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Hydrometallurgy 76 (2005) 233 – 238

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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 4.2104 mol m2 s1.
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.


Fundamental studies on gold oxidation play an
Recent publications by Ritchie et al. (2001) and important role in rationalising the complex leaching
Muir and Aylmore (2003) have reviewed the behaviour of different types of gold ores and the
advantages and problems associated with gold effect of the background reagents, some of which are
leaching and recovery using thiosulfate in the essential for gold oxidation.
presence of ammonia and copper(II). The increased It is generally accepted that the reaction mecha-
interest in non-ammoniacal thiosulfate systems for nism and rate of a heterogeneous reaction, such as
leaching and recovery of gold (Ji et al., 2003) gold dissolution, involves the following steps:
highlights the importance of kinetic studies in
(i) diffusion (mass transfer) of reactants to the
surface,
* Tel.: +61 8 93602833; fax: +61 8 93606343. (ii) surface adsorption,
E-mail address: gamini@murdoch.edu.au. (iii) chemical reaction at surface,
0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.11.002
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 while the peak potentials decreased with increasing
the bulk solution. thiosulfate concentration. At higher potentials, thio-
sulfate was also oxidized while gold was passivated
Depending on the slowest step the reaction is (Wang, 1992). Zhang and Nicol (2003) also showed
chemically controlled (step iii or iv) or diffusion that the rate of anodic oxidation of gold in non-
controlled (step i or v). ammoniacal alkaline (0.1 M NaOH) sodium thio-
Wang (1992) measured the anodic currents of a sulfate solutions increased with the increase in
gold electrode in sodium thiosulfate solutions at pH sodium thiosulfate concentration from 0.1 to 1 M.
10 in the absence of ammonia. The peak currents In most fundamental studies the thiosulfate ion
showed a 2-fold increase with a 20-fold increase in 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) 233–238 235

ered to be equal to the molar concentration of the 2. Chemical speciation and rate of gold oxidation
relevant salt added, for example sodium thiosulfate
or ammonium thiosulfate. However, there is Fig. 1 shows a log–log plot of association
evidence for association between the thiosulfate constants of thiosulfate vs. sulfate with the three
ions and cations such as H+, Na+, K+ to form cations H+, Na+ and K+. The approximate linear
ion-pairs of the type MS2O3 (Sillen and Martell, relationship indicates the validity of the equilibrium
1964; Hogfeldt, 1982). Moreover, recent electro- constants reported in the literature (Sillen and Martell,
chemical results reported by Chandra and Jeffrey 1964; Hogfeldt, 1982), thus, they can be used in
(2004) showed that the gold oxidation from a the present analysis. The rate data (R Au) are shown in
rotating disc in a non-ammoniacal solution of Fig. 2, to highlight the effect of initial thiosulfate
potassium thiosulfate was faster than that in sodium concentration (0.1–1 M) based on the electrochemical
thiosulfate at the same salt concentration of 0.2 M data presented by Zhang and Nicol (2003). Fig. 2
and at an applied potential of 0.25 V, under argon. also plots the concentrations of the three species
This has been related to the association between Na+, NaS2O3 and S2O32 calculated in the present
thiosulfate and the alkali metal ion, but no attempt study based on equilibrium constants reported in
has been made for a quantitative analysis. Recent Fig. 1. No attempt was made to correct for ionic
concurrent thermodynamic and kinetic analysis of activity coefficients. It is clear that the concentration
literature data on gold oxidation has shown the of NaS2O3 is much higher than that of S2O32.
importance of considering the adsorption of thio- The increase in R Au seems to be proportional to
sulfate ion onto the gold surface (Senanayake, 2004). the increase in concentration of NaS2O3 and/or
This short communication presents a detailed anal- S2O32.
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 3. Reaction order with respect to S2O32 and
thiosulfate (NaS2O3) ions rather than free thiosulfate NaS2O3
(S2O32).
Fig. 3 shows the log–log plots of R Au vs. [S2O32]
þ
M þ S2 O2
3 ¼ MS2 O
3 ð1Þ or [NaS2O3]. The slopes of these curves can be


