Hydrometallurgy 156 (2015) 63–70

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Hydrometallurgy

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Kinetics of metallic silver leaching in the O2–thiosulfate system

I. Rivera a, F. Patiño a, A. Roca b, M. Cruells b
a
Universidad Autónoma del Estado de Hidalgo, Área Académica de Ciencias de la Tierra y Materiales, Carretera Pachuca-Tulancingo Km 4.5, Pachuca-Hidalgo 42081, México
b
Universitat de Barcelona, Departament de Ciència dels Materials i Enginyeria Metallúrgica, Facultat de Química, Barcelona, Spain

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

Article history: In recent years, many researchers have studied processes for extracting gold and silver from ores using alterna-
Received 28 December 2014 tives that are less harmful and aggressive to the environment than cyanides. Thiosulfate solutions represent one
Received in revised form 7 May 2015 such alternative. Metallic silver can be dissolved in O2–thiosulfate in different experimental conditions. Silver
Accepted 22 May 2015
dissolution was obtained without the formation of passivation layers on the surface of the silver plate used.
Available online xxxx
The kinetic study conducted indicated that the process is affected by a stirring speed of between 8.3
Keywords:
and 15 s−1 (the reaction rate increased threefold), and the reaction orders were 1 (oxygen partial pressure
Silver 0.2–1 atm), 0.41 (thiosulfate concentration 25–200 mol m−3), 0 (thiosulfate concentration 200–
Leaching 600 mol m−3), 0.35 (hydronium concentration 1 · 10−8–1 · 10−7 mol m−3) and 0 (hydronium concentration
Thiosulfate 1 · 10−6–1 · 10−2 mol m−3). The apparent activation energy of the process was 4.5 kJ mol−1. Kinetics is con-
Oxygen trolled by a mass transfer of oxygen in the solid–liquid interface. In the presence of copper ions and oxygen,
Cu (II) the reaction rate increased by 30% with respect to the process without copper. However, the thiosulfate partially
decomposed and a layer of silver sulfide formed on the surface of the silver. The process was applied to a metallic
silver powder, which showed a similar behavior to the silver plate.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction of additives and electrolytes on the dissolution of gold in thiosulfate so-

In extractive metallurgy, noble metals such as Au and Ag have been
leached using cyanide solutions and oxygen as oxidants for over a
hundred years. Since the late 1970, however, many researchers have
focused on investigating alternative systems that are less harmful to
humans and less aggressive to the environment (Jeffrey et al., 2001).
Alymore and Muir (2001) presented a review of major studies pub-
lished in this field and concluded that an efficient leaching process can
be achieved by maintaining appropriate concentrations of ammonia
and thiosulfate in a solution, with copper (II) as an oxidant. Oxygen is
required to maintain the system's potential (Eh) to leach gold and con-
vert the reduced cuprous ion into the cupric state for further gold
leaching. The process cannot be applied commercially without reliable
techniques for recovering gold from the ammoniacal thiosulfate liquors
(Grosse et al., 2003).
Copper–ammonium–thiosulfate solution has been viewed as a
leaching system with great potential. In this process, Cu2+ ions oxidize
the noble metals, while thiosulfate forms stable complexes with them.
Ammonium ions also form a stable complex with copper ions to prevent
their precipitation. The role of ligands and oxidants in thiosulfate
leaching of gold has been studied by Senanayake (2005), and the effect
E-mail address: roca@ub.edu (A. Roca).
lutions has been studied by Chandra and Jeffrey (2004) and Senanayake
(2012a,b).
This process has advantages over the cyanide process, namely the
reduced interference from foreign cations and the lower environmental
impact (Abbruzzese et al., 1995). Although this process is considered
to be a relatively non-toxic process, thiosulfate can decompose to
polythionates and sulfates while consuming oxygen, or to sulfides in
anaerobic conditions. The ammonia in air is considered to be as toxic
as cyanide, and strict safety measures are required during this process
(Muir and Aylmore, 2004).
A critical study of gold leaching in non-cyanide lixiviant systems was
conducted by Senanayake (2004), particularly by using thiosulfate as a
ligand (Senanayake, 2007). According to this author, silver dissolves
faster than gold, and Ag(I) catalyzes the dissolution of gold. Senanayake
also analyzed gold leaching in different lixiviant systems and showed
the validity of the shrinking particle model (kinetics controlled by the
chemical reaction). This author concluded that further studies are need-
ed to rationalize the complex gold leaching process in non-cyanide
media.
Thiosulfate is a metastable anion that readily decomposes in aque-
ous solution. Thiosulfate oxidation by copper (II) and/or oxygen during
leaching leads to the formation of tetrathionate (S4O2− 6 ), trithionate
(S3O3− 2−
6 ), sulfate (SO4 ) and other sulfur species such as polysulfides
and polythionates or elemental sulfur, which causes the consumption
of excess thiosulfate.

