Hydrometallurgy 149 (2014) 1–11

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

Study of thiosulfate leaching of silver sulfide in the presence of EDTA and

sodium citrate. Effect of NaOH and NH4OH
D.M. Puente-Siller, J.C. Fuentes-Aceituno ⁎, F. Nava-Alonso
Centro de Investigación y de Estudios Avanzados del IPN Unidad Saltillo, Av. Industria Metalúrgica 1062, Parque Industrial Saltillo Ramos Arizpe, Ramos Arizpe, Coahuila 25900, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: In this research, an analysis of the effect of NaOH and NH4OH on the silver sulfide leaching kinetics was per-
Received 25 October 2013 formed using thiosulfate–copper solutions in the presence of EDTA and sodium citrate, in order to develop
Received in revised form 20 May 2014 an alternative green hydrometallurgical process for the sustainable recovery of precious metals. For that
Accepted 13 June 2014
purpose, silver sulfide leaching experiments were carried out with different thiosulfate–copper solutions
Available online 6 July 2014
at room temperature. The different copper species present in the leaching systems were elucidated with
Keywords:
the aid of species distribution thermodynamic diagrams. The solid residues of all leaching experiments
Silver leaching were morphologically and chemically characterized by Scanning Electron Microscopy (SEM) and Energy
Thiosulfate Dispersive X Ray Spectroscopy (EDXS), in order to identify the solid products formed, and to elucidate
EDTA the effect of the morphology of the solid and its composition on the silver sulfide leaching kinetics. The re-
Citrate sults of this study showed that the cupric tetraamine complex (Cu(NH3)24 +), generated by the NH4OH pres-
Silver sulfide ence in the leaching solutions containing EDTA or citrate, enhances the silver leaching kinetics. The
ammoniacal–citrate and ammoniacal–EDTA system showed the formation of a porous layer composed by
copper oxides and copper sulfides on the silver sulfide particle. The ammoniacal–citrate system presented
a degradation of thiosulfate which inhibits the silver sulfide leaching kinetics. On the other hand, when the
sodium hydroxide is employed, the complexes Cu(EDTA)OH3 − and Cu2(cit)2OH3 − are formed and play a
similar role to that of the Cu(NH3)2+ 4 in systems containing ammonium hydroxide. The solid residues pre-
sented a porous layer composed by copper oxides and copper sulfides through which the fluid reactants
have to diffuse in order to leach the silver, with the NaOH–EDTA and NaOH–citrate systems. This research
also reveals that the thiosulfate–copper–NaOH–citrate system could be a promising alternative process to
leach silver from silver sulfide.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction mechanism is by a chemical substitution reaction between cuprous or

The gold and silver thiosulfate leaching has been studied extensive-
ly during the last decades (Aylmore, 2001; Aylmore and Muir, 2001;
Baláz et al., 2000; Breuer and Jeffrey, 2003; Fuentes-Aceituno et al.,
2005; Lam and Dreisinger, 2003; Muir and Aylmore, 2005; Senanayake,
2005; Zipperian and Raghavan, 1988), and can be considered as an al-
ternative green process to the conventional cyanidation (Abbruzzese
et al., 1995). The last investigations have revealed the high efficiency
of the thiosulfate–copper–ammonia leaching solutions: the precious
metals can be recovered from sulfide ores in 48 h. However, the reac-
tion mechanism in this leaching system has been proved to be very
complicated. Basically, the next issues are known: the thiosulfate is
employed as the precious metal complexing agent, cupric ions (Cu2+)
are the oxidizing agent for silver and gold, and ammonia stabilizes
the cupric ions in solution avoiding their precipitation. On the other
hand, according to Eqs. (1) and (2), the silver sulfide leaching
⁎ Corresponding author. Tel.: +52 844 438 9600x8512.
E-mail address: juan.fuentes@cinvestav.edu.mx (J.C. Fuentes-Aceituno).
cupric ions and the silver contained in the sulfide matrix, producing a
thiosulfate–silver complex (Aylmore and Muir, 2001):
þ þ 2− 3−
2Cu þ Ag2 S→2Ag þ Cu2 SðChalcociteÞ þ 4S2 O3 → 2AgðS2 O3 Þ2 ð1Þ
2þ þ 2− 3−
Cu þ Ag2 S→2Ag þ CuSðCoveliteÞ þ 4S2 O3 →2AgðS2 O3 Þ2 : ð2Þ
Other authors (Alonso and Lapidus, 2009; Alonso et al., 2007;
Feng and Van Deventer, 2010, 2011; Fuentes-Aceituno et al., 2005;
Puente-Siller et al, 2013) have proposed the EDTA as an additional
complexing agent for copper, which has the ability to maintain the
cupric ion species in solution for longer time. Despite the improve-
ment found in the gold and silver leaching kinetics at low EDTA
concentrations (Feng and Van Deventer, 2011; Puente-Siller et al.,
2013), the EDTA has the disadvantage to produce many multimetal-
lic complexes when it is in contact with the ore. Consequently, the
EDTA consumption and the process cost are increased. Therefore,

http://dx.doi.org/10.1016/j.hydromet.2014.06.004
0304-386X/© 2014 Elsevier B.V. All rights reserved.
2 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11

Table 1
Gibbs free energy of formation and Log K for thiosulfate, copper, EDTA and citrate species used in the construction of thermodynamic diagrams.

