Accepted Manuscript

An electrochemical study of silver recovery in thiosulfate

solutions. A window towards the development of a simultaneous
electroleaching-electrodeposition process

D.A. Urzúa-Abarca, J.C. Fuentes-Aceituno, A. Uribe-Salas, Jae-

chun Lee

PII: S0304-386X(17)30701-6
DOI: doi:10.1016/j.hydromet.2018.01.017
Reference: HYDROM 4741
To appear in: Hydrometallurgy
Received date: 21 August 2017
Revised date: 18 January 2018
Accepted date: 20 January 2018

Please cite this article as: D.A. Urzúa-Abarca, J.C. Fuentes-Aceituno, A. Uribe-Salas, Jae-
chun Lee , An electrochemical study of silver recovery in thiosulfate solutions. A window
towards the development of a simultaneous electroleaching-electrodeposition process. The
address for the corresponding author was captured as affiliation for all authors. Please
check if appropriate. Hydrom(2017), doi:10.1016/j.hydromet.2018.01.017

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 ACCEPTED MANUSCRIPT

An Electrochemical Study of Silver Recovery in Thiosulfate Solutions. A Window

Towards the Development of a Simultaneous Electroleaching-Electrodeposition

Process

D.A. Urzúa-Abarcaa, J.C. Fuentes-Aceituno*a, A. Uribe-Salasa and Jae-chun Leeb

a
Centro de Investigación y de Estudios Avanzados del IPN-Saltillo, Av. Industria

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Metalúrgica # 1062, Parque Industrial Saltillo Ramos Arizpe, Ramos Arizpe, Coahuila,

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25900, México.
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral

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Resources (KIGAM), Daejeon 305-350, Korea.

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*Corresponding author: J.C. Fuentes-Aceituno (juan.fuentes@cinvestav.mx)
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Tel: +52 844 4389600, Ext 8512
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Abstract

The simultaneous electroleaching-electrodeposition of silver was studied systematically to

develop an alternate process for the recovery of metallic silver. The system was assessed
employing electrochemical and microstructural characterization techniques in a thiosulfate-
ammonia medium. The electrochemical studies revealed the dependence of silver
electroleaching rate in thiosulfate-ammonia solutions on different processes controlled by

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anodic potential. At the anodic potential below 200 mV SHE, the silver is electro-oxidized

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and complexed by the applied potential and thiosulfate, respectively. Increasing the
potential up to 445 mV SHE, the thiosulfate is oxidized and the silver leaching current is

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decreased due to the diffusional control of the leaching. It was also found that the sulfite
species formed from the thiosulfate decomposition can leach s mall amounts of metallic

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silver. Finally, at potentials from 695 to 795 mVSHE, the thiosulfate is further decomposed
and a silver sulfide film is generated which inhibits the silver dissolution. The simultaneous
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electroleaching-electrodeposition of silver was also studied in an electrolytic cell with
graphite electrodes at room temperature. The results showed that a 74% of silver can be
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recovered at a low applied current density of 0.066 mA/cm2 with a negligible thiosulfate
decomposition and a current efficiency of 76.54%. On the other hand, when the current is
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increased the silver recovery and current efficiency is decreased, due to the oxidative
decomposition of thiosulfate which promotes the formation of silver sulfide. These results
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are corroborated by the X-ray diffraction and SEM-EDS analyses.

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Keywords : Simultaneous electroleaching-electrodeposition; electro-oxidation; silver;

thiosulfate; recycling.
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1. Introduction

Currently cyanidation is the most used process in the hydrometallurgical industry to carry
out the leaching of precious metals from different sources (Zhang, 2004; Aylmore and
Muir, 2001). However, the main disadvantage of this process is the environmental risk
associated with the cyanide toxicity (Eisler and Wiemeyer, 2004; Aylmore, 2016a;

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Aylmore, 2016b). In view of this, the alternative hydrometallurgical techniques that have of

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late been investigated involve the use of thiourea and thiosulfate as the lixiviants

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(Abbruzzese et al., 1995; Xu et al. 2015; Deutsch and Dreisinger, 2013a, 2013b; Grosse et
al., 2003; Senanayake 2004, 2012; Örgül and Atalay, 2000, 2002; Yang et al., 2008;
Aylmore et al., 2014; Puente-Siller et al., 2013, 2014, 2017; Alvarado-Macías et al., 2015,

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2016). AN
As regards the metallic silver, it can be found in different wastes, e.g., the so-called urban
ores. From the sustainability point of view, it is extremely important to recover metallic
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silver from these urban ores. In this context, it is important to mention the attempts made
on the dissolution of metallic silver and silver compounds from the printed circuit boards
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(PCBs), electronics, spent catalysts, fabrics containing silver nanoparticles, jewelry, and X-
ray and photographic films (Ficeriová et al., 2008; Gurung et al., 2013; Jadhav and
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Hocheng, 2012; Pasricha et al., 2012; Pan-Pan et al., 2014; Ajiwe and Anyadiegwu, 2000;
Atia et al., 2014). The dissolution of metallic silver has been reported using the alternative
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leaching systems in the presence of thiosulfate or ozone (Viñals et al., 2005; Puente-Siller
et al., 2013, 2014, 2017; Alvarado-Macías et al., 2015, 2016; Rivera et al., 2015). From a
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kinetic viewpoint, the thiosulfate systems seem to be the most promising for the extraction
of precious metals including the silver (Aylmore and Muir, 2001). Recently, Barrick
developed a thiosulfate leaching process on commercial scale at Goldstrike, Nevada,
U.S.A. (Aylmore, 2016a; Aylmore, 2016b). However, the main disadvantage of the
thiosulfate systems relates to the susceptibility of thiosulfate to the oxidative degradation to
different polythionates due to the interaction of thiosulfate ions with the oxidizing agents
(e.g. cupric tetraamine), commonly found in the thiosulfate systems (Aylmore and Muir,
2001). Actually, Puente-Siller et al. (2013, 2014) and Alvarado-Macías et al. (2015, 2016)
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have recently shown that Cu-S coatings are formed on the silver particles due to the
degradation of thiosulfate. The coating of the Cu-S inhibits the direct contact between the
lixiviant and unreacted silver particles.

