased, the solubility of oxygen decreases and
this affects the reaction rate.. The remaining electrochemical experiments were con-
ducted at 708C.

Fig. 5. Voltammograms that result when the anodic and cathodic limits are reduced. Experimental conditions:
T s 208C, 0.5 M NaCl, 1 M H 2 SO4 , 20 mV sy1 .
152 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155

Fig. 6. Effect of temperature on the oxidationrreduction of chalcopyrite in the presence of 0.5 M NaCl.
Experimental conditions: 1 M H 2 SO4 , 20 mV sy1 .

3.3. Steady-state measurements

The cyclic voltammetry experiments described above were performed at a constant
scan rate of 20 mV sy1 . Although these provide very useful information about the
electrochemical reactions occurring, one still knows little about how passive the
chalcopyrite is at steady state. In particular, it is important to compare the passive states
in the presence and absence of chloride ions. This goal was achieved by using the
steady-state techniques of chronoamperometry and chronopotentiometry.
Fig. 7 shows the currenttime transients for chalcopyrite oxidation at a fixed
potential of 615 mV. This potential was chosen as it is close to the mixed potential that

Fig. 7. Currenttime curves representing the oxidation of chalcopyrite at a fixed potential of 615 mV in the
presence and absence of 0.5 M NaCl. Experimental conditions: T s 708C, 1 M H 2 SO4 .
 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 153

is developed during the direct leaching of chalcopyrite in a mixed chloridesulfate

solution. It can be seen that initially, the current decreases rapidly with time whether
chloride is present or not; this corresponds to the initial removal of iron and copper from
the lattice and subsequent formation of the passive film. After a relatively short period,
however, the current reaches a constant value that is the steady-state passive current. It
is clear from Fig. 7 that the steady-state current for chalcopyrite in the presence of 0.5 M
sodium chloride is about seven times that in the absence of chloride. These results
confirm that the passive film is much less protective in the presence of chloride ions
than when chlorides are absent. Chalcopyrite should thus leach more rapidly in the
presence of chlorides. Direct leaching experiments conducted with the same concentrate
confirmed this w4x. After 7 h of leaching, copper extraction was 92% in the presence of
0.5 M NaCl and only 29% without chloride.
Another important factor to consider in leaching is the REDOX potential. It is
generally believed that an increase in the solution REDOX potential i.e. more oxidis-
ing. increases the leaching rate. This is not always true, particularly when passivation
occurs as it does here.. Fig. 8 shows the currenttime responses at 615 and 815 mV.
These potentials represent the leaching in dilute and concentrated solutions of ironIII.
E 0 at 258C for the reduction of FeIII. to FeII. is 0.771 V.. It is clear from Fig. 8 that
despite the differences in the electrode potential, the steady-state passive currents are
similar for a system containing chloride ions. However, in the absence of chloride, the
steady-state current at 815 mV was found to be 25 mA as compared to 2.5 mA at 615
mV.. These results explain why chalcopyrite leaching in the absence of chloride only
occurs under aggressive conditions e.g. oxygen pressure leaching w1x.. Under these
conditions, the sulfide sulfur is oxidised to sulfate.
The results discussed above can be well summarised by a simple chronopotentiome-
try experiment. Fig. 9 shows the potentialtime response for the galvanostatic polarisa-

Fig. 8. Currenttime curves representing the oxidation of chalcopyrite in the presence of NaCl at 615 and 815
mV. Experimental conditions: T s 708C, 0.5 M NaCl, 1 M H 2 SO4 .
154 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155

Fig. 9. Potentialtime curves representing the oxidation of chalcopyrite in the presence and absence of NaCl at
a fixed current of 50 mA. Experimental conditions: T s 708C, 1 M H 2 SO4 .

tion of the chalcopyrite electrode at 50 mA. Like the currenttime curves, these curves
also show the formation of the passive film, with potential increases representing an
increase in the degree of passivation. However, the most important feature of these
curves is the steady-state potential; it is clear from Fig. 9 that this value is much more
positive in the absence of chloride ions. So to achieve an equivalent leaching rate, the
required mixed potential for solutions containing chloride will be much lower than that
for solutions containing no chloride.

