Minerals Engineering 23 (2010) 471477

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Effect of chloride ions on leaching rate of chalcopyrite

Kyoungkeun Yoo a, Soo-kyung Kim a, Jae-chun Lee a,*, Mayumi Ito b, Masami Tsunekawa b, Naoki Hiroyoshi b
a
b

Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources, Gwahang-no 92, Yuseong-gu, Daejeon 305-350, Republic of Korea
Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628, Japan

a r t i c l e

i n f o

Article history:
Received 30 May 2009
Accepted 15 November 2009
Available online 16 December 2009
Keywords:
Chalcopyrite leaching
Chloride leaching solution
Chlorocuprate(I)
Cuprous ion

a b s t r a c t
The effect of chloride on chalcopyrite leaching has been investigated by performing batch leaching tests
with three kinds of leaching solutions and using Hiroyoshis model, which suggests that a zone of rapid
leaching exists between the critical potential (Ec, equilibrium redox potential for the reduction of CuFeS2
to Cu2S) and the oxidation potential (Eox, equilibrium redox potential for the oxidation of Cu2S). The results
of the leaching tests show that the leaching rate in hydrochloric acid solution is the fastest and that the relationship between the Cu leaching rate and oxidationreduction potential (ORP) follows Hiroyoshis model.
Thermodynamic calculations indicate that, with an increase in the chloride concentration, the concentration of cuprous ions increases as the chlorocuprate(I) complex ions are formed and the contribution of
cuprous ions to the critical potential is greater than that of cupric ions, even though the concentration of
cuprous ions is lower than that of cupric ions. This fact suggests that the formation of chlorocuprate(I) ions
in a chloride solution may improve the chalcopyrite leaching rate by increasing the critical potential.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Chalcopyrite (CuFeS2) is the most abundant copper sulphide
occurring underground (Wang, 2005). Several hydrometallurgical
processes have been proposed for recovering copper from chalcopyrite (Hiroyoshi et al., 2002; Peacey et al., 2003; Prasad and Pandey, 1998). However, with the exception of heap and dump
bioleaching, these hydrometallurgical processes have not been
commercially successful, because chalcopyrite is one of the most
refractory materials to leach (Wang, 2005). To improve the low
leaching rate, several methods have been investigated, including
increasing the temperature and pressure (Habashi, 2006); adding
a modier such as activated carbon (Nakazawa et al., 1998), coal
(Barta et al., 1999), silver (Carranza et al., 1997), and iron powder
(Sanchez et al., 1996); grinding the chalcopyrite particles to less
than 20 lm (Balz, 2003); and adjusting the redox potential
(Hiroyoshi et al., 2002, 2004).
Hiroyoshi and co-workers studied the effect of the redox potential on the leaching rate of chalcopyrite and reported that the
leaching rate increased in relatively low redox potential ranges
(Hiroyoshi et al., 1997, 2000, 2001, 2002, 2004). From these results,
they proposed a new model that involved the formation of intermediate Cu2S at an optimum redox potential, which exists between the equilibrium redox potential for the reduction of
CuFeS2 to Cu2S (equilibrium critical potential, Ec) and that for the
oxidation of Cu2S (equilibrium oxidation potential, Eox). Further-

* Corresponding author. Fax: +82 42 868 3418.

E-mail address: jclee@kigam.re.kr (J.-c. Lee).
0892-6875/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2009.11.007

more, the leaching rate was found to increase at this redox potential, as shown in Fig. 1 (Hiroyoshi et al., 2007). This model was
called redox potential dependence of chalcopyrite leaching, and
the critical potential and oxidation potential were described as
according to the following equations (Hiroyoshi et al., 2000, 2001).