In order to reduce the thiosulfate degradation, different researchers have proposed the use
of complexing agents for cupric ions to lower the redox potential thereby moderating the
oxidizing ability of the system (Puente-Siller et al., 2013, 2014, 2017; Feng and Van

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Deventer, 2010). This suggests that silver may be leached in thiosulfate solutions using a

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device such as an electrolytic cell which can ensure the control of the oxidizing ability of

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the system and can minimize the thiosulfate degradation. Several authors have reported the
fundamental electrochemistry of gold in thiosulfate media (Pedraza et al., 1998; Zhang and

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Nicol, 2003; Baron et al., 2011, 2013; Breuer and Jeffrey, 2002; Jeffrey et al. 2003, 2008;
Zelinsky and Novgorotseva, 2013; Gudkov et al., 2010a; Zhang and Nicol, 2005; Zelinsky,
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2015; Zelinsky, 2014; Chu et al., 2003). However, only a few works related to the
electrochemistry of silver in thiosulfate solutions are reported in the literature, stressing the
electro-dissolution of silver electrodes (Bek and Shevtsova, 2011; Yavors´kyi et al., 1999).
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On the other hand, various electrolytic processes have been developed to electro- leach the
metals such as copper, nickel, cadmium etc, contained in different materials, e.g., minerals
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or e-wastes (Fuentes-Aceituno et al., 2008a; Martínez-Gómez et al., 2016; Guimaraes et al.,

2014; Hazotte et al., 2016). One of the main advantages of the electrolytic processes is
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related to the possibility of achieving the selective leaching of a metal of choice (Guimaraes
et al., 2014) depending upon the electrode potential (Fuentes-Aceituno et al., 2008a).
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Furthermore, it has been demonstrated that an electrolytic process can be versatile; i.e., it is
possible to carry out the simultaneous electroleaching-electrodeposition of metals such as
copper, nickel and cadmium (Guimaraes et al., 2014; Hazotte et al., 2016).

In this research, the electroleaching of silver with thiosulfate solutions has been studied in a
single chamber-three electrodes electrochemical cell, using carbon paste electrodes at
different applied anodic potentials to ensure the desired oxidizing conditions instead of a
chemical oxidant; this is attempted to gain a better understanding of the electroleaching
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behavior of silver and establish the most suitable conditions to accelerate the leaching
kinetics. This novel concept was employed to maximize the silver recovery and minimize
the energy consumption and thiosulfate decomposition in the simultaneous electroleaching-
electrodeposition (SEE) process at room temperature. This information can be used in
future to develop an efficient SEE reactor for the recovery of metallic silver contained in
different wastes, using thiosulfate solutions without using any chemical oxidizing agents
(e.g., cupric ions).

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2. Materials and Methods

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2.1. Materials

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Carbon paste electrodes (CPE) with and without electro-active species (Ag, Ag2 S) were
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prepared using graphite powder (Alfa Aesar, 99.9995%, 2-15 m), silicone oil (Sigma
Aldrich,  = 0.96 g/mL) as binder, silver powder (Alfa Aesar, 99.99%, 1.3-3.2 m), silver
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sulfide powder (Alfa Aesar, 99%, 5-15 m) as the electro-active species. These materials in
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the desired proportions were thoroughly mixed in an agate mortar to prepare the carbon
paste while using a polyethylene syringe (0.7 cm length and 0.2 cm inner diameter) as the
container for the paste. A platinum wire immersed in the mixture was welded to a copper
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wire with silver solder to establish the electrical contact with the carbon paste electrode. A
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1200-grit silicon carbide paper was used for renewing and polishing the carbon paste
electrode surface in all cyclic voltammetry tests.
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All electrolytic media were prepared in a 50 mL volumetric flask using reagent grade
chemicals (sodium thiosulfate, sodium sulfite and ammonium hydroxide ). All solutions
used in this study employed deionized water. High purity nitrogen was bubbled into the
solutions to eliminate the dissolved O2 and CO 2 .

Voltammetry and chronoamperometry tests were carried out in a conventional single

chamber-three electrodes electrochemical cell which consisted of a 100 mL beaker (Pyrex)
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with a three holes Teflon cap, a calomel reference electrode, SCE (Radiometer Analytical),
a graphite counter-electrode (Alfa Aesar, 99.99%), a carbon paste CPE with or without
electro-active species (Ag and Ag2 S), as the working electrode, and a magnetic stirrer. The
electrochemical cell was connected to a potentiostat/galvanostat (Versastat 4-400, PAR).

2.2. Preparation of the carbon paste electrodes with electro-active species (CPE-Ag or
CPE-Ag2 S)

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The procedure for preparing the carbon paste electrode containing the electro-active species
is as follows: 0.8 g of graphite powder and 0.2 g of the electro-active species (silver or
silver sulfide) were mixed in an agate mortar for 40 min, adding 0.20 mL of silicone oil to

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obtain a homogeneous paste (Fuentes-Aceituno et al., 2008b). Carbon paste electrodes
without the electro-active species were prepared in the same manner. The mixture was then
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placed in the polyethylene syringe and was compacted using the plunger. The exposed area
of the carbon paste electrodes to the electrolytic medium was about 0.0314 cm2 .
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2.3. Electrochemical experiments for the dissolution of silver

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Since one of the objectives of the present investigation is to study the dissolution of silver
as well as the oxidative destruction of thiosulfate at different conditions of anode potential
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employing carbon paste electrodes with and without electro-active species, several
solutions of thiosulfate and sulfite were assessed by cyclic and linear voltammetry or
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chronoamperometry techniques.

The electrolytic medium consisting of 50 mL of a 0.1, 0.2 and 0.3 M Na2 S2O3 or 0.2 M
Na2 S2 O3 with 0.05 M Na2 SO3 solution at pH 10.2, adjusted with ammonium hydroxide, and
room temperature was poured in the cell, and a stream of nitrogen was bubbled into the
solution for 30 minutes. Then the CPE (with or without silver) was placed in the cell as the
working electrode. The cell was connected to the potentiostat/galvanostat and open circuit
potential (OCP) measurements were performed until obtaining stationary potential
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readings. Then cyclic voltammograms were recorded with a potential sweep velocity of 25
mV/s from the OCP in the positive direction at different vertex (inversion) potentials (E )
(800 and 1000 mV SHE), finishing the cycle at the OCP. In order to electrochemically
characterize the solid products formed on the CPE-Ag surface during the anodic scan,
cyclic voltammograms were recorded with the pre-treated CPE-Ag and a fresh CPE-Ag2 S,
sweeping the potential at 25 mV/s from the OCP into the cathodic direction up to -800
mVSHE, and then finishing the cycle at the OCP.

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Stirred chronoamperommetric experiments were carried out using a CPE with 8.1 mg Ag

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impregnated on the exposed CPE surface. This electrode was prepared as follows: the CPE
surface was placed putting pressure on the silver powder (Alfa Aesar, 99.99%, 1.3-3.2 m)

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contained in a plate. A solution containing 0.2 M Na2 SO3 at pH 10.2 (adjusted with
ammonia) was assessed at room temperature. The chronoamperommetric curves were
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recorded applying an anodic potential of 425 mV SHE during 133 min. Samples of the
leaching solution were withdrawn at the end of the experiment to analyze silver by atomic
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absorption spectrometry (VARIAN Spectra AA 240).

