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Short review
Abstract
The current status of the mechanism of gold cyanidation based on diffusion and surface adsorptionreaction models are
reviewed. Published rate data based on chemical oxidation from flat gold surfaces in pure aerated cyanide solutions are
analysed to show a reaction order of 2.7 with respect to cyanide at low concentrations. At higher cyanide concentrations, the
reaction rate reaches a limiting value of R Au(lim) = 7.3 10 6 mol m 2 s 1, independent of the cyanide concentration and
stirring rate. This chemically controlled dissolution of gold in pure cyanide solutions is considered to be different from the
widely reported cyanide or oxygen diffusion controlled dissolution of gold, depending on their relative concentrations. The
proposed reaction mechanism to rationalise this behaviour involves the formation of a heterogeneous redox transition state
(Au.H2O)2.(CN)23.(O2) which produces the intermediate Au(I)(OH)(CN) on the gold surface. Oxygen is reduced to
hydrogen peroxide which may degrade in three ways: (i) oxidize gold to produce the same gold(I) intermediates on surface,
(ii) oxidize cyanide to cyanate (iii) disproportionate to water and oxygen. The surface adsorbed Au(I) intermediate reacts with
cyanide to produce more stable Au(CN)2 in solution. The proposed surface chemical model rationalises the reaction order of
c 3 at low cyanide concentrations and calculates an intrinsic rate constant of k Au = 8.6 10 6 mol m 2 s 1 for gold
cyanidation by oxygen. This value is in reasonable agreement with the value of k = 6.9 10 6 mol m 2 s 1 based on the
model proposed by Wadsworth et al. [Wadsworth, M.E., Zhu, X., Thompson, J.S., Pereira, C.J., 2000. Gold dissolution and
activation in cyanide solution: kinetics and mechanism. Hydrometallurgy, 57, 111.], which considered the mass transfer away
from the active crystalline gold surface site followed by fast charge transfer, combined with two-electron reduction of oxygen
on the gold surface.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Gold cyanidation; Reaction mechanism; Surface transition state; Kinetics; Rate constants; Gold(I) speciation
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Current status of reaction mechanism . . . . . . . . . . . . . . .
2.1. Limitations of diffusion model due to effect of impurities .
2.2. Formation of surface films . . . . . . . . . . . . . . . . .
2.3. Surface adsorptionreaction models . . . . . . . . . . . .
2.4. Need for further studies . . . . . . . . . . . . . . . . . .
3. Gold(I) speciation: justification and importance . . . . . . . . . .
4. Analysis of rate data. . . . . . . . . . . . . . . . . . . . . . . .
4.1. Levich equation . . . . . . . . . . . . . . . . . . . . . .
4.2. Rate data . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Reaction mechanism. . . . . . . . . . . . . . . . . . . . . . . .
6. Summary and conclusions . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Gold cyanidation has been reported to involve the
chemical reactions shown in Eq. (1) (Bodlander, 1896)
and Eq. (3) (Elsner, 1846), where Eq. (3) can be
treated as the sum of the two partial reactions shown
in Eqs. (1) and (2). Hydrogen peroxide produced at
the interface by reduction of oxygen can react with
gold (Eq. [(2)), or with cyanide ion (Eq. (4)), or
disproportionate to H2O + 0.5O2; while cyanate produced in solution further degrades to other products.
2Au4CNO2 2H2 O2AuCN
2 2OH H2 O2
1
2Au 4CN H2 O2 2AuCN
2 2OH
4Au 8CN O2 2H2 O 4AuCN
2 4OH
3
CN H2 O2 CNO H2 O
Kudryk and Kellogg (1954) highlighted the importance of understanding the rate controlling factors of
gold cyanidation which would allow correct choice of
conditions such as agitation, temperature, and the
reagent concentrations. They showed the electrochemical nature of the gold cyanidation reaction and that
the rate is determined by the rate of diffusion of
cyanide or dissolved oxygen to the gold surface,
depending on their relative concentrations.
