hydrometallurgy

ELSEVIER Hydrometallurgy 46 (1997) 251-269

On the solution chemistry of cyanidation of gold

and silver bearing sulphide ores. A critical
evaluation of thermodynamic calculations
Yu Zhang, Zhaoheng Fang I, Mamoun Muhammed *
Department qf Inorganic Chemistry, Royal Institute of Technology, S-100 44 Stockholm, Sweden
Received 16 January 1997; accepted 14 April 1997

Abstract

The use of thermodynamic calculations for cyanidation of gold/silver and their minerals is
reviewed. In literature there are a number of studies based on thermodynamic calculations to
describe the chemistry of cyanide leaching of gold and/or silver from sulphide minerals.
Disagreements between computational and experimental results are usually significant. In the
present study, a critical evaluation of thermodynamic calculations, including the authors own
recalculations, for cyanide leaching of gold/silver are carried out in order to interpret the
experimental results. The solution chemistry of the leaching process is discussed with reference to
both computational and experimental results. The competition of cyanide complexation of gold,
silver and other metals, especially copper and iron, as well as the influence of sulphide, during
cyanide leaching is particularly considered. It is demonstrated that the oxidation rate (kinetics) of
sulphide determines the characteristics of the cyanide leaching sulphide, the different metal
species precipitate, as cyanide is consumed during leaching, in the order of FeOOH(s) >
Cu(OH),(s) > AgCN(s) > Ag,O(s) > Au(s). In the case of incomplete oxidation of sulphide, the
precipitation order is Ag,S(s) > FeOOH(s) > Cu(OH),(s) > Au(s). Based on these calculations,
experimental results of cyanide leaching can be now well interpreted. 0 1997 Elsevier Science
B.V.

1. Introduction

It has been more than a hundred years since MacArthur and the Forrests first
developed a chemical metallurgical process for gold production based on the use of an

* Corresponding author.
Present address: Institute of Chemical Metallurgy, Academica Sinica, Beijing, China.

0304386X/97/$17.00 0 1997 Elsevier Science B.V. All rights reserved.

PIZ SO304-386X(97)00021-2
252 Y. Zhang et al./Hydrometullurgy 46 (1997) 253-269

alkaline cyanide solution [l]. The chemistry of dissolution in cyanide solution of gold,
silver and other metals that co-exist in minerals has been studied by many workers
[l-6]. However, interactions between various components during the leaching process
and their impact on the recovery of gold and/or silver are not fully understood yet. In
recent years, some efforts have been made based on thermodynamic calculations for a
systematic study of chemical processing, especially cyanidation, of gold/silver minerals
[6-S]. The results of these calculations are mainly represented in thermodynamic
predominance diagrams for the systems containing one or two metals. From a chemical
point of view, however, few of these diagrams can be adopted without confusion. Many
of the diagrams contain erroneous results. As an example, it was reported [6-81 that the
cyanide complex of a metal (say, Au(CN);) could be dominant amongst the metal
species even at a molar ratio of cyanide to metal less than 0.01. Even more of the
diagrams were calculated under some unrealistic conditions, e.g., pH up to 16 [6], or
total concentration of a metal up to 100 M [7]. Disagreements between computational
and experimental results, as well as the arguments in literature, have hardly been
discussed. According to some of the earlier studies [8], the presence of sulphide would
not significantly affect the cyanidation of silver. In practice, it has been found that
sulphide minerals limit the leaching of silver. Whether there were some misconceptions
in chemistry comprehension, or errors in computation algorithms or diagram construc-
tions, the reliability of such references is certainly questionable. On the other hand,
thermodynamic calculations are performed by assuming a priori that all possible
reactions in a defined system should be always at equilibrium. Obviously, such an
assumption alone is hardly valid in practice since many of the chemical processes
involve the reactions between several phases. Especially when heterogeneous reactions
(dissolution, precipitation, absorption, adsorption, etc.), as well as some of the redox
reactions, are involved in a process like leaching, kinetics of the reactions becomes of
great importance. The validity of thermodynamic calculations for such systems is then
strongly dependent on specifications and treatments of the kinetic-limited reactions.
Moreover, little attention has been paid to an overall analysis of the compositional
correlation between different components in the cyanidation systems. None of the
published calculations has shown how the competition between gold/silver and other
metals (Cu, Fe, etc.) for cyanide complexation affects the leaching process in terms of
either thermodynamics or kinetics.
In the present studies, comprehensive chemical calculations of heterogeneous systems
of gold/silver are made on a more rational basis with and without kinetic considerations
for comparison. The process analysis is carried out based on the experimental verifica-
tion of the computational results. In this paper, the cyanidation of gold-bearing sulphide
ores is considered. The competition of the reactions of gold, silver and major associated
metals, copper and iron, as well as the influence of sulphide, during cyanide leaching is
particularly considered.