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2.3.1. Characterization of the CPE-Ag surface

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Linear voltammetry and multiple cyclic voltammetry experiments were performed with a
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CPE-Ag in a solution of 0.2 M Na2 S2 O3 and pH 10.2 (adjusted with ammonia). The
multiple cyclic voltammetry experiments were performed sweeping the potential at 25
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mV/s from the OCP to 150 and 350 mVSHE. Linear voltammetry tests were repeated by
sweeping the potential from the OCP to 150, 364 and 695 mV SHE, these anode potentials
were held constant for 10 minutes. The CPE-Ag surface was then characterized by SEM
(PHILIPS XL-30 ESEM) and EDS techniques.
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2.4. Simultaneous electroleaching-electrodeposition (SEE) of silver in an undivided

electrolytic cell

The simultaneous electroleaching-electrodeposition of silver was evaluated in a 0.5 L batch

electrolytic cell (Fig. 1). The 5 Graphite plates with a total surface area of 121.21 cm2 were
employed as the cathode and 9 graphite plates with a total area of 230.76 cm2 were used as
the anode, respectively, which were connected to a power supply (Tektronix, PWS4305) to

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perform the simultaneous electroleaching-electrodeposition experiments at the

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galvanostatic regime.

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The procedure employed to carry out the electroleaching-electrodeposition experiments
was as follows: 0.5 L of an aqueous solution of 0.2 M thiosulfate at pH 10.2 and room

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temperature was placed in the electrolytic cell with 123 mg of pure silver powder (Alfa
Aesar, 99.99%, 1.3-3.2 m). The cell was magnetically stirred at 700 min-1 . A constant
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current of: 8, 12, 24 or 36 mA was applied in the electrolytic cell. Several samples were
withdrawn from the reactor at 2, 5, 10, 15, 20, 30, 40, 60, 90, 120, 180, 240 min, and the
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dissolved silver was analyzed by atomic absorption spectrometry (Spectra AA 220FS). The
quantification of the thiosulfate decomposition was carried out in some experiments, using
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the iodimetric titration method reported by Paredes-Soto (2014) and Puente-Siller et al.
(2017). The silver deposited on the cathode was digested in nitric acid and the silver
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concentration was quantified by atomic absorption spectrometry. In order to determine the

different secondary products that can be formed during the electroleaching process, the
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solid residues were filtered, rinsed with deionized water and were air dried. The solid
products were characterized by X-ray diffraction and SEM-EDS techniques.
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Fig. 1. Electrochemical cell employed to carry out the electroleaching-electrodeposition

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tests

3. Results and discussion

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3.1. Cyclic Voltammetry study for the silver electroleaching in thiosulfate solutions
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As one of the main objectives of the present research is to determine the most suitable
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conditions to electroleach the metallic silver in thiosulfate solutions employing an

electrolytic cell with graphite electrodes, the electroleaching tests were performed using
conventional techniques coupled with the surface characterization studies.

3.1.1. Silver electro-oxidation in thiosulfate-ammonia solutions

In order to have a similar scenario to that found in an electrolytic cell with graphite
electrodes (Fig. 1), the silver electroleaching was examined employing carbon paste
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electrodes with and without the presence of silver. Fig. 2 shows the cyclic voltammogram
obtained for a CPE immersed in a 0.2 M thiosulfate solution at pH 10.2. Fig. 2a reveals that
the thiosulfate decomposition along with oxygen evolution substantially increases at
potentials above 600 mVSHE, where the oxidation current is increased.

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Fig. 2. Cyclic voltammogram of the CPE without electro-active species: a) Voltammogram

recorded from the OCP to the positive direction at 25 mV/s without stirring, in a solution of
0.2 M S2O 32-, pH 10.2 (adjusted with ammonia) and 25°C. b) Zoom to the Figure 2a in the
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potential range from 200 to 700 mVSHE.

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Moreover, by magnifying the potential domain from 200 to 700 mV SHE (see Fig. 2b), the
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destruction of thiosulfate also occurs under these potentials as low as 200 mV SHE, although
at a lower rate. This suggests that silver electroleaching should be carried out at anode
potentials lower than 200 mVSHE to prevent the irreversible consumption of thiosulfate. It
can however, be observed from Figure 2b that thiosulfate decomposition is accelerated
when the anodic potential is higher than 600 mV SHE. It is possible to say from a
mechanistic view-point that the thiosulfate can be decomposed to other undesired products
when the anode potential is increased. For example, thiosulfate is oxidized to sulfite and
polythionates at pH 10.2, according to Zipperian et al., (1988) and Aylmore and Muir
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(2001). In this way, thiosulfate oxidation can produce tetrathionate according to Eq. (1)
(Breuer and Jeffrey, 2002):

2S2 O3 2- S4 O6 2- + 2e- (1)

In alkaline solutions tetrathionate can further decompose to sulfite according to Eq. (2) and
Eq. (3) (Zhang and Dresinger, 2002):

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4S4 O6 2- + 6OH- 5S2 O 3 2- + 2S3 O6 2- + 3H2 O (2)

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2S3 O6 2- + 6OH- S2 O3 2- + 4SO 3 2- + 3H2 O (3)

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Fig. 3 illustrates the cyclic voltammogram obtained for a CPE-Ag immersed in a 0.2M
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thiosulfate solution at pH 10.2, adjusted with ammonium hydroxide. The voltammogram
was recorded by sweeping the potential from the OCP to the positive direction at an anodic
vertex potential of 1045 mVSHE, and then reversing up to the cathodic vertex potential of -
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155 mV SHE, while finishing the cycle at the OCP. Three oxidation peaks identified as a), b)
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and c), are observed, during the anodic scan at 200, 400 and 695 mVSHE, approximately. It
is important to mention that these anodic peaks (Fig. 3) did not appeared in the CPE
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without silver (Fig. 2), which reveals that the anodic peaks a), b) and c) are associated with
three electrochemical events taking place with silver and the solution. Regarding peak a), it
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is possibly related to the electro-oxidation of metallic silver to the silver-thiosulfate

complexes, as stated in Eq. (4):
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Ag + xS2 O 3 2- [Ag(S2 O 3 )x ]1-2x + e- (4)

where x corresponds to 1, 2 or 3.

Actually, peak a) found in Fig. 3 is consistent with a previous research performed with pure
silver electrodes immersed in thiosulfate electrolytes (Bek and Shevtsova; 2010),
suggesting the production of silver thiosulfate complexes at this peak (a).
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In order to further confirm that peak a) is related to Eq. (4), the thiosulfate concentration
must be varied and the response to the current of peak be measured.

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Fig. 3. Cyclic voltammogram for the CPE-Ag employing a solution of 0.2 M S2 O3 2-, pH
10.2 (adjusted with ammonia) and 25°C. The voltammogram was obtained scanning the
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potential from the OCP to the positive direction at 25 mV/s.