http://dx.doi.org/10.1016/j.hydromet.2015.05.009
0304-386X/© 2015 Elsevier B.V. All rights reserved.
64 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70
Depending on the experimental conditions, thiosulfate can be
oxidized or disproportionated (Alymore and Muir, 2001) according to
the following equations:
S2 O3 2− þ 2O2 þ H2 O ¼ 2SO4 2− þ 2Hþ
2 S2 O3 2− þ ½ O2 þ H2 O ¼ S4 O6 2− þ 2OH−
3 S2 O3 2− þ H2 O ¼ 2SO4 2− þ 4S0 þ 2OH−
3 S2 O3 2− þ 6OH− ¼ 4SO3 2− þ 2S2− þ 3H2 O
S2 O3 2− ¼ SO3 2− þ S0 :
In the presence of oxygen, thiosulfate is oxidized to sulfate and
tetrathionate, depending on the amount of oxygen dissolved in the
solution.
Our research team (González-Lara et al., 2009) studied the nature
and kinetics of the reaction between thiosulfates and Cu(II) ions at a
pH of between 4 and 5. This reaction produced a precipitate of CuS,
and the remaining sulfur was oxidized to sulfate. The effects of temper-
ature and the hydronium, initial copper (II) and initial thiosulfate
concentrations were determined. An empirical mathematical model
based on the kinetic study was also presented. This process was applied
to an industrial fixing bath that originated in the photography industry;
after this procedure, the resulting effluent contained less than 10 mg L−1
of thiosulfates. This behavior should be taken into account in gold and
silver leaching in the S2O2−
3 –Cu
2+
–NH3 system.
In parallel with studies on gold leaching in thiosulfate media, studies
have also been conducted on silver and silver sulfide leaching in
the thiosulfate–ammonia–cupric ion system (Briones and Lapidus,
1998; Deutsch and Dreisinger, 2013a,b) and in the presence of EDTA
(Puente-Siller et al., 2013, 2014). The reactions can be described as
electrochemical. The Eh-pH for the ammoniacal thiosulfate and silver
system has been studied by Alymore and Muir (2001). These authors
concluded that, for high and low concentrations of ammonia and thio-
sulfate, silver combines preferentially with thiosulfate. At high Eh and
pH values, silver oxide (Ag2O) precipitates, but if the potential values
are too low, silver is not dissolved and silver sulfide does not form
(Ag2S) in any pH range. Flett et al. (1983) found that silver recovered
better in the absence of ammonia. At high copper concentrations, the
reaction was chemically controlled and the rate rapidly increased with
temperature; however, at 30 °C and low copper concentrations, the
reaction was controlled by copper diffusion (Jeffrey, 2001).
The chemistry of the copper–ammonium–thiosulfate system is com-
plicated due the simultaneous presence of the Cu(NH3)2+ 4 /Cu(NH3)2
redox couple and complexing ligands such as thiosulfate, Ag(S2O3)5− 3
and Cu(S2 O 3 )53 −. Studies conducted by different authors have
clearly shown the complicated behavior involved in thiosulfate
leaching of noble metals under different conditions and highlight
the need for further studies to gain a proper understanding of
the process that minimizes reagent consumption and maximizes
metal extraction.
The present work is intended as a kinetic study of silver dissolution
in the O2–thiosulfate system, in the absence of Cu(II), to determine
the effects of the stirring rate, temperature, oxygen partial pressure,
thiosulfate concentration and hydronium concentration. The presence
of copper salt in the system was also evaluated in relation to the inter-
action between copper and thiosulfate ions and the possibility of
thiosulfate destruction by Cu(II) in the presence of oxygen.
2. Materials and experimental procedure
2.1. Materials
Silver plates (99.9% weight) with 1 mm thickness and a 19.8 cm2
ð1Þ surface area were used in the kinetic experiments to measure specific
rates of metallic silver with oxygen in thiosulfate media. A silver powder
(99.9% Ag) consisting of aggregates of spheroidal grains (1–10 μm) was
ð2Þ used in the application experiments. Fig. 1 is an image of the silver
powder obtained by scanning electron microscopy, secondary electrons
(SEM-SE).
ð3Þ
2.2. Experimental procedure
ð4Þ The leaching system consisted of a 500-mL thermostated reactor
with magnetic stirring. The reactor included a gas entrance device to
the solution through a diffuser and a pH-meter with continuous pH
ð5Þ measurement. A 10 mol m−3 sulfuric acid solution and 10 mol m− 3
NaOH were used for pH maintenance. These were diluted solutions
and, together with the high stirring rates used, did not affect the possi-
ble degradation of thiosulfates. The leaching rates were determined
after solution sampling and silver analysis by atomic absorption
spectrometry (AAS).
2.3. Characterization methods
The silver in the liquids was determined by AAS, as indicated above.
Solids generated during the study of silver reactivity in the oxygen–
thiosulfate system were characterized by X-ray diffraction (XRD) and
scanning electron microscopy (SEM) with X-ray energy dispersive
analysis (EDS). The thiosulfate concentration in the solution was
determined by ionic chromatography. This technique was carried out
under the following conditions: an electric conductivity detector, a
mobile phase of sodium carbonate (2.0 mM) and sodium bicarbonate
(0.75 mM), a flux of 1.5 mL min− 1 and an ionic separation column
were used. Patterns of species such as thiosulfates, sulfites, sulfates
and tetrathionates were also used.
3. Results and discussion
3.1. Preliminary experiments
Two experiments were carried out under the following experimental
conditions.
Experiment 1: stirring rate, 16.7 s−1; temperature, 298 K (25 °C);
sodium thiosulfate concentration, 200 mol m−3; pH, 9; and oxygen
pressure, PO2 = 1 atm.
Experiment 2: the same conditions but conducted at 333 K (60 °C).
+
Fig. 1. Metallic silver powder (SEM-SE).
 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70 65