CuFeS2 3Cu2 4e 2Cu2 S Fe2


0:75
a 2
RT
ln  Cu 0:25
F
aFe2

2Cu2 S0 4e Cu2 S

Ec E0c

Eox E0ox

0:5
RT 
ln aCu2
F

where Ec represents the critical potential by cupric ions (Cu2+), E0c is

the standard critical potential, Eox is the oxidation potential, E0ox is
the standard oxidation potential, R is the gas constant, T is the temperature, F is the Faraday constant, and ai is the activity of species i.
Because chalcopyrite is not reduced to chalcocite at a potential
higher than Ec, chalcopyrite is leached directly into cupric ions,
where chalcopyrite is coated with elemental sulphur generated by
the following reaction:

CuFeS2 4Fe3 Cu2 5Fe2 2S0

Although chalcopyrite can be reduced to chalcocite at a potential

lower than Eox, chalcocite is not leached to copper ions. At potentials
between Ec and Eox, chalcopyrite is reduced to chalcocite and then
leached to cupric ions at the same time, as shown in Fig. 1.

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K. Yoo et al. / Minerals Engineering 23 (2010) 471477

acterised using a Ru-200B X-ray diffractometer (Rigaku, Japan).

The X-ray diffraction (XRD) data were collected under the following conditions: radiation, Cu Ka, 30 kV, 40 mA; step scanning
method; scan speed, 8 deg/min; angle range, 1080/2h.
Three types of leaching solutions were prepared with reagentgrade FeCl36H2O (Junsei Chemical Co.) or Fe2(SO4)3nH2O (SigmaAldrich Inc.). The leaching solutions contained 0.1 kmol m3
Fe3+ as an oxidant in 0.1 kmol m3 HCl solution, 0.1 kmol m3
H2SO4 solution, or a mixture of 0.1 kmol m3 HCl and H2SO4 (1:1).

Log K

CuFeS2
Cu2S

Cu2S

Cu2+

CuFeS2

Cu2+

2.2. Leaching procedure

E
Eox

Ec

Fig. 1. A schematic representation of the relationship between the CuFeS2 leaching

rate (K) and the redox potential (E) based on the reaction model proposed by
Hiroyoshi et al. (2007). Ec = equilibrium redox potential for the reduction of CuFeS2
to Cu2S; Eox = equilibrium redox potential for the oxidation of Cu2S.

The critical potential in a sulphate solution is determined by the

cupric ions because copper species exist only as cupric ions or copper metal in a sulphate system. In a chloride solution, cuprous ions
need to be considered for determining the critical potential because there are various stable cuprous ion species such as chlorocuprate(I) ions (Lin et al., 1991). However, the effect of cuprous
ions on the critical potential has not been investigated in a chloride
solution. In addition to sulphate, chloride is a very important medium for leaching chalcopyrite. Much research has been carried out
on chalcopyrite leaching in a chloride medium. The principal
chemical reactions in the chloride leaching of chalcopyrite can be
described by the following equations (Wang, 2005):

CuFeS2 3FeCl3 CuCl 4FeCl2 2S0

CuFeS2 4FeCl3 CuCl2 5FeCl2 2S0

CuFeS2 3CuCl2 4CuCl FeCl2 2S

Generally, the leaching rate of chalcopyrite has been found to be

faster in chloride than in sulphate (Dutrizac, 1981). Some researchers have reported that this fast leaching rate in chloride results
from the morphological reason that a porous coating layer is
formed on the chalcopyrite particles during the leaching procedure
in a chloride medium (Lu et al., 2000; Havlk and Kammel, 1995).
However, there has been little research on the mechanism of chalcopyrite leaching in a chloride medium.
In the present study, chalcopyrite leaching tests were performed in chloride and sulphate solutions, and then the results
were analyzed using the model devised by Hiroyoshi and co-workers (1997, 2000, 2001, 2002, and 2004). Finally, the effect of chlorocuprate(I) ions on the critical potential and leaching rate of
chalcopyrite was thermodynamically investigated.