2. Chemical and computational considerations

It is well known that gold and silver are among the least reactive metals. Gold is
distributed mostly in native state in nature. Although native silver exists also in nature,
 Y. Zhang et al. / Hydrornetallurg)>46 (19971251-269 253

Table 1
Analysis of a gold and silver bearing sulphide concentrate
Chemical analysis Mineralogical analysis

element wt% mineral wt%

cu 9.3 CuFeS, 26.1

Fe 36.4 FeSz 11.9
Pb 1.84 FeSl 10 37.0
s 0.7 silicate 20.9
mg/kg
Au 55.0-56.3
Ag 150

silver sulphide, Ag,S, is a more common mineral 191. In some ores, both metals may
exist also as tellurides and selenides [8,9]. Table 1 presents as a sample case the
composition of a gold/silver bearing sulphide ore considered in the present work. As
shown, pyrite (FeS,) and chalcopyrite (CuFeS,) are major constituents.

2.1. Chemical reactions

2.1.1. Cyanidation of natbe metals

Dissolution of gold or silver in cyanide solutions can be described in a pair of
electrochemical reactions [ 101,

Au(s) + 2CNPo Au(CN), + e- (la)

Ag(s) + 2CN-= Ag(CN), + em (lb)
and
O,(g) + 2H++ 2eeo H,O, (2a)
O,(g) + 2H,O + 4eP w 40HP (2b)
Ag can form higher complexes with cyanide [7], i.e.,

Ag( CN); + nCN w Ag( CN),,::- (3)

where n = 1 or 2. It is apparent, from a chemical point of view, that the dissolution of
Au and Ag is mainly due to reactions 1 and 2. To estimate the conditions for a complete
dissolution of Au and Ag in the ores, the thermodynamic limitation, or equilibria, of
reactions 1 and 2 should be always considered.

2.1.2. Cyanidation of sulphide minerals

The dissolution reactions of sulphide minerals can be described by the following
equations:

Ag,S(s) +2&N-+ 2Ag(CN);,+ + S- (4)

FeS,(s) + 6CN-+ Fe(CN)z- + S:- (5)
CuFeS,(s) + lOCN_+ Cu(CN)i- + Fe(CN)i- + 2S2- (6)
254 Y. Zhang et al. / Hydrometallurgy 46 (1997) 251-269

where n = 2, 3 or 4. Since FeSJs) and CuFeS,(s) are the major constituents, the
cyanide consumption depends mainly on the extent of Eqs. (5) and (6). For selective
recovery of Au and Ag, the reaction rates of Eqs. (5) and (6) should be suppressed to as
low a level as possible.

2.1.3. Oxidation of soluble species

Since the Au/Ag leaching operates under oxidizing atmosphere, the produced
sulphide ions may be oxidized in the following sequence,

s2- -+ s:- -+ so + s,o;- + so:- + so;- (7)

while the oxidation of cyanide proceeds as follows,
CN-+ (CN), + CNO- (or SCN-) (8)
The oxidation of S2- may enhance the overall dissolution of sulphide minerals given by
Eqs. (4)-(6). However, the extent of the sulphide oxidation is limited by kinetics rather
than thermodynamics. The reactions given in Eq. (8) are important for controlling excess
consumption of cyanide ions. It has been reported that the oxidation of cyanide by
oxygen in air proceeds very slowly and may be neglected in the absence of a catalyst [6].
However, the presence of Cu(II)-species enhances the oxidation of cyanide [ 11,121, e.g.,

2Cu(CN);- e 2Cu(CN);- + (CN),(g) (9)

2Cu(CN);- + 20H-o Cu(CN);- + Cu(CN$ + CNO-+ H,O ( 10)
CL@) also forms Cu(CN&, depending on pH and cyanide concentration.
On the other hand, Fe@)-species can be oxidized to Fe(III)-species, i.e.,

Fe(CN)i- e Fe(CN):- + eP (11)

2.1.4. Precipitation of metal compounds

It is known that solid cyanides of Ag or Cu can be formed in acidic solutions, i.e.,

Ag(CN), + H+o AgCN(s) + HCN (2)

and

Cu(CN), + H+ = CuCN(s) + HCN (13)

As free CN- is consumed during leaching, the precipitation may also result from the
cyanidation competition between different metal species. In alkaline solutions, Ag,O(s),
FeOOH(s), CuO(s) or Cu(OH),(s) may be formed when free [CN-] is too low, such as,

CuFeS,( s) + 2CN- + 30H- + Cu(CN), + FeOOH(s) + 2S2- (14)