298K 75 -1
400
8.3 s
333K 70
-1
65 13.3 s
350 60 -1
15 s
55
Silver dissolution (ppm)

-1

x100
300
50 16.7 s
45
250

-2
40

mol Ag m
35
200
30
25
150
20
15
100
10
5
50
0
0 2000 4000 6000 8000 10000 12000 14000
0
0 2000 4000 6000 8000 10000 12000 14000 16000 Time (s)
Time (s)
Fig. 4. Leaching of silver plate: effect of stirring rate, silver dissolution vs. time.
Fig. 2. Preliminary experiments at 298 and 333 K: silver dissolution vs. time.

chromatography). No elemental sulfur or sulfides, typical of thiosulfate

Fig. 2 shows the silver dissolution versus time for both experiments.
300 ppm of silver (298 K) and 350 ppm of silver (333 K) were dissolved
in a 14,400 s (240 min) reaction. Fig. 3 shows mol of silver dissolved by
unit surface area versus time for both experiments. These results show
linear rates, as expected, due to the constant surface area of the solid.
Their slopes, the specific silver dissolution rates, were the following.
Experiment 1 (298 K, 25 °C): 4.97 · 10−5 mol Ag m−2 s−1.
Experiment 2 (333 K, 60 °C): 5.75 · 10−5 mol Ag m−2 s−1.
The reaction rate increased slightly (≅ 15%) with temperature be-
tween 298 K and 333 K.
The surface of the silver plates was examined by SEM-EDS. Any dif-
ference in metallic silver was detected on the surface of the silver. Silver
passivation was not detected. This is consistent with results presented
in Figs. 2 and 3. During the process, hydronium ion consumption was
detected and a sulfuric acid solution of 10 mol m−3 was used to keep
pH constant during each experiment. XRD only detected metallic silver.
No appreciable consumption of thiosulfate was detected during the
process in the experimental conditions employed; where it was detect-
ed, the degradation was less than 5% (analyzed by ion chromatography).
No sulfites, sulfates or polythionates were detected (also analyzed by ion
90
80
70
x100
degradation, were detected in the system (determined by XRD, SEM
and EDS). Thus, the reaction developed was:
2 Ag0 ðsÞ þ 4 S2 O3 2− ðaqÞ þ H2 O þ ½ O2ðaqÞ → 2 AgðS2 O3 Þ2 3− ðaqÞ ð6Þ
þ 2 OH −
ðaqÞ :
Based on the results obtained in this preliminary study of the
process, a kinetic study was carried out. The effects studied were:
stirring rate, temperature, oxygen partial pressure, thiosulfate concen-
tration, hydronium concentration and the presence of copper ions in
the system.
3.2. Kinetic study of silver leaching in the O2–S2O2−
3 system
3.2.1. Effect of stirring rate
The experimental conditions employed were: temperature, 298 K;
thiosulfate concentration, 200 mol m−3; pH, 9; and PO2 = 1 atm. The
stirring rates studied, in s−1, were: 8.3, 13.3, 15 and 16.7. Fig. 4 shows
the silver dissolved in mol Ag m−2 versus time. The leaching showed
linear rates, as expected due to the constant surface area of silver.
Table 1 includes the results obtained in terms of the specific silver
leaching rates.
Fig. 5 is the plot of the silver leaching rate versus the stirring rate.
This figure shows that the stirring rate has an important effect on the sil-
ver leaching rate. A change of regime appears at a stirring speed of
298K around 13.3 (s−1), from laminar to turbulent flow, which reduces the
333K Nernst boundary layer and increases oxygen transport in the solid–
liquid interface; as a consequence, the reaction rate increased. These
results indicate that the rate-limiting step of the process is probably
oxygen transport in the solid–liquid interface.