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Fig. 4 shows the cyclic voltammograms obtained for 0.1, 0.2 and 0.3 M thiosulfate at pH
10.2. The voltammograms were recorded by sweeping the potential from the OCP to the
positive direction up to an anodic vertex potential of 845 mV SHE, and ending the cycle at
the OCP. The same oxidation peaks (a, b and c) are observed in both voltammograms (Figs.
3 & 4). It is evident that the thiosulfate concentration has a significant impact on the silver
oxidation current, since an increase of the thiosulfate concentration from 0.1 to 0.3 M
enhances the silver dissolution current of the first anodic peak. As mentioned before, this
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anodic peak corresponds to the electro-oxidation of metallic silver to the silver–thiosulfate

complexes [Ag(S2 O 3 )x ]1-2x , according to Eq. (4).

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Fig. 4. Cyclic voltammograms for the CPE-Ag immersed in solutions with different
thiosulfate concentration, pH 10.2 and 25°C. The voltammograms were obtained scanning
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the potential from the OCP to the positive direction at 25 mV/s without stirring.
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From a kinetic point of view, it was expected that an increase in the thiosulfate
concentration from 0.2 to 0.3 M, would promote a higher silver dissolution rate. However,
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according to Bek and Shevtsova (2010), the silver electroleaching is most probably
controlled by the diffusion of thiosulfate ions at the silver-solution interface and potentials
higher than 200 mVSHE.
The regularities of diffusion mass-transfer can be described by the Randles-Sevcik equation
(Eq. 5) (Bek and Shevtsova, 2010):

Im = 2.69x105 n3/2 SD1/2 (dE/dt)1/2 C (5)

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where Im is the peak current, mA; n is the number of electrons involved in the elementary
act of ionization and, according to Eq. (4), n = 1; S is the electrode surface area, cm2 ; D and
C are the diffusion coefficient (cm2 /s) and concentration of ligand (mol/cm3 ) in the bulk
solution; and dE/dt is the potential scan rate, mV/s.
Therefore, anodic polarizations were carried out for a CPE-Ag immersed in 0.2 M
thiosulfate at pH 10.2 varying the potential scan rate (Fig. 5). This information was used to
validate that the silver electroleaching at 200 mV SHE (peak a in Figs. 3 & 4) is controlled by

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the diffusion of thiosulfate ions at the silver-solution interface. As can be seen, the current

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is increased when the potential scan rate is increased. Furthermore, it is also possible to

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observe in Fig. 5 that the current (Im) of the first peak (a) increases linearly with increasing
the square root of the potential scan rate. This result is consistent with the Randles-Sevcik

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equation (Eq. 5) and ratifies the diffusion nature of the silver dissolution process at 200
mVSHE.
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Fig. 5. The dependence of current recorded at the first anodic peak of the polarization
curves on the square root of the potential scan rate. The anodic polarization curves were
obtained scanning the potential from the OCP to the positive direction at different scan rate
without stirring, using 0.2 M thiosulfate at pH 10.2 and 25°C.
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This diffusional control is in good agreement with the low increase in the current recorded
at peak a) when the thiosulfate concentration is increased from 0.2 to 0.3 M (Fig. 4).
Furthermore, according to Fig. 2, thiosulfate can be also anodically decomposed at
potentials higher than 200 mV SHE. Therefore, besides the thiosulfate consumption by silver
(Eq. 4), the thiosulfate decomposition promotes the depletion of thiosulfate ions in the
vicinity of electrode layer and consequently setting up a diffusional control regime.
Furthermore, the dependence of the thiosulfate concentration with the silver dissolution rate

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is also in good agreement with the results reported for the conventional leaching conducted

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(no-electrolytic) at varying thiosulfate concentrations (Zipperian et al., 1988; Abbruzesse et

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al., 1995).

Up to now, the results of Fig. 2, 3 and 4 have revealed that the first anodic peak is related to

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the electro-oxidation of metallic silver to the silver-thiosulfate complexes, according to Eq.
(4). From Figs. 3 and 4 it is also evident that the anodic current decreases at anodic
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potentials above 200 mV SHE, which suggests the decreased formation rate of silver-
thiosulfate, due to a diffusional control of the process (Fig. 5). On the other hand, the cyclic
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voltammograms presented in Figs. 3 and 4, clearly show the formation of two oxidation
peaks, which have not been reported in previous researches, at potentials higher than 200
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mVSHE, particularly the peaks b and c at 400 and 695 mV SHE, respectively (Fig. 3). Thus
two important points emerge here: a) thiosulfate is decomposed to polythionates and sulfite
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species when the applied potential is higher than 200 mV SHE, according to equations 1, 2
and 3, and b) the oxidation peaks (b and c) are related to two electrochemical events of the
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metallic silver with different species of the leach solution. Under this scenario, the
possibility to produce the silver-sulfite complexes Ag(SO 3 )3 -5 and Ag(SO 3 )2 -3 in alkaline
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solutions, is quite likely as reported by Baltrunas et al. (2008); these species can coexist
depending on the sulfite concentration in solution, according to Eq. (6), where x = 2 or 3.

Ag + xSO 3 2- Ag(SO 3 )x 1-2x + e- (6)

Furthermore, according to Kal´nyi et al. (2012) and Gudkov et al. (2010b) silver sulfite
complexes can be produced when metallic silver is oxidized in sulfite solutions. The sulfite
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species in the thiosulfate leach solution can be produced when the anodic potential is
increased above 200 mV SHE (see Eq. 1, 2 and 3). Therefore, probably once sulfite species
are produced, the remaining metallic silver on the electrode surface is electro-oxidized,
according to Eq. (6). Further evidence of this statement is presented in the next section, to
determine if the electrochemical event shown in Eq. (6) can occur at peak b) or c) of Fig. 2.

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3.1.2. Silver electro-oxidation in sulfite medium

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Cyclic voltammetries were carried out with a CPE-Ag immersed in two different solutions

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at pH 10.2: 0.2 M S2 O32- and 0.2 M S2 O 32- with 0.05 M SO3 2- (see Fig. 6), in order to
elucidate the phenomena occurring at peak b) and c) of Fig. 2. It may be mentioned that the

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addition of more ammonia in the thiosulfate-sulfite solution was necessary to reach pH
10.2, compared to that of the plain thiosulfate solution.
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Fig. 6. Cyclic voltammograms for the CPE-Ag at 25°C and pH 10.2 (adjusted with
ammonia), in the following solutions: 0.2 M S2 O3 2-, or 0.2 M S2O32- with 0.05 M SO3 2-.
The voltammograms were obtained scanning the potential from the OCP to the positive
direction at 25 mV/s without stirring.