Leaching tests were performed in a glass reactor with a water

jacket, as shown in Fig. 2. For each test, 150 cm3 of a leaching solution was added to the reactor and heated to 80 C. Nitrogen gas
was introduced to the solution for 1 h before the leaching test.
After adding 4.5 g of the ground chalcopyrite powder, the reactor
was sealed with a silicon cap, which had two holes tted with a
thermometer and a redox electrode (saturated with Ag/AgCl). The
redox potential was measured at designated times, and samples
were withdrawn to measure the copper concentration. The solution was agitated with a magnetic stirrer at 550 rpm during the
leaching test.
3. Results and discussion
Fig. 3 shows the XRD pattern of the ground chalcopyrite concentrate. The peaks of chalcopyrite (JCPDS 35-752) and pyrrhotite
(JCPDS 5-490) were observed, but that of silicate was not detected
in the XRD measurement.
Fig. 4 shows the oxidationreduction potential (ORP) as a function of the leaching time in the HCl, H2SO4, and mixed solutions.
The decrease in the ORP then remains constant. In this experiment,
the leaching tests were terminated after the ORP leveled out. The
ORP could be determined in this leaching system according to
the following Nernst equation:

E E0

RT Fe3 
ln 2
F
Fe 

where [i] represents the concentration of species i. As shown in Eq.

(5), the concentration of ferrous ions increases during the chalcopyrite leaching process, and eventually the ORP decreases with time.
The most rapid decrease in the ORP is observed in the hydrochloric
acid solution, and a rapid decrease in the ORP is observed before the
formation of a plateau in each of the solutions in Fig. 4.

ORP Electrode
Thermometer
Silicon cap

Water
Jacket

2. Experimental
2.1. Materials
The chalcopyrite concentrate used in this study was obtained
from the Omine Mine, Tono City, Japan. The concentrate contained
25.6% Cu, 38.1% Fe, and 2.0% Si, and its mineralogical composition
was 74.8% chalcopyrite, 22.3% pyrrhotite, and 2.9% quartz. The concentrate particles were ground with an alumina mortar and then
dry-sieved with a 200-mesh sieve. The ground particles were char-

Magnetic
bar

Magnetic Stirrer
Fig. 2. Leaching reactor.

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K. Yoo et al. / Minerals Engineering 23 (2010) 471477

Intensity

C:chalcopyrite
P:pyrrhotite

K Cu

Cutn1  Cutn
tn1  tn

n 0; 1; 2; 3; . . . ; Cut0

initial Cu concentration
ORPtn1 ORPtn
2
initial ORP

ORPAve
C
C
P

Fig. 3. XRD pattern of the chalcopyrite concentrate powder. C: chalcopyrite (JCPDS

35-752), P: pyrrhotite (JCPDS 5-490).

ORP / mV

11
3

2 / deg

H2SO4
HCl

n 0; 1; 2; 3; . . . ; ORPt0

Mixture

Time / minutes
Fig. 4. Variation of the oxidationreduction potential as a function of leaching time.

Fig. 5 shows that copper concentrations as a function of the

leaching time. The concentrations increase with time and reach
plateaus during the leaching tests. The increase in the concentration in the hydrochloric acid solution is the most rapid and shows
the highest extracted Cu concentration. The rapid leaching of chalcopyrite in a chloride solution is a well-known phenomenon
(Dutrizac, 1981; Flett, 2002). The results in Fig. 5 agree well with
the conventional studies. In sulphuric acid, the copper concentration increases gradually and then rapidly from 1600 min. Similar
trends are observed in the hydrochloric acid solution and mixture,
although it is difcult to recognize these trends in Fig. 5. These results indicate that there are rapid increases in the Cu concentration. A rapid decrease in the ORP and an increase in the Cu
concentration would result from a fast leaching rate of chalcopyrite. Therefore, the relation between the copper leaching rate and
ORP was investigated as follows.
First, the copper leaching rate and ORPAve were obtained using
the following equations:

