Hydrometallurgy 194 (2020) 105299

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Redox potential-dependent chalcopyrite leaching in acidic ferric chloride T

solutions: Leaching experiments
⁎
Nguyen Thi Phuong Thaoa, , Shushi Tsujia, Sanghee Jeonb, Ilhwan Parkb,
Carlito Baltazar Tabelinc, Mayumi Itob, Naoki Hiroyoshib
a
Graduate school of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628, Japan
b
Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628, Japan
c
School of Minerals and Energy Resources Engineering, The University of New South Wales, Sydney, NSW 2052, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: The redox potential dependence of chalcopyrite leaching was investigated in acidic ferric chloride solutions
Chalcopyrite using a specially designed batch leaching experimental setup that accurately determined and monitored changes
Leaching of solution redox potential with time. The concentration ratio of ferric (Fe3+) to ferrous (Fe2+) ions and leaching
Ferric chloride rate-redox potential relationship were then determined from measured redox potential data assuming chalco-
Redox potential
pyrite oxidation with Fe3+ occurred stoichiometrically. A distinct peak was observed in the leaching rate vs.
redox potential plot; that is, the leaching rate increased with increasing redox potential, reaching a (local)
maximum (i.e., the peak rate) at a certain redox potential (i.e., the peak redox potential) followed by the gradual
decrease in leaching rate at higher redox potentials. For example, in the experiment performed at
[Cu2+] = [Fe2+] = 0.01 kmol m−3 in HCl (0.1 kmol m−3) at 343 K, the rate continuously increased with
increasing redox potential, reaching the fastest rate of 9.7 × 10−8 mol s−1 g−1 (peak rate) at 0.442 V (peak
redox potential). After passing this redox potential peak, the rate started to decrease, slowing down to
2.9 × 10−8 mol s−1 g−1 at 0.487 V. Using this setup, the effects of temperature and solution composition (Cu2+,
Fe3+ and HCl concentrations) on the peak rate and peak redox potential were investigated. The results showed
that the peak rate increased with increasing temperature, decreased with increasing HCl and Fe3+ concentra-
tions but was not strongly affected by Cu2+ concentration. In comparison, the peak redox potential was less
dependent on the temperature and concentrations of HCl and Fe3+. Although the role of Cu2+ was apparently
not crucial in the occurrence of the peak rate, it exerted a relatively strong influence on the peak redox potential;
that is, the peak redox potential increased with increasing Cu2+ concentration. Based on these results, an em-
pirical equation for the relationship between peak redox potential and Cu2+ concentration was derived.

1. Introduction One of the biggest challenges in copper hydrometallurgy is how to

Pyrometallurgy is the major route for extracting copper from its
primary sulfide minerals (Yoo et al., 2007; Lim et al., 2019; Sohn,
2019). With the exhaustion of high-grade copper deposits, however,
exploitation of vast, low-grade copper ores has become the norm and
will be problematic to conventional pyrometallurgical operations be-
cause of the lower quality of concentrates and presence of high amounts
of impurities like arsenic (i.e., ‘dirty’ concentrates) (Baba et al., 2012;
Watling, 2013). Because of these, hydrometallurgical approaches to
extract copper are currently being explored as an alternative processing
strategy for low-grade ores and ‘dirty’ concentrates (Hiroyoshi et al.,
1997; Sandstrom et al., 2005).
establish the leaching method suitable for chalcopyrite (CuFeS2), the
primary and most abundant sulfide mineral of copper (Dutrizac, 1981;
Hiroyoshi et al., 1998). To address this challenge, it is important to
understand the mechanisms and factors affecting the leaching rate of
chalcopyrite. The dissolution of chalcopyrite proceeds via an electro-
chemical mechanism (Hiroyoshi et al., 2004; Nicol et al., 2017), a
process whereby distinct anodic and cathodic reactions occur almost
simultaneously on the surface of the mineral via the transfer of elec-
trons between distinct anodic and cathodic sites through the crystal
lattice (Tabelin et al., 2017a; Williamson and Rimstidt, 1994). This type
of mineral dissolution has been well studied in other sulfide minerals
like marmatite ([Zn, Fe]S), pyrite (FeS2) and arsenopyrite (FeAsS)