Comparing the voltammograms of the thiosulfate and thiosulfate-sulfite solutions (see Fig.
6), it can be noted that the anodic peak b) is more defined and its current higher in the

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thiosulfate-sulfite solution, than that of the thiosulfate solution. Furthermore, peak b)

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occurs in the same potential range found with the thiosulfate solution, i.e. from around 345

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to 445 mV SHE. This result reveals that oxidation peak, b) in Fig. 6 corresponds to the
oxidation of silver to Ag(SO 3 )x 1-2x , as stated in Eq. (6). Also the peak b) of Fig. 6 coincides

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with the anodic potential found by Kal´nyi et al. (2012) to electro-oxidize the metallic
silver or silver alloys in sulfite alkaline solutions.
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In order to validate that metallic silver can be electro-dissolved in sulfite at an anodic
potential similar to that of peak b) (Fig. 6), Fig. 7 presents the results of a
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chronoamperometric experiment performed using a CPE containing 8.1 mg of silver

powder impregnated on its surface and a 0.2 M sulfite solution at pH 10.2. In this
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experiment a constant anodic potential of 425 mVSHE was applied during 133 min with
stirring.
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Fig. 7. Chronoamperometry of a CPE with impregnated silver particles on its surface, in a

solution of 0.2 M SO3 2- at pH 10.2 (adjusted with ammonia) and 25°C.
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Fig. 7 reveals that the anodic current decreases from 0.9 mA to 0.02 mA in about 120 min.
This decrease in the recorded current is related to the progressive silver leaching and to the
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shrinking surface of the silver particles that occur at this potential condition. In fact, the
measured silver concentration in the solution at the end of the experiment was found to be
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134.15 ppm Ag which corresponds to 82.8% of metallic silver initially present. This result
demonstrates that silver electro- leaching can also be carried out in the presence of sulfite
only, as per equation (6).

On the other hand, Figs. 3, 4 and 6 show the formation of peak c) at anodic potentials of
~695 mV SHE. As reported in the case of gold electrodes, the excessive oxidation of
thiosulfate can also produce a passivating film of sulfur compound (Pedraza et al., 1988). A
similar phenomenon may also occur in the silver electro-oxidation at very oxidizing
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conditions such as that of peak c). Therefore, with the aim of confirming this phenomenon,
additional multiple cyclic voltammetry and chronoamperometric experiments, and
microstructural characterization of the CPE-Ag surfaces were conducted, and the results
obtained are discussed.

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3.2. Characterization of the CPE-Ag surface obtained in thiosulfate-ammonia solutions

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under different anodic applied potentials

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With the aim of showing that below 150 mV SHE there is no formation of a sulfur film on the
electrode surface, it was decided to perform a multiple cyclic voltammetry test using a

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CPE-Ag immersed in a 0.2 M thiosulfate solution at pH 10.2, sweeping the potential from
the OCP to 150 mV SHE in the anodic direction. Fig. 8 presents the voltammograms showing
that the anodic current is gradually decreased from cycle to cycle, which further confirm
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the gradual dissolution of silver without being limited by any sulfur film on its surface.
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Fig. 8. a) Multiple cyclic Voltammograms (11 cycles) for the CPE-Ag electrode in a fresh
solution of 0.2 M S2 O32-, pH 10.2 and 25 °C; sweep rate: 25 mV/s without stirring. b)
Morphology of the CPE-Ag surface subjected to an anodic potential of 150 mVSHE during
10 min., c) EDS spectrum (Chemical composition) of the reacted CPE-Ag surface.
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The current decrease observed is associated with the gradual consumption of the reactants
(i.e., shrinking of silver particle and thiosulfate depletion) to produce a silver-thiosulfate
complex, according to Eq. (4). The Tafel equation shown in Eqs. (7, 8 and 9) can be used to
study the kinetics and mechanism of an electrochemical event (Fuentes-Aceituno and
Lapidus, 2012):

E = a + blni (7)

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a = -(RT)/(αnF) ln io

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(8)

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b = RT/αnF (9)

where, R is the universal gas constant, T is the temperature, α is the charge transfer

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coefficient, n is the number of transferred electrons, F is the Faraday´s constant and i0 is the
exchange current.
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The polarization data shown in Fig. 8a were analyzed for each cycle from 25 to 55 mV SHE,
using Eqs 7, 8 and 9 to determine any change in the Tafel slope parameter (b) and i0 , which
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are related to the controlling electrochemical mechanism and kinetics of the

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electrochemical event. Fig. 9 illustrates the evolution of the i0 in each cycle. As can be seen,
the i0 is decreased from cycle to cycle, which reveals that the silver electroleaching kinetics
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is gradually decreased due to a gradual consumption of reactants (silver and thiosulfate).

This behavior is consistent with the gradual decrease in the anodic current recorded as
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shown in Fig. 8a. The Tafel plots shown in Fig. 9 (see inlet figure) reveals that the Tafel
slope is practically the same in each polarization cycle ~36.91 mV/dec, which suggests that
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the same electrochemical event is taking place during all the cycles shown in Fig 8a. As
mentioned before this electrochemical event corresponds to the silver electro-oxidation in
the thiosulfate medium to produce a silver-thiosulfate complex, according to Eq. (4).
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Fig. 9. Evolution of the exchange current density and the anodic Tafel plots during the
multiple cyclic voltammetries shown in Fig. 8a.
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Figs. 8 b and c show the morphology and chemical composition of the CPE-Ag surface
subjected to an anodic potential of 150 mV SHE during 10 min, showing no evidence of
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formation of elemental S0 or any other sulfide compound (Fig. 8c), which is consistent with
the constant Tafel slope shown in Fig. 9, i.e., the silver electroleaching is taking place in
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Fig. 8a.

The EDS analysis reveals the presence of Ag, Si, C and O, the last three elements being
related to the binder employed in the CPE fabrication. In turn, the morphology of the CPE-
Ag surface (Fig. 8b) reveals the appearance of corrosion pits on the silver particle surface,
which are related to the leaching of silver. In order to show that the appearance of these pits
is a consequence of the electroleaching or corrosion of silver, Fig. 10a and b show the
micrographs of a fresh CPE-Ag without any treatment and the same CPE-Ag pre-treated in
a solution of 0.2 M thiosulfate at pH 10.2 and 150 mVSHE during 20 min. It is interesting to
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observe from these figures (area marked in circles) that some silver particles have been
effectively leached (Fig. 10b) applying this anodic potential during the test. It is also
evident that another silver particle was not completely leached (see silver particle located at
the left of the micrographs shown in Fig. 10a and b). Probably this silver particle was not
significantly leached due to the presence of abundant silicone oil on its surface. However, it
is possible to see some attack at the edges located in the upper part of the particle.

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Fig. 10. Characterization of a CPE-Ag with and without anodic applied potential. a)
Morphology of the CPE-Ag without any treatment, b) Morphology of the same CPE-Ag
treated at 150 mVSHE during 20 min.
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This result is in good agreement with the occurrence of the corrosion pits shown in Fig. 8b,
which are related to the progressive silver leaching as well as with the gradual decrease in
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current shown in Fig. 8a.

