Hydrometallurgy 63 (2002) 257 – 267

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A new reaction model for the catalytic effect of silver ions

on chalcopyrite leaching in sulfuric acid solutions
Naoki Hiroyoshi *, Masatoshi Arai, Hajime Miki,
Masami Tsunekawa, Tsuyoshi Hirajima
Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628, Japan

Received 22 May 2001; received in revised form 20 September 2001; accepted 9 November 2001

Abstract

Chalcopyrite leaching in sulfuric acid solutions depends on the redox potential determined by the concentration ratio of
ferric to ferrous ions, and the leaching rate is higher at redox potentials below a critical value. Previously, the authors have
proposed a reaction model to interpret this phenomenon. The present study applied the model to interpret the catalytic effect of
silver ions on chalcopyrite leaching. The model assumes that at lower potentials, chalcopyrite leaching proceeds in two steps:
first, chalcopyrite is reduced by ferrous ions to form Cu2S that is more rapidly leached; next, the intermediate Cu2S is oxidized
by ferric and/or dissolved oxygen to release cupric ions. During the chalcopyrite reduction, hydrogen sulfide is released to the
liquid phase. Silver ions react with the hydrogen sulfide to form silver sulfide precipitate and decrease the concentration of
hydrogen sulfide in the liquid phase, causing a rise in the critical potential of Cu2S formation and broadening of the potential
range where rapid copper extraction takes place. To confirm the model, the redox potential dependence of chalcopyrite leaching
was investigated in the presence of various concentrations of silver ions with 0.1 kmol m
3 sulfuric acid containing known
concentrations of ferrous and ferric ions at 298 K in air. The critical potential increased with increasing concentrations of silver
ions. This agrees with the model proposed here but cannot be explained by the conventional model proposed by Miller et al.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Chalcopyrite; Leaching; Copper; Catalyst; Silver ions; Redox potential

1. Introduction this due to the extremely slow leaching kinetics of the

Copper has mainly been produced by smelting, but
sulfur dioxide is emitted from copper sulfides during
the process, causing air pollution. Much effort has
been made to develop hydrometallurgical alternatives
that do not emit sulfur dioxide. However, hydrome-
tallurgical processes have not been fully successful in
*
Corresponding author. Tel./fax: +81-11-706-6315.
E-mail address: hiroyosi@eng.hokudai.ac.jp (N. Hiroyoshi).
most common copper source, chalcopyrite (CuFeS2).
To improve chalcopyrite leaching, several catalysts
and/or promoters have been proposed, such as surfac-
tants (Duncan et al., 1964; Duncan and Trussel, 1964;
Sandoval et al., 1990, 1991; Hiroyoshi et al., 1995,
1997), carbon particles (Bryner et al., 1967; Wan et
al., 1984; Nakazawa et al., 1998), iron powder (San-
chez et al., 1996), hematite (Sanchez et al., 1997), or
silver ions (Miller and Portillo, 1979; Carranza et al.,
1997; Palencia et al., 1998; Romeo et al., 1998;
Bruynesteyn et al., 1983). Silver ions are the most

