Minerals Engineering 178 (2022) 107397

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

Kinetic limitations of gold leaching in ferric chloride media Part I: Batch

reactor studies
Kresimir Ljubetic , Wenying Liu *
Department of Materials Engineering, University of British Columbia, 309-6350 Stores Road, Vancouver, BC V6T 1Z4, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: The global gold industry is under increasing pressure to search for alternative technologies to replace cyanidation
Gold dissolution due to the inefficiency of cyanide in treating low grade refractory gold ores and increased public scrutiny on the
Gold-chloride complexation use of cyanide in gold mining. Chloride has been identified as a promising candidate to replace cyanide. Despite
Aqueous gold-iron-chloride speciation
extensive efforts to investigate gold leaching in chloride media, gold leaching in ferric chloride media at mod­
erate temperatures relevant to heap leaching has not been well studied. Sponsored by Barrick Gold Corporation,
we investigated the thermodynamics and kinetics of gold dissolution in ferric chloride media at moderate
temperatures using batch leaching and electrochemical techniques. The Part I of this study reports the effects of
four key process variables, initial ferric concentration, total chloride concentration, redox potential of the
leaching solution, and the type of chloride salts, on the rate and extent of gold dissolution in ferric chloride
media. A series of batch reactor leaching tests was carried out using pure gold as the model mineral. The
experimental results showed that the leaching process was either under thermodynamic or kinetic control
depending on the leaching conditions. The gold extraction increased with the initial ferric concentration up to
0.3 M, after which a negative effect was observed. This was thought to be caused by the transition from cathodic
reduction of the oxidant controlling the kinetics to anodic oxidation of gold controlling the kinetics. Increasing
total chloride concentration and the redox potential of the leaching solution also increased the gold extraction.
Gold extraction was higher in the presence of the monovalent salts than in the presence of the divalent salts.

1. Introduction double refractory, high preg-robbing ores at Goldstrike, Nevada (Choi,

Cyanidation is the most commonly used hydrometallurgical tech­
nique for extracting gold from gold bearing ores. However, the use of
cyanide is not effective in treating refractory sulfidic gold ores due to
excessive reagent consumption and unsatisfactory gold recovery (La
Brooy et al., 1994). The presence of preg-robbing carbon in carbona­
ceous gold ores renders cyanidation ineffective due to preferential
adsorption of gold cyanide complexes to carbonaceous materials
(Schmitz et al., 2001). Furthermore, the increasingly stringent envi­
ronmental regulations prompt several countries to ban the use of cya­
nide (Seisko et al., 2018). The combination of the above factors leads to
a great deal of efforts from both industry and academia to search al­
ternatives to cyanide.
The most studied alternatives are thiosulfate, thiourea, and halides
(Aylmore, 2016). Despite the progress made in the laboratory scale, no
commercial plants have been built using non-cyanide lixiviants, except
the thiosulfate leaching plant built by Barrick for the treatment of
2013; Miller et al., 2016). Among the alternatives studied, thiosulfate
seems to attract the most attention. However, the conditions for gold
leaching are relatively narrow due to the complex chemistry and the
instability and/or high consumption of this reagent (Hilson and Mon­
hemius, 2006; Senanayake, 2012; Zhang et al., 2021). Thiourea has also
been proposed as an alternative reagent, but its application has been
hindered due to potential carcinogenic properties and higher cost than
cyanide (Aylmore, 2005). Chloride is considered as a promising alter­
native to cyanide due to its low toxicity and potential applicability to
processing refractory sulfidic gold ores. Chlorination was the commer­
cial process for recovery of gold before cyanidation (Ferron et al., 2003).
Gold dissolution in chloride media has mostly been studied with
electrochemical techniques (Seisko et al., 2018). Despite the relevant
information provided by the electrochemical studies, fewer studies have
investigated the batch leaching of gold in ferric chloride media. Those
batch leaching studies focus on gold leaching in chloride media with
ferric as the oxidant at temperatures as high as 200 ◦ C and under

* Corresponding author.
E-mail address: wenying.liu@ubc.ca (W. Liu).