Chemical species ΔG0298 (KJ/mol) Reference

H2S2O3 −543.5 Aylmore and Muir (2001)

HS2O3 −541.8
S−2
2 79.7
S−2
3 73.8
S−2
4 69.4
S−2
5 66.1
S2O−2
4 −600.6
S3O−2
6 −958.0
S5O−2
6 −956.0
HS2O− 4 −434.2
H2S2O4 −436.3
−2
S2O6 −966.0
S2O−2
8 −1115.0
S4O−2
6 −1040.4
SO−2
3 −486.5
H2S −27.3
S−2 91.9
HS− 12.6
Cu(S2O3)− −540.991
Cu(S2O3)5−
3 −1624.65
Cu(S2O3)3−
2 −1084.07
Cu(NH3)+2
2 −32.259
Cu(NH3)+2
3 −73.212
Chemical reactions Log K
2+
Cu + 4NH3 = Cu(NH3)2+ 4 12.464
Cu2+ + H2O = 2H+ + CuO −7.876
Cu + EDTA = Cu(EDTA)2−
2+ 4−
20.57 Software Medusa©
Cu2+ + EDTA4− + H2O = H+ + Cu(EDTA)OH3− 8.5
2Cu2+ + 2Cit3- + H2O = H+ + Cu2(Cit)2OH3− 13.3

the search of new alternative complexing agents for copper is neces-
sary; for example, the amino acids can be an interesting alternative,
because they are cheaper, efficient and more selective than EDTA
(Feng and Van Deventer, 2011).
Sodium citrate, in alkaline solutions, has the ability to produce
strong metallic complexes with a wide range of heavy metals such as
Cu (II), Ni(II), Co(II), Pb(II) and Fe(III); for that reason it is often used
as an effective complexing agent (Gyliene et al., 2004).
Several studies have demonstrated the formation of Cu–citrate
complexes (Hong et al., 2007). In this sense, alkaline citrate solutions
(pH 8–11) at a temperature range from 30 to 50 °C can be employed
to complex high concentration of cupric ions in the form of a stable
Cu (II)–citrate species. The Cu (II)–citrate complex concentration is
favored when the pH is increased (Eskhult et al., 2008).
Silva et al. (2012) have found a high silver leaching kinetics with
the citrate–thiosulfate system at acid conditions; on the other hand,
Deutsch and Dreisinger (2013) proposed the use of citrate for
complexing the iron instead of copper in acid solutions; they found
that the thiosulfate decomposition can be reduced in this alternative
thiosulfate–citrate–iron system. Senanayake and Zhang (2012) demon-
strated an increase in the thiosulfate leaching efficiency at an alkaline
pH, when ammonium hydroxide is added to the leaching solution to
increase the pH and to complex the copper, the silver leaching kinetics
increases (Aylmore, 2001; Breuer and Jeffrey, 2000; Briones and
Lapidus, 1998; Puente-Siller et al., 2013).
According to Aylmore and Muir (2001), the gold dissolution in
the thiosulfate systems is passivated by a sulfide layer due to the
absence of ammonium hydroxide and to the oxidative decomposi-
tion of thiosulfate. This suggests that the ammonium species are
preferentially adsorbed on the gold surface avoiding its passivation.
However, ammonium hydroxide has a negative impact in the envi-
ronment; therefore Fuentes-Aceituno et al. (2005) tried to replace
the ammonium hydroxide by caustic soda (NaOH) employing thio-
sulfate–copper–EDTA solutions. The authors observed slower silver
leaching kinetics with NaOH than with NH4OH.
In this research, the silver sulfide leaching with thiosulfate–copper
systems containing NaOH or NH4OH was evaluated. The effect of EDTA
and sodium citrate in the silver sulfide leaching kinetics was also evalu-
ated. This information is important in order to find suitable conditions
to carry out the silver sulfide dissolution in a sustainable manner.

