Minerals Engineering 18 (2005) 898–900

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Technical note

Optimization of extraction of silver from silver sulphide

concentrates by thiosulphate leaching
a,* b
Sevda Ayata , Hüseyin Yildiran
a
University of Dokuz Eylul, Faculty of Engineering, 35100 Bornova, Izmir, Turkey
b
University of Ege, Science Faculty, Chemistry Department, 35100 Bornova, Izmir, Turkey

Received 5 November 2004; accepted 12 January 2005

Available online 31 May 2005

Abstract

A novel method of extracting silver from silver sulphide concentrates is provided in this study. The method is selective for silver
in the presence of 1.0 M of thiosulphate solution with acetic acid–ammonium acetate buffer at pH 4.15. The conditions are calcu-
lated using related equilibria constants and then tested with experiments.

2005 Elsevier Ltd. All rights reserved.

Keywords: Sulphide ores; Leaching; Hydrometallurgy; Extractive metallurgy

1. Introduction However, as researchers have claimed there are sev-

The silver metal industry has been seeking alternative
reagents for leaching metals from sulphide ores for
many years. The well known toxicological affects of cya-
nide and difficulties of waste treatment and other diffi-
culties such as increasing regulatory scrutiny of new
projects and a lowering of cyanide discharges to accept-
able levels are of considerable concern to the industry. It
is anticipated that approval for any new project using
cyanide would be extremely difficult in the world. Thus,
the political and environmental cost of using cyanide be-
comes too high and the establishment of an economic
and environmentally viable option for extracting silver
without the use of cyanide would seem essential.
Recently, world industry attention has tuned to a rel-
atively cheap and non-toxic reagent i.e., thiosulphate,
and various studies with thiosulphate have been re-
ported in the literature (Abbruzzese et al., 1995; Zippe-
rian et al., 1988; Kerley, 1981, 1983).
*
Corresponding author. Tel.: +90 232 388 78 66; fax: +90 232 388 78
65.
E-mail address: sevda.ayata@deu.edu.tr (S. Ayata).
eral obstacles that must be overcome before a viable
and economic process is ready to replace cyanide (Muir
and Alymore, 2004).
This study describes a novel procedure for silver dis-
solution from silver sulphide concentrates with a signif-
icant concentration, i.e., more than 5 · 10
3 M, with a
low cost and environmentally safe process. For this pur-
pose, the solubility equilibria of silver sulphide, the re-
dox reaction between thiosulphate and hydrogen
sulphide and also complexation reactions between thio-
sulphate and silver should be taken into account. Re-
lated reactions are presented in Table 1.
Silver ions are known to form strong complexes with
thiosulphate. However, the complexing ability of thio-
sulphates is not great enough to extract silver from silver
sulphide concentrates alone. The pH of the medium is
also crucial in terms of its decomposition and it has to
be maintained at pH > 4.0. In order to increase the sol-
ubility of silver sulphide concentrates, sulphide should
be oxidised to elemental sulphur. There are also risks
in thiosulphate oxidation such as tetrathionate forma-
tion (Ayata and Yildiran, 2001; Muir and Alymore,
2004).

0892-6875/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.01.020
 S. Ayata, H. Yildiran / Minerals Engineering 18 (2005) 898–900 899

Table 1
Equilibria constants and standard electrode potentials of related reactions (Martel and Sillen, 1964)
Reactions Constants (at 25 C)
þ ¼
Ag2 S $ 2Ag þ S ð1Þ pKsp(Ag2S) = 49.0