1

where Kcu represents the copper leaching rate (g m min ), [Cu]t

and ORPt are the copper concentration and ORP measured at time
t, respectively, and ORPAve is the average of the ORPs measured at
tn+1 and tn.
Fig. 6 shows the relation between the copper leaching rate and
the average ORP. At ORP less than 600 mV of all solutions, the
leaching rates are almost kept constant with decreasing ORP, and
they increase and then decrease in the ORP ranges between
380 mV and 480 mV. The highest rates for the three solutions are
56.00, 10.73, and 0.65 g m3 min1, respectively. This result suggests that the leaching rate increases with an increase in the chloride concentration. The leaching rates are the highest between 435
and 445 mV. These ORP values are much lower than 580 mV,
which is the standard potential of Eq. (9) measured at 80 C in
the preliminary study (not published). The result in Fig. 6 suggests
that the leaching rate increases in a relatively low ORP range and
that the leaching behaviour of chalcopyrite in a chloride solution
follows the model by Hiroyoshi.
In this study, another leaching rate was obtained from the ORP
difference (DORP) at a designated time interval. This ORP difference rate is given by

ORPrate

ORPtn1  ORPtn
t n1  tn

n 0; 1; 2; 3; . . . ; ORPt0

initial ORP

12

On the basis of Eqs. (11) and (12) and the data in Fig. 4, the relationship between ORPrate and ORPAve is shown in Fig. 7. As shown
in Fig. 7, ORPrate decreases as ORPAve decreases to around 500 mV;

Leaching rate / gm-3 min-1

10

HCl
Mixture
H2SO4

ORPAve / mV

HCl
Mixture
H2SO4

Time / minutes
Fig. 5. Variation of Cu leaching concentration as a function of leaching time.

ORP difference rate / mV min-1

Cu concentration / gm-3

Fig. 6. Cu leaching rate vs. average oxidationreduction potential.

HCl
Mixture
H2SO4

ORPAve / mV
Fig. 7. Change of ORP rate vs. average ORP.

K. Yoo et al. / Minerals Engineering 23 (2010) 471477

it increases and then decreases as ORPAve decreases to less than

500 mV. The trend in Fig. 7 is in good agreement with those in Figs.
1 and 6. The relation between the ORP difference rate and the Cu
leaching rate was investigated as follows.
During chalcopyrite leaching, Cu2+ and Fe2+ are dissolved out
from chalcopyrite, as can be seen in Eq. (5). When x kmol m3
Cu2+ is leached, the Fe3+ and Fe2+ concentrations are changed
according to the following equations:

Fe3  Fe3 0  4x

13

Fe2  Fe2 0 5x

14

4
Fe3 

log(a Cu ) or log(a Ag )

dx
Fe2  dt

16

2CuFeS2 6Ag 2e Cu2 S 2Fe2 3Ag2 S

+

The critical potential by Ag

equation:


3
aAg
RT

ln 
F
aFe2

Fig. 8. Critical potential (Ec(Ag+)) as a function of the logarithm of silver ion activity
and Ec(Cu2+) as a function of the logarithm of cupric ions at 298 K and 1 atm (ferrous
ion activity is 0.1) (Hiroyoshi et al., 2002).