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Equivalent cyclic voltammetry and microstructural characterization tests were also

performed with a CPE-Ag immersed in a 0.2 M thiosulfate solution at pH 10.2, increasing
the anodic potential from the OCP to 350 mV SHE. Fig. 11a shows the multiple cyclic
voltammograms recorded. It is evident that the anodic current decreased drastically from
the first to the second cycle, dropping to zero at the fourth cycle. This behavior reveals that
silver electroleaching is hindered. As mentioned above, silver leaching presents a diffusive
control when the anodic potential is increased above 200 mV SHE, due to a decrease in the
interfacial thiosulfate concentration, which is probably caused by the consumption of
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thiosulfate through the Equations 1, 2, 3 and 4. Therefore, the interfacial thiosulfate

concentration is decreased considerably in each voltammetry cycle.

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Fig. 11. a) Multiple cyclic Voltammograms (11 cycles) for the CPE-Ag electrode in a
solution of 0.2 M S2 O32-, pH 10.2 and 25°C, sweep rate: 25 mV/s without stirring b)
Morphology of the CPE-Ag surface subjected to an anodic potential of 364 mV SHE during
10 min. c) EDS spectrum (Chemical composition) of the reacted CPE-Ag surface.

As mentioned before, the increase in anodic potential above 200 mV SHE results in the
oxidation of thiosulfate (Eq. 1) to polythionates, and promotes the formation of sulfite
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species (Eq. 2 and 3). As shown in Fig. 6 and 7, the sulfite species may complex silver in
the anodic potential domain from 345 to 445 mVSHE (peak b in Fig. 6). The formation of
sulfur compounds on the CPE-Ag is also possible when the anodic potential is increased up
to the range 345 to 445 mV SHE. Therefore, it would be interesting to characterize the solid
products formed on the CPE-Ag subjected to this potential range. SEM and EDS analyses
(Figures 11b and 11c), for the CPE-Ag surface subjected to an anodic potential of 364
mVSHE for 10 min, clearly reveal absence of a sulfur layer or sulfur compound on the silver

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surface. The EDS (Fig. 11c) only shows the presence of Ag, Si, C and O as mentioned

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before; particularly the last three elements are related to the non-conductive binder. The

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micrograph of this CPE-Ag surface (see zoom in Fig. 11b) shows the pitting of the silver
particles, which are associated with the silver leaching process.

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Finally, Fig. 12a displays the back scattered electron image of a CPE-Ag immersed in a 0.2
M thiosulfate solution at pH 10.2, that was set to an anodic potential of 695 mV SHE during
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10 min. This anodic potential corresponds to the potential where the electrochemical event
labeled as peak c) takes place (Fig. 3). Fig. 12a also shows that the silver particles have
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fewer pits compared to that of Figures 8b and 11b; this is related to the low silver
dissolution under this anodic potential.
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Fig. 12. SEM images of the CPE-Ag surface subjected to an anodic potential of 695 mV SHE
during 10 min. a) Morphology of the reacted surface. b) EDS spectrum (Chemical
composition) of the reacted CPE-Ag surface.
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Fig. 12b displays the EDS analysis of the CPE-Ag surface, revealing the presence of Ag, S,
Si, C, and O; it is interesting to emphasize the presence of sulfur on the surface. This means
that a sulfur species film can be produced under this anodic potential (695 mV SHE), which
inhibits silver dissolution. The presence of this sulfur species film reveals that thiosulfate
oxidative degradation is accelerated at this anodic condition (peak c, Fig. 3). Actually,

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according to Fig. 2b, thiosulfate degradation is favored at this anodic potential (695

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mVSHE), e.g., the recorded anodic current at 695 mVSHE was about 0.00018 mA, which is

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partially associated with the excessive thiosulfate decomposition. Under the oxidizing
conditions, thiosulfate can be oxidized to tetrathionate (Eq. 1) and can also be
disproportionated into sulfite and sulfide ion (Aylmore and Muir (2001); Groose et al.,

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2003), according Eq. (10): AN
3S2 O3 2- + 6OH- = 4SO 3 2- + 2S2- + 3H2 O (10)

Sulfide ion (S2-) or even hydrogen sulfide ion (HS -) promotes the precipitation of silver as
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an insoluble sulfur compound (Aylmore and Muir, 2001; Gudkov et al., 2010a and b).
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Therefore, the presence of Ag and S in the EDS analysis (Fig. 12b) can be related to the
formation of silver sulfide on the metallic silver surface.
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In order to confirm that the sulfur film produced at this anodic potential consisted of silver
sulfide, a CPE-Ag was pre-treated at 695, 745 and 795 mV SHE during 20 min in a 0.2 M
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thiosulfate solution at pH 10.2. These pre-treated electrodes were then immersed in a fresh
solution of 0.2 M thiosulfate at pH 10.2, and a cyclic voltammogram was recorded from the
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OCP to -800 mV SHE concluding the cycle at the OCP. Fig. 13 shows the cyclic
voltammograms carried out in the cathodic direction for the CPE-Ag pre-treated at 695, 745
and 795 mVSHE, where the formation of a peak labeled as d) appeared at -735 mVSHE.
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Fig. 13. Cyclic voltammograms for the CPE-Ag pre-treated at 695, 745 and 795 mV SHE
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employing a solution of 0.2 M S2 O3 2-, pH 10.2 and 25°C. The voltammograms were
obtained scanning the potential from the OCP to the negative direction at 25 mV/s
employing a fresh solution of 0.2 M S2 O3 2-, pH 10.2 and 25°C.
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This peak represents the reduction of the solid products formed during the anodic pre-
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treatment, in the present case it may be related to the reduction of silver sulfide to metallic
silver. It is also interesting to observe that when the potential of the anodic pre-treatment is
increased, the current magnitude of the reduction peak d) is increased. This reveals that the
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quantity of the silver sulfide formed at 795 mV SHE is higher than that of 695 and 745
mVSHE. In order to confirm that peak d) represents the reduction of silver sulfide to silver, a
CPE-Ag2 S was prepared and a cyclic voltammogram (Fig. 14) was recorded in 0.2 M
thiosulfate at pH 10.2, sweeping the potential from the OCP to the vertex potentials of -755
and 545 mVSHE, while finishing the cycle at the OCP.
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Fig. 14. Cyclic voltammogram for the CPE-Ag2 S employing a solution of 0.2 M S2 O32-, pH
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10.2 (adjusted with ammonia) at 25°C. The voltammogram was obtained scanning the
potential from the OCP to the negative direction at 25 mV/s.
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Fig. 14 shows the appearance of the same peak d) at -735 mV SHE, confirming that the peak
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d) of Fig. 13 corresponds to the reduction of silver sulfide to metallic silver. Further the
appearance of two re-oxidation peaks in Fig. 14 corresponds to the oxidation of the metallic
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silver formed during the reduction (peak d, Fig. 14). These re-oxidation peaks are
associated with the electroleaching of metallic silver as shown in Figures 3 and 4.