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2
3
3
3
4
5
5
6
6
7
8
11
11
The theoretical and practical aspects of gold cyanidation have been frequently reviewed (Cornejo and
Spottiswood, 1984; Nicol et al., 1987; Li et al., 1992;
Fleming, 1992), while the fundamental aspects of gold
cyanidation reaction and their relevance to leaching of
gold from ores have been advanced by Cathro (1963),
Cathro and Koch (1964), MacArthur (1972), Nicol
(1980), Kirk et al. (1980), Dorin and Woods (1991);
Osseo-Asare et al. (1984), Lorenzen and van Deventer (1992); Zheng et al. (1995), Guan and Han
(1994), Crundwell and Godorr (1997), Wadsworth
et al. (2000), Jeffrey and Ritchie (2000a,b, 2001)
and Xue and Osseo-Asare (2001). Significant progress has been made in recent years on mixed
electrochemical-transport (diffusion) models that
are capable of explaining the effect of oxygen
pressure, cyanide concentration and agitation (Li
et al., 1992; Wadsworth et al., 2000).
Despite long-term interest and industrial application, the reaction mechanism of gold cyanidation by
oxygen is still being debated and/or investigated
especially in the following three areas:
(i) stoichiometry and chemical or diffusion controlled nature of the reaction,
(ii) nature of the passivation layer on gold surface,
(iii) effect of host minerals and impurities in the
solid state or solution.
Although a number of different leaching models
have been presented, it is difficult to categorise them
due to the fact that each model considers a number
Aus
CN
i
13
14
Au2 CN 3ads AuCN
ads AuCN 2ads
15
AuCN
ads
0
AuCN
ads AuCNads e
AuCN0ads
CN
i Y AuCN2 i
AuCN
2 i Y AuCN2 b
Aus 2CN
b AuCN2 b e
AuCN
ads CNads
AuCN
2 e fast charge transfer step
16
7
RAu k a Utot CN 3 = f1 KCN 3 g
8
9
10
11
HO
2 H2 O 2e 3OH
12
17
18
Table 1
Stability constants of gold(I) and silver(I) complexes
Complex
Ionic strength
log b a
Ag(CN)
2
Ag(OH)(CN)
Ag(OH)
2
Ag(OH)0
Au(CN)
2
Au(OH)(CN)
Au(OH)
2
Au(OH)0
Au(CH3CN)+2
Au(CH3CN)(OH)0
1(NaClO4)
1(NaClO4)
0
0 (or dil)
0.025(KCN)
20.1
12.8
3.6 (4.2 at 18 8C, 0.2 KNO3)
2.3 (3.9)
36.6, 38.3
23.3b
22
10.2, 20.6
3.1
10.7
(i) intermediate gold(I) species involved in the surface reaction with oxygen and cyanide
(ii) a reaction mechanism involving the simultaneous reaction of gold and oxygen on gold
(iii) a rate constant for the intrinsic surface reaction.
a
At 25 8C, Hogfeldt (1982); Sillen and Martell (1964); Kissner
et al. (1997); Stefansson and Seward, 2003; Nicol et al., 1987.
b
See text.
21
Au2O
Au(OH)
Au(CN) +Au(OH)
Au(CN)
Au(CNO)
Au(OH)
+Au(OH)(CN)
700
Au(OH)(CN)
800
600
500
-4.5
-6.5
y = 2.74x - 7.37
R2 = 1.00
-7.5
0
0.4
0.8
-
1.2
1.6
-3
II
III
OH2
Au
IV
Au
5. Reaction mechanism
It is possible to consider the chemical dissolution of
gold in oxygenated cyanide solutions as a reaction that
involves the simultaneous reduction of oxygen and
oxidation of gold as shown in Fig. 3. The three cases
shown in Fig. 3 consider the involvement of 2 gold
atoms per oxygen molecule and (a) reaction without
the involvement of cyanide producing Au(OH)0, (b)
reaction with only one cyanide ion producing
Au(OH)0 + Au(OH)(CN), and (c) reaction with two
cyanide ions producing Au(OH)(CN). Eqs. (23)(26)
consider only the case described in Fig 3b because it
is representative of the other two extreme cases.