Fig. 3. Log–log plots of gold oxidation rate vs. concentration of S2O2
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 m2 s1)
because the equilibrium constant for adsorption of
3 6 3
4a 4.810 210 4.810 4.2104 ions onto an electrode, and the rate constant cannot be
4b +4.57 6107 4.57 1.3107
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 Þ1  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 Hogfeldt, E., 1982. Stability Constants of Metal-ion Complexes,
(0.2 M) of the two salts. This leads to a faster rate of 2nd Supplement, IUPAC Chemical Data Series No. 2, Part A,
Inorganic Ligands. Pergamon, Oxford.
gold oxidation (Eq. (7)) in potassium thiosulfate Ji, J., Fleming, C., West-Sells, P.G., Hackl, R.P., 2003. A novel
compared to that in sodium thiosulfate as shown in thiosulfate system for leaching gold without the use of copper
Fig. 5. and ammonia. In: Young, C.A., Alfantazy, A.M., Anderson,
The ammonium ion also forms an ion-pair C.G., Dreisinger, D.B., Harris, B., James, A. (Eds.), Hydro-
metallurgy-2003. TMS, Warrendale, pp. 227 – 244.
NH4SO4 with an association constant of 101.1
Jiang, T., Chen, J., Xu, S., 1993. A kinetic study of gold leaching
(Hogfeldt, 1982). Thus, the linear relationship given with thiosulfate. In: Hiskey, J.B., Warren, G.W. (Eds.), Hydro-
in Fig. 1 can be used to calculate an association metallurgy, Fundamentals, Technology and Innovations. AIME,
constant of 100.93 for NH4S2O3. Chandra and Jeffrey Littleton, CO, pp. 119 – 126. Chap. 7.
(2004) reported that the change in background salt Muir, D.M., Aylmore, M.G., 2003. Thiosulfate as an alternative
from 0.2 M potassium thiosulfate to 0.2 M ammonium to cyanide for gold processing—issues and impediments.
Miner. Process. Extr. Metall. (Trans. Inst. Min. Metall., C)
thiosulfate caused a 3-fold increase in the rate of gold 113, C2 – C12.
oxidation (Fig. 5). However, the predicted concen- Pedraza, A.M., Villegas, I., Freund, P.L., 1988. Electro-oxidation of
tration of NH4S2O3 is comparable with that of thiosulfate ion on gold. J. Electroanal. Chem. 250, 443 – 449.
KS2O3 (Fig. 5). This suggests the possible involve- Ritchie, I.M., Nicol, M.J., Staunton, W.P., 2001. Are there realistic
ment of ammonia due to the formation of a mixed alternatives to cyanide as a lixiviant for gold at the present time?
In: Young, E.D., Twidwell, L.G., Anderson, C.G. (Eds.),
ligand complex Au(NH3)(S2O3), proposed by Wang Cyanide: Social, Industrial and Economic Aspects. TMS,
(1992). Thus, further analysis of anodic oxidation Warrendale, pp. 427 – 440.
kinetics of gold in ammoniacal-thiosulfate solutions in Senanayake, G., 2004. Analysis of reaction kinetics, speciation
alkaline pH range will be reported in a future and mechanism of gold leaching and thiosulfate oxidation
communication. 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
5. Conclusion Society, London.
Wang, X.H., 1992. Thermodynamic equilibrium calculations on
Association of thiosulfate ion with sodium ion gold silver lixiviant systems relevant to gold extraction from
complex ores. Electrochemistry in Minerals and Metals Pro-
leads to a higher concentration of NaS2O3 compared cessing, vol. III. The Electrochemical Society, Pennington, NJ,
to free S2O32. Thus, it is important to consider the pp. 452 – 477.
involvement of actual species such as NaS2O3 to Zhang, Z., Nicol, M.J., 2003. An electrochemical study of the
rationalise the oxidation kinetics of gold. dissolution of gold in thiosulfate solutions: Part I. Alkaline
solutions. J. Appl. Electrochem. 33, 767 – 775.

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.