2. Materials and methods

For the silver sulfide leaching tests, different thiosulfate systems

Fig. 1. Effect of EDTA and citrate on silver sulfide leaching in the presence of ammoni-
um hydroxide (0.1435 g silver sulfide (− 300 + 400 mesh), 200 mL solution, 0.2 M
thiosulfate, 0.05 M Cu(II), 0.025 M EDTA or sodium citrate, 0.6 M NH4OH, pH 10.2,
room temperature and 400 min−1).
were evaluated employing ammonium or sodium hydroxide with
EDTA or sodium citrate as cupric ion complexing agents. Species
distribution diagrams were constructed for each system and a
 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 2. Distribution of copper species at different pH values for the S2O3–Cu–NH3–EDTA–H2O system. The conditions for the diagram construction were 0.2 M S2O3, 0.025 M EDTA, 0.05 M
Cu(II), 0.6 M NH4OH and EH = 0.46 V at 25 °C.
microstructural characterization of the solid residues obtained in the
leaching tests was carried out.
2.1. Leaching tests
All silver sulfide leaching experiments were performed in an agi-
tated batch reactor (250 mL glass beaker), magnetically stirred at
400 min− 1 during 5 h. The reactor was provided with a pH electrode
(SENSOREX) and a redox potential electrode with calomel reference
(Cole-Parmer). The general procedure for the leaching experiments
was as follows: 200 mL of the solution containing 0.2 M, 0.25 M or
0.3 M thiosulfate, 0.05 M cupric sulfate and 0.025 M EDTA (or sodium
citrate) as cupric ion complexing agents were placed in the reactor at
25 °C. All solutions were prepared with reagent grade chemicals and
deionized water, and the pH value was adjusted at 10.2 with ammo-
nium or sodium hydroxide. After adjusting pH, 0.1435 g of Ag2S (Alfa
Aesar, 99.99%, − 300 + 400 mesh or − 400 + 500 mesh) was placed
in the reactor while stirring. The pH and redox potential were mea-
sured before the silver sulfide addition and during the leaching
experiments. Samples of the leach solution were withdrawn at dif-
ferent times during the leach period for analysis of silver and copper
by atomic absorption spectrophotometry (VARIAN Spectra AA 240).
All samples for silver and copper analyses were analyzed at the end of
Fig. 3. Distribution of copper species at different pH values for the S2O3–Cu–NH3–Citrate–H2O system. The conditions for the diagram construction were 0.2 M S2O3, 0.025 M Citrate, 0.05 M
Cu(II), 0.6 M NH4OH and EH = 0.48 V at 25 °C.
3
the experiment, and until the analysis they were kept in dark vessels to
prevent the precipitation of silver by light. Once the experiment was con-
cluded, the residue was filtered, rinsed with deionized water and left to
air dry. The liquor solution containing 0.2 M thiosulfate, 0.05 M cu-
pric sulfate and 0.025 M sodium citrate was placed in the reactor
with 0.1435 g of fresh Ag2S (− 300 + 400 mesh) at 25 °C using the
same methodology described above, in order to evaluate its silver
leaching ability in a second step and the possible decomposition of
thiosulfate in this used solution. Samples of the solid residues were
digested in nitric acid solutions to complete the metallurgical
balances.
2.2. Elaboration of the thermodynamic diagrams
In order to elucidate the predominant copper species in each lea-
ching system, species distribution diagrams were constructed using
the Medusa© Software. The diagrams were constructed considering
the equilibrium data contained in the Hydra database of the Medusa©
suite software (Puigdomenech, 2004), complemented with thermody-
namic data reported by Aylmore and Muir (2001). The software is
based in an algorithm developed by Eriksson (1979), which minimizes
the Gibbs free energy of reactions in equilibrium that can occur in the
aqueous leaching systems, and determines the predominating species
4 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 4. Scheme of the silver sulfide leaching with the thiosulfate–copper–ammonia system in the presence of EDTA or sodium citrate.
under specific solution conditions. Table 1 presents the Log K data used
in this work.
2.3. Microstructural characterization
In order to confirm the generation of solid products on the silver
sulfide surface; the solid residues obtained in the leaching tests were
characterized by SEM (Phillips XL30ESEM), and the local chemical com-
position of the residues was determined by EDXS (EDAX Genesis), some
solid residues were mounted in epoxy resin (STRUERS) with a setting
time of 24 h. After this time, the samples were polished to a mirror
like finish, and a graphite coating was employed to improve the
efficiency of SEM analysis.
3. Results and discussion
The results of this study are discussed in two parts; the first part
presents the silver sulfide leaching with the thiosulfate–copper–EDTA
and the thiosulfate–copper–citrate systems, both with ammonium
hydroxide; and the second section shows a similar analysis, in which
ammonium hydroxide was replaced by sodium hydroxide as the pH
conditioner agent. The results are discussed from a thermodynamic,
kinetic and microstructural view-point.
Fig. 5. Effect of EDTA and citrate on silver sulfide leaching in the presence of ammoni-
um hydroxide (0.1435 g silver sulfide (− 400 + 500 mesh), 200 mL solution, 0.2 M
thiosulfate, 0.05 M Cu(II), 0.025 M EDTA or sodium citrate, 0.6 M NH4OH, pH 10.2,
room temperature and 400 min−1).
3.1. Leaching tests with the thiosulfate–copper–EDTA and thiosulfate–
copper–citrate systems in the presence of ammonium hydroxide
Fig. 1 displays the silver extraction (%) vs time curves for the leaching
of silver sulfide with a solution containing 0.2 M thiosulfate, 0.05 M
Cu2+ and 0.025 M EDTA (or sodium citrate) as cupric ion complexing
agents. The pH of these leaching systems was adjusted at 10.2 with am-
monium hydroxide. In both systems, the silver extraction was very simi-
lar during the first 25 min of leaching; however, the silver leaching
kinetics with the sodium citrate complexing agent is enhanced in the pe-
riod of time from 1 h to 3 h. Furthermore the silver leaching kinetics for
the citrate system was higher than with the EDTA system. With the citrate
system, 60% of the silver is dissolved in the first hour, while 40% is dis-
solved with the EDTA system. Nevertheless, the silver leaching rate in
the sodium citrate and EDTA systems was inhibited after a period of
time. This behavior was perceivable in the sodium citrate system after
the second hour, and the maximum silver recovery obtained was 90%
after 8 h. On the other hand, the EDTA leaching system showed that the
silver extraction increased continuously and reached 89.8% after 5 h of
the experiment and 90% approximately at the end of the experiment.
A possible reason for the high silver leaching kinetics and the inhibi-
tion phenomenon found with the sodium citrate system could be that
the cupric ion complexes formed are different in both systems (EDTA
and citrate). Fig. 2 shows a species distribution diagram for the thiosul-
fate–copper–ammonia–EDTA system at 25 °C and a potential of 0.46 V
vs SHE (which corresponds to the experimental redox potential mea-
sured for the EDTA test in Fig. 1). The formation of two copper species is
observed at pH 10.2 (the pH of the leaching tests): the cupric tetraamine
Fig. 6. Effect of the initial thiosulfate concentration in the silver sulfide leaching with the
ammoniacal citrate system (0.1435 g silver sulfide (−300 + 400 mesh), 200 mL solution,
0.2 M, 0.25 M or 0.3 M thiosulfate, 0.05 M Cu(II), 0.025 M sodium citrate, pH 10.2 adjusted
with NH4OH, room temperature and 400 min−1).
 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11 5

experiment). This diagram shows that the cupric tetraamine complex

Cu(NH3)2+ 4 is the predominating species at pH 10.2, and that the CuO
is also present. The CuO can be precipitated from the leaching solution
according to Eq. (7):