⁎
Corresponding author.
E-mail address: thaok56diachat@gmail.com (N.T. Phuong Thao).

https://doi.org/10.1016/j.hydromet.2020.105299
Received 25 October 2019; Received in revised form 1 February 2020; Accepted 28 February 2020
Available online 05 March 2020
0304-386X/ © 2020 Elsevier B.V. All rights reserved.
N.T. Phuong Thao, et al.
Fig. 1. XRD pattern of the chalcopyrite sample.
(Igarashi et al., 2020; Li et al., 2019a, 2019b; Meng et al., 2019; Park
et al., 2019, Park et al., 2018; Seng et al., 2019a, 2019b; Tabelin et al.,
2012, 2013, 2018, 2019; Tomiyama et al., 2019, Tomiyama et al.,
2020). Chalcopyrite leaching is typically done under strongly acidic
conditions (pH < 2) to limit the precipitations of not only extracted
copper ions (i.e., Cu2+) but also Fe3+, the primary oxidant essential for
chalcopyrite dissolution as explained below.
CuFeS2 + 4 Fe3 + = Cu2 + + 5 Fe2 + + 2 S0
Previous studies have shown that the leaching rate of chalcopyrite
in acid solutions strongly depended on the redox potential of the system
(Velásquez-Yévenes et al., 2010; Yévenes et al., 2010; Nicol et al.,
2010), which is determined by the concentration ratio of Fe3+ to Fe2+
(Hiroyoshi et al., 2001, 2002, 2004, 2007; Kametani and Aoki, 1985;
Sandstrom et al., 2005; Third et al., 2001). It is also well-known that the
rate of chalcopyrite dissolution in sulfate media depended on the redox
potential; that is, the highest leaching rate is obtained at a specific value
of redox potential, which has been termed as the peak or optimum
redox potential (Hiroyoshi et al., 2008; Zhao et al., 2015). Kametani
and Aoki (1985) conducted one of the earliest studies to elucidate the
redox potential-dependent of chalcopyrite leaching and reported the
fastest leaching rate at 0.470 V (vs. Ag/AgCl). Ahmadi et al. (2010)
Fig. 2. A schematic diagram of the leaching experimental setup.
Hydrometallurgy 194 (2020) 105299
used the electrochemical bioleaching method and found the peak redox
potential at around 0.400–0.425 V vs. Ag/AgCl. Meanwhile, Third et al.
(2001) found that high copper extraction can be obtained at a lower
redox potential of 0.380 V vs. Ag/AgCl, but redox potential higher than
0.420 V vs. Ag/AgCl would inhibit chalcopyrite dissolution. Although
different values of the peak redox potential have been reported, most
probably due to differences in experimental conditions, the general
agreement was that the leaching rate is higher at lower redox poten-
tials.
To explain why faster chalcopyrite leaching rates are achieved at
low redox potentials, Hiroyoshi et al., (2000) proposed a reaction
model assuming Cu2S formation as an intermediate phase. At lower
redox potentials, chalcopyrite is reduced by Fe2+ in the presence of
Cu2+ to form Cu2S (Eq. (2)). This Cu2S-intermediate phase is then
oxidized by dissolved oxygen (Eq. (3)) and/or Fe3+ (Eq. (4)) to release
Cu2+.
CuFeS2 + 3 Cu2 + + 3 Fe2 + = 2 Cu2 S + 4 Fe3 + (2)
Cu2 S + 4 Fe3 + =2 Cu2 + +S+4 Fe2 + (3)
Cu2 S + 4H+ + O2 = 2 Cu2 + + S + 2 H2 O (4)
(1)
The oxidation rate of this Cu2S-intermediate phase is faster than that
of chalcopyrite, which causes rapid copper extraction at low redox
potentials. Based on this model, Hiroyoshi et al. (2008) conducted an
electrochemical study to investigate the effects of various parameters
on the optimum redox potential (Eop) and proposed an empirical
equation to predict the Eop for chalcopyrite leaching in sulfate media as
a function of Cu2+ and Fe2+ concentrations as follows:
Eop = 0.691 + 0.030 log [Cu2 +] + 0.013 log [Fe2 +] (5)
More recently, Yoo et al. (2007, 2010) reported that the redox po-
tential dependence of chalcopyrite leaching rate in HCl solutions was
very similar to that observed in H2SO4 solutions, and it also exhibited
the peak redox potential. One interesting difference in these two acidic
media was that the peak leaching rate was higher in HCl than in H2SO4.
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N.T. Phuong Thao, et al. Hydrometallurgy 194 (2020) 105299