https://doi.org/10.1016/j.mineng.2022.107397
Received 18 August 2021; Received in revised form 3 January 2022; Accepted 6 January 2022
Available online 20 January 2022
0892-6875/© 2022 Elsevier Ltd. All rights reserved.
K. Ljubetic and W. Liu Minerals Engineering 178 (2022) 107397

pressure oxidation conditions (Liu and Nicol, 2002). The present by fixing the [Fe(III)]/[Fe(II)]. But the experimentally measured oxi­
research, sponsored by Barrick Gold Corporation, investigated the dation–reduction potential (ORP) of the solution slightly increased with
thermodynamics and kinetics of gold leaching in ferric chloride media at the initial ferric concentration, increasing by 8 mV at the highest ferric
moderate temperatures relevant to heap leaching using batch leaching concentration tested. This might be attributed to the increase in the ratio
and electrochemical techniques. The research findings are reported in of the actual oxidized/reduced couple. Conversely, for the tests at con­
Part I (batch reactor studies), Part II (electrochemical studies), and Part stant initial ferric concentration and Fe(III)/Fe(II) ratio, the solution
III (kinetic analysis). Part IV is a technical note briefly describing ORP slightly decreased with increasing chloride concentration. This was
leaching of an actual gold oxide ore in ferric chloride media. attributed to ferric ions forming complexes with chloride to a greater
This paper (Part I) presents the effects of four key process variables extent than ferrous ions (Muir, 2002).
on gold dissolution in ferric chloride media using batch reactor leaching.
The process variables studied are the initial ferric concentration, the 2.2. Material preparation
total chloride concentration, the redox potential of the leaching solu­
tion, and the type of chloride salts. Pure gold wire was used as a model The gold wire used in all experiments was of 99.95% purity and 0.1
mineral. Even though the experimental extraction of pure gold may not mm in diameter (0.15 g/m, Alfa-Aesar). The chemicals used were iron
be directly transferable to leaching of an actual gold ore, conducting (III) chloride hexahydrate (>99%, extra pure grade, Acros Organics),
batch leaching tests with gold wire is essential for gaining fundamental iron(II) chloride tetrahydrate (98%, Alfa Aesar), sodium chloride
understanding of the factors that limit gold leaching under different (>99%, Ward’s Science), potassium chloride (99.0–100.5%, BDH),
conditions. calcium chloride anhydrous (>91%, Ward’s science), magnesium chlo­
ride anhydrous (>98%, VWR), hydrochloric acid (36.5–38%, VWR), and
2. Experimental sodium hydroxide (>97%, Anachemia). All chemicals were of reagent
grade unless indicated differently. For ICP-OES analysis, a gold standard
2.1. Experimental design of 999 ± 2 mg/L (Sigma Aldrich) was used for standards preparation and
nitric acid (67–70%, Aristar plus grade VWR) was used for sample
The experimental objective was to quantify the effect of four process preservation. The following stock solutions were prepared: FeCl3 (100
variables: initial ferric concentration ([Fe(III)]), total chloride concen­ g/L), FeCl2 (10 g/L), KCl (250 g/L), CaCl2 (300 g/L), and MgCl2 (300 g/
tration ([Cl− ]T), solution redox potential (ORP), and the type of chloride L).
salts, on the leaching of gold in acidic ferric chloride media at constant
pH and temperature. The objective was achieved by conducting a series 2.3. Procedure for the batch leaching tests
of batch reactor leaching tests using pure gold wire as the model min­
eral. Table 1 summarizes the conditions under which these leaching tests For all experiments, a 500-mL jacketed reactor with a rubber stopper
were performed. All redox potentials were reported versus the standard was used. The agitation was set at 400 RPM and performed by a me­
hydrogen electrode (SHE). Using the rotating disk electrode method, Liu chanical agitator (Cole-Parmer model Ultra-Compact) with a 2-blade
and Nicol (2002) showed that it was ferric not dissolved oxygen that 1–5/8′′ diameter impeller coated with polypropylene to prevent corro­
acted as the actual oxidant for gold dissolution in ferric chloride solu­ sion. The temperature of the leaching system was maintained constant
tions at temperatures up to 100 ◦ C. Therefore, dissolved oxygen was not by circulating water through the jacketed reactor using a water bath
considered as a variable and electrolyte solution was not deaerated in (Fisher Scientific Isotemp GPD05).
this study. The pH value was chosen to be consistent with the studies The ferric to ferrous ratio of the leaching solution was adjusted by
carried out by Seisko et al. (2018). The temperature was fixed at 35 ◦ C to adding a calculated volume of a ferric chloride stock solution (100 g/L)
prevent ferric precipitation and to study gold extraction in a tempera­ and a ferrous chloride stock solution (10 g/L). The initial concentration
ture range relevant to heap leaching. of total iron in the leaching solution was analyzed by an ICP-OES
For the tests that studied the effect of the initial ferric concentration, (Agilent model 5110). The total chloride concentration was controlled
attempts were made to maintain the redox potential at a constant value by adding a calculated volume of a 300 g/L NaCl stock solution (or other
salts from stock solutions indicated in Section 2.2). A total volume of
250 mL of leaching solution at desired reagent concentrations was used
Table 1 for all tests. After transfer of the leaching solution, the temperature
Experimental conditions for the batch leaching tests to investigate the effect of control was started. For each test, a 4-cm length of gold wire (~6 mg)
process variables on gold dissolution in ferric chloride media. pH 1 and 35 ◦ C. was cut from the roll and weighed with an analytical balance (Entris 64I-
Leaching Initial [Fe [Fe Total Initial Type of 1S) at least four times to obtain the initial mass. Once the leaching so­
parameter (III)] as (III)]/ [Cl− ], M ORP, V vs chloride lution reached the desired temperature, the pH and ORP of the solution
FeCl3, M [Fe(II)] SHE salts
were measured. The initial pH was adjusted to 1 by adding HCl or NaOH.
[Fe(III)] 0.02 800 3 0.877 NaCl The gold wire was placed inside the reactor using a plastic spatula as a
0.05 0.878
holder ensuring the wire was immersed in the solution and not in contact
0.1 0.879
0.3 0.880 with the agitator. The leaching duration was set at seven days with the
0.5 0.883 wire mass measured on a daily basis. The solution pH and ORP were also
0.75 0.885 measured daily. After the ORP measurement, the probe was removed
[Cl− ]T 0.3 800 1 0.894 NaCl from the solution. Therefore, no platinum dissolution was expected.
1.5 0.889
2 0.886
2.5 0.882 2.4. Mass loss method and leachate analysis
3 0.88
ORP 0.3 13 3 0.773 NaCl Gold extraction over the course of leaching was calculated by a mass
34 0.798
loss method (Hojo et al., 2017). The initial mass of the gold wire prior to
89 0.823
236 0.849 leaching was first measured. Then the mass loss during leaching was
800 0.880 monitored by periodically removing the wire from the solution, rinsing
Type of 0.3 800 3 0.872 KCl it in an 18% HCl solution to remove the ferric chloride solution, drying it
chloride 0.884 CaCl2 manually with Kimwipes, and weighing it at least four times to obtain
salts 0.883 MgCl2
the average mass at specific leaching intervals. The mass loss was

