Hydrometallurgy 76 (2005) 233 – 238

www.elsevier.com/locate/hydromet

Short communication

Kinetic model for anodic oxidation of gold in thiosulfate

media based on the adsorption of MS2O3
ion-pair
Gamini Senanayake*
A.J. Parker Cooperative Research Centre for Hydrometallurgy, Department of Mineral Science and Extractive Metallurgy,
Murdoch University, Perth, WA 6150, Australia
Received 6 September 2004; received in revised form 9 November 2004; accepted 15 November 2004

Abstract

It has been the general practice amongst researchers to use the molar concentration of thiosulfate salts to be the same as that
of S2O32
ions involved in various equilibrium or rate expressions for interpreting gold oxidation kinetics. However, chemical
speciation analysis based on the association of thiosulfate ion with monovalent cations (ion-pair formation) shows that the
concentration of free S2O32
ions is lower than that of associated MS2O3
ions (M=Na, K, NH4). Analysis of literature data on
electrochemical oxidation rates of gold in non-ammoniacal alkaline sodium thiosulfate solutions based on the adsorption of
NaS2O3
shows that the rate constant for gold oxidation is 4.210
4 mol m
2 s
1.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Gold oxidation; Thiosulfate; Ion-pair; Adsorption; Oxidation mechanism

1. Introduction thiosulfate systems in the absence of ammonia.

Recent publications by Ritchie et al. (2001) and
Muir and Aylmore (2003) have reviewed the
advantages and problems associated with gold
leaching and recovery using thiosulfate in the
presence of ammonia and copper(II). The increased
interest in non-ammoniacal thiosulfate systems for
leaching and recovery of gold (Ji et al., 2003)
highlights the importance of kinetic studies in
* Tel.: +61 8 93602833; fax: +61 8 93606343.
E-mail address: gamini@murdoch.edu.au.
0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.11.002
Fundamental studies on gold oxidation play an
important role in rationalising the complex leaching
behaviour of different types of gold ores and the
effect of the background reagents, some of which are
essential for gold oxidation.
It is generally accepted that the reaction mecha-
nism and rate of a heterogeneous reaction, such as
gold dissolution, involves the following steps:
(i) diffusion (mass transfer) of reactants to the
surface,
(ii) surface adsorption,
(iii) chemical reaction at surface,
234 G. Senanayake / Hydrometallurgy 76 (2005) 233–238

Fig. 1. Log–log plot of K(MS2O

3 ) vs. K(MSO4 ) for association of thiosulfate and sulfate ions with cations (data at I=0 and 25 8C from Sillen
and Martell, 1964; Hogfeldt, 1982).

(iv) desorption/stabilisation, sodium thiosulfate concentration from 0.05 to 1 M,

(v) diffusion of products away from the surface into
the bulk solution.
Depending on the slowest step the reaction is
chemically controlled (step iii or iv) or diffusion
controlled (step i or v).
Wang (1992) measured the anodic currents of a
gold electrode in sodium thiosulfate solutions at pH
10 in the absence of ammonia. The peak currents
showed a 2-fold increase with a 20-fold increase in
while the peak potentials decreased with increasing
thiosulfate concentration. At higher potentials, thio-
sulfate was also oxidized while gold was passivated
(Wang, 1992). Zhang and Nicol (2003) also showed
that the rate of anodic oxidation of gold in non-
ammoniacal alkaline (0.1 M NaOH) sodium thio-
sulfate solutions increased with the increase in
sodium thiosulfate concentration from 0.1 to 1 M.
In most fundamental studies the thiosulfate ion
concentration in solution [S2O32
] has been consid-

Fig. 2. Effect of sodium thiosulfate concentration on gold oxidation rates and chemical species distribution in Na2S2O3/0.1 M NaOH/0.25 V/25
8C (rate data from Zhang and Nicol, 2003).
 G. Senanayake / Hydrometallurgy 76 (2005) 233–238
ered to be equal to the molar concentration of the
relevant salt added, for example sodium thiosulfate
or ammonium thiosulfate. However, there is
evidence for association between the thiosulfate
ions and cations such as H+, Na+, K+ to form
ion-pairs of the type MS2O3
(Sillen and Martell,
1964; Hogfeldt, 1982). Moreover, recent electro-
chemical results reported by Chandra and Jeffrey
(2004) showed that the gold oxidation from a
rotating disc in a non-ammoniacal solution of
potassium thiosulfate was faster than that in sodium
thiosulfate at the same salt concentration of 0.2 M
and at an applied potential of 0.25 V, under argon.
This has been related to the association between
thiosulfate and the alkali metal ion, but no attempt
has been made for a quantitative analysis. Recent
concurrent thermodynamic and kinetic analysis of
literature data on gold oxidation has shown the
importance of considering the adsorption of thio-
sulfate ion onto the gold surface (Senanayake, 2004).
This short communication presents a detailed anal-
ysis of literature data by taking into account the
ion-association described in Eq. (1) and thus ration-
alising the rate data on the basis of associated
thiosulfate (NaS2O3
) ions rather than free thiosulfate
(S2O32
).
þ
M þ S2 O2