0.6 0.003
B

Cu extracted, x / kmol m-3

A

Redox potential, E / V
0.5 0.002

0.4 0.001

0.3 0.000
0 2000 4000 0 2000 4000
Time, t / s Time, t / s

x 10-7 x 10-7
Cu extraction rate, r/ mol s-1 g-1

1.2 1.2

Cu extraction rate, r / mol s-1 g-1

C D

0.8 0.8

0.4 0.4

0.0 0.0
0 2000 4000 0.35 0.45 0.55
Time, t / s Redox potential, E / V
Fig. 3. An example of experimental data and calculated results: A redox potential vs. leaching time, B copper extracted amount vs. leaching time, C copper extraction
rate vs. leaching time, and D copper extraction rate vs. redox potential. (Conditions: temperature of 343 K, HCl concentration of 0.1 kmol m−3, initial Fe3+
concentration of 0.01 kmol m−3, initial Cu2+ concentration of 0.01 kmol m−3, solid-to-liquid ratio of 0.3 g CuFeS2/15 ml, and agitation speed of 400 rpm).

These previous results suggest that the redox potential-controlled
leaching of chalcopyrite in HCl solutions is very attractive for extracting
copper from low-grade copper sulfide ores and ‘dirty’ concentrates. To
develop the redox-controlled leaching system, it is crucial to know the
value of the peak redox potential under a given condition. Un-
fortunately, very few studies have been done to investigate the redox
potential dependence of chalcopyrite leaching in HCl solutions, and the
factors affecting the peak redox potential in HCl media are still not well
understood.
This study investigated the effects of temperature and solution
composition on the redox potential-dependent leaching of chalcopyrite
in acidic ferric chloride solutions using a specially designed leaching
experimental setup. Based on the results, the effects of temperature and
solution composition on the peak redox potential (Ep) and peak
leaching rate (rp) were discussed and an empirical equation to predict
the value of Ep as a function of Cu2+ concentration is proposed.
Arizona, USA was used in this study. The specimen was dry-ground in a
vibratory disc mill (RS 100, Retsch Inc., Germany) and dry-sieved to
obtain a 38–53 μm fraction. To remove the oxidized layer and fine
particles on the surface of chalcopyrite, the ground sample was washed
using a modified "washing method" based on the technique developed
by McKibben and Barnes (1986). This involves ultrasonic cleaning in
ethanol, washing in 0.1 M HNO3, multiple rinsing in deionized water,
and dewatering in a vacuum desiccator (Park et al., 2018, 2020; Tabelin
et al., 2017b). The XRF results showed that the sample is mainly
composed of Cu (30 wt%), Fe (34 wt%) and S (22 wt%), including Si
(8.2 wt%), Ca (3.7 wt%), Zn (0.8 wt%) in minor to moderate amounts.
As shown in Fig. 1, the XRD pattern confirmed that the sample is mainly
composed of chalcopyrite with minor amounts of quartz, sphalerite and
montmorillonite.
2.2. Methods

2. Materials and methods The leaching experimental setup is shown in Fig. 2. First, 3 g of
chalcopyrite sample and 12 ml of a solution containing a predetermined
2.1. Materials concentration of HCl was added into the double-jacketed glass reactor,
and the suspension was agitated by magnetic stirring (2.3 × 0.5 φ cm
A chalcopyrite specimen obtained from Copper Queen Mine, stirring bar and a stirring speed of 400 rpm). The ORP electrode, which

3
N.T. Phuong Thao, et al. Hydrometallurgy 194 (2020) 105299

x 10-7
10
343 K A

Cu extraction rate, r / mol s-1 g-1

313 K
298 K

0.1

0.01
0.35 0.45 0.55
Redox potential, E / V

x 10-7
1 0.47
B C
rp / mol s-1 g-1

0.1 0.45
Ep / V

0.01 0.43
y = 338207e-10246x
R² = 0.9999
0.001 0.41
0.0028 0.0031 0.0034 290 310 330 350