4. Conclusions

The carbon paste electrode is a very useful means of studying the electrochemical
behaviour of chalcopyrite concentrates. The use of concentrates instead of ground
minerals allows the establishment of results that reflect potential industrial processes of
interest; in this case, the mixed sulfatechloride leaching of a Mt. Isa Mines copper
concentrate. It was shown that at low overpotentials, the mineral surface is passivated,
and the experimental results were consistent with the formation of a metal-deficient
sulfide surface. Both transient- and steady-state techniques showed that chloride ions
significantly enhance the oxidation of chalcopyrite, particularly at elevated temperatures.
The results of this study have also been found to be in a very good agreement with those
results obtained by direct leaching of the same concentrate.

References

w1x R.P. Hackl, D.B. Dreisinger, E. Peters, J.A. King, Passivation of chalcopyrite during oxidative leaching
in sulfate media, Hydrometallurgy 39 1995. 2548.
 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 155

w2x I. Lazaro, N. Martinez-Medina, I. Rodriguez, E. Arce, I. Gonzalez, The use of carbon paste electrodes
with non-conducting binder for the study of minerals: chalcopyrite, Hydrometallurgy 38 1995. 277287.
w3x D.W. Price, G.W. Warren, The influence of silver ion on the electrochemical response of chalcopyrite
and other mineral sulfide electrodes in sulfuric acid, Hydrometallurgy 15 1986. 303324.
w4x Z.Y. Lu, M.I. Jeffrey, F. Lawson, The effect of chloride ions on the dissolution of chalcopyrite in acidic
solutions: I. A kinetic study, Hydrometallurgy 1998. Submitted for publication.
w5x F. Lawson, C.Y. Chen, L.S.Y. Lee, Leaching of copper sulfides and copper mattes in oxygenated
chloridersulfate leachants, Miner. Process. Extr. Metall. Rev. 8 1992. 183203.
w6x Z.Y. Lu, F. Lawson, Atmospheric pressure leaching of pentlandite concentrates using acidic
chloridersulfate leaching, in: X. Yang, Q. Chen, A. He Eds.., Proceedings of the Third International
Conference on Hydrometallurgy, International Academic Publishers, Beijing, 1998, pp. 191197.
w7x G.W. Warren, M.E. Wadsworth, T.G. Wang, The effect of electrolyte composition on the cathodic
reduction of CuFeS 2 , Hydrometallurgy 14 1985. 133149.
w8x T. Biegler, D.A. Swift, Anodic electrochemistry of chalcopyrite, J. Appl. Electrochem. 9 1979.
545554.
w9x G.H. Kelsall, Q. Yin, D.J. Vaughan, K.E.R. England, Electrochemical oxidation of pyrite in acidic
aqeuous electrolytes I, in: R. Woods, F.M. Doyle, P. Richardson Eds.., Electrochemistry in Minerals and
Metals Processing IV, The Electrochemical Society, Pennington, NJ, 1996, pp. 131142.
w10x A.J. Parker, R.L. Paul, G.P. Power, Electrochemistry of the oxidative leaching of copper from chalcopy-
rite, J. Electroanal. Chem. 118 1981. 305316.
w11x J.B. Hiskey, Chalcopyrite semiconductor electrochemistry and dissolution, in: R.G. Reddy, R.N. Weizen-
bach Eds.., Extractive Metallurgy of Copper, Nickel and Cobalt, The Minerals, Metals and Materials
Society, Warrendale, PA, 1993, pp. 949969.
w12x A.N. Buckley, R. Woods, The galena surface revisited, in: R. Woods, P. Richardson, F. Doyle Eds..,
Electrochemistry in Minerals and Metals Processing IV, The Electrochemical Society, Pennington, NJ,
1996, pp. 112.