3.3. Simultaneous electroleaching-electrodeposition (SEE) of silver

Having established the silver electroleaching with electrochemical and surface

characterization techniques, the simultaneous electroleaching-electrodeposition of silver
employing thiosulfate-ammonia solutions in an undivided electrolytic cell is examined,
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with the aim of developing an alternative technology which permits the recovery of
metallic silver minimizing the thiosulfate decomposition and the energy consumption. It is
worth mentioning that, this first paper is only focused on the electrochemistry for the silver
electroleaching to arrive at the suitab le electric potential that can facilitate the silver
electroleaching while minimizing the thiosulfate decomposition. For this reason, the effect
of the applied current in the SEE process is presented in the next section and the results are
discussed based on the fundamental electrochemistry study shown in the previous sections.

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The effect of time, temperature, and thiosulfate concentration on the silver recovery with

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the SEE process will be presented and discussed in our next paper.

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3.3.1. Effect of the applied current

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In order to determine the effect of the applied current on the silver recovery, the SEE
process was examined using a leaching solution containing 123 mg of silver powder, 0.2M
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thiosulfate at pH 10.2 (adjusted with ammonia) and applying a constant current of 8, 12, 24
and 36 mA during 4 h. Table 1 shows the percentage (%) of silver electrodeposited on the
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cathode and the silver (%) present in the leaching solution at 240 min at different applied
constant currents.
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Table 1. Silver recovery using the SEE process at different applied currents and 240 min.
Electrolytic medium: 0.2 M S2 O 3 2-, pH 10.2, 25°C.

Test % Ag % Ag Current Density Current

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Deposited Solution (mA/cm ) Efficiency
Cathode 
Anode
8 mA 74.12 0.45 0.066 0.035 76.54

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12 mA 64.91 0.37
0.099

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0.052 44.75

24 mA 33.24 0.6

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0.198 0.104 11.41

36 mA 1.36 0.8 0.31

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0.297 0.156
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Table 1 shows that when the SEE process is carried out at 8 mA, the silver recovery (% Ag
deposited on the cathode) is the highest among all the assessed currents i.e., 74.12%. On the
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other hand, the % of silver recovered at 12, 24 and 36 mA corresponds to 64.91, 33.24 and
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1.36%, respectively. Results also showed that on applying the lower current of 6 mA, the
silver electroleaching kinetics decreased (data not included in this paper), as expected due
to the dependence of kinetics on the potential related to the applied current. These results
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infer that the SEE process is more efficient for the silver recovery at the lower applied
current, which is most probably due to a decrease in the rate of parasite reactions e.g.,
decomposition of the electrolytic medium.

The current efficiency can be calculated using Eq. (11) as a function of the mass of silver
deposited on the cathode at 240 min:

%φ = (Q Ag/Qtot )100% = (mAgFn/It)100% (11)

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where Q Ag = cumulative charge used in the reduction of [Ag(S2 O3 )x ]1-2x to Ag according to

Equation 4, Q tot = total cumulative charge passed through the cell, mAg = moles of silver
deposited on the cathode, F = Faraday’s constant, I = applied current, t = time (s) and n =
number of electrons transferred, according to Equation 4, n = 1.

As can be seen the current efficiency is considerably decreased when the applied current is
increased, e.g., a current efficiency of 76.54, 44.75, 11.41 and 0.31% is obtained for the

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SEE process operated at 8, 12, 24 and 36 mA, respectively. This result reveals that in the

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experiment performed at 8mA, the current was predominantly used to achieve the

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electroleaching-electrodeposition of silver, with minimal decomposition of the electrolytic
medium. On the other hand, the considerable decrease of the current efficiency found at 12,
24 and 36 mA, is a consequence of the favored electrolytic medium decomposition. In fact,

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the current efficiency for the case operated at 36mA corresponds to 0.31%, which indicates
almost complete consumption of the current is related to the decomposition of the
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electrolytic medium; e.g., decomposition of thiosulfate as well as the reactions involving
evolution of hydrogen and oxygen. As shown in Figures 2 and 12, the anodic
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decomposition of thiosulfate is significant at anodic potentials higher than 695 mV SHE;

actually the massive decomposition of thiosulfate at these potentials could promote and
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accelerate the precipitation of silver as silver sulfide. Therefore, the anodic and cathodic
potentials as well as the cell voltage were measured in the experiments shown in Table 1.
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These measurements are illustrated in Fig. 15, for the experiments performed at 8, 12, 24
and 36 mA.
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Fig. 15. Evolution of a) anodic potential, b) cathodic potential and c) cell voltage for the
SEE process shown in Table 1 at different applied currents. Conditions (SEE experiments):
0.2 M thiosulfate, pH 10.2, 25 ºC.
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It is evident from Fig. 15, that an increase in the applied current promotes an increase in the
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anodic and cathodic potentials (Figures 15a and b), which consequently increases the cell
voltage (Fig. 15 c). An excessive increase in the cell energy would favor the decomposition
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of the electrolytic medium. The average anodic potential for the SEE experiments
performed at 8, 12, 24 and 36 mA corresponds to 640, 710, 800 and 850 mV SHE,
respectively. According to Fig. 3 and 12, silver sulfide formation is favored at ~695 mV SHE.
Thus, besides the silver electroleaching-electrodeposition reaction, the precipitation of
silver sulfide due to the accelerated thiosulfate decomposition, also takes place at 12, 24
and 36 mA, where the anodic potential was higher than 695 mVSHE.

On the other hand, the SEE test performed at 8 mA has no silver sulfide formation, in view
of the lower anodic potential (Figure 15a) recorded (< 695 mV SHE) during the experiment.
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Consequently, the energy in the cell is predominantly consumed to ensure the silver
electroleaching-electrodeposition process, minimizing the thiosulfate degradation and silver
precipitation as silver sulfide. Fig. 16 shows the thiosulfate concentration measured in the
systems operated at 8 mA and 36 mA. As can be seen, the thiosulfate concentration is
practically the same during all the test (~0.2M) for the system operated at 8 mA, revealing
that the thiosulfate decomposition is negligible under this energetic condition. Whilst for
the system operated at 36 mA, it is found that the thiosulfate concentration decreased from

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0.2 to 0.1M approximately, indicating that thiosulfate is significantly decomposed. This

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result is very important in terms of the process operability due to the next issue; the

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minimization of the thiosulfate degradation at 8 mA, suggests that the thiosulfate solution
can be re-utilized to perform the SEE process for silver recovery. Despite the negligible

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decomposition of thiosulfate found at 8 mA (Fig. 16), the current efficiency is 76.54%,
probably this low current efficiency can be related to the occurrence of other parasite
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reactions involving the evolution of hydrogen and oxygen. Actually, it has been reported in
the literature that hydrogen evolution can take place on carbon surfaces at underpotential
energetic conditions, i.e., near the open circuit potential (Fuentes-Aceituno and Lapidus,
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2012; El-Deab and Saleh; 2003). On the other hand, the electrolytic cell shown in Fig. 1
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must be improved in order to maximize the direct contact of silver particles with the anode,
assessing the effect of time, temperature, and thiosulfate concentration on the silver
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recovery. This result also suggests that the SEE process can be evaluated employing a
different leaching-stable medium or additives which retard or avoid the evolution of
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hydrogen and oxygen. Optimizing all this may increase the current efficiency; the details
will be presented in the next paper(s).
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Fig. 16. Quantification of the thiosulfate concentration during the experiments performed at
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8 mA and 36 mA with 0.2 M thiosulfate, pH 10.2, 25 ºC.