T-1/ K-1 Temperature / K

Fig. 4. Effects of temperature on the redox potential dependence of chalcopyrite leaching: A copper extraction rate as function of redox potential, B the peak rate as a
function of leaching temperature, and C the peak redox potential as a function of leaching temperature. (Conditions: HCl concentration of 0.1 kmol m−3, initial Fe3+
concentration of 0.01 kmol m−3, initial Cu2+ concentration of 0.01 kmol m−3, solid-to-liquid ratio of 0.3 g CuFeS2/15 ml, and agitation speed of 400 rpm).

is a combination Pt electrode with KCl-saturated Ag/AgCl reference 3. Results and discussion

electrode, was inserted into the solution. This ORP electrode was then
connected to a potentiometer and a data logger to measure and record
the values of redox potential continuously. The reactor was then sealed
by a silicon cap with gas inlet and outlet tubes, ultrapure nitrogen gas
(99.999%) was introduced into the solution to remove dissolved
oxygen, and the suspension was heated to the desired temperature by
connecting the reactor to a thermostat recirculating water bath. After
1 h and confirming that the redox potential has stabilized, 3 ml of a
solution containing predetermined concentrations of HCl, FeCl3 and
CuCl2 was added to start the reaction. The amount of extracted copper
was calculated from the measured redox potential, which will be ex-
plained in detail later. After finishing the experiments, the leachate was
collected by filtering the suspension through a 0.2 μm syringe-driven
membrane filter (LMS Co. Ltd., Japan), and the filtrates containing
dissolved Cu and Fe were analyzed by inductively coupled plasma
atomic emission spectroscopy (ICP-AES) (ICPE-9820, Shimadzu Cor-
poration, Japan).
3.1. An example of the results and calculation method
The overall reaction of chalcopyrite leaching in acidic ferric
chloride solution is described in Eq. (1). The redox potential of leaching
solution, E (V vs. Ag/AgCl), is expressed by the Nernst equation for
Fe3+/Fe2+ redox pair (Eq. (6)).
RT [Fe3 +]
E = E 0′ + ln
F [Fe 2 +] (6)
where R is the gas constant (8.3145 J K−1 mol−1), T is the absolute
temperature (K), F is the Faraday constant (96,485C mol−1), [Fe3+] is
the Fe3+ concentration in molarity, [Fe2+] is the Fe2+ concentration in
molarity, and E0′ is the formal redox potential for Fe3+/Fe2+ redox pair
(V). In this paper, the redox potential is referred to V vs. Ag/AgCl.
In the acidic chloride solutions of our experiments, both Fe3+/Fe2+
and Cu2+/Cu+ redox couples are present, but the effects of Cu2+/Cu+
can be neglected in our calculations. This is because both redox couples

4
N.T. Phuong Thao, et al. Hydrometallurgy 194 (2020) 105299

x 10-7
1.2
HCl 0.01 M A

Cu extraction rate, r / mol s-1 g-1

HCl 0.1 M
HCl 1 M

0.8

0.4

0.0
0.35 0.45 0.55
Redox potential, E / V

x 10-7
10 0.47
B C
rp / mol s-1 g-1

0.45
Ep / V

1
0.43
y = 5E-08x-0.179
R² = 0.8829
0.1 0.41
0.01 0.1 1 0.01 0.1 1

HCl conc. / kmol m-3 HCl conc. / kmol m-3

Fig. 5. Effects of HCl concentration on the redox potential dependence of chalcopyrite leaching: A copper extraction rate as function of redox potential, B the peak
rate as functions of HCl concentration, and C the peak redox potential as functions of HCl concentration. (Conditions: temperature of 343 K, initial Fe3+ con-
centration of 0.01 kmol m−3, initial Cu2+ concentration of 0.01 kmol m−3, solid-to-liquid ratio of 0.3 g CuFeS2/15 ml, and agitation speed of 400 rpm).