0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 1 ) 0 0 2 2 8 - 6
258 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
effective catalyst that has been proposed, but the
processes using silver ion are costly and unless ores
contain silver minerals, silver ion would not be used
in practice. However, it is still important to establish
the mechanism of the catalytic effect of silver ions to
develop cheaper and more effective catalysts or meth-
ods for improving chalcopyrite leaching.
Miller and Portillo (1979) have proposed a reaction
model for interpreting the catalytic effect of silver ions
on chalcopyrite leaching in acidic ferric sulfate solu-
tions. In the absence of silver ions, this model suggests
that oxidative leaching of chalcopyrite with ferric ions
is retarded by a dense elemental sulfur layer formed on
the mineral surface during the leaching, acting as a
diffusion barrier. In the presence of silver ions, chal-
copyrite leaching proceeds according to the following
reactions:
CuFeS2 þ 4Agþ ¼ Cu2þ þ Fe2þ þ 2Ag2 S ð1Þ
2Ag2 S þ 4Fe3þ ¼ 4Agþ þ 4Fe2þ þ 2S ð2Þ
The copper extraction rate is higher with silver ions
because the mixed product layer of elemental sulfur
and Ag2S is porous and non-protective.
In many reports (Price and Warren, 1986; Ahonen
and Touvinen, 1990; Sukla et al., 1990; Ballester,
1987; Escudero et al., 1993; Mier et al., 1994; Gómez
et al., 1999), the above model has been used to
interpret the behavior of chalcopyrite leaching in the
presence of silver ions. The present study, however,
proposes a new model and compares it with the
conventional model based on experimental results.
The new model is an application of a previous model
that had been proposed to interpret the redox potential
dependence of chalcopyrite leaching (Hiroyoshi et al.,
2000, 2001).
2. Models
2.1. Redox potential dependence of chalcopyrite lea-
ching in the absence of silver ions
Chalcopyrite leaching in sulfuric acid solutions
depends on the redox potential determined by the
concentration ratio of ferric to ferrous ions, and the
leaching rate is higher at redox potentials below a
critical value (Hiroyoshi et al., 2000, 2001). To inter-
pret this phenomenon, the following reaction model
was proposed (Hiroyoshi et al., 2000, 2001). The
leaching solutions of chalcopyrite contain cupric,
ferric, and ferrous ions, and the potential of an inert
electrode like platinum immersed in the solution, E, is:
RT aFe3þ RT ½Fe3þ 
E ¼ E
þ ln ¼ E
V þ ln 2þ ð3Þ
F aFe2þ F ½Fe 
where ai and [i] indicate the activity and molarity of
species i, R is the gas constant, T is the absolute
temperature, and F is the Faraday constant; E
and
E
V indicate the standard redox potential and the
formal potential of a ferric/ferrous ion redox pair,
respectively. The value of E
is 0.771 V and the value
of E
V in 0.1 kmol m
3 sulfuric acid solutions is about
0.67 V at 298 K, 1 atm against a standard hydrogen
electrode (SHE). In this paper, all redox potentials are
shown as the value at 298 K under 1 atm against SHE.
Since the redox potential, E, is an indicator of the
oxidizing power of the solutions, it is termed ‘‘sol-
ution potential’’ in this report. At higher solution
potentials, cupric ions are extracted more slowly from
chalcopyrite by direct oxidation with ferric ions and/
or dissolved oxygen, according to:
CuFeS2 þ 4Fe3þ ¼ Cu2þ þ 5Fe2þ þ 2S ð4Þ
CuFeS2 þ 4Hþ þ O2 ¼ Cu2þ þ Fe2þ þ 2S
þ 2H2 O ð5Þ
At lower potentials, chalcopyrite is reduced by
ferrous ions in the presence of cupric ions to form
Cu2S (Eq. (6)) and the intermediate Cu2S is oxidized
by dissolved oxygen and/or ferric ions to release
cupric ions (Eqs. (7) and (8)) as:
CuFeS2 þ 3Cu2þ þ 3Fe2þ ¼ 2Cu2 S þ 4Fe3þ ð6Þ
Cu2 S þ 4Hþ þ O2 ¼ 2Cu2þ þ S þ 2H2 O ð7Þ
Cu2 S þ 4Fe3þ ¼ 2Cu2þ þ S þ 4Fe2þ ð8Þ
 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267 259

The oxidation rate of the intermediate Cu2S is The critical potential of Cu2S formation for this react-
higher than that of chalcopyrite and this causes the ion, Ec(H2S), is given by:
rapid copper extraction at lower potentials.
RT ðaHþ Þ3
The thermodynamic criterion for the rapid copper EcðH2 SÞ ¼ Ec0 þ ln :
extraction according to Eqs. (6) – (8) is given by: F ðaFe2þ ÞðaH2 S Þ1:5

Ec > E > Eox ð9Þ Ec0 ¼
0:221 V ð15Þ

Fig. 1 shows the critical potential, Ec(H2S), as a

where Ec and Eox are, respectively, the critical potential
function of the activity of hydrogen sulfide. For com-
of Cu2S formation and the oxidation potential of Cu2S,
parison, the critical potential defined by Eq. (10),
defined by:
Ec(Cu2+ ), and the oxidation potential of Cu2S, Eox,
are also shown in this figure. In all cases, the acti-
RT ðaCu2þ Þ0:75
Ec ¼ Ec0 þ ln : vities of cupric and ferrous ions as well as protons
F ðaFe2þ Þ0:25 were assumed to be 0.1. As shown in Fig. 1, the value
of Ec(Cu2+ ) is higher than Eox, indicating that rapid
Ec0 ¼ 0:681 V ð10Þ copper extraction may occur at the solution redox
potentials between Ec(Cu2+ ) and Eox (Eq. (9)). From
RT
Eox ¼ Eox0 þ lnðaCu2þ Þ0:5 : Fig. 1, Ec(H2S) is lower than Eox unless hydrogen
F sulfide activity is lower than about 10
10.
Usually, such a low hydrogen sulfide activity would
Eox0 ¼ 0:561 V ð11Þ not be achieved in a leaching system involving metal
sulfides like chalcopyrite and Eq. (14) can be ignored
as the reaction forming the intermediate Cu2S. In the
These potentials correspond to the electrode poten-
presence of silver ions, however, hydrogen sulfide ac-
tials of the following half-cell reactions, respectively:
tivity would be extremely low because silver ions react
with hydrogen sulfide to form silver sulfide, which has
CuFeS2 þ 3Cu2þ þ 4e
¼ 2Cu2 S þ Fe2þ ð12Þ
very low solubility, according to:

2Cu2þ þ S þ 4e
¼ Cu2 S ð13Þ 2Agþ þ H2 S ¼ Ag2 S þ 2Hþ ð16Þ

If it is assumed that in the presence of silver ions,
To avoid confusion, the critical potential Ec defined
hydrogen sulfide formed due to chalcopyrite reduction
by Eq. (10) is termed Ec(Cu2+ ) in the following.

2.2. Redox potential dependence of chalcopyrite lea-

ching in the presence of silver ions

In the above model, the reduction of chalcopyrite

to the intermediate Cu2S plays a key role in explaining
the rapid copper extraction at low redox potentials and
this reaction involves cupric ions as a reactant (Eq. (6)
or Eq. (12)). However, it is well established that
chalcopyrite is reduced to Cu2S even without cupric
ions according to the following reaction (Nicol,
1975):

2CuFeS2 þ 6Hþ þ 2e
Fig. 1. Critical potential (Ec(H2S)) as a function of the logarithm of
hydrogen sulfide activity at 298 K under 1 atm. Dotted lines indicate
Ec(Cu2+ ) and Eox. Activities of ferrous, cupric ions and protons are
¼ Cu2 S þ 2Fe2þ þ 3H2 S ð14Þ assumed to be 0.1.
260 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267

Table 1
Standard Gibbs free energy changes of formation for the species involved in Eq. (17), at 298 K under 1 atm (unit: kJ mol
1)
Species, i Cu2+ Fe2+ Cu2S CuFeS2 Ag + Ag2S
DGi0 64.98
84.94
86.73
190.6 77.11
39.46
References Yazawa and Yazawa and Yazawa and Yazawa and Wagman et Wagman et
Eguchi (1975) Eguchi (1975) Eguchi (1975) Eguchi (1975) al. (1982) al. (1982)

(Eq. (14)) is removed from the aqueous phase accord- potential of solution, E, is higher than Ec(Ag + ), no
ing to Eq. (16), the overall reaction is given by: Cu2S forms and copper is extracted slowly from the
chalcopyrite by Eq. (4) and/or Eq. (5). At potentials
2CuFeS2 þ 6Agþ þ 2e
between Eox and Ec(Ag + ), Cu2S is formed according
to Eq. (17) and rapid copper extraction occurs due to
¼ Cu2 S þ 2Fe2þ þ 3Ag2 S ð17Þ the oxidation of the intermediate Cu2S according to
Eq. (7) and/or Eq. (8). The electron donor for Eq. (17)
The critical potential (redox potential) for this is ferrous ions in liquid phase. A part of the Ag2S
reaction is: formed during the chalcopyrite reduction (Eq. (17)) is
3 dissolved by oxidation with dissolved oxygen and/or
RT ðaAgþ Þ
EcðAgþ Þ ¼ Ec0 þ ln : ferric ions. The anode reaction of the Ag2S dissolution
F ðaFe2þ Þ
is:
Ec0 ¼ 2:365 V ð18Þ
Ag2 S ¼ 2Agþ þ S þ 2e
ð20Þ
0
The value of Ec in this equation was calculated from
Eq. (19) using the reported values (Yazawa and Egu- Silver ions released according to this reaction are
chi, 1975; Wagman et al., 1982) of the standard Gibbs again used in the chalcopyrite reduction by Eq. (17).
free energy of formation for the related species, DGi0, When the redox potential of the solution is lower than
shown in Table 1. Eox, copper is not extracted because the intermediate
Cu2S is not oxidized.
1 If the diffusion of related species are sufficiently
Ec0 ¼
fðDG0Cu2 S þ 2DG0Fe2þ þ 3DG0Ag2 S Þ
2F rapid, the copper extraction rate in the range between