2þ þ
Cu þ H2 O ¼ 2H þ CuO: ð7Þ

Furthermore, this species distribution can be related to the higher

silver leaching kinetics found with the sodium citrate system compared
with that of the EDTA system: the presence of the Cu(NH3)2+ 4 species
Fig. 7. Scheme of the catalyzed air oxidation of thiosulfate in the presence of copper promotes an increase in the chemical substitution rate of copper by
sulfide.
the silver contained in the sulfide matrix. As mentioned before, the
sodium citrate system presented a decrease in the silver leaching kinet-
complex (Cu(NH3)2+ 4 ) and the cupric complex with EDTA Cu(EDTA)
2−
ics at leaching times higher than 1.5 h. According to the thermodynamic
according to Eqs. (3) and (4) respectively:
diagram shown in Fig. 3, at pH 10.2 the cupric oxide (CuO) can precip-
2þ 2þ itate from the solution (Eq. (7)) along with the copper sulfide (CuS,
Cu þ 4NH3 ¼ CuðNH3 Þ4 ð3Þ Eq. (5)) on the unreacted silver sulfide surface. These layers of copper
oxides and copper sulfides behave as barriers for the silver sulfide
leaching and decrease the direct contact between the fluid reactants
2þ 4− 2−
Cu þ EDTA ¼ CuðEDTAÞ : ð4Þ and the unreacted silver sulfide particles. In the EDTA system the CuO
species exists in a lower proportion than in the citrate system, as can
According to Table 1, the Cu(EDTA)2− complex has a bigger Log K be seen in Fig. 2. Experimental evidence of the copper oxides and copper
value than the Cu(NH3)2+4 complex. Therefore it is possible to say that sulfides species is presented in the microstructural characterization
the cupric tetraamine is less stable than the Cu(EDTA)2 − complex, shown in the next section. According to the results described above,
and this suggests that the copper associated to the cupric tetraamine Fig. 4 shows the most important steps that take place during the silver
achieves the chemical substitution of the silver contained in the sulfide sulfide leaching.
matrix and that the thiosulfate ions complex the silver, according to Fig. 5 presents the silver extraction % vs time curves for fresh silver
Eq. (5): sulfide (− 400 + 500 mesh) with a smaller particle size than that of
Fig. 1. The leaching solutions contained 0.2 M thiosulfate, 0.05 M Cu2+
2þ 2− 3−
CuðNH3 Þ4 þ Ag2 S þ 4S2 O3 →2AgðS2 O3 Þ2 þ CuS þ 4NH3 : ð5Þ and 0.025 M EDTA (or sodium citrate) as cupric ion complexing agents.
The pH of these leaching systems was adjusted to 10.2 with ammonium
The Cu(EDTA)2 − complex could also participate in the chemical hydroxide. This figure reveals that a decrease in the size particle
substitution of silver in the sulfide matrix, according to Eq. (6): promotes an increase in the silver sulfide leaching kinetics during the
first hour, reaching an extraction of 80% and 55% with the citrate and
2− 2− 3− 4−
CuðEDTAÞ þ Ag2 S þ 4S2 O3 →2AgðS2 O3 Þ2 þ CuS þ EDTA : ð6Þ EDTA system respectively. It is also evident that citrate system present-
ed a higher silver sulfide leaching kinetics than the EDTA system, as was
However, the substitution reaction would be easier and faster with shown in Fig. 1 for a particle size of −300 + 400 mesh. Furthermore,
the cupric tetraamine (Eq. (5)) than with the Cu(EDTA)2− due to its the same silver leaching inhibition phenomenon is observed with the
smaller stability in the aqueous solution. citrate system at longer time than 1 h.
On the other hand, in the presence of sodium citrate the copper It has been shown from a thermodynamic point of view, that copper
predominating species is the Cu(NH3)24 +. Fig. 3 presents a species oxides and copper sulfides species formed on the unreacted silver
distribution diagram for this system at 25 °C and a fixed potential of sulfide particle can be responsible of decreasing the silver sulfide
0.48 V vs SHE (the redox potential measured in the leaching leaching kinetics (Fig. 1) with the sodium citrate and EDTA system at
higher time than 3 h and 5 h respectively. Test in Fig. 5 presented the
same decrease in the silver sulfide leaching kinetics with the citrate
system and a silver sulfide particle size of −400 + 500 mesh. However,
the silver sulfide leaching kinetics could possibly be hindered at these
processing times due to a decrease or high consumption of reactants
in the leaching solutions. In this sense, the pH of the leaching experi-
ment with the sodium citrate system (Fig. 1) was monitored in order
to follow any possible loss of ammonia. It was found that pH changed
from 10.2 (at the beginning) to approximately 9.9 (at the end of the
experiment). This change in pH is not significant; therefore, according
to the thermodynamic diagram shown in Fig. 3, the cupric tetraamine
exists also at pH 9.9. In addition, the copper content in this leaching
solution changed from 3168.89 ppm to 2889 ppm. This decrease in
the copper concentration is related to the consumption of cupric ions
in the substitution reaction shown in Eq. (5). It is evident that the
copper loss is not stoichiometric, which means that the copper is also
consumed by another reaction, e.g. the precipitation of cupric ions to
CuO (Eq. (7)). However, this change in copper concentration does not
hinder the silver sulfide dissolution kinetics. Therefore the only reactant
that can be oxidatively decomposed in these systems is the thiosulfate.
Fig. 8. Silver sulfide leaching using the ammoniacal–citrate liquor solution obtained at
3 h from Fig. 1 (0.1435 g silver sulfide (− 300 + 400 mesh), 200 mL solution, 0.2 M
In this sense, Fig. 6 presents the effect of the initial thiosulfate concen-
thiosulfate, 0.05 M Cu(II), 0.025 M sodium citrate, 0.6 M NH 4 OH, pH 10.2, room tration on the silver sulfide (−300 + 400 mesh) leaching with an am-
temperature and 400 min−1). moniacal–citrate solution containing 0.2 M, 0.25 M or 0.3 M thiosulfate,
6 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 9. Morphology of the pure silver sulfide (−300 + 400 mesh).
0.05 M Cu2+ and 0.025 M sodium citrate as the cupric ion complexing
agent. The pH of these leaching systems was 10.2. The concentration
of ammonium hydroxide was 0.6 M, 0.55 M and 0.47 M for the 0.2 M,
0.25 M and 0.3 M thiosulfate system respectively. The silver extraction
at 8 h was 89%, 75% and 60% approximately with the 0.2 M, 0.25 M
and 0.3 M thiosulfate respectively. These results are interesting because
it was expected that an increase in the thiosulfate concentration would
increase the silver sulfide leaching kinetics (Eq. (5)), according to the
theory of chemical reaction kinetics; however, Fig. 6 shows the con-
trary effect, and this suggests that besides Eq. (5), the thiosulfate
decomposition must be also occurring in this ammoniacal–citrate
leaching system. Actually, Aylmore and Muir (2001) suggested that
some thiosulfate degradation to tetrathionate occurs in the ammonia-