are present in the aqueous phase, promoting their rapid equilibration temperatures (0.586, 0.546 and 0.531 V at 343, 313 and 298 K, re-
(Eq. (7)) (Miki and Nicol, 2008, 2011), so the values of redox potentials spectively). The E0’ values depended on solution composition and
for Fe3+/Fe2+ and Cu2+/Cu+ pairs are the same as described in Eq. slightly shifted from that of the standard solution. However, the shift
(8). This means that regardless of the presence of Cu2+/Cu+ redox pair, was within 0.01 V under the experimental conditions used in this study,
the concentration ratio of Fe3+ to Fe2+ can be determined from the and it has negligible effects on the calculation results (e.g., the relation
measured values of redox potential, E, and the amount of Fe3+ con- between copper extraction rate and redox potential that will be shown
sumption needed for calculating copper extraction from chalcopyrite later).
can be evaluated from the change in E value. Fig. 3A shows the changes in redox potential in leaching experi-
(7) ments done at 343 K in 0.1 kmol m−3 HCl solution with initial Fe3+
Cu+ + Fe3 + = Cu2 + + Fe2 +
concentration, [Fe3+]0, of 0.01 kmol m−3 and initial Cu2+ concentra-
0′ RT [Fe3 +] 0′ RT [Cu2 +] tion, [Cu2+]0, of 0.01 kmol m−3. Assuming the reaction in Eq. (1),
E = EFe + ln = ECu + ln
F [Fe 2 +] F [Cu+] (8) when x kmol m−3 of Cu2+ is extracted, 4 x kmol m−3 of Fe3+ are
consumed and 5 x kmol m−3 of Fe2+ are formed and the redox po-
During the leaching experiments, Fe3+ are consumed while Fe2+ tential is given by
are formed according to Eq. (1), resulting in a decrease in the redox
potential. Copper extraction amount and rate can be calculated from RT [Fe3 +]0 − 4x
the measured redox potential. Details of the calculation method is ex- E = E 0′ + ln
F [Fe2 +]0 + 5x (9)
plained below using a representative experimental result.
Calculations used the values of formal electrode potential (E0’) de- Equation (9) can be rearranged to
termined by measuring the redox potential of a standard solution
(0.1 M HCl with 0.01 M Fe3+, Fe2+ and Cu2+) at different

5
N.T. Phuong Thao, et al. Hydrometallurgy 194 (2020) 105299

Fig. 6. Effects of ferric ion concentration on the redox potential dependence of chalcopyrite leaching: A copper extraction rate as a function of redox potential, B the
peak rate as functions of Fe3+ concentration, and C the peak redox potential as functions of Fe3+ concentration. (Conditions: temperature of 343 K, HCl con-
centration of 0.1 kmol m−3, initial Cu2+ concentration of 0.01 kmol m−3, a solid-to-liquid ratio of 0.3 g CuFeS2/15 ml, and agitation speed of 400 rpm).

(E − E 0′)F
[Fe3 +]0 − [Fe2 +]0 exp RT
x=
(E − E 0′)F
4 + 5 exp RT
Using this equation, copper extraction, x, can be calculated from the
measured redox potential, E. The value of [Fe3+]0 is decided from the
amount of FeCl3 added in the experiments, and [Fe2+]0 is calculated by
substituting the measured value of redox potential at time 0 (when
Fe3+ and Cu2+ solution was added) to E in the Nernst equation (Eq.
(9)) assuming x = 0. Fig. 3B shows copper extraction, x, calculated
from the data set of redox potential, E, shown in Fig. 3A.
The rate of copper extracted from chalcopyrite (r, kmol s−1 g−1)
was calculated from the increments of copper extraction (Δx) and time
(Δt) using
∆X Vs
r=
∆t M
−6 3
where, Vs is solution volume (15 × 10 m ) and M is the weight of the
chalcopyrite sample added (3 g). Fig. 3C shows the copper extraction
rate, r, calculated from the data set shown in Fig. 3B.
By combining the measured redox potential, E, shown in Fig. 3A and
copper extraction rate, r, shown in Fig. 3C, the relationship between the
copper extraction rate, r, and the redox potential, E, can be plotted as
(10) shown in Fig. 3D. In this figure, the peak behavior of chalcopyrite
leaching was observed. At low redox potentials, the leaching rate in-
creased with increasing redox potential and reached a peak (i.e., peak
rate, rp) while at higher redox potentials, the leaching rate decreased
with increasing redox potential. The peak rate, rp, was observed at
around 0.442 V and the redox potential value that gives the peak rate is
defined as peak redox potential, Ep, in this paper.
3.2. Effects of temperature
To examine the effects of temperature on the redox potential de-
pendence of chalcopyrite leaching, experiments were carried out at
various temperatures (298, 313 and 343 K). The concentration of HCl
(11) was 0.1 kmol m−3, and initial concentrations of both Fe3+ and Cu2+
were 0.01 kmol m−3.
Fig. 4A shows the relationship between the copper extraction rate
and redox potential at different temperatures. At all temperatures
evaluated, a peak redox potential was observed in the copper extraction
rate vs. redox potential plots and the peak rate increased with

6
N.T. Phuong Thao, et al. Hydrometallurgy 194 (2020) 105299

x 10-7
1.2
Cu 0.1 M A

Cu extraction rate, r / mol s-1 g-1

Cu 0.05 M
Cu 0.01 M
Cu 0.001 M
0.8

0.4

0.0
0.35 0.40 0.45 0.50
Redox potential, E / V

x 10-7
10 0.47
B C
rp / mol s-1 g-1

0.45
Ep / V

y = -7E-08x + 1E-07
0.43
R² = 0.9789
0.1 0.41
0.00 0.01 0.10 0.00 0.01 0.10

[Cu2+] / kmol m-3 [Cu2+] / kmol m-3

Fig. 7. Effects of cupric ion concentration on the redox potential dependence of chalcopyrite leaching: A copper extraction rate as a function of redox potential, B the
peak rate as functions of Cu2+ concentration, and C the peak redox potential as functions of Cu2+ concentration. (Conditions: temperature of 343 K, HCl con-
centration of 0.1 kmol m−3, initial Fe3+ concentration of 0.01 kmol m−3, a solid-to-liquid ratio of 0.3 g CuFeS2/15 ml, and agitation speed of 400 rpm).

increasing temperature. As illustrated in Fig. 4B, the temperature de-
pendence of the peak rate could be expressed using an Arrhenius-type
equation (Eq. (12)). From Fig. 4B, the value of Ea is estimated at
~85 kJ/mol.
E
rp = A exp ⎛− a ⎞
⎝ RT ⎠
where A is a constant, and Ea is the activation energy.
Fig. 4C shows the relationship between peak redox potential, Ep, and
temperature. The values of Ep were almost the same at different tem-
peratures, indicating that Ep is independent of the leaching tempera-
ture.
3.3. Effects of HCl concentration on chalcopyrite leaching
To examine the effects of HCl concentration on the redox potential
dependence of chalcopyrite leaching, experiments were carried out
with various HCl concentrations at 343 K. The initial concentrations of
Fe3+ and Cu2+ were 0.01 kmol m−3.
Fig. 5A shows the copper extraction rate vs. redox potential plot
obtained at different HCl concentrations. The results showed that HCl
concentration had a significant effect on the leaching rate. As shown in
Fig. 5B, the peak rate decreased with increasing HCl concentration.
Fig. 5C showed the relationship between peak redox potential, Ep, and
HCl concentration. The results showed that Ep did not change sig-
nificantly when HCl concentration varied, indicating that the value of
(12)
Ep is not affected by HCl concentration.
3.4. Effects of ferric ion concentration
The effects of Fe3+ concentration on the redox potential depen-
dence of chalcopyrite leaching were investigated by varying the initial
concentrations of Fe3+ at 343 K. The concentration of HCl was 0.1 kmol
m−3 and the initial concentration of Cu2+ was 0.01 kmol m−3.
Fig. 6A shows the copper extraction rate vs. redox potential plot
obtained with different initial Fe3+ concentrations. The leaching rate
increased with decreasing initial Fe3+ concentration.
Fig. 6C shows the relationship between the peak redox potential, Ep,
and initial Fe3+ concentration. The results showed that the Ep did not
change significantly when the initial Fe3+ concentration was varied.

7
N.T. Phuong Thao, et al.
0.46
y = 0.470 + 0.015 Log x
R2 = 0.999
0.45
Ep / V
0.44
15 mV / decade
0.43
0.00 0.01 0.10
Total [Cu2+] / kmol m-3
Fig. 8. Relationship between total Cu2+ concentration and peak redox poten-
tial (Ep) (Conditions: temperature of 343 K, HCl concentration of 0.1 kmol m−3,
initial Fe3+ concentration of 0.01 kmol m−3, a solid-to-liquid ratio of 0.3 g
CuFeS2/15 ml, and agitation speed of 400 rpm).
During the experiments, Fe3+ was reduced to Fe2+ according to Eq. (1).
Considering this, the results in Fig. 6C indicate that the peak redox
potential is independent of both Fe3+ and Fe2+ concentrations.
3.5. Effects of cupric ions concentration
To examine the effects of Cu2+ concentration on the redox potential
dependence of chalcopyrite leaching, experiments were carried out by
varying the initial concentrations of Cu2+ at 343 K. The concentration
of HCl was 0.1 kmol m−3 and the initial concentration of Fe3+ was 0.01
kmol m−3.
Fig. 7 shows the effects of Cu2+ concentration on the redox po-
tential dependence of chalcopyrite leaching. On the copper extraction
rate vs. redox potential plot (Fig. 7A), a shift of peak position was ob-
served when Cu2+ concentration was varied. Moreover, the peak
copper extraction rates were almost constant with different Cu2+ con-
centration (Fig. 7B) while the peak redox potential increased with in-
creasing Cu2+ concentration (Fig. 7C). The slope of the trend line in Ep
vs. Cu2+ concentration plot (Fig. 7C) is 10 mV/decade. During the
experiments, Cu2+ concentration increased with time due to the ex-
traction of copper from chalcopyrite. Because of this, when the redox
potential reached Ep, the concentration of Cu2+ in the solution was
different from the initial concentration. To account for this difference,
Cu2+ concentration was calculated by summing up the initial dosage
and extracted amounts of Cu2+. Considering this, the values of Ep are
plotted against the total Cu2+ concentration when redox potential
reached Ep (Fig. 8). In this figure, the experimental data can be fitted
with a straight line with a slope of 15 mV/decade.
As described above, the peak redox potential is independent of
temperature as well as the concentrations of HCl, Fe3+ and Fe2+. The
only factor that influenced the peak redox potential was Cu2+ con-
centration. From the results shown in Fig. 8, the value of peak redox
potential for chalcopyrite leaching in acidic ferric chloride solutions can
be expressed as a function of Cu2+ concentration (Eq. (13)).
Ep = 0.470 + 0.015Log[Cu2 +] (13)
4. Conclusions
The redox potential dependence of chalcopyrite leaching in acidic
ferric chloride solutions was investigated using a specially designed
batch leaching setup under different temperatures with varying con-
centrations of Fe3+, Cu2+ and HCl. From the redox potential data
8
Hydrometallurgy 194 (2020) 105299
recorded as a function of time, the amount of extracted copper was
calculated, and copper extraction rate vs. redox potential curve was
plotted.
In the copper extraction rate vs. redox potential curve, a peak be-
havior was observed; that is, the copper extraction rate increased with
increasing redox potential, reaching a maximum value (peak rate) at a
certain redox potential (peak redox potential). After this peak, the rate
decreased with increasing redox potential. The peak rate (rp) increased
with increasing temperature; however, it decreased with increasing HCl
and Fe3+ concentrations. Meanwhile, rp was not significantly affected
by Cu2+ concentration. The peak redox potential (Ep) was less depen-
dent on temperature and the concentrations of HCl, Fe3+ and Fe2+. A
major factor affecting Ep was Cu2+ concentration; that is, Ep increased
with increasing Cu2+ concentration, as shown in the following em-
pirical equation:
Ep = 0.470 + 0.015Log[Cu2 +]
Declaration of Competing Interest
None.
Acknowledgements
All persons who have made substantial contributions to the work
reported in the manuscript (e.g., technical help, writing and editing
assistance, general support), but who do not meet the criteria for au-
thorship, are named in the Acknowledgements and have given us their
written permission to be named. If we have not included an
Acknowledgements, then that indicates that we have not received
substantial contributions from non-authors.
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