ð2DG0CuFeS2 þ 6DG0Agþ Þg ð19Þ

Fig. 2 shows the critical potentials of Ec(Ag + )

defined by Eq. (18) as a function of silver ion activity.
In this figure, the critical potential defined by Eq. (10),
Ec(Cu2+ ), is also shown as a function of cupric ion
activity. In both cases, the ferrous ion activity was
assumed to be 0.1. As shown in the figure, Ec(Ag + )
is much higher than Ec(Cu2+ ), even at low activities
of silver ions, indicating that silver ions determine the
critical potential of Cu2S formation in a system
containing silver ions.
Based on the above, the authors will now propose a
reaction model to interpret the catalytic effect of silver
ions on chalcopyrite leaching. Fig. 3 is a schematic
Fig. 2. Critical potential (Ec(Ag + )) as a function of the logarithm of
presentation of the redox potential dependence of silver ion activity and Ec(Cu2+ ) as a function of the logarithm of
chalcopyrite leaching in the presence of silver ions cupric ions at 298 K under 1 atm. Dotted line indicates stability
on the basis of the proposed model. When the redox limits of water.
 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
Fig. 3. Schematic representation of the redox potential dependence
of chalcopyrite leaching in the presence of silver ions on the basis of
the proposed model.
Eox and Ec(Ag + ) increases to a maximum value with
increasing potential and then decreases (Fig. 3), be-
cause the Cu2S oxidation determines the copper
extraction rate at potentials near Eox and the chalco-
pyrite reduction to Cu2S determines the extraction rate
at potentials near Ec(Ag + ). An increase in silver ion
concentration causes a rise in Ec(Ag + ) but not in Eox,
resulting in an increase in the maximum rate of copper
extraction as indicated by Fig. 3. In actual leaching
systems, the range of solution potentials is limited by
the presence of ferrous ions extracted from the chal-
copyrite and by the ferric ions formed due to oxidation
of ferrous ions. Since the value of Ec(Ag + ) is higher
than the stability limit of water even at the silver ion
activity of 10
7 (Fig. 2), no critical potential is ob-
served and the copper extraction rate increases monot-
onically with the potential in the presence of high
concentrations of silver ions.
The formation of Ag2S according to Eq. (1) would
also occur as a parallel reaction. In addition to the
Ag2S formation, metallic silver may be also formed
according to Eq. (21) (Price and Warren, 1986) and
Eq. (22).
CuFeS2 þ 4Agþ ¼ Cu2þ þ Fe2þ þ 2S þ 4Ag ð21Þ
Agþ þ Fe2þ ¼ Ag þ Fe3þ ð22Þ
These reactions are not essential for interpreting
the catalytic effect of silver ions but they may still
influence the leaching, because these reactions cause
261
the decrease in silver ion concentration and a shift in
the critical potential for Cu2S formation.
To verify the proposed model, the effect of silver
ions on the redox potential dependence of chalcopyr-
ite leaching was investigated by shaking-flask leach-
ing experiments as will be described in the next
section.
3. Experimental
3.1. Method
Massive chalcopyrite was crushed to
65 mesh
(0.212 mm) and light gangue minerals like SiO2 were
removed by heavy liquid separation with tetrabromo-
ethane (specific gravity, 2.96); next, the sink was
washed with acetone. To remove adhered clay miner-
als, the washed sample was decanted after ultrasonic
treatment in distilled water several times and dried in
air. Then the sample was dry-ground in a ceramic-ball
mill and the product (median stokes diameter on
weight basis, 5.5 mm) was used for the experiments.
Chemical analysis confirmed that the sample contains
28.0 wt.% copper, 29.7 wt.% iron, 32.9 wt.% sulfur,
1.08 wt.% silica, and 0.03 wt.% silver. With X-ray
diffraction (XRD) analysis, chalcopyrite, quartz and
pyrite were detected in the sample.
The leaching solutions were 0.1 kmol m
3 sulfuric
acid containing various concentrations of ferrous and
ferric sulfates. A known concentration of cupric sulfate
or silver sulfate was also added to the solutions. For the
preparation of the solution, distilled – deionized water
and reagent grade chemicals were used. The redox
potential of the solutions before adding chalcopyrite
was measured at room temperature with a high-resist-
ance potentiometer using a platinum electrode and a
saturated Ag – AgCl reference electrode, and it was
converted to a value against SHE. This potential is
expressed as the ‘‘initial solution potential’’.
Leaching experiments were performed with 50-
cm3 Erlenmeyer flasks containing 10 cm3 of leaching
solutions and 0.1 g of the chalcopyrite. Flasks were
capped with gas permeable plugs and shaken recip-
rocally (amplitude, 40 mm; shaking rate, 120 strokes
min
1) in a water bath at 298 K in air. After 24 h, the
suspension was filtered with a membrane filter (pore
size: 0.2 mm), and the copper, iron and silver concen-
262 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267