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K. Ljubetic and W. Liu Minerals Engineering 178 (2022) 107397

calculated as the difference between the initial mass and the measured
average mass at a specific leaching time. The gold extraction was
calculated by the mass loss divided by the initial mass of the wire.
The mass loss method was corroborated by analyzing the gold con­
centration in the final leachate by ICP-OES to close the mass balance (Fu
et al., 2017). To prepare a leachate sample for ICP-OES analysis, 210 μL
of nitric acid (67–70%) was first added to a 10-mL volumetric flask, into
which the leachate sample was transferred to reach a final volume of 10
mL. Gold standards were prepared by adding 210 μL of nitric acid in a
10-mL volumetric flask, followed by addition of a calculated volume of
the 999 mg/L standard and a freshly prepared leaching solution of the
same composition as that used in the leaching test to reach the final
volume of 10 mL. Using the leaching solution as the standards matrix
minimized the background interference when analyzing gold concen­
tration at a wavelength of 242.794 and 267.594 nm. The standards were
prepared in the concentration range of 0 to 25 mg/L.
To estimate the rate of gold dissolution, the instantaneous area was
calculated with Eq. (1), considering a cylindrical geometry and
assuming unidirectional leaching. L is the length in cm, r0 is the initial Fig. 1. Average gold extraction as a function of time. Error bars showing the
radius of the wire in cm, ρAu is the molar density of gold in g/cm3, and m standard deviations of the three repeated tests under the condition of 0.3 M
is the mass loss at each leaching time in g. initial ferric, 3.0 M chloride, 0.880 V (i.e., Fe(III)/Fe(II) ratio of 800), pH 1,
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ and 35 ◦ C.
ρ π r2 L − m
A ≈ 2πL Au 0 + πr20 (1)
ρAu πL end of leaching using ICP-OES. The final gold extraction was then
A scanning electron microscope coupled with energy-dispersive X- calculated by multiplying the solution gold concentration and the so­
ray spectroscopy (FEI Quanta 650) was used to examine the changes in lution volume, divided by the initial mass of the gold wire. The gold
the morphology and elemental composition of the gold wire surfaces in extraction obtained by the two methods had a relative difference of 5%,
the course of leaching. which was calculated as the absolute difference between the value ob­
tained by the mass loss method and that obtained by the solution
analysis method divided by the value obtained by the mass loss method.
2.5. Test method reproducibility An additional test was selected for verification of the mass loss method
at 2.0 M chloride, with other conditions remaining the same as shown in
To verify the reproducibility of the test method, one leaching test was Fig. 1. The ICP-OES results showed a gold concentration of 3.00 × 10− 5
repeated in triplicate under the same conditions: 0.3 M initial ferric, 3.0 M (5.91 mg/L) and the mass loss method obtained a value of 2.88 × 10− 5
M total chloride (NaCl), initial potential 0.880 V, (corresponding to Fe (5.67 mg/L), corresponding to a relative difference of 4% in the gold
(III)/Fe(II) ratio of 800), pH 1, and 35 ◦ C. The average gold extraction at extraction obtained by the two methods. Therefore, the mass loss
a specific leaching time was calculated using the average mass loss ob­ method was deemed valid and used to obtain the cumulative gold
tained from the three repeated tests, as shown by Eq. (2). The standard extraction data throughout this study.
deviation of the mass loss at a specific leaching time was calculated To confirm the occurrence of gold dissolution, the surfaces of the
according to Eq. (3), which was then converted to the standard deviation gold wire prior to leaching and after exposure to the leaching solution
of the gold extraction at a specific leaching time. were examined by a scanning electron microscope (SEM). Fig. 2 shows
∑3 that after 7 days of being subjected to the leaching solution, the gold
x = i=1
xi
(2) wire surface was corroded and became rough. The SEM images were
3 consistent with the experimental results shown in Fig. 1, suggesting that
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ gold was dissolved in the acidic ferric chloride solution under the con­
∑3
i=1 (xi − x)
2
ditions tested.
s= (3)
3− 1