15

In Eq. (16), the leaching rate of copper, dx/dt, from chalcopyrite

is proportional to the differentiation of E with respect to time. Figs.
6 and 7 show similar trends, but the highest rates are observed at
435445 mV for the copper leaching rate and at 410420 mV in
the rate of change of the ORP. This difference results from the fact
that the ferric and ferrous concentrations in Eq. (16) change during
the leaching test. However, the ORP rate is very useful for approximately tracking the leaching rate of chalcopyrite without measuring the copper concentration.
As shown in Figs. 6 and 7, the high leaching rate zone becomes
broader and the critical potential (Ec) increases as the chloride concentration increases. As mentioned in the introduction, chlorocuprate(I) ions between cuprous and chloride ions are formed in a
chloride solution; therefore, the effect of chlorocuprate(I) ions on
the leaching rate and the critical potential (Ec) should be investigated. However, because it was difcult to analyze the cuprous
ion concentration under the experimental conditions in this study,
the effect of the complex ions could not be examined experimentally. Therefore, the effect of cuprous ion on the critical potential
and the chalcopyrite leaching rate was investigated
thermodynamically.
Hiroyoshi reported that the chalcopyrite leaching rate could be
improved by increasing the critical potential (Hiroyoshi et al.,
2002). The leaching rate was found to be fast when Ag+ ions were
added into a chalcopyrite leaching system (Ahonen and Tuovinen,
1990; Escudero et al., 1993; Gmez et al., 1999; Price and Warren,
1986). Hiroyoshi and co-workers investigated the effect of an Ag+
ion addition on chalcopyrite leaching based on the model by
Hiroyoshi (Hiroyoshi et al., 2002; Miki et al., 2003). Chalcopyrite
is reduced to chalcocite by adding Ag+ according to the following
equation:

Ec Ag E0c

Ec(Cu2+)

17

The critical potential by silver ions is higher than that by cupric

ions over the entire activity range (Hiroyoshi et al., 2002). This increase in the Ec suggests that the higher leaching rate zone between Eox and Ec was expanded, as shown in Fig. 9. Therefore,
Hiroyoshi and co-workers reported that the leaching rate of chalcopyrite could be accelerated by the addition of silver ions, thus
increasing the critical potential (Hiroyoshi et al., 2002). Fig. 9
shows a pattern similar to those shown in Figs. 6 and 7. This fact
suggests an increase in the critical potential in the chloride solution. Therefore, the increase in the critical potential by the addition
of the copper species was investigated in a chloride solution.
The copper species exists as cupric ions or copper metal in a sulphate medium. Therefore, the critical potential in a sulphate solution is determined by the cupric ions, as shown in Eq. (2). However,
in a chloride solution, cuprous ions should be considered for the
critical potential because cuprous ions exist as the chlorocuprate(I)
ions. Lin and co-workers (1991) reported the distribution of copper
ions with increasing chloride concentration, as shown in Fig. 10. All
of the copper species exist as cupric ions or copper metal at a low
chloride concentration. However, as the chloride concentration in
2
creases, cuprous ion species such as CuCl, CuCl2 , CuCl3 , and
3
CuCl4 are formed as chlorocuprate(I) ions, and the standard potential between cupric and cuprous species also increases. This fact
indicates that the concentration of cuprous ion species increases
with an increase in the concentration of chloride ions. Therefore,
the effect of cuprous ion species on the critical potential is discussed below.

HIgh Ag+ concentration

Cu extraction rate

!
dFe3 
1 dFe2 

Fe3  dt
Fe2  dt
1

When Eqs. (13) and (14) are differentiated with respect to time and
substituted in Eq. (15), we obtain the following equation:

dE RT

dt
F

Ec(Ag+)

2+

where [i]0 represents the initial concentration of species i, and x is

the concentration of cupric ions. Eq. (9) is differentiated with respect to time into Eq. (15).

dE RT

dt
F

Critical potential, Ec / V

474

Low Ag + concentration

is dened by the following

18

where Ec(Ag+) represents the critical potential by Ag+

The critical potentials by Cu2+ (Ec(Cu2+)) and Ag+ (Ec(Ag+)) as
functions of the activities of these species are shown in Fig. 8.

Eox

Ec(Ag+)

Adding Ag + ions

Ec(Ag+)

Redox potential of solution

Fig. 9. Schematic representation of the redox potential dependence of chalcopyrite
leaching in the presence of silver ions on the basis of Hiroyoshis model (Hiroyoshi
et al., 2002).

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K. Yoo et al. / Minerals Engineering 23 (2010) 471477

CuCl+

Table 1
Standard Gibbs free energies used.