3 ¼ MS2 O

3 ð1Þ
Fig. 3. Log–log plots of gold oxidation rate vs. concentration of S2O2

235
2. Chemical speciation and rate of gold oxidation
Fig. 1 shows a log–log plot of association
constants of thiosulfate vs. sulfate with the three
cations H+, Na+ and K+. The approximate linear
relationship indicates the validity of the equilibrium
constants reported in the literature (Sillen and Martell,
1964; Hogfeldt, 1982), thus, they can be used in
the present analysis. The rate data (R Au) are shown in
Fig. 2, to highlight the effect of initial thiosulfate
concentration (0.1–1 M) based on the electrochemical
data presented by Zhang and Nicol (2003). Fig. 2
also plots the concentrations of the three species
Na+, NaS2O3
and S2O32
calculated in the present
study based on equilibrium constants reported in
Fig. 1. No attempt was made to correct for ionic
activity coefficients. It is clear that the concentration
of NaS2O3
is much higher than that of S2O32
.
The increase in R Au seems to be proportional to
the increase in concentration of NaS2O3
and/or
S2O32
.
3. Reaction order with respect to S2O32
and
NaS2O3

Fig. 3 shows the log–log plots of R Au vs. [S2O32
]
or [NaS2O3
]. The slopes of these curves can be


3 and NaS2O3 (data from Fig. 2).
236 G. Senanayake / Hydrometallurgy 76 (2005) 233–238

considered as the reaction order with respect to each following equations, where M+ represents Na+ or
species. Thus, for electrochemical oxidation of gold K+:
the reaction order with respect to [S2O32
] and Adsorption
[NaS2O3
] appears to be c3 and 1, respectively.
The fact that NaS2O3
is more predominant than pAu þ MS2 O


3 ¼ pAuðS2 O3 ÞMðadsÞ ð2Þ
S2O32
(Fig. 2) suggests that it is more appropriate to
consider the rate data and reaction mechanism on the Anodic oxidation
basis of NaS2O3
rather than S2O32
.
pAuðS2 O3 ÞM
0
ðadsÞ ¼ pAuðS2 O3 ÞMðads=aqÞ þ e ð3Þ

4. Adsorption/electrochemical kinetic model Desorption/stabilisation

The electrochemical oxidation of gold in sodium pAuðS2 O3 ÞM0ðads=aqÞ þ MS2 O

3

thiosulfate solutions can be expressed by the ¼ M2 AuðS2 O3 Þ

2ðaqÞ ð4Þ

Fig. 4. Plot of (a) [NaS2O

3]

1
or (b) [S2O2

3 ]

1
against (R Au)
1 to examine validity of Eq. (8).
 G. Senanayake / Hydrometallurgy 76 (2005) 233–238 237

Table 1 1 summarizes the values of K ads=
intercept and

Surface thermodynamic (K ads) and kinetic (k Au) parameters for gold k Au=
slope/intercept based on Fig. 4a–b. However,
oxidation
the negative value for K ads and k Au can be ruled out
Figure Intercept Slope K ads k Au (mol m
2 s
1)
because the equilibrium constant for adsorption of

3
6
3
4a
4.810 210 4.810 4.210
4 ions onto an electrode, and the rate constant cannot be
4b +4.57 610
7
4.57
1.310
7
negative. These observations support the validity of
(unacceptable)
the mechanism proposed in Eqs. (2)–(4); and the rate
expression in Eq. (8) based on the adsorption of
Assuming a surface coverage of h the adsorption NaS2O3
.
equilibrium constant can be written in the form of Eq. If Au(S2O3)M(ads)0 produced at the gold surface is
(5), and h can be expressed by Eq. (6). Assuming Eq. not diffused away or reacted, it is likely to be further
(3) to be the rate controlling step and expressing the oxidized, leading to the oxidation of thiosulfate rather
rate by Eq. (7), where k Au is the rate constant, Eq. (8) than gold. For example, Pedraza et al. (1988) noted
can be used to examine the validity of this model and that thiosulfate ions decompose when in contact with
reaction mechanism. gold at an open circuit, leaving several sulfur
containing species which do not block the surface.
   Thus, thiosulfate from the solution is oxidized on the
Kads ¼ h= ð1
hÞ MS2 O

3 ð5Þ
electrode surface. Moreover, Jiang et al. (1993)
     suggested that gold dissolution by thiosulfate is
h ¼ Kads MS2 O


3 = 1 þ Kads MS2 O3 ð6Þ passivated by the buildup of a sulfur layer produced
by the degradation of thiosulfate.
RAu ¼ kAu h ð7Þ The mechanism described in Eqs. (2)–(4) also
explains the higher rates of oxidation of gold in
 