In Eqs. (2) and (3), xi is the mass loss at a specific leaching time, x is
the average mass loss of the three repeated tests at that leaching time,
and s is the sample standard deviation.
3. Results and discussion
3.1. Test method reproducibility
Fig. 1 shows the average gold extraction over time, with error bars
showing the standard deviation of the data. The average standard de­
viation of the gold extraction, i.e., the average of all standard deviations
at specific leaching times, was calculated to be 1.8%. Therefore, the 95%
confidence interval was calculated to be ±3.5%. Any observed differ­
ence in extraction greater than ±3.5% was deemed statistically
significant.
This set of test conditions was also selected to verify the validity of
the mass loss method by the solution analysis method. The solution
analysis method involved analyzing gold concentration in solution at the
3.2. Effect of different leaching variables on gold extraction
3.2.1. Effect of the initial ferric concentration
Fig. 3(a) shows the gold extraction over time at different initial ferric
concentrations with a fixed Fe(III)/Fe(II) ratio of 800 and a total chlo­
ride concentration of 3.0 M. Fig. 3(b) shows gold dissolution in µmol per
unit area. These values were calculated based on instantaneous surface
area of gold available for leaching, which increases as leaching pro­
gresses. The experimental results indicated that increasing ferric con­
centration up to 0.3 M led to an increase in the gold dissolution. Further
increase in the initial ferric concentration had a detrimental effect on the
gold extraction. It was hypothesized that the highest extraction obtained
at 0.3 M Fe(III) was associated with the transition of kinetic control from
the cathodic reduction of Fe(III) on the gold surface to the anodic
oxidation of gold. Part II of this research studied in detail the kinetics of
the cathodic and anodic processes using electrochemical techniques.
The corresponding pH and ORP changes during leaching are shown
in Fig. 3(c) and (d), respectively. When the initial ferric concentration

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K. Ljubetic and W. Liu Minerals Engineering 178 (2022) 107397

Fig. 2. SEM images of the gold wire surfaces: (a) prior to leaching; (b) after 7 days of leaching under conditions: 0.3 M initial ferric, 3.0 M chloride and 0.880 V (i.e.,
Fe(III)/Fe(II) ratio of 800), pH 1 and 35 ◦ C.

Fig. 3. (a) Gold extraction over time at different initial ferric concentrations; (b) Gold dissolution in µmol/cm2; (c) Change in the solution potential over time; (d) pH
change over time. Leaching conditions: initial Fe(III)/Fe(II) ratio of 800 (0.880 V), 3.0 M total chloride, initial pH 1, and 35 ◦ C.