CuCl2

Eh / V

Cu2+

CuCl

CuCl2-

CuCl43-

Species

DG (kJ mol1)

Reference

CuFeS2
Cu2S
Cu+

CuCl2
2

190.6
86.73
50.2
248.03
377.9

Hiroyoshi et al. (2002)

Hiroyoshi et al. (2002)
Lin et al. (1991)
Lin et al. (1991)
Lin et al. (1991)

3

506.9

Lin et al. (1991)

64.96
66.81
196.95
131.14
341.37

Lin et al. (1991)

Lin et al. (1991)
Lin et al. (1991)
Lin et al. (1991)
Bard et al. (1985)

CuCl3
CuCl32-

Cu

Log a ClFig. 10. The Ehlog aCl diagram for the Cu+/Cu2+ClH2O system (Lin et al., 1991).

Chalcopyrite can be reduced by cuprous ion species according

to the following equations:


CuFeS2 3CuCl2 e 2Cu2 S FeCl2 4Cl

19

CuCl4
Cu2+
CuCl+
CuCl2
Cl
FeCl2

Table 2
Calculated standard potentials (E0c ) of critical potentials in Eqs. (2), (19)(21), (24),
and (25).
Species


2

CuFeS2 3CuCl3 e 2Cu2 S FeCl2 7Cl

3

20


CuFeS2 3CuCl4 e 2Cu2 S FeCl2 10Cl

21

where CuCl was not considered because of the low solubility of CuCl
(KSP = 1.72  107) (Lin et al., 1991).
The critical potentials by the cuprous ion species can be obtained according to the following equations:


Ec CuCl2

E0c


3
aCuCl2
RT

ln 

F
aFeCl2 aCl 4

22


3


aCuCl2
RT
2
3
Ec CuCl3 E0c
ln 

F
aFeCl2 aCl 7

23


3


aCuCl3
RT
3
4
Ec CuCl4 E0c
ln 

F
aFeCl2 aCl 10

24

As can be seen in Fig. 10, cupric ions also form complex ions
such as CuCl+ and CuCl2, as the chloride ion concentration increases. The critical potentials by these complex ions can be induced by the following reactions:

Equation
Standard potential, E0c
(V)

CuCl2

CuCl3

CuCl4

Cu2+

CuCl+

CuCl2

19
1.084

20
1.124

21
1.191

2
0.681

24
0.660

25
0.684

2

3

However, in the chalcopyrite leaching system, the cuprous ion

and cupric ion concentrations are not independent. Therefore, the
critical potential of each species was revised as discussed below.
The concentration of each species was determined. First, the total copper concentration can be dened according to the following
equation:

h
i h
i h
i

 

2
3
CuT  Cu CuCl2 CuCl3 CuCl4 Cu2


CuCl CuCl2 ;

29

where CuT represents the total copper in a leaching solution and [i]
is the concentration of species i. In this study, the activity coefcient
is assumed to be 1.
Lin et al. (1991) dened the thermodynamic equilibrium constant between copper ions and chloride ion through the following
set of equations:


Cu 2Cl CuCl2 ;

K1

CuCl2 

30

Cu Cu 2

2

CuFeS2 3CuCl 4e 2Cu2 S FeCl2 Cl

CuFeS2 3CuCl2 4e 2Cu2 S FeCl2 4Cl

25

Ec CuCl

E0c

RT
a 3


ln  CuCl
4F
aFeCl2 aCl

27


3
aCuCl2
RT
ln 

4F
aFeCl2 aCl 4

28

Ec CuCl2 E0c

The standard critical potentials were calculated at 298 K and

1 atm using the data in Table 1 and are listed in Table 2. Each critical potential was obtained using the standard potentials listed in
Table 2 and Eqs. (2), (22)(24), (27), and (28) under the assumption
of the activities of other ions being 0.1. The standard potentials of
the cuprous species are higher than those of the cupric species. The
calculated critical potentials as functions of the activities of all the
copper ion species are shown in Fig. 11. The critical potentials by
the cuprous ion species increase more rapidly than those by the
cupric ion species as the activities of copper ion species increase.