60
3.2.2. Effect of temperature
50 The experimental conditions employed were: stirring rate, 16.7 s−1;
-2
mol Ag m

40 thiosulfate concentration, 200 mol m−3; pH, 9; and PO2 = 1 atm. The

30

20
Table 1
10
Leaching rates of silver: effect of stirring rate.
0
Stirring rate (s−1) Leaching rate (mol Ag m−2 s−1)
0 2000 4000 6000 8000 10000 12000 14000 16000

Time (s) 8.3 1.73 · 10−5

13.3 2.80 · 10−5
15 3.75 · 10−5
Fig. 3. Preliminary experiments at 298 and 333 K: silver dissolved by unit surface area vs.
16.7 4.97 · 10−5
time.
66 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70

Table 2
Leaching rates of silver: effect of temperature.

Temperature in K (°C) Leaching rate (mol Ag m−2 s−1)

286 (13) 4.69 · 10−5

298 (25) 4.97 · 10−5
310 (37) 5.34 · 10−5
321 (48) 5.54 · 10−5
333 (60) 5.75 · 10−5

3.2.4. Effect of thiosulfate concentration

Fig. 5. Leaching of silver plate: effect of stirring rate.
temperatures studied in K, were: 286, 298, 310, 321 and 333. Fig. 6
shows the experimental results obtained. Table 2 presents the leaching
rates of silver at different temperatures.
Fig. 7 is a graph showing the natural logarithm of the silver rate ver-
sus 1000/T. The apparent activation energy obtained was 4.5 kJ mol−1.
This value indicates that temperature had a small effect on the reaction
rate.
3.2.3. Effect of oxygen partial pressure
The experimental conditions employed were: stirring rate, 16.7 s−1,
temperature, 298 K; thiosulfate concentration, 200 mol m−3; and pH, 9.
Two experiments were conducted at different oxygen partial pressures:
the first with PO2 = 0.2 atm and the second with PO2 = 1 atm. Fig. 8
shows silver leaching versus time for both experiments. Values of spe-
cific silver rates obtained (in mol Ag m− 2 s− 1) were: 0.93 · 10− 5
The experimental conditions employed were: stirring rate, 16.7 s−1;
pH, 9 and PO2 = 1 atm. The thiosulfate concentration was varied be-
tween 25 and 600 mol m−3. Fig. 9 shows silver leaching versus time
for all experiments. Tables 3 and 4 presents the specific leaching rates
of silver at different temperatures. Fig. 10 is the logarithm of specific sil-
ver rates versus the logarithm of thiosulfate concentration. Between 200
and 600 mol m−3, the reaction rate was almost the same in all cases that
obtained the highest values of all experiments (5 10−5 mol Ag m−2 s−1)
and the apparent reaction order in this interval of concentrations was 0.
The leaching rate depends only on the oxygen partial pressure. Between
25 and 200 mol m−3, the reaction rates were lower than
5 · 10−5 mol Ag m−2 s−1 and the apparent reaction order in this interval
of concentrations was 0.41. The reaction rate depends on the oxygen
pressure and thiosulfate concentration.
Degradation of the thiosulfates was not appreciable in any experi-
ment. No sulfites, sulfates or polythionates (ion chromatography)
-9,75
-9,80
-1

(0.2 atm) and 4.97 · 10−5 (1 atm). Consequently, the apparent order
Log mol Ag m s
-2

of reaction is n = 1 (the silver leaching rate is proportional to the oxy- -9,85

gen partial pressure in the system).