Fig. 4. Liquid samples collected at the end of 7 days of leaching at different initial ferric concentrations. Leaching conditions: initial Fe(III)/Fe(II) ratio of 800 (0.880
V), 3.0 M total chloride, initial pH 1, and 35 ◦ C.

4
K. Ljubetic and W. Liu
was in the range of 0.02 to 0.1 M, the solution ORP decreased in the
course of leaching. The maximum drop of 27 mV was observed at the
lowest Fe(III) concentration tested (0.02 M). In this ferric concentration
range, the solution pH remained constant throughout leaching, sug­
gesting that Fe(III) precipitation, which generates acid, occurred to a
minimal extent. There were no discernible iron precipitates in the
leachates, as shown by the images in Fig. 4. Further analysis of the total
iron concentration in solution by ICP confirmed that the Fe(III) loss was
less than 1% of the initial Fe(III) added. This level of precipitation is
insufficient to cause a significant drop in the redox potential. However,
as shown by the Nernst equation, at a low ferric concentration (0.02 M)
and a very high ferric/ferrous ratio (8 0 0), the redox potential of the
ferric/ferrous couple is sensitive to the conversion of ferric to ferrous
ions. The largest drop observed at 0.02 M initial Fe(III) was attributed to
the sensitivity of the redox potential to the conversion of ferric to
ferrous.
In contrast, at 0.5 M and 0.75 M initial Fe(III), the solution ORP
remained constant, but the pH decreased from 1 to 0.87 for 0.5 M Fe(III)
and to 0.67 for 0.75 M Fe(III) after seven days of leaching. The decrease
in pH suggested that iron precipitation occurred to a certain extent,
which was visually observed in the images shown in Fig. 4. The analysis
of the total iron concentration in solution by ICP confirmed that the total
iron loss was 4.2% at 0.5 M initial Fe(III) and 10.9% at 0.75 M initial Fe
(III). At 0.3 M initial Fe(III), the gold extraction was the highest and the
solution ORP and pH remained constant during leaching, even though
2.9% of the initial Fe(III) was confirmed to precipitate. Therefore, 0.3 M
was chosen as the standard initial Fe(III) concentration for all subse­
quent leaching tests. These results indicate that applying higher initial
ferric concentrations is essential for preventing the redox potential to
drop significantly when a high ferric to ferrous ratio is used.
Fig. 5. Effect of the total chloride concentration on gold dissolution at 0.3 M ferric, Fe(III)/Fe(II) of 800, pH 1, and 35 ◦ C: (a) Gold extraction; (b) Gold dissolution in
µmol/cm2; (c) Solution potential; (d) pH over time.
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Minerals Engineering 178 (2022) 107397
3.2.2. Effect of the total chloride concentration
It has been shown that the total chloride concentration influences the
thermodynamics of both the anodic gold oxidation and the cathodic
ferric reduction. On the one hand, increasing chloride concentration
lowers the reduction potential of the AuCl2− /Au couple, enabling the
dissolution of gold at lower potentials (Kelsall et al., 1993). On the other
hand, increasing chloride concentration slightly decreases the ORP of
the Fe(III)/Fe(II) couple due to the stronger complexation of chloride
with ferric than with ferrous ions (Hashemzadeh and Liu, 2019). To
investigate the effect of the total chloride concentration on the kinetics
of gold leaching, a set of leaching tests was carried out at varying
chloride concentrations in the range of 1.0 to 3.0 M, a constant initial
ferric concentration of 0.3 M, the ferric/ferrous ratio of 800, pH 1, and
35 ◦ C.
Fig. 5(a) and (b) show that increasing the total chloride concentra­
tion had a positive effect on the kinetics of gold extraction when other
leaching parameters were fixed. Solution ORP values remained constant
during leaching for all total chloride concentrations tested. Despite the
slight decrease in the ORP of the Fe(III)/Fe(II) couple with increasing
chloride concentration, the overall effect was that a higher chloride
concentration was associated with a faster kinetics and a higher gold
extraction.
3.2.3. Effect of ORP
The redox potential of a leaching solution is a key factor in con­
trolling gold dissolution behavior in chloride media (Viñals et al., 1991).
To experimentally evaluate the effect of redox potential on the kinetics
of gold leaching, a set of leaching tests was carried out at different po­
tentials with a constant total chloride concentration of 3.0 M, pH 1, and
35 ◦ C. The potential was adjusted by varying the ferrous concentration
K. Ljubetic and W. Liu Minerals Engineering 178 (2022) 107397