cal–copper–thiosulfate leaching solutions. The oxidation reaction,
Fig. 10. Microstructural characterization of the solid residue obtained with the
S2O3–Cu–EDTA–NH3 system and silver sulfide (− 300 + 400 mesh). Experimental
conditions: 0.2 M thiosulfate, 0.025 M EDTA, 0.05 M Cu(II), 0.6 M NH4 OH, pH =
10.2, room temperature and 400 min−1. a) Morphology at 5 h leaching, b) chemical
composition of the residue at 5 h.
which is promoted by cupric ions, is shown in Eq. (8):
2þ 2− 5− 2−
2CuðNH3 Þ4 þ 8S2 O3 ¼ 2CuðS2 O3 Þ3 þ S4 O6 þ 8NH3 : ð8Þ
According to the theory of chemical reaction kinetics, an increase in
the concentration of thiosulfate can accelerate the kinetics of Eq. (8).
Furthermore, according to Aylmore and Muir (2001) the reduction of
cupric ions by thiosulfate ions is extremely rapid in a pure aqueous
solution; however, in the presence of ammonia, this electrochemical
reaction (Eq. (8)) is slower and is dependent on the ammonia concen-
tration. The ammonia concentration in the leaching experiments of
Fig. 6 was different, i.e. more ammonia was employed for adjusting
the pH at 10.2 with the 0.2 M thiosulfate solution than with the 0.25
M and 0.3 M thiosulfate solutions respectively. Therefore, the thiosulfate
Fig. 11. Microstructural characterization of the solid residue obtained with the
S2O3–Cu–citrate–NH3 system and silver sulfide (− 300 + 400 mesh). Experimental
conditions: 0.2 M thiosulfate, 0.025 M citrate, 0.05 M Cu(II), 0.6 M NH4OH pH =
10.2, room temperature and 400 min−1. a) Morphology at 5 h leaching, b) chemical
composition of the residue at 5 h.
 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 12. Morphology of the solid residue obtained in Fig. 4 with the A) S2O3–Cu–EDTA–NH3
system and B) S2O3–Cu–Citrate–NH3. Experimental conditions: 0.2 M thiosulfate, 0.025 M
EDTA or citrate, 0.05 M Cu(II), 0.6 M NH4OH pH = 10.2, room temperature and 400 min
−1
. botroidal shape observed in the pure silver sulfide (Fig. 9) has been
decomposition is occurring in the ammoniacal–citrate systems, and this
decrease in thiosulfate concentration along with the copper oxides and
copper sulfide layers formed on the silver sulfide particle affect the
Fig. 13. Effect of EDTA and citrate on silver sulfide leaching in the presence of sodium
hydroxide (0.1435 g silver sulfide (− 300 + 400 mesh), 200 mL solution, 0.2 M
thiosulfate, 0.05 M Cu(II), 0.025 M EDTA or sodium citrate, 0.05 M NaOH, pH 10.2,
room temperature and 400 min−1).
7
silver leaching kinetics after a period of 3 h for mesh − 300 + 400,
and after 1 h for −400 + 500 mesh. Furthermore, besides the thiosul-
fate oxidation shown in Eq. (8); according to Chanda and Rempel
(1985) it is also possible that copper sulfide layers may act as a catalyst
for the thiosulfate oxidative decomposition in the presence of air. Fig. 7
displays a scheme for this catalytic reaction.
Fig. 8 shows the silver extraction (%) vs time curve for the leaching of
fresh silver sulfide (−300 + 400 mesh) with the filtered liquor solution
of the ammoniacal–citrate experiment of Fig. 1. The liquor solution was
obtained from a first silver sulfide leaching experiment carried out dur-
ing 3 h with a solution containing 0.2 M thiosulfate, 0.05 M Cu2+ and
0.025 M sodium citrate as the cupric ion complexing agent. Fig. 8
reveals that at 3 h the silver extraction was 27%; this silver extraction
using fresh silver sulfide was lower than with the fresh solution
shown in Fig. 1, where the silver extraction was 86% approximately at
the same processing time. This experiment shows two interesting issues
regarding the decrease in the silver sulfide leaching kinetics observed in
Fig. 1: a) thiosulfate decomposition is taking place in this thiosulfate–
citrate system, and is in good agreement with the results shown in
Fig. 6; and b) the copper oxides and copper sulfides formed on the silver
sulfide particles of Fig. 1 also affect the silver sulfide leaching kinetics.
Experimental evidence regarding the formation of these copper oxides
and copper sulfides layers on the silver sulfide particles is presented in
the next section.
3.1.1. Microstructural characterization of the solid residues
Fig. 9 presents a micrograph of the pure silver sulfide used in this
work, while Figs. 10a and 11a show the micrographs of the solid resi-
dues obtained from the silver sulfide leaching of Fig. 1 using the EDTA
and sodium citrate systems, respectively. From these figures, it is possi-
ble to see the morphological change between the pure silver sulfide and
both solid residues. In particular, Fig. 10a, which corresponds to the
solid residue obtained with the EDTA system, revealed that the
transformed in a cluster shape. The clusters permit the formation of
porosities where the fluid reactants would have to diffuse in order to
react with the silver sulfide sites. On the other hand, the EDXS analysis
of Fig. 10b revealed the presence of oxygen, sulfur and copper on the
silver sulfide surface, which suggests the generation of porous layers
of copper oxides and copper sulfides species where the cupric
tetraamine oxidizing agent should diffuse through in order to carry
out the chemical substitution with the silver contained in the unreacted
sulfide matrix. The copper oxide species is produced by the precipita-
tion of cupric ions (Eq. (7)) at pH higher than 10.2 as was observed in
the thermodynamic diagram presented in Fig. 2, while the copper
sulfide species is generated as a consequence of the chemical substitu-
tion of copper by silver in the silver sulfide particle (Eqs. (5) and (6)).
By comparing the solid residue generated with the sodium citrate
leaching system with that of the EDTA system (see Figs. 11a and
10a), it is possible to observe in Fig. 11a a decrease in the size of
the silver sulfide particle. Fig. 11a shows the solid particles dis-
persed, and it is evident that they have a different morphology
than the botroidal shape found in the initial silver sulfide particles.
Furthermore, the EDXS analysis of Fig. 11b, as in the case of the
EDTA system, revealed the presence of copper oxides and copper
sulfide species on the silver sulfide particles.
Finally, Fig. 12a and b shows the micrographs of the solid residues
obtained from the silver sulfide (−400 + 500 mesh) leaching of Fig. 5
using the EDTA and sodium citrate systems, respectively. It is possible
to observe a morphological change between these solid residues.
Fig. 12a revealed the formation of clusters, while Fig. 12b showed
the formation of clusters and dispersed particles similar to those
found in Fig. 11a. Furthermore the chemical composition of the solid
residues shown in Fig. 12a and b is the same as that shown in
Figs. 10b and 11b.
8 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11