2.2. Computer-aided calculations

Many computer programs are reported for performing thermodynamic calculations

[6-81. The computer program used in the present studies is a modified version of
SOLGASWATER [ 13-151. The system variables to be calculated by this program are
 Y. Zhang et al./ Hydrometallurgy 46 (1997) 251-269 25.5

the concentrations of different species involved. The concentration of a gas or solid is

assumed to be completely dissolved in the solution. The relationships between the
dependent variables [complex], and independent variables [componentlj can be generally
expressed as follows:

[complex], =fi([component],, [component],, .) (15)

where [componentlj (j = 1, 2, . . . ) represents the concentrations or activities of the
respective components. In the present system, eight components, H+, Au+, Ag+, Cu+,
Fe*+, S*-, CN-, and O,(g) ( or e-1 have been considered. The values of [component],
have been given with reference to the operational conditions. These are considered as
independent variables when the kinetics of the reactions are not included. The thermody-
namic data used in the present work were taken from literature [8,12,16-251. The
stability constants have been critically selected and, whenever possible, modified to the
conditions of ionic strength of O-l M, temperature of 25C and pressure of 1 atm. The
chemical reactions with their respective equilibrium constants concerned are listed in
Table 2. The reactions that are much slower than the dissolution of Au and Ag (Eqs.
(la>, (lb), (2a) and (2b)) are eliminated. The present chemical calculations differ from
those previously made by others [6-81 mainly in the following respects.
(1) The extent of sulphide oxidation shown in Eq. (71, which may affect the recovery
of Ag, was not considered in any of the earlier studies.
(2) The mechanism of copper cyanidation shown in Eqs. (6), (9) and (lo), which
increases the permanent loss of cyanide, was not taken into account for the previous
calculations.
(3) The competition between cyanidation of Au, Ag, Fe and Cu, which results in
precipitation of certain compounds in sequence, has now been considered.

2.3. Presentations of the results

The results of thermodynamic calculations can be graphically represented as predomi-

nance diagrams, i.e., pe-pH, log[metal]-pH, log[CNP]-pH and logpO,-pH diagrams
[6-81. The pe-pH diagrams are useful mainly in the general cases when the
oxidizing/reducing agents are not necessarily specified. Since oxygen has been always
considered as an operative oxidizing agent in a cyanidation process, plotting the data as
pO,-pH diagram, as a specified part of the pe-pH diagram, would be more informative.
For constructing log[CNP] (or log[metal])-pH (or ~0,) diagrams, it is thus practical to
assign a constant for oxygen partial pressure instead of a redox potential as generally
presented in literature [6,8]. In order to show the influence of sulphide or competition
between different metals, it is also interesting to plot the data as log[CN-]-log[S2P] or
log[metal],-log[metal], diagrams at a constant pH. However, a predominance diagram
only shows the dominant species, which has a molar fraction higher than 0.5 relative
distribution, of a component in question. Other species that exist at a lower concentra-
tion than that of the predominant species may be practically significant and yet are not
presented in such a diagram. Thus, the solubility, concentration or distribution (relative
concentration) diagrams are usually more meaningful. In a distribution diagram, the
fractions (Y, of the different species, except for those at cy, < 0.001, with respect to a
256 Y. Zhang et al./Hydrometallurgy 46 (19971 251-269

Table 2
Chemical reactions and equilibrium constants (25 C, 1 atm and I = 0)
Reaction log K Ref.

2H,O = 0,@+4H+ +4C -83.10 [I41

Au+ fe- = Au(s) 28.60 [I81
Au=AAu++2em ~ 47.31 [1X1
Au + 3H,O = Au(OH), + 3H+ + 2em - 5 1.50 [I81
Au+ +2HzO= Au02(s)+4H+ +3e- - 89.80 [I81
Ag+ +e- = Ag(s) 13.51 [I41
Ag+ +H,O = AgO(s)+2H +e- -30.12 [I41
2Ag+ +3H20 = Ag,0,(s)+6Ht +4em - 113.24 [I41
CL? + + 2e- = CL&) 11.42 [I41
CL?+ +e- = Cu+ 2.68 [I41
Fe+ + 2e- = Fe(s) - 14.89 [141
Fe?+ = Fe3+ +e- - 13.02 [I41
2HS = Sz- +2H+ +2e- - 10.06 1181
HS- = S(s)+H+ +2em 2.20 [I81
2HS-+3Hz0=S,0:m+8H++8em - 27.00 [I81
HS+3H,O=S&g-+7Hf+6em ~ 37.2X [I81
HS +4H,O = SOi- +9H+ +8em - 34.08 [I81
H,O=OH- +H+ - 13.98 [241
AL&OH), + Hz0 = ALI