CuCl3 

31

Cu Cl 3
3

3

Cu 4Cl CuCl4 ;

Critical potential, Ec / V

K2

26


2

Cu 3Cl CuCl3 ;

K3

CuCl4 

32

Cu Cl 4

Ec(CuCl43-) Ec(CuCl32-) Ec(CuCl2-)

Ec(CuCl2)

Ec(Cu2+)

Ec(CuCl+)

Logarithm of activities of copper ion species

Fig. 11. Critical potentials as a function of the logarithm of copper ion activities at
298 K and 1 atm (other ion activities are assumed to be 0.1).

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K. Yoo et al. / Minerals Engineering 23 (2010) 471477

Cu2 2Cl CuCl2 ;

K4

CuCl 
2

33

Cu Cl 

K5

CuCl2 

34

Cu2 Cl 2

The equilibrium constants obtained by Lin et al. (1991) are


2
3
listed in Table 3. By substituting [CuCl2 ], [CuCl3 ], [CuCl4 ], [CuCl+],
and [CuCl2] in Eq. (29) by Eqs. (30)(34) and by using the data in
Table 3, Eq. (29) can be rearranged as follows






CuT  Cu  1 106:29 Cl 2 106:07 Cl 3 105:70 Cl 4




Cu2  1 100:089 Cl  100:52 Cl 2

E0 0:159 V

36

This reaction can be represented by the following equation:

E E0

RT Cu2 
ln
F
Cu 

37

The cupric concentration in Eq. (35) was substituted by Eqs.

(36) and (37), and Eq. (35) can be rearranged as the following
equation:


CuT  Cu f1 106:29 Cl 2 106:07 Cl 3 105:70 Cl 4

EE0 F

RT

Ec(Cu 2+ )

Logarithm of total copper concentration

35

The relation between Cu2+ and Cu+ can be expressed in the following reaction:

Cu2 e Cu ;

Ec(CuCl 2 )

Critical potential, Ec/ V

38

1 100:089 Cl  100:52 Cl 2 g

This equation can be rearranged as Eq. (39).

n




Cu  CuT = 1 106:29 Cl 2 106:07 Cl 3 105:70 Cl 4


EE0 F


39
e RT 1 100:089 Cl  100:52 Cl 2
The concentration of cuprous ions is expressed in terms of the
total copper concentration, chloride concentration, and redox potential. The concentrations of the cuprous and cupric ion species
were obtained using the calculated cuprous ion concentration. Finally, each critical potential was determined. The critical potentials

of CuCl2 and Cu2+, which are dominant ions in the solution with
less than 0.1 kmol m3 chloride (Fig. 10), are compared and discussed below, because less than 0.1 kmol m3 chloride was used
for the leaching of chalcopyrite in this study.

Fig. 12 shows the critical potentials by CuCl2 and Cu2+ with the
concentration of total copper, calculated under the following conditions: the redox potential is 0.6 V and the concentrations of the
other species are 0.1 kmol m3. The concentration of the chlorocuprate(I) complex formed is very low, as discussed below; therefore, the chloride ion concentration is also assumed to be
0.1 kmol m3. In Fig. 12, both critical potentials increase with an
increase in the total copper concentration. When the total copper
concentration is very low, the critical potential of Cu2+ is higher


than that of CuCl2 , but the critical potential of CuCl2 becomes
higher at a total copper concentration of more than

0.001 kmol m3. The concentrations of CuCl2 and Cu2+ calculated
3
at a total copper concentration of 10 kmol m3 are calculated
to be 5.58  107 and 8.83  104 kmol m3, respectively. These

results suggest that the effect of CuCl2 on the critical potential beTable 3
Equilibrium constants of Eq. (27)(31).