The results obtained in the study of different variables, the effect of -9,90
the stirring speed, the apparent reaction order of 1 with respect to the
oxygen partial pressure and the apparent activation energy obtained
(4.5 kJ mol−1) confirm that the rate-limiting step is oxygen transport -9,95

in the solid–liquid interface. This behavior is different to that observed

by Senanayake (2004 and 2005), who indicated that kinetics is con- -10,00
trolled by the chemical reaction (shrinking particle model). This is prob- 3,0 3,1 3,2 3,3 3,4 3,5

ably due to the fact that the oxidant systems used in both cases differed: 1000/T (K )
-1

the work by Senanayake used Cu(II) or Fe(III) as an oxidant and this

study used oxygen. Fig. 7. Leaching of silver: effect of temperature. Determination of the activation energy.

90 80

80
286K 70 P O2 = 0.2 atm
298K P O2 = 1 atm
70 310K 60
mol Ag m x100

321K
mol Ag m x100

60
50
333K
-2

50
-2

40
40
30
30
20
20

10 10

0 0
0 2000 4000 6000 8000 10000 12000 14000 16000 0 2000 4000 6000 8000 10000 12000 14000 16000
Time (s) Time (s)

Fig. 6. Leaching of silver plate: effect of temperature. Fig. 8. Leaching of silver plate: effect of oxygen partial pressure.
 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70 67

80 -4,25
-3
25 mol m -4,30
70 -3
50 mol m
100 mol m
-3 -4,35
60
-3
150 mol m
mol Ag m x100

-4,40

Log leaching rate

-3
50 200 mol m
-3
400 mol m -4,45
-2

-3
40 600 mol m
-4,50

30 -4,55

20 -4,60

10 -4,65

-4,70
0
0 2000 4000 6000 8000 10000 12000 14000 16000 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0
Time (s) Log thiosulfate concentration

Fig. 9. Leaching of silver plate: effect of thiosulfate concentrations. Fig. 10. Leaching of silver plate: effect of thiosulfate concentrations. Determination of the
reaction order of the process.

were detected after any of the experiments. No typical products of

80
thiosulfate degradation were detected (elemental sulfur or sulfides). 75 -8 -3
1·10 mol m
70 -7 -3
1·10 mol m
65 -6 -3
1·10 mol m
3.2.5. Effect of hydronium concentrations 60 -4 -3

The experimental conditions employed were: stirring rate, 16.7 s−1,

1·10 mol m
55

mol Ag m x100
-2 -3
1·10 mol m
temperature, 298 K; PO2 = 1 atm and thiosulfate concentration, 50

200 mol m−3. The hydronium concentration varied between 1 · 10−8 45

-2

40
and 1 · 10−2 mol m−3. Thiosulfate degradation can occur when the hy- 35
dronium concentration in the system is higher than 1 · 10−1 mol m−3, 30
and under these conditions elemental sulfur forms. For this reason, the 25
study was conducted with hydronium concentrations lower than this 20
15
value. Fig. 11 includes the silver leaching rates versus time for all exper-
10
iments. Table 4 shows the values obtained for the silver leaching rate at 5
different hydronium concentration. Fig. 12 is the logarithm of the specif- 0
ic silver rates versus the logarithm of hydronium concentration. The re- 0 2000 4000 6000 8000 10000 12000 14000 16000
action order was 0.35 for hydronium concentrations between 1 · 10−8 Time (s)
and 1 · 10−7 mol m−3, with reaction rates between 1.60 · 10−5 and
5.10 · 10−5 mol Ag m−2 s−1, and 0 for hydronium concentrations be- Fig. 11. Leaching of silver plate: effect of hydronium concentrations.
tween 1 · 10−6 and 1 · 10−2 mol m− 3, with reaction rates of
5.10 · 10−5 mol Ag m−2 s−1. study was conducted without ammonia solution, as is usual in gold
and silver leaching studies using copper solutions.
3.2.6. Effect of the presence of Cu2+ An experiment was carried out with the same experimental condi-
The experimental conditions employed were: stirring rate, 16.7 s−1, tions, but with a PO2 = 0 atm (PN2 = 1 atm) for comparative purposes.
temperature, 298 K; pH 9; PO2 = 1 atm and thiosulfate concentration, Here, nitrogen was first sparged to displace the oxygen, and then the
200 mol m−3. The amount of copper added was 15 mol m−3. This copper salt was added to the system. The nitrogen sparging was main-
tained throughout the whole experiment. Values of specific silver