trations in the filtrate were determined by a SEIKO

SPS7800 inductively coupled plasma atomic emission
spectrometer (ICP-AES). The redox potential of the
filtrate (final solution potential) was also measured.
The XRD analysis was carried out for residue
leached in 0.1 kmol m
3 sulfuric acid containing
0.1 kmol m
3 ferrous ions and 0.01 kmol m
3 silver
ions. During the preparation of the solution used for
this experiment, metallic silver was precipitated by
Eq. (22). The chalcopyrite sample was added to the
solution with the metallic silver precipitate and it was
leached in the same manner as mentioned above.
After 24 h, the residue was recovered by filtration
using 5A filter paper and it was washed with 0.1 kmol
m
3 sulfuric acid and distilled water in this order.
The residue was then air-dried at room temperature
and used for XRD analysis with a JEOL JDX-3500 X-
ray diffractometer using Cu Ka radiation.

3.2. Results

3.2.1. Redox potential dependence of chalcopyrite

leaching in the absence of silver ions
The effect of the redox potential on chalcopyrite
leaching in the absence of silver ions was investigated
with and without 0.02 kmol m
3 cupric ions. The
initial redox potential of solutions containing 0.1 kmol
m
3 ferrous ions was adjusted by adding various
concentrations of ferric ions. As shown in Fig. 4, the
amounts of copper extracted after 24 h were larger at
lower potentials and the potential range where rapid
copper extraction occurs was expanded to higher
potentials by adding cupric ions.
The vertical dotted lines shown in Fig. 4 indicate
the calculated values of the critical potential, Ec
(Cu2+ ), in the presence of 0.1 kmol m
3 ferrous
ions and 0.02 kmol m
3 cupric ions. The activity
coefficients are assumed to be 1, i.e. the critical
potential was calculated by substituting the concen-
trations of ferrous and cupric ions for their activities in
Eq. (10). The calculated value agreed with the exper-
imental results and this confirms the validity of Eqs.
(9) and (10).
In the absence of cupric ions, the value of the critical
potential is calculated to be
1 from Eq. (10). In the
experiments, however, the larger copper extraction at
lower potentials was observed even without the addi-
tion of cupric ions (Fig. 4). This may be caused by the
Fig. 4. Effect of cupric ion addition on chalcopyrite leaching in 0.1
kmol m
3 sulfuric acid at 298 K in air as a function of solution
potential. Leaching time was 24 h. Initial ferrous ion concentration
was 0.1 kmol m
3 and the initial solution potential was adjusted by
adding ferric ions. Silver ions were not added. The dotted line
indicates the critical potential, Ec(Cu2+ ), calculated from Eq. (10)
for a ferrous ion activity of 0.1 and a cupric ion activity of 0.02.
presence of cupric ions released from the chalcopyrite
during the leaching. As in Fig. 4, about 1  10
3 to
4  10
3 kmol m
3 of copper ions were extracted
after 24 h. Assuming that the activity coefficients are 1,
the critical potential is calculated from Eq. (10) to be
0.563 V with 1  10
3 kmol m
3 of cupric ions and to
be 0.589 V with 4  10
3 kmol m
3 of cupric ions in
the presence of 0.1 kmol m
3 ferrous ions. These
calculated values closely correspond to the experimen-
tal results in Fig. 4.
3.2.2. Redox potential dependence of chalcopyrite
leaching in the presence of silver ions
The proposed model predicts a rise in the critical
potential caused by silver ions. To confirm this, the
dependence of chalcopyrite leaching on the solution
 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
potential was investigated in the presence of various
concentrations of silver ions. The initial concentra-
tions of ferrous and cupric ions were 0.1 and 0 kmol
m
3, respectively. Fig. 5 shows the amount of copper
extracted after 24 h as a function of the initial and
final solution potentials. When the concentration of
silver ions added was less than 5  10
5 kmol m
3,
the amount of extracted copper is larger at lower
potentials than at higher potentials, and the potential
region of the rapid copper extraction expanded to
higher potentials with increasing silver ion addition.
By adding 1  10
4 kmol m
3 silver ions, the redox
potential dependence of chalcopyrite leaching changes
drastically, i.e. the amount of extracted copper in-
creased with increasing potential.
When less than 5  10
5 kmol m
3 silver ions
were added, the concentrations of silver ions after 24
h were below the detection limit of ICP-AES (10
8
kmol m
3) at any potential. With the initial silver ion
Fig. 5. Effect of silver ions on chalcopyrite leaching in 0.1 kmol
m
3 sulfuric acid at 298 K in air. Leaching time was 24 h. Initial
ferrous ion concentration was 0.1 kmol m
3 and initial solution
potential was adjusted by adding ferric ions. Cupric ions were not
added.
263
Fig. 6. The silver ion concentrations after 24 h as a function of final
solution potential in chalcopyrite leaching with 10
4 kmol m
3
silver ions. Experimental conditions are the same as in Fig. 5. The
solid line indicates the equilibrium concentration of silver ions cal-
culated from Eq. (23). The dotted line indicates the detection limit
of the Ag assay by ICP-AES.
concentration of 1  10
4 kmol m
3, small amounts
of silver ions were detected after 24 h (Fig. 6). If it is
assumed that the activity coefficient of silver ions is 1,
the relation between the solution potential and the
equilibrium silver ion concentration for the reaction
shown in Eq. (20) is given by:
RT
E ¼ E0 þ ln½Agþ  : E0 ¼ 1:01 V ð23Þ
F
For comparison, the equilibrium silver ion concen-
tration calculated from Eq. (23) is also shown in Fig. 6
(solid line). The experimental values of silver ion
concentration after 24 h were almost the same as the
calculated values.
The model predicts that the redox potential de-
pendence of chalcopyrite leaching in the presence of
silver ions is influenced by the ferrous ion activity, i.e.
the critical potential would drop with increasing fer-
rous ion concentration (Eq. (18)). To check this, the
leaching with 0.1 and 0.5 kmol m
3 ferrous ions was
compared; the concentration of silver ions added was
1  10
5 kmol m
3. As shown in Fig. 7, the increase
in ferrous ion concentration caused a critical potential
drop and this agrees with the predictions of the pro-
posed model.
3.2.3. XRD analysis of the chalcopyrite samples
Fig. 8 shows the XRD patterns of unleached
chalcopyrite and the residue from the leaching in 0.1
kmol m
3 sulfuric acid containing 0.1 kmol m
3
264 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
ferrous ions and 0.01 kmol m
3 silver ions. The
unleached sample shows peaks corresponding to chal-
copyrite, pyrite and quartz. There is an unidentified
peak at a 2h value of 31.0
with the unleached sample
(‘‘Peak 2’’ in the figure). This peak was not detected in
the leaching residue, and it may be due to complex
metal oxide or sulfate formed on the chalcopyrite sur-
face during sample preparation and storage. In addition
to these peaks, a series of peaks corresponding to Ag2S
also appeared in the residue. There were no peaks
corresponding to chalcocite (Cu2S) in the XRD pattern
of the residue, but a small peak appears around a 2h
value of 28.5
(‘‘Peak 1’’ in the figure). Miller and
Portillo (1979) reported the presence of a peak at a 2h
value of 28.2– 28.4 in the XRD patterns of chalcopyrite
immersed in silver sulfate solutions and this may be
‘‘Peak 1’’ in Fig. 8. A compound corresponding to this
Fig. 7. Effect of initial ferrous ion concentration on chalcopyrite
leaching in 0.1 kmol m
3 sulfuric acid containing 10
5 kmol m
3
silver ions at 298 K in air. Leaching time was 24 h. Initial solution
potential was adjusted by adding ferric ions. Cupric ions were not
added.
Fig. 8. XRD patterns for (A) chalcopyrite residue leached in 0.1 mol
dm
3 H2SO4 containing 0.1 kmol m
3 ferrous ions and 10
2
kmol m
3 of silver ions in air at 298 K for 24 h and (B) unleached
chalcopyrite.
peak may be geerite (Cu8S5) that has the strongest peak
at a 2h value of 28.5
. There are other Cu – Fe – S
minerals which have strongest or 2nd XRD peaks at
2h values of 28 –29
, such as spionkopite (Cu39S28),
nukundamite(Cu3.38Fe0.62S4), idaite(Cu5FeS6), and
bornite(Cu5FeS4).
4. Discussion
Based on the proposed model for chalcopyrite
leaching in the presence of silver ions, the following
are predicted: (1) there is rapid copper extraction below
a critical potential, (2) a rise in the critical potential with
increasing silver ion concentration, (3) decreases in the
critical potential with increasing ferrous ion concen-
tration, (4) formation of Ag2S below the critical poten-
tials, and (5) formation of intermediate Cu2S below the
critical potentials. Predictions (1) to (3) are substanti-
ated with the results of the leaching experiments shown
in Figs. 5 and 7.
In the XRD patterns of the leaching residue (Fig.
8), Ag2S was detected and this agrees with predic-
tion (4). In the leaching experiments with 1  10
4
kmol m
3 silver ions added, the silver ion concen-
tration remaining in solution after 24 h was almost
the same as the equivalent concentration of the ions
dissolved due to the Ag2S oxidation (Fig. 6) and the
concentration increased with increasing solution
potentials. From this result, it is concluded that
 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
Ag2S once formed on chalcopyrite is oxidized to re-
lease Ag + into solution as may be inferred from the
model. The proposed model assumes that Ag2S is
mainly formed according to chalcopyrite reduction to
Cu2S (Eq. (17)). If only Eq. (17) relates to the Ag2S
formation, the concentration of silver ions would not
change at solution redox potentials above the critical
potential, but this does not agree with the exper-
imental results. For example, in the leaching experi-
ments with 1  10
5 kmol m
3 silver ion addition
(Fig. 5), silver ions were not detected in the liquid
phase after 24 h even above the critical potential
estimated from the copper extraction (about 0.61 V).
This would indicate that not only Eq. (17) but also
Eq. (1) relate to the Ag2S formation.
In the XRD patterns of the leaching residue (Fig.
8), chalcocite (Cu2S) was not detected but a small
peak appeared at a 2h value of 28.5
. As pointed out
in Section 3.2.3, this peak may correspond to geerite
(Cu8S5) or some other Cu – Fe– S mineral. The pro-
posed model assumed that chalcocite(Cu2S) is the
intermediate formed by chalcopyrite reduction due
to its simple stoichiometory and the ease of getting
exact thermodynamic data. However, it is reported
that actual products of the chalcopyrite reduction are
both bornite(Cu5FeS4) and djurelite(Cu1.96S) (Avraa-
mides et al., 1980; Sohn and Wadsworth, 1980). In
addition to this, the cyclic voltammogram of the chal-
copyrite electrode in diluted sulfuric acid shows that
several anodic peaks appear after the cathodic scan,
indicating that the reduction product of chalcopyrite is
oxidized in several steps through a number of inter-
mediates (Warren, 1985). Considering the above, it is
reasonable to assume that several intermediates coex-
ist on chalcopyrite in the actual leaching system, al-
though for simplicity, the model assumes only Cu2S to
be the intermediate.
As above, there is an uncertainty about the identity
of the actual intermediate, but the model proposed
here well interprets the redox potential dependence of
chalcopyrite leaching in the presence of silver ions.
The following part will discuss whether the conven-
tional model proposed by Miller and Portillo (1979)
can interpret the observed redox potential dependence
of the leaching.
According to Miller and Portillo (1979), the rate-
determining step in the leaching is a discharge of
ferric ions on the surface of Ag2S crystallites present
265
in the mixed product layer. If this is the case, the
amounts of Ag2S on the chalcopyrite surface would
affect the leaching rate, i.e. the rate would increase
with the increasing amounts of Ag2S. In the conven-
tional model, the amount of Ag2S is determined by
subtracting the amount of Ag2S extracted by Eq. (2)
from the amount of Ag2S formed according to Eq. (1).
From Eq. (1), it would be expected that an increase in
silver ion addition causes an increase in the amount of
Ag2S formed on chalcopyrite. From Eq. (2), it would
also be predicted that the amount of Ag2S remaining
on the chalcopyrite increases with decreasing redox
potential of the solution, because the decrease in po-
tential causes a decrease in the concentration ratio of
ferric to ferrous ions, resulting in the suppression of
Ag2S extraction. Therefore, the rapid copper extraction
at low potentials and the rise in the critical potential
with silver ions (Fig. 5) may be due to the increase in
the amount of Ag2S remaining on the chalcopyrite
surface.
Considering the above, it seems possible to interpret
the effect of silver ions on the redox potential depend-
ence of chalcopyrite leaching from the conventional
model. However, the conventional model cannot inter-
pret details of the experimental results. As shown in
Fig. 5, the critical potential was raised by 10
5 kmol
m
3 silver ion addition. In this case, it may be assumed
that most silver ions added are precipitated as Ag2S,
because the silver ion concentration after 24 h was less
that 10
8 kmol m
3, as mentioned above. Therefore,
the minimum amount of Ag2S that is needed to improve
copper extraction can be estimated to be less than (1/
2)  10
5 kmol m
3  10 cm3 for 0.1 g of chalcopyr-
ite. In the leaching experiments with 5  10
5 kmol
m
3 silver ion addition, the concentration of silver
ions after 24 h was also less than 10
8 kmol m
3 and
the amount of Ag2S precipitated would be larger than
the estimated minimum amount at any potential. So, it
may be expected that rapid copper extraction would
occur at all redox potentials with 5  10
5 kmol m
3
silver ion addition. However, Fig. 5 shows that the
amounts of extracted copper decreased with increasing
potential even when 5  10
5 kmol m
3 silver ions
were added. This indicates that the amount of Ag2S
formed on chalcopyrite does not affect copper extrac-
tion directly.
Thus, it is difficult to interpret the effect of silver
ions on the redox potential dependence of the leaching
266 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
based on the conventional model. Furthermore, the
conventional model cannot interpret the redox poten-
tial dependence of the leaching in the absence of silver
ions shown in Fig. 4.
The new model proposed here interprets the redox
potential dependence of the leaching both with and
without silver ions well. In other words, the new mo-
del is more general than the conventional model pro-
posed by Miller and Portillo (1979).
The present study successfully applied the redox
potential dependence model of chalcopyrite leaching
to interpret the catalytic effect of silver ions on the
leaching, although some details of the model may
need further discussion. In the model for the leaching
with silver ions, hydrogen sulfide is assumed to be an
intermediate of chalcopyrite reduction (see Eqs. (14),
(16) and (17)) but does not appear in the model for the
leaching without silver ions. Similar to silver ions,
cupric ions react with hydrogen sulfide to make metal
sulfides. Therefore, it could seem natural to modify
the model for the leaching without silver ions to
contain hydrogen sulfide as an intermediate of chal-
copyrite reduction. However, this poses the following
problem.
Usually, the precipitate formed by the reaction of
cupric ions with hydrogen sulfide is not Cu2S but CuS
as follows:
Cu2þ þ H2 S ¼ CuS þ 2Hþ ð24Þ
Assuming that hydrogen sulfide formed by Eq.
(14) is removed according to Eq. (24), the overall
reaction of the chalcopyrite reduction is given by:
2þ
ions on the redox potential dependence of chalcopy
2CuFeS2 þ 3Cu þ 2e
¼ Cu2 S þ 2Fe2þ þ 3CuS ð25Þ
This differs from Eq. (12) used in the model in
Section 2.1. The critical potential (redox potential) for
this reaction is:
RT ðaCu2þ Þ1:5
EcðCu2þ Þ ¼ Ec0 þ ln : This result can be interpreted by a reaction model
F ðaFe2þ Þ
Ec0 ¼ 1:198 V ð26Þ
The value of Ec0 in this equation was calculated by
using
53.6 kJ mol
1 as the value of the standard
Gibbs free energy of formation for CuS (Wagman et
al., 1982). Assuming activity coefficients as 1, the Ec
value in the presence of 0.1 kmol m
3 ferrous ions and
0.02 kmol m
3 cupric ions is calculated to be 1.106 V,
and this is much higher than the experimental result in
Fig. 4. Moreover, the reduction products of chalcopyr-
ite in the presence of cupric ions have been reported to
be bornite (Cu5FeS4) and djurelite (Cu1.96S) (Avraa-
mides et al., 1980; Sohn and Wadsworth, 1980), and
CuS has not been reported. Because of these incon-
sistencies, it is difficult to justify Eq. (25) for describ-
ing the redox potential dependence of chalcopyrite
leaching.
The intermediate hydrogen sulfide could also be
deleted from the model for the chalcopyrite leaching
with silver ions by disregarding Eqs. (14) and (16), and
by using only Eq. (17) (the overall reaction) as the basis
of the model. This superficial revision may be accept-
able because there is no direct evidence that hydrogen
sulfide is an intermediate for chalcopyrite reduction in
the presence of silver ions. However, the model inclu-
ding hydrogen sulfide as an intermediate can be ap-
plied to describe the effect of several other factors on
chalcopyrite leaching, such as other metal ions that
make metal sulfide like silver ions and activated carbon
acting as hydrogen sulfide absorber (Hiroyoshi et al.,
2001a,b). As a result, the model including the inter-
mediate hydrogen sulfide may be more useful than the
model without the hydrogen sulfide.
5. Conclusion
The present study investigated the effect of silver
rite leaching by shaking-flask leaching experiments
with sulfuric acid solutions containing various concen-
trations of ferric and ferrous ions. Copper extraction
from chalcopyrite was enhanced at redox potentials
of solutions below a critical value and the critical po-
tential rose with increasing amounts of silver ions ad-
ded.
which assumes the formation of intermediate Cu2S due
to chalcopyrite reduction at low potentials and the
subsequent oxidation of the intermediate product.
The silver ions remove hydrogen sulfide formed during
the reduction, causing a rise in the critical potential of
Cu2S formation.
 N. Hiroyoshi et al. / Hydrometallurgy 63 (2002) 257–267
Acknowledgements
The authors express appreciation for support of this
research by a grant from the Ministry of Education,
Culture, Sports, Science and Technology.
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