Fig. 6. Effect of solution ORP on gold dissolution at 0.3 M ferric, 3.0 M chloride, pH 1, and 35 ◦ C: (a) Gold extraction; (b) Gold dissolution in µmol/cm2; (c) Solution
potential over time.

at a fixed ferric concentration of 0.3 M. dissolution at potentials lower than 0.823 V. When the potential was
Fig. 6 shows the effect of the ORP on gold extraction and dissolution increased to 0.849 V, 18.5% extraction was obtained at the end of the
per unit area for seven days of leaching. There was negligible gold leaching test. Further increase in the solution potential to 0.880 V led to

Fig. 7. SEM images of gold wire after exposure to 0.3 M ferric, 3.0 M chloride, pH 1 and 35 ◦ C at different initial ORP: (a) 0.773 V; (b) 0.798 V; (c) 0.823 V; (d) 0.849
V; (e) 0.880 V.

6
K. Ljubetic and W. Liu
an extraction of 40.7%. The kinetics of gold leaching was faster at higher
potentials. The SEM images in Fig. 7 show that as the solution ORP was
increased, the surfaces of the gold wire became rougher, which was in
line with the higher extraction reported in Fig. 6.
3.2.4. Effect of the type of chloride salt
To investigate the effect of the type of chloride salts on the leaching
kinetics, batch leaching tests were carried out in the presence of four
different chloride salts: NaCl (baseline), KCl, CaCl2 and MgCl2. They
were added into the leaching solution to achieve a fixed total chloride
concentration of 3.0 M. Other leaching parameters were kept constant:
0.3 M initial Fe(III), ferric to ferrous ratio of 800, pH 1, and 35 ◦ C.
Fig. 8(a) and (b) show that the rates of gold extraction with the
monovalent salts were much higher than those with the divalent salts. In
addition, the final extractions at the end of seven days of leaching were
also much higher with the monovalent salts. Between the two mono­
valent salts, the initial leaching kinetics with NaCl was faster than with
KCl. For the two divalent salts, MgCl2 was associated with a faster initial
kinetics than CaCl2. The results of these tests show that the kinetics of
gold leaching in ferric chloride media is dependent not only on the free
chloride concentration, but also on the type of chloride salt added to the
solution.
The solution pH and potential were measured over the course of
leaching (Fig. 8(c) and (d)) to determine whether the presence of
different chloride salts affected their behavior. In the presence of the
monovalent salts, the pH of the solution remained constant, whereas in
the presence of the divalent salts, pH gradually decreased. The divalent
salts seemed to promote iron precipitation, resulting in a decrease in pH.
The different extent of iron precipitation was attributed to the difference
in the salting-out effect. Rieger (1994) described a series of cations that
Fig. 8. (a) Effect of the type of chloride salts on gold dissolution at 0.3 M ferric, 3.0 M chloride, [Fe(III)]/[Fe(II)] of 800, pH 1, and 35 ◦ C: (a) Gold extraction; (b)
Gold dissolution in µmol/cm2; (c) Solution potential; (d) pH over time.
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Minerals Engineering 178 (2022) 107397
show decreasing salting-out effect: Mg2+ > Ca2+ > Na+ > K+. Magne­
sium chloride is depicted as a strong salting-out agent due to its high
solubility. ICP analysis of the solution at the end of leaching confirmed
the decreasing percentage of the total iron precipitated: 8.7% with
Mg2+; 8.3% with Ca2+; 2.9% with Na+; 2.0% with K+. As higher levels of
iron precipitation were observed with the divalent cations, it was hy­
pothesized that the iron precipitates could coat the wire surfaces pre­
venting further dissolution. As shown by Ljubetic (2021), the SEM-EDS
analysis of the wire surface showed no traces of iron present on the wire
surfaces. Given that the resolution of EDS was 1–2 μm in depth, the
precipitate layer might be too thin to be detected. Additional tests were
done where the wire surface was polished at the end of leaching to
remove any possible solid layer formed and placed back into the original
leaching solution. This treatment did not improve gold extraction,
indicating that iron precipitation was not responsible for the different
leaching kinetics observed.
3.3. Thermodynamic and kinetic limitations
To determine whether a leaching process is under thermodynamic or
kinetic control at specific leaching conditions, the soluble gold con­
centration experimentally determined at the end of leaching was
compared with that predicted by the thermodynamic calculations. If the
concentration experimentally determined approximates the equilibrium
value calculated, the leaching process is considered to reach equilibrium
and is thermodynamically controlled. If the concentration experimen­
tally determined is lower than the equilibrium value calculated, the
process does not reach equilibrium and is kinetically controlled. The
experimental gold concentration was determined in the range of
extraction where the leaching curve plateaued. This was done by
K. Ljubetic and W. Liu
averaging the two consecutive extraction values whose difference was
within the 95% confidence interval.