Table 3
Presents the specific leaching rates of silver at different thiosulfate concentration.
-4,3
Thiosulfate concentration (mol m-3) Leaching rate (mol Ag m-2 s-1)
-5
25 2.08·10
-4,4
50 2.75·10-5
Log leaching rate

100 3.45·10-5
150 4.30·10-5 -4,5
200 4.97·10-5
400 5.07·10-5
600 4.90·10-5 -4,6

-4,7
Table 4
Leaching rates of silver: effect of hydronium concentrations.
-4,8
pH Hydronium concentration (mol m−3) Leaching rate (mol Ag m−2 s−1)

11 1 · 10−8 1.60 · 10−5 -8 -7 -6 -5 -4 -3 -2

10 1 · 10−7 3.57 · 10−5 Log hydronium concentration
9 1 · 10−6 4.97 · 10−5
7 1 · 10−4 5.10 · 10−5
Fig. 12. Leaching of silver plate: effect of hydronium concentrations. Determination of the
5 1 · 10−2 5.04 · 10−5
reaction order of the process.
68 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70
Fig. 13. SEM-SE image of the precipitate detected on the surface of the silver plate.
rates (linear behavior) obtained, in mol Ag m−2 s−1, were: 4.97 · 10−5
(without copper ion or O2 and with N2), 7 · 10−5 (with copper ion and
O2) and 2.37 · 10−5 (with copper but without oxygen). These values
were obtained after 4 h of reaction. When oxygen and copper were
used, there was a combined oxidation effect of both (the sum of
4.97 · 10−5 and 2.37 · 10−5 is 7.34 · 10−5). This was approximately
the specific rate obtained in the experiment where both oxidant sys-
tems (oxygen and copper) were used. Thus, in the presence of oxygen
and copper, the reaction rate increased by approximately 30% with re-
spect to the process where copper was not used. The main reaction be-
tween silver and copper in the absence of oxygen can be expressed as:
Ag0 ðsÞ þ Cu2þ ðaqÞ þ 5 S2 O3 2− ðaqÞ → AgðS2 O3 Þ2 3− ðaqÞ ð7Þ
5−
þ CuðS2 O3 Þ3 ðaqÞ :
Several reactions were produced in parallel, and these mostly relat-
ed to thiosulfate decomposition. In the presence of copper ions in the
system, a milky product formed. X-ray diffraction indicated that this
product was elemental sulfur, which suggested that there was some de-
composition of the thiosulfate (see Reactions 3 and 5). Furthermore, a
thin layer of black precipitate was detected on the surface of the silver
plate (see Fig. 13, SEM image, secondary electrons). EDS indicated
Fig. 14. EDS of the precipitate detected in the silver plate.
(Fig. 14) that it was a porous layer that probably consisted of copper-
silver sulfide (partial decomposition of thiosulfate) and caused oxida-
tion of the silver plate without restrictions in the experimental condi-
tions employed. Fig. 15 is an X-ray diffractogram of this solid that
confirms the presence of CuAgS and AgCl (see Reaction 4). The presence
of some chloride was the result of a small amount of contamination of
the system by chloride. The precipitate of CuAgS can cause restrictions
in the reaction rate at times greater than 4 h.
An additional experiment was carried out, but in this case
60 mol m−3 of copper salt was used. This experiment was also conducted
for 4 h. At the end of the experiment, the silver plate appeared to have a
coating of silver-copper sulfide and after some additional time, the thio-
sulfate in the solution decomposed with the formation of the copper-
silver sulfide.
These results are similar to those obtained by our research team
(González-Lara et al., 2009), who studied the interaction between
thiosulfates and Cu (II) ions. Under certain experimental conditions,
the decomposition caused a precipitate of CuS and sulfate formation
was observed.
3.3. Leaching of a silver powder with the oxygen–thiosulfate system
The experimental conditions employed were: stirring rate, 16.7 s−1,
temperature, 298 K; pH 9; PO2 = 1 atm and thiosulfate concentration,
200 mol m−3. 5 g of silver powder was used in 500 dm−3 of solution.
Fig. 16 is a graph of silver conversion X versus time. Two rate
values were obtained, one in the interval between 0 and 3600 s
(1.32 · 10−5 s−1) and the other between 3600 and 14400 s
(0.98 · 10−5 s−1). No products other than metallic silver were detected
by XRD or SEM-EDS on the surface of the powder, and no passivation
layers were detected in the experimental conditions employed. The initial
silver powder presented a particle size of between 1 and 10 μm, and in the
first step of leaching, the smallest sizes were dissolved (0–3600 s) and a
leaching rate higher than the value in the step between 3600 and
14400 s was obtained. Particles smaller than 3 μm were not detected
after 4 h of reaction (see Fig. 17 obtained by SEM-SE), and therefore the
highest reaction rate values were obtained when the smallest particles
were present in the system. No thiosulfate decomposition was detected
in the experimental conditions employed (ion chromatography). No for-
mation of elemental sulfur or sulfides was detected (XRD and SEM).
 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70 69