Fig. 14. Distribution of copper species at different pH values for the S2O3–Cu–NaOH–EDTA–H2O system. The conditions for the diagram construction were 0.2 M S2O3, 0.025 M EDTA, 0.05
M Cu(II), 0.05 M NaOH and EH = 0.45 V at 25 °C.

3.2. Leaching tests with the thiosulfate–copper–EDTA and thiosulfate–
copper–citrate systems in the presence of sodium hydroxide
The use of ammonium hydroxide in the thiosulfate leaching
systems is one of the most critical issues due to its negative impact
on the environment. In this section, the silver sulfide leaching ki-
netics was studied using sodium hydroxide instead of ammonium
hydroxide as pH conditioner. Fig. 13 shows the silver extraction
vs time curves employing pure silver sulfide (− 300 + 400 mesh)
in a leaching solution with 0.2 M thiosulfate, 0.05 M Cu 2 + , and
0.025 M EDTA (or sodium citrate) at 25 °C during 5 h. Both leaching
solutions were adjusted at pH 10.2 using sodium hydroxide. In spite of
the similar silver extraction obtained during the first 15 min of leaching
(see Fig. 13), the silver extraction was always higher with the sodium
citrate system than with the EDTA system. In addition, it is interesting
to observe that both systems presented a decrease in the silver sulfide
leaching kinetics at processing times higher than 3 h. This decrease
can be associated with the instability of the leaching solutions, which
promotes a decrease in the thiosulfate concentration (Eq. (9)) as well
as with the formation of copper sulfides (Eq. (2)) on the unreacted
silver sulfide particles.
2þ 2− 5− 2−
2Cu þ 8S2 O3 ¼ 2CuðS2 O3 Þ3 þ S4 O6
A comparison of the silver leaching curves in the presence of
ammonium hydroxide (Fig. 1) and sodium hydroxide (Fig. 13) as
pH conditioners revealed that the leaching solutions containing
EDTA–ammonium hydroxide and citrate–ammonium hydroxide
had a higher silver leaching kinetics than the leaching solutions in
the presence of sodium hydroxide. In addition, the thiosulfate–am-
monia–citrate–copper system was the most efficient in terms of sil-
ver leaching kinetics during the initial stage: 80% of silver can be
leached in the first 1.5 h; unfortunately after this time, as was men-
tioned before, the silver sulfide leaching kinetics is decreased due
to the oxidative degradation of thiosulfate in the leaching solutions
(Eq. (8)) as well as by the formation of a layer composed by copper
oxides and copper sulfides (see Figs. 4 and 7).
A thermodynamic analysis and the microstructural characterization
of the solid residues obtained in the leaching experiments were carried
out, in order to better understand the differences between the EDTA
and sodium citrate leaching systems in the presence of ammonium
and sodium hydroxide. Fig. 14 presents a species distribution diagram
elaborated for the S2O3–Cu–NaOH–EDTA system at 0.45 V vs SHE (ex-
perimental redox potential) and at 25 °C. From this diagram, the for-
mation of the Cu(EDTA)2 − and CuO species appeared at pH 10.2,
according to Eqs. (4) and (7); these copper species were also thermo-
dynamically observed in the leaching solution containing EDTA–am-
ð9Þ monium hydroxide (Fig. 2). However, under this pH condition, a