The equilibrium gold concentration at a constant temperature is
determined by two fundamental factors: the redox potential of the
oxidizing agent and the activity of free chloride. The gold dissolution
process reaches equilibrium when the redox potential of the AuCl2− /Au
couple is equal to the redox potential of the Fe(III)/Fe(II) couple, to
which an experimentally measured value is assigned. Take 0.3 M initial
Fe(III) and 3.0 M total chloride as an example. By equating EAuCl−2 /Au to
the measured solution potential of 0.880 V and using the corresponding
free chloride activity of 1.5985 obtained with speciation calculations
(Ljubetic, 2021), the gold concentration at equilibrium was determined
to be 9.17 × 10− 5 M. This concentration is the theoretical maximum
soluble gold concentration attainable at this specific set of conditions.
Similar calculations were done to determine the equilibrium gold con­
centration for all four variables studied.
• Thermodynamic or kinetic control at different initial Fe(III)
concentrations
Fig. 9(a) compares the experimental gold concentrations with the
equilibrium values calculated at different initial ferric concentrations
and a fixed total chloride concentration of 3.0 M. The equilibrium
concentration decreases with increasing initial ferric concentration due
to the decrease in the free chloride activity resulting from increasing
levels of ferric-chloride complexation. As the initial ferric concentration
was raised, the experimental concentration moved closer to the equi­
librium concentration. In the ferric concentration range of 0.02 to 0.5 M,
the experimental concentrations were lower than the equilibrium
values, suggesting that the process did not reach equilibrium and the
Fig. 9. Comparison of the soluble gold concentrations experimentally obtained with the calculated equilibrium values: (a) at different initial ferric concentrations;
(b) at different total chloride concentrations; (c) at different ORP; (d) in the presence of different chloride salts.
8
Minerals Engineering 178 (2022) 107397
process is restricted by kinetics. At the highest ferric concentration
tested (0.75 M), the experimental concentration approximated the
equilibrium value, indicating that the leaching process reached equi­
librium and the process is limited by thermodynamics.
In the ferric concentration range (0.02–0.5 M) where leaching is
limited by kinetics, the leaching process exhibited distinctive kinetic
behavior in the lower and higher ferric concentration ranges. In the
lower concentration range of 0.02–0.3 M, the initial leaching rate
increased with the initial ferric concentration. Because this increase in
the leaching rate corresponds to the increase in the activity of FeCl2+,
the leaching kinetics was considered to be controlled by the cathodic
reduction of FeCl2+, i.e., the rate being greater at a higher FeCl2+ ac­
tivity. In this concentration range, the leaching kinetics did not respond
to the decrease in the chloride activity. In contrast, in the higher con­
centration range of 0.3–0.5 M, the gold extraction rate decreased with
increasing initial ferric concentration. This decrease was attributed to
the transition of the leaching kinetics from cathodic to anodic control, i.
e., the oxidation of gold to AuCl2− , which was slowed down by the
decrease in the chloride activity caused by complexation.
• Thermodynamic or kinetic control at different total chloride
concentrations
Fig. 9(b) compares the experimental gold concentrations with the
equilibrium values calculated at different total chloride concentrations
and a fixed initial ferric concentration of 0.3 M. The equilibrium gold
concentration increases with the total chloride concentration resulting
from the increase in the chloride activity. When the total chloride con­
centration was less than 1.5 M, the experimental gold concentration
approached the equilibrium value, indicating that leaching reached
K. Ljubetic and W. Liu
equilibrium and the process is controlled by thermodynamics. At total
chloride concentrations higher than 1.5 M, the leaching process is
restricted by kinetics, as supported by the experimental gold concen­
trations being lower than the equilibrium values. In the region of kinetic
control, the leaching kinetics was controlled by the anodic oxidation of
gold because the ferric concentration used (0.3 M) was in the region of
anodic control. The leaching rate increased with the increase in the total
chloride concentration due to the concurrent increase in the free chlo­
ride activity.
• Thermodynamic or kinetic control at different solution potential
Fig. 9(c) compares the experimental gold concentrations with the
equilibrium values calculated at different solution potentials, 0.3 M
initial ferric, and 3.0 M total chloride. At below 0.823 V, the potential
was too low for gold dissolution to occur and therefore the leaching is
limited by thermodynamics. When the potential was higher than 0.823
V, the experimental gold concentrations were lower than the equilib­
rium values, indicating that the process transitioned to kinetic control.