Fig. 15. X-ray diffractogram of solids generated on the surface of the silver plate: 1—metallic silver; 2—AgCl; 3—AgCuS.

4. Conclusions
– The leaching reaction of silver in the oxygen–thiosulfate system
was:
2 Ag0 ðsÞ þ 4 S2 O3 2− ðaqÞ þ H2 O þ ½ O2 ðaqÞ → 2 AgðS2 O3 Þ2 3− ðaqÞ
þ 2 OH− ðaqÞ :
The thiosulfate concentration was constant during the process. No
oxidation or decomposition was detected. No passivation layers
were detected on the silver surface.
– An important effect of the stirring rate on the silver leaching rate was
detected. A change of regime, from laminar to turbulent flow, ap-
peared at a stirring speed of around 13.3 (s−1), and this increased
the oxygen transport in the solid–liquid interface and, thus, the reac-
tion rate. The rate of the process doubled between 8.3 and 15 s−1.
– The apparent activation energy of the process was 4.5 kJ mol− 1
(1.1 kcal mol−1). The order of reaction with respect to the oxygen
partial pressure was 1. Kinetics is controlled by mass transfer of
oxygen in the solid–liquid interface.
0,5
– The reaction order with respect to the thiosulfate concentration was
n = 0.41 between 25 and 200 mol m− 3. When the thiosulfate
concentration varied between 200 and 600 mol m−3, the reaction
order was 0.
– The reaction order with respect to hydronium concentration
was 0.35 between 1 · 10−8 and 1 · 10−7 mol m−3 and 0 between
1 · 10−6 and 1 · 10−2 mol m−3.
– The reaction between silver and copper in solution in the absence of
oxygen can be expressed as:
Ag0 ðsÞ þ Cu2þ ðaqÞ þ 5 S2 O3 2− ðaqÞ → AgðS2 O3 Þ2 3− ðaqÞ
þ CuðS2 O3 Þ3 5− ðaqÞ :
– In the presence of oxygen and copper, the reaction rate increased by
approximately 30% with respect to the process where copper was
not used. However, some thiosulfate decomposition and the forma-
tion of elemental sulfur and a porous layer of silver sulfide were de-
tected. When a higher copper concentration was used, thiosulfates
decomposed to sulfide and sulfates.
– The leaching process in the oxygen–thiosulfate system was applied
to a silver powder and resulted in similar behavior as that obtained
with silver plate. Two rate values were obtained, one in the interval
between 0 and 3600 s (1.32 · 10−5 s−1) and the other between 3600

0,4
Silver conversion

0,3

0,2

0,1

0,0
0 2000 4000 6000 8000 10000 12000 14000 16000

Time (s)

Fig. 16. Leaching of silver powder. Fig. 17. Metallic silver powder after leaching (SEM-SE).
70 I. Rivera et al. / Hydrometallurgy 156 (2015) 63–70
and 14400 s (0.98 · 10−5 s−1). The highest reaction rate values were
obtained when the smallest particles were present in the system
(between 0 and 3600 s). No passivation layers of silver sulfide
were observed in the experimental conditions employed.
Acknowledgments
We thank the Centres Científics i Tecnològics de la Universitat de
Barcelona for their assistance in the characterization studies carried
out in this work.
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