Agþ þ 2S2 O¼ 3
log bAgðS2 O3 Þ3

2 ¼ 13.3
3 $ AgðS2 O3 Þ2 ð2Þ

S¼ þ 2Hþ $ H2 S ð3Þ pK 1 þ pK 2 ¼ 22

2H2 S þ S2 O¼ þ
3 þ 2H $ 4S þ 3H2 O ð4Þ e0 (S/H2S) = 0.15 V

e0 (SO2/S) = 0.46 V
e0 (Ag+/Ag) = 0.80 V

The overall reaction can be written as 2.2. Reagents

2Ag2 S þ 9S2 O¼
3 þ 6H $þ
4AgðS2 O3 Þ3

2 þ 4S þ 3H2 O
In order to extract a significant amount of silver ions,
i.e., more than 5.0 · 10
3 M, optimal thiosulphate con-
centration can be calculated to be 1.0 M by considering
the above equilibria and related calculations. The solu-
tion pH can be maintained at around 4.15 by using
CH3COOH/NH4CH3COO buffer with a buffer capacity
of 0.01 M. It should be noted that all metal sulphides
can be extracted by using this proposed method except
gold and platinum sulphide. For this reason, the ores
or concentrates including different kinds of metal sulp-
hides should react with SO2 prior to the leaching proce-
dure. Therefore, all these sulphides except silver and
copper can be eliminated.
ð5Þ
In all experiments particles of about 50 l diameter of
Ag2S were used. Technical quality sodium thiosulphate,
acetic acid and ammonium acetate and analytical qual-
ity silver nitrate (Merck) were used.
2.3. Methods
The reaction mixture including the concentrate and
leaching solutions were placed in the reactor. The reac-
tion was carried out until the dominant black colour of
the silver sulphide faded and the pH increase has ended
(at about 4.30). In order to determine the efficiency of
the extraction the solutions were subjected to chemical
analysis by AAS.

2.4. The leaching tests

2. Experimental
2.1. Equipments
All leaching tests were performed in a closed reactor
with a stirring apparatus under thermostatic conditions
(±1 C). The electrolyses were carried out using a poten-
tiostat (Junke&Kunkel) with anion permeable mem-
brane and a stirring apparatus in the electrolysis tank.
The pH was measured using a Jenway 3040 Ion Ana-
lyser (±0.02). The silver contents of all the solutions
were determined using a GBC atomic absorption
spectrometer.
The leaching liquor was prepared to include 1.0 M
solution of sodium thiosulphate, X M acetic acid and
0.04 M ammonium acetate buffer at pH 4.15. Appropri-
ate volumes of leaching liquor were transferred into the
reactor containing a known amount of silver sulphide as
given in Table 2.
2.5. The electrolysis tests
A 100 mL aliquot of the leaching liquor (d) including
extracted silver ions were subjected to the electrolysis. An

Table 2
Silver concentration (·103 M) determined after extraction of Ag2S at different time intervals under various conditions using thiosulphate solutions
Experimental conditions Silver concentration (·103 M) at different extraction durations (h)
[S2 O¼
3 ] (M) pH T (C) 2 4 6 8 24
a 0.1 4.15 25 <0.1
b 1.0 7.15 25 <0.1
c 1.0 4.15 25 3.1 ± 0.2 3.3 ± 0.2 3.5 ± 0.2 3.6 ± 0.2 3.8 ± 0.2
d 1.0 4.15 50 3.2 ± 0.2 3.5 ± 0.2 3.6 ± 0.2 3.8 ± 0.2 3.9 ± 0.2
900 S. Ayata, H. Yildiran / Minerals Engineering 18 (2005) 898–900
electrolysis cell containing an anion permeable mem-
brane and a stirring apparatus under thermostatic condi-
tion (50 ± 1 C) was used. Electrochemical deposition of
silver was realized by applying 1.0 V between a silver
cathode and a titanium anode placed at a distance of
1.0 cm.
3. Results and discussions
The leaching experiments were carried out at room
temperature since higher temperatures had no signifi-
cant affect on the efficiency of the extraction. The solu-
tion pH can be maintained at around 4.15 by using
CH3COOH/NH4CH3COO buffer. On increasing the
pH the extraction efficiency was found to be low as ex-
pected. Table 2 shows the chemical analysis results of
the extracted solutions. Silver ion concentration found
to be below the detection limit of the AAS after the elec-
trolysis and 0.036 ± 0.02 g of silver was deposited on the
silver cathode. The final solution was subjected to chem-
ical analysis by AAS and 1.0 · 10
4 M of silver ion con-
centration was found in this solution.
4. Conclusions
As follows from Table 2, the extraction efficiency de-
pends upon the concentration of thiosulphate in the
cases of (a) and (c), and the pH as in the case of (b)
and (c). Compared to the results of (c) and (d), the tem-
perature has no significant effect on the efficiency of the
extraction. The silver concentrations determined after
certain time intervals indicate that reactions including
the solubilization, complexation, redox and protonation
steps are fast enough to attain high efficiency in 2 h.
As it was emphasized earlier, all metal sulphides ex-
cept some precious metals such as Au, Pt, Ag and Cu
should react with SO2 at appropriate conditions prior
to the procedure. As a result of this removal, Ag and
Cu can be extracted by the proposed leaching proce-
dure. In addition, silver and copper ions can be selec-
tively deposited by electrolysis not only as free ions
but also in their complex forms depending upon their
reduction potentials. This constitutes an advantage of
the method for solving both the extraction and purifica-
tion problems. Another benefit of the method is that the
procedure allows reagent recycling after electrolysis
step.
Acknowledgements
The authors would like to thank chemist Cahit De-
miralp for his valuable help in the laboratory studies,
Dr. Nil Ertas and Dr. Stephan Astley for their help
and reading the text and Sevim Yildiran for her patience
during the study.
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