In the potential range where kinetics controls the gold dissolution, the
dissolution rate was faster at higher potentials. This could be explained
by the process being controlled by the anodic oxidation of gold at 0.3 M
initial ferric, the rate of which was rendered faster by an increase in the
solution potential.
• Thermodynamic or kinetic control with different types of chloride
salts
Fig. 9(d) compares the experimental gold concentrations with the
equilibrium values calculated with different types of chloride salts, a
fixed initial ferric concentration of 0.3 M, and 3.0 M total chloride. As
expected, the equilibrium concentration is proportional to the activity of
free chloride, with the highest equilibrium concentration calculated
with MgCl2 due to the highest free chloride activity (2.1171) and the
lowest equilibrium concentration calculated with KCl due to the lowest
chloride activity (1.3869). In the case of KCl, the experimental gold
concentration approached the equilibrium value and therefore leaching
is likely to be limited by thermodynamics. For the other three chloride
salts tested, the experimental concentrations were lower than the
equilibrium values, supporting that leaching is limited by kinetics. Even
though the soluble gold concentrations at equilibrium were higher with
the divalent salts, the actual experimental concentrations measured
were much lower and the kinetics was also much slower than with NaCl.
More importantly, the gold extraction curves plateaued prior to
completion in all leaching tests performed at 35 ◦ C. Crundwell and
Godorr (1997) proposed that the surface of gold during cyanidation can
be passivated by an adsorbed layer of the intermediate, AuCNads, the
formation of which has little influence on the reaction kinetics in the
initial stages but has a dominant influence in the later stages of leaching.
As proposed by Diaz et al. (1993), the dissolution of gold in chloride
media also involves the formation of an adsorbed intermediate, AuClads.
Its accumulation on the wire surfaces as leaching progressed may have
eventually led to a halt in the leaching reaction.
4. Conclusions
The feasibility of using acidic ferric chloride media for gold leaching
was proved by performing a series of batch leaching tests by varying four
variables: initial ferric concentration, total chloride concentration, so­
lution potential, and the type of chloride salts used. The gold extraction
increased with the initial ferric concentration up to 0.3 M, after which a
negative effect was observed. Increasing the total chloride concentration
in the range investigated had a positive effect on the gold dissolution.
The solution ORP must be raised to higher than a threshold value,
beyond which gold dissolved with faster kinetics at a higher potential.
The gold extraction was much higher with the monovalent salts than
9
Minerals Engineering 178 (2022) 107397
with the divalent salts. The leaching process was either under thermo­
dynamic or kinetic control depending on the leaching conditions.
The following kinetic mechanisms were proposed. In the ferric
concentration range of 0.02 to 0.3 M, the process was controlled by the
cathodic reduction of FeCl2+, the rate of which increased with the ac­
tivity of FeCl2+. In the ferric concentration range of 0.3 to 0.5 M, the
leaching process transitioned to be controlled by the anodic oxidation of
gold, the kinetics of which decreased with decreasing free chloride ac­
tivity resulting from increasing levels of ferric-chloride complexation.
When the total chloride concentration was sufficiently high, the leach­
ing kinetics was controlled by the anodic oxidation of gold and the
leaching rate increased with the total chloride concentration. Beyond
the threshold value of ORP, the leaching process was controlled by the
anodic dissolution of gold and the rate of leaching increased with the
solution potential.
Regardless of the mechanisms by which the variables investigated
affected the kinetics of gold leaching in ferric chloride media, the
leaching process did not progress to completion under all experimental
conditions studied. It was hypothesized that the plateauing of the
leaching curves was caused by the formation of the reaction interme­
diate, AuCNads. The adsorption and accumulation of this species on the
gold wire surface may have affected the charge transfer process on the
gold electrode surface, leading to the termination of the leaching pro­
cess. Part II of this research investigated the formation and solubilization
of the adsorbed species on gold electrode surface using electrochemical
techniques (Ljubetic, 2021).
CRediT authorship contribution statement
Kresimir Ljubetic: Data curation, Formal analysis, Investigation,
Methodology, Visualization, Writing – original draft. Wenying Liu:
Conceptualization, Funding acquisition, Project administration, Super­
vision, Validation, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors acknowledge the financial support of Barrick Gold
Corporation through the Mitacs Accelerate Program (IT07402).
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