Fig. 15. Distribution of copper species at different pH values for the S2O3–Cu–NaOH–Citrate–H2O system. The conditions for the diagram construction were 0.2 M S2O3, 0.025 M citrate, 0.05
M Cu(II), 0.05 M NaOH and EH = 0.49 V at 25 °C.
 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 16. Microstructural characterization of the solid residue obtained with the S2O3–Cu–
EDTA–NaOH system. Experimental conditions: 0.2 M thiosulfate, 0.025 M EDTA, 0.05 M
Cu(II), 0.05 M NaOH, pH = 10.2, room temperature and 400 min−1. a) Morphology at 5
h leaching, b) chemical composition of the residue at 5 h and c) morphology of the solid
residue polished transversally at 5 h leaching.
different copper–EDTA complex can be produced: Fig. 14 shows the
possibility to form a Cu(EDTA)OH3− complex, according to Eq. (10):
2þ 4− þ 3−
Cu þ EDTA þ H2 O ¼ H þ CuðEDTAÞOH : ð10Þ
This complex is related probably to the decrease in the silver
leaching kinetics with the EDTA system employing sodium hydrox-
ide because of the consumption of available cupric ions needed to
produce Cu(EDTA)OH3 −. Nevertheless, if Table 1 is observed, the
stability constant for Cu(EDTA)OH3 − complex is lower than the sta-
bility constant for Cu(NH3)24 +, which suggests that Cu(EDTA)OH3 −
is less stable than cupric tetraamine. In addition, the Cu(EDTA)
9
OH3 − complex could be beneficial for the silver sulfide leaching:
this low stability Cu(EDTA)OH 3 − complex can participate in the
chemical substitution reaction with silver contained in the silver
sulfide matrix, according to Eq. (2). However, the silver sulfide
leaching kinetics of the thiosulfate–Cu–NaOH–EDTA system was
slower than that of the thiosulfate–Cu–ammonium hydroxide–
EDTA system (see Figs. 13 and 1, respectively). This fact could be re-
lated with the lower concentration of Cu(EDTA)OH3 −. In Fig. 14, it is
possible to see that the Cu(EDTA)OH3 − is not predominating in the
leaching system; the Cu(EDTA)2 − species predominates at pH 10.2
and is more stable than the Cu(EDTA)OH3 − species. On the basis of
these last results, it is possible to say that the presence of
Cu(NH3 )24 + species in the thiosulfate–ammonium hydroxide–
EDTA–copper system promotes an increase in the silver sulfide
leaching kinetics. Furthermore, according to the thermodynamic
diagram of Fig. 14, the CuO species is also produced in this sodium
hydroxide–EDTA system. The microstructural characterization of
the solid residue is presented in the next section.
Fig. 15 shows a species distribution diagram for the S2O3–Cu–NaOH–
citrate system at 0.49 V vs SHE (experimental redox potential) and at
25 °C. In this diagram, the CuO is the predominating copper species at
pH 10.2, and it is possible to observe only one cupric–citrate soluble
species which corresponds to the formation of the complex Cu2(cit)2-
OH3− according to Eq. (11).
2þ 3− þ 3−
2Cu þ 2Cit þ H2 O ¼ H þ Cu2 ðCitÞ2 OH : ð11Þ
This copper complex achieves the chemical substitution of silver
contained in the silver sulfide matrix, in the same way as stated in
Eq. (2) and Fig. 4. The silver leaching curves presented in Fig. 13
revealed a slower silver leaching kinetics with this citrate system
than with the citrate–ammonia system of Fig. 1. Probably this differ-
ence in the kinetic behavior must be associated with the absence of
ammonium hydroxide in the leaching system of Fig. 13 (cupric
tetraamine complex is not produced). According to Table 1 the Cu2(-
cit)2 OH3 − complex has a bigger Log K value than the Cu(NH3 ) 24 +
species; this suggests that cupric ions produce stronger complexes
with citrate than with ammonia, and probably these stronger bind-
ing forces between cupric ions and citrate can affect the silver sulfide
leaching kinetics. Furthermore, according to the thermodynamic
diagram shown in Fig. 15, the CuO species predominates at pH 10.2
in the citrate–NaOH system due to the absence of ammonium hy-
droxide. Therefore, the silver sulfide leaching kinetics is also affected
by a decrease in the cupric ion concentration through the
predominating formation of CuO (Eq. (7)). In addition, this CuO
along with the CuS (main solid product of Eq. (2)) layer can decrease
the direct interaction of the fluid reactants with the unreacted silver
sulfide particle (Fig. 4) and also may promote the catalytic oxidative
decomposition of thiosulfate according to Fig. 7.
3.2.1. Microstructural characterization of the solid residues
In this section, microstructural characterizations of the solid
residues obtained with the EDTA–NaOH and citrate–NaOH leaching
systems are presented in order to complement the understanding
about the nature of the silver sulfide leaching. Fig. 16a shows a
micrograph of the solid residue obtained with the S2O3–Cu–EDTA–