1 potassium thiosulfate compared to that in sodium
MS2 O

3 ¼ kAu Kads ðRAu Þ
1
Kads ð8Þ thiosulfate reported by Chandra and Jeffrey (2004). A
higher equilibrium constant for the formation of
Fig. 4a shows a better linear relationship for the KS2O3
compared to that for NaS2O3
(Fig. 1) leads
plot of [NaS 2 O 3
]
1 vs. (R Au )
1 compared to to a higher concentration of the singly charged
[S2O32
]
1 vs. (R Au)
1 shown in Fig. 4b. Thus, Table associated ion [KS2O3
]=0.137 M compared to

Fig. 5. Effect of background salt on speciation and rate of anodic oxidation of gold at 0.25 V, pH 6–7, 30 8C (rate data from Chandra and Jeffrey,
2004).
238 G. Senanayake / Hydrometallurgy 76 (2005) 233–238
[NaS2O3
]=0.115 M at the same molar concentration
(0.2 M) of the two salts. This leads to a faster rate of
gold oxidation (Eq. (7)) in potassium thiosulfate
compared to that in sodium thiosulfate as shown in
Fig. 5.
The ammonium ion also forms an ion-pair
NH4SO4
with an association constant of 101.1
(Hogfeldt, 1982). Thus, the linear relationship given
in Fig. 1 can be used to calculate an association
constant of 100.93 for NH4S2O3
. Chandra and Jeffrey
(2004) reported that the change in background salt
from 0.2 M potassium thiosulfate to 0.2 M ammonium
thiosulfate caused a 3-fold increase in the rate of gold
oxidation (Fig. 5). However, the predicted concen-
tration of NH4S2O3
is comparable with that of
KS2O3
(Fig. 5). This suggests the possible involve-
ment of ammonia due to the formation of a mixed
ligand complex Au(NH3)(S2O3)
, proposed by Wang
(1992). Thus, further analysis of anodic oxidation
kinetics of gold in ammoniacal-thiosulfate solutions in
alkaline pH range will be reported in a future
communication.
5. Conclusion
Association of thiosulfate ion with sodium ion
leads to a higher concentration of NaS2O3
compared
to free S2O32
. Thus, it is important to consider the
involvement of actual species such as NaS2O3
to
rationalise the oxidation kinetics of gold.
References
Chandra, I., Jeffrey, M.I., 2004. An electrochemical study of the
effect of additives and electrolyte on the dissolution of gold in
thiosulfate solutions. Hydrometallurgy 73, 305 – 312.
Hogfeldt, E., 1982. Stability Constants of Metal-ion Complexes,
2nd Supplement, IUPAC Chemical Data Series No. 2, Part A,
Inorganic Ligands. Pergamon, Oxford.
Ji, J., Fleming, C., West-Sells, P.G., Hackl, R.P., 2003. A novel
thiosulfate system for leaching gold without the use of copper
and ammonia. In: Young, C.A., Alfantazy, A.M., Anderson,
C.G., Dreisinger, D.B., Harris, B., James, A. (Eds.), Hydro-
metallurgy-2003. TMS, Warrendale, pp. 227 – 244.
Jiang, T., Chen, J., Xu, S., 1993. A kinetic study of gold leaching
with thiosulfate. In: Hiskey, J.B., Warren, G.W. (Eds.), Hydro-
metallurgy, Fundamentals, Technology and Innovations. AIME,
Littleton, CO, pp. 119 – 126. Chap. 7.
Muir, D.M., Aylmore, M.G., 2003. Thiosulfate as an alternative
to cyanide for gold processing—issues and impediments.
Miner. Process. Extr. Metall. (Trans. Inst. Min. Metall., C)
113, C2 – C12.
Pedraza, A.M., Villegas, I., Freund, P.L., 1988. Electro-oxidation of
thiosulfate ion on gold. J. Electroanal. Chem. 250, 443 – 449.
Ritchie, I.M., Nicol, M.J., Staunton, W.P., 2001. Are there realistic
alternatives to cyanide as a lixiviant for gold at the present time?
In: Young, E.D., Twidwell, L.G., Anderson, C.G. (Eds.),
Cyanide: Social, Industrial and Economic Aspects. TMS,
Warrendale, pp. 427 – 440.
Senanayake, G., 2004. Analysis of reaction kinetics, speciation
and mechanism of gold leaching and thiosulfate oxidation
by ammoniacal copper(II) solutions. Hydrometallurgy 75,
55 – 75.
Sillen, L.G., Martell, E., 1964. Stability Constants of Metal-ion
Complexes, Special Publication Nos. 17 and 26. Chemical
Society, London.
Wang, X.H., 1992. Thermodynamic equilibrium calculations on
gold silver lixiviant systems relevant to gold extraction from
complex ores. Electrochemistry in Minerals and Metals Pro-
cessing, vol. III. The Electrochemical Society, Pennington, NJ,
pp. 452 – 477.
Zhang, Z., Nicol, M.J., 2003. An electrochemical study of the
dissolution of gold in thiosulfate solutions: Part I. Alkaline
solutions. J. Appl. Electrochem. 33, 767 – 775.