Au(OH)0
OH2 O
OH2 O
OH
OH
OH
OH
OH
OH
Au(OH)0
OH2
CNAu(OH)(CN)-
Au
OH2 O
OH2 O
Au
Au(OH)
OH2
CNAu(OH)(CN)-
Au
OH2 O
OH2 O
Au
Au(OH)(CN)-
CNFig. 3. Formation of Au(I) intermediates in surface reaction with O2 and (a) 0; (b) 1; (c) 2 CN ions (I) gold surface, (II) adsorbed water and/or
cyanide, (III) oxygen, (IV) adsorbed Au(I) species after reaction, (V) hydrogen peroxide.
23
30
RAu k Au
31
32
Desorption/stabilisation
pAuOHads CN pAuOHCN
ads=aq OH
25
pAuOHCN ads=aq CN p AuCN
2
OH :
26
The equilibration shown in Eq. (23) can be considered as the formation of a surface adsorbed transition state followed by the redox reaction which
produces the adsorbed gold(I) species and hydrogen
peroxide. The two unstable species Au(OH)0 and
Au(OH)(CN) formed on the surface react with cyanide to produce more stable Au(CN)2 in solution as
shown in Eqs. (25)(26), while hydrogen peroxide
can react in the manner described before. The reaction
model in Fig. 3 shows a maximum of 2CN ions
involved in the surface reaction mechanism. It is
important to rationalise the reaction order of 23
demonstrated by the slope of linear relationship in
Fig. 2 at low cyanide concentrations. Thus, a general
form of the surface reaction is shown in Eqs. (27)
(28), which involves nCN ions. The equilibrium
constant for Eqs. (23), surface coverage (h), and the
rate expression are given by Eqs. (29)(31).
General surface reaction
2Au 2H2 O nCN O2
Au:H2 O2 :CN n :O2
27
28
29
33
Then,
RAu k Au K ads O2 CN n from Eq: 32:
34
35
In the case of solutions of low cyanide concentrations, Eq. (32) simplifies to Eq. (34). This explains the
value of n between 2 and 3 obtained as the reaction
order with respect to cyanide at low concentrations
(Fig. 2). Moreover, Eq. (32) can be rearranged to Eq.
(35) that can be used to plot [CN] n vs. (R Au) 1 to
obtain values for K ads and k Au. Fig. 4a shows the
relevant plots for n = 1 and 2 while Fig. 4b and c
represent n = 3 and n = 4 respectively. In all cases,
the dissolved oxygen concentration can be considered
as c0.25 mM, because the experiments were carried
out in air saturated solutions. The best linear relationship is given by n = 3 (Fig. 4b) with slope of 3 10 8
and intercept in the range 3.3 10 3 to 3.7
10 3 for the two data sets reported by Jeffrey and
Ritchie (2001) and Wadsworth et al. (2000). The value
of k Au = slope/(-intercept) = 8.6 10 6 mol m 2 s 1
based on the average intercept is close to the limiting
rate of R Au(lim) = 7.3 10 6 mol m 2 s 1 calculated
from the plateau in Fig. 2 described in Section 4.
Thus, the limiting rate of gold cyanidation in pure
impurity-free solutions at high cyanide concentrations is approximately equal to the intrinsic rate
constant. The slope showing a reaction order of 2.7
indicates the predominant reactions represented by
Eqs. (36)(38), which involve 2 or 3 cyanide ions in
10
(a)
0.6
{[CN-]free}-n
0.4
0.2
n=2
0
0.E+00
2.E+06
4.E+06
6.E+06
(RAu)-1
(b)
0.2
{[CN-]free}-n
y = 3E-08x - 0.0033
R2 = 0.9999
n=3
y = 3E-08x - 0.0037
R2 = 0.9998
0
0.E+00
2.E+06
4.E+06
6.E+06
4.E+06
6.E+06
(RAu)-1
(c)
0.05
{[CN-]free}-n
0.04
0.03
n=4
0.02
0.01
0
0.E+00
2.E+06
(RAu)-1
Fig. 4. Plot of {[CN]free} n vs. (R Au) 1 using data from Fig. 2 to examine the validity of Eq. (35). (a) n = 1 or 2, (b) n = 3, (c) n = 4.
11
AuCN
2
AuOHCN H2 O2 OH
37
38
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