NaOH system, where a change in the morphology is evident when
compared with the micrograph of the pure silver sulfide shown in
Fig. 9. Fig. 16a reveals that solid particles are linked as a network.
In addition, it is possible to observe porosities on the surface where
the fluid reactants would have to diffuse in order to leach the silver
sulfide located in the inner side of the particles. The corresponding
EDXS analysis shown in Fig. 16b reveals the presence of copper sul-
fide and silver sulfide; it was expected that the copper and silver
concentrations would vary through the particle depth. Therefore
experimental evidence of this fact is presented in Fig. 16c for a
10 D.M. Puente-Siller et al. / Hydrometallurgy 149 (2014) 1–11
Fig. 17. Microstructural characterization of the solid residue obtained with the S2O3–Cu–
Citrate–NaOH system. Experimental conditions: 0.2 M thiosulfate, 0.025 M citrate, 0.05
M Cu(II), 0.05 M NaOH, pH = 10.2, room temperature and 400 min−1. a) Morphology
at 5 h leaching, b) chemical composition of the residue at the bright zone (porous
layer), c) chemical composition of the residue at the dark zone (compact layer).
solid particle with a transversal cut that reveals a proportion of the
unreacted silver sulfide (light zone) coated by the copper sulfide
and copper oxide layer (dark zone). The elemental analysis (EDXS
not shown here) confirmed a decrease in the copper concentration
from 23.7% to 18.9% in the boundary and center of the light particle,
respectively; this result suggests the existence of a gradient in the
soluble copper concentration through the particle.
The solid products formed with the thiosulfate leaching system
containing sodium citrate–sodium hydroxide are very similar to
those obtained in the EDTA–sodium hydroxide system. However,
there are some interesting morphological changes in the solid resi-
due. For example, Fig. 17a corresponds to the micrograph of the
solid residue obtained with this system (S2O3–Cu–citrate–NaOH), and
a morphological change in the particles is observed when compared
with the pure silver sulfide (Fig. 9) and with the solid residue obtained
with the sodium citrate–ammonia system (Fig. 11a). Furthermore, the
particles are linked together forming a network with porosities (see
light zones in Fig. 17a); as mentioned before, the fluid reactants
would have to diffuse through the porosities in order to leach the re-
maining silver sulfide contained inside the particles. This porous layer
decreases the direct contact between the fluid reactants and the
unreacted silver sulfide. In addition, a compact layer appears (dark
zone in Fig. 17a) with less porosity than in the light zones. The absence
of porosities in the compact layer (dark zone) can inhibit the direct
contact of fluid reactants with the unreacted silver sulfide more than
in the porous layer (light zone). The EDXS analysis (Fig. 17b) reveals
that light zones are mainly composed by silver sulfide with low quanti-
ties of copper sulfide and copper oxide, while the dark zone (compact
layer) consists principally of copper sulfide and low quantities of copper
oxide and silver sulfide (see Fig. 17c).
4. Conclusions
On the basis of the results obtained for the silver sulfide leaching
tests, the following facts can be stated:
1. The silver sulfide leaching with the thiosulfate–ammonium
hydroxide system employing EDTA or sodium citrate as cupric
ion complexing agents presented a higher silver leaching kinetics
than the thiosulfate–NaOH systems, due to the presence of the
cupric tretraamine complex in the ammoniacal leaching
solutions.
2. The thiosulfate–citrate–ammonia system had the highest silver
dissolution kinetics in the first minutes of leaching. However, the
silver sulfide leaching kinetics is decreased at processing times
higher than 3 h due to the oxidative degradation of thiosulfate as
well as to the presence of copper sulfides and copper oxides on the
unreacted silver sulfide particle.
3. In the cases of the caustic soda–silver sulfide leaching systems stud-
ied in the presence of EDTA and sodium citrate, it was found that the
silver leaching kinetics was affected by the formation of a porous
layer composed by copper sulfides and copper oxides.
4. The NaOH–citrate system showed a similar silver leaching kinetics as
the ammoniacal EDTA system; therefore, the thiosulfate–copper–
NaOH–citrate leaching system can be considered an alternative
sustainable leaching process with a very promising possibility to
substitute ammonium hydroxide by NaOH.
Acknowledgments
The authors are grateful to CONACYT (Mexico) for the postgraduate
scholarship granted to Damaris M. Puente-Siller.
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