3.3.2. Characterization of the leach solid residues obtained during the silver
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electroleaching
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In order to confirm that silver sulfide is formed when the SEE is operated at applied
currents higher than 8 mA, the solid residues obtained during the silver electroleaching tests
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shown in Table 1 were characterized by X-ray diffraction and SEM-EDS techniques.

The XRD analysis (Fig. 17) illustrates the formation of silver sulfide in the SEE
experiments performed at applied currents higher than 8 mA, e.g., the presence of silver
sulfide is perceivable in the solid residues obtained at 12 and 36 mA. On the other hand, the
solid residue obtained at 8 mA shows the presence of only the unreacted metallic silver. As
previously mentioned, the formation of silver sulfide in the experiments performed at 12
and 36 mA, can be related to the excessive thiosulfate decomposition found at potentials
higher than 695 mV SHE (Fig. 2), which promotes the formation of silver sulfide (peak c of
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Fig. 3, Fig. 12). Actually, both the experiments (i.e., at 12 and 36 mA) were operated at
average anodic potentials of 710 and 850 mV SHE (see Fig. 15a). Furthermore, as shown in
Fig. 16 a half of the thiosulfate present initially is decomposed when the current in
increased to 36 mA.

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Fig. 17. X-ray diffraction patterns of the leach solid residues obtained from the silver
electroleaching carried out at 240 min and 8, 12 or 36 mA. The SEE experiments were done
using 0.2 M thiosulfate at pH 10.2 and 25ºC.

With respect to the leach solid residues obtained at 12 and 36 mA, the presence of metallic
silver is observed, which is consistent with the results shown in Table 1. In order to
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complement the X-ray characterization analysis, the solid residues obtained at 12 and 36
mA, were also characterized by SEM-EDS techniques as shown in Fig. 18. Fig. 18a and b
confirm the formation of silver sulfide on the silver particles for the experiments performed
at 12 and 36 mA. As discussed above, silver sulfide species are formed from the oxidative
decomposition of thiosulfate. Furthermore, the formation of a considerable amount of silver
sulfide in the solid residues (Fig. 18a and b) coats the unreacted metallic silver particles
retarding the electroleaching.

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Up to now, the results presented in this paper for pure silver, revealed the possibility to

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electroleach-electrodeposit the silver simultaneously in thiosulfate solutions, establishing
the electrochemical and surface characterization techniques as important evidence of the
energetic conditions as well as the products that can be formed under different scenarios.

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This concept could be applied with a waste containing other metals like Cu, to evaluate the
effect of other solid impurities on the silver recovery efficiency with the SEE process.
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However, this information will be presented in our next paper.
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Fig. 18. SEM-EDS characterization of the leach solid residues obtained during the silver
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electroleaching at a) 12 mA and b) 36 mA.

4. Conclusions
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In this investigation, the simultaneous electroleaching-electrodeposition of silver has been

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studied systematically in thiosulfate solutions. Initially the investigation involved the silver
electroleaching process using electrochemical techniques complemented with SEM-EDS
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characterization. The results show that silver is electro-oxidized to the complex

[Ag(S2 O3 )x ]1-2x at an anodic potential lower than 200 mV SHE. It is further observed that
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excessive thiosulfate oxidation is avoided by using a potential below 200 mV SHE. In

addition, an increase of the thiosulfate concentration from 0.1 M to 0.3 M promotes an
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increase of the silver dissolution current at 200 mV SHE. When the anodic potential is
increased up to 345 a 445 mV SHE, silver can also be electro-oxidized in the presence of
sulfite ions generated from the oxidative decomposition of thiosulfate. The excessive
thiosulfate decomposition produces a silver sulfide film on the surface of silver particles at
an anodic potential of 695 mVSHE; this sulfur layer hinders the silver dissolution reaction.

The simultaneous electroleaching-electrodeposition of silver was then studied using a

conventional undivided electrolytic cell with graphite electrodes, at different applied
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currents. The results reveal that the system operated at the lowest applied current i.e., 8 mA,
is most efficient to recover the silver (74%) minimizing the formation of parasite reactions.
On the other hand, when the system is operated at 12, 24 and 36 mA, it is possible to
recover a 64, 33 and 1% of silver, respectively. The inefficient silver recovery is related to
the occurrence of parasite reactions, such as the excessive thiosulfate decomposition which
is favored at the anodic potentials higher than 695 mV SHE. The X-ray diffraction and SEM-
EDS analyses reveal the formation of silver sulfide on the silver particles at 12 and 36mA.

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The results also provide the possibility of silver recovery using the “simultaneous

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electroleaching-electrodeposition process” in the presence of less toxic reagents such as

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thiosulfate, while applying the lower currents. Furthermore, this opens up a promising
opportunity to continue investigating the SEE process from a kinetic and optimization

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viewpoint, considering alternative electrode materials, aiming at the silver recovery from
urban ores.
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Acknowledgements
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The authors are grateful to CONACyT (México) for the postgraduate scholarship awarded
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to Daniel Alejandro Urzúa-Abarca. Also, the collaboration of Ana Elena Muñiz, Felipe
Márquez, Sergio Rodriguez Arias and Socorro García in this investigation is duly
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recognized.
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Abbruzzese, C., Fornari, P., Massidda, R., Veglió, F., Ubaldini, S., 1995. Thiosulphate
leaching for gold hydrometallurgy. Hydrometallurgy. 39, 265-276.

Ajiwe, V.I.E., Anyadiegwu, I.E., 2000. Recovery of silver from industrial wastes, cassava
solution effects. Separation and Purification Technology. 18, 89-92.

Alvarado-Macías, G., Fuentes-Aceituno, J.C., Nava-Alonso, F., 2015. Silver leaching with
the thiosulfate-nitrite-sulfite-copper alternative system. Hydrometallurgy. 152, 120-

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HIGHLIGHTS

 The SEE process is a novel and promising alternative for silver recovery.

 Metallic silver can be recovered with a current efficiency of 76%.

 Thiosulfate decomposition is decreased at E<200 mVSHE.

 Silver sulfide is precipitated at I > 8 mA and E > 695mVSHE.

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 About 74% silver can be recovered at 8mA and 4h.

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