Fig. 12. The comparison of the critical potentials of Cu2+ and CuCl2 as a function of
the total copper concentration (298 K and 1 atm, other ion activities are assumed to
be 0.1).

comes dominant even though the concentration of Cu2+ is approx

imately 1000 times greater than that of CuCl2 .

Fig. 13 shows the critical potentials by CuCl2 and Cu2+ with the
concentration of chloride ions. The critical potentials are calculated
under the following conditions: the redox potential is 0.6 V, total
copper concentration is 0.01 kmol m3, and concentrations of the
other species is 0.1 kmol m3. In Fig. 13, the critical potential of
Cu2+ is kept almost constant over all of the chloride ion concentra
tions and that of CuCl2 increases rapidly with an increase in the
chloride ion concentration. The critical potential is determined
only by the Cu2+ ions at a low chloride ion concentration under
conditions similar to those for the sulphate solution. The critical

potential by CuCl2 becomes higher than that by Cu2+ with an increase in the chloride ion concentration to a value higher than
0.01 kmol m3, where the concentrations of CuCl and Cu2+ are
5.77  106 and 9.98  103 kmol m3, respectively. Although the

concentration of Cu2+ is much higher than that of CuCl2 at

3
0.01 kmol m Cl, the critical potential of CuCl2 is higher than that
of Cu2+.
Chloride leaching for chalcopyrite has been widely known for
its fast leaching rate as well as high solubility and production of
elemental sulphur, but there has been limited work done to determine its mechanism. Therefore, in this study, the behaviour of copper ions with an increasing Cl concentration and the effect of
adding chloride ions on the critical potential of copper ion species
were investigated using Hiroyoshis model. Although the calculations were conducted under restricted conditions such as a constant total Cu concentration or ORP, the calculation results show
that the critical potential of cuprous ion species is higher than that
of cupric ion species at a high chloride concentration.
Hiroyoshi reported that the leaching rate of chalcopyrite would
increase with an increase in the critical potential. Therefore, this

Critical potential, Ec / V

Cu2 Cl CuCl ;

Ec(Cu 2+ )
Ec(CuCl 2 )

Logarithm of chloride concentration

K1

K2

K3

K4

K5

1.995  106

1.202  106

5.012  105

1.288

0.2991

Fig. 13. The comparison of the critical potentials of Cu2+ and CuCl2 as a function of
chloride ion concentration (298 K and 1 atm, other ion activities are assumed to be
0.1).

K. Yoo et al. / Minerals Engineering 23 (2010) 471477

result reveals that the chlorocuprate(I) ions formed in a chloride

solution could improve the chalcopyrite leaching rate by increasing
the critical potential. Therefore, the above results indicate that the
effect of cuprous ion species on the improvement of the chalcopyrite leaching rate is more substantial than that of cupric ion
species.
4. Conclusions
Chalcopyrite leaching experiments were performed in chloride,
sulphate, and mixed solutions, and the behaviours of copper ions in
chloride and the effect of cuprous ion species on the critical potential were investigated thermodynamically on the basis of the model by Hiroyoshi.
The copper leaching rate is the fastest in the chloride solution,
and the trend of the chalcopyrite leaching in the chloride solution
seems to follow Hiroyoshis model. Cuprous species exists as chlorocuprate(I) ions in the chloride solution, and the critical potential
increases more rapidly in the chloride solution than in the sulphate
solution, as the cuprous ions becomes more dominant with an increase in the chloride concentration. These results indicate that the
increase in the critical potential by cuprous ion species in a chloride solution improves the chalcopyrite leaching rate.
Acknowledgments
The authors express appreciation for support of this research by
a grant from Korea Institute of Geoscience and Mineral Resources.
The authors would like to thank Dr. Hyo Shin Yu for helpful advice
on writing this paper. The authors also wish to thank Miss. MyungHwa Kim for her kind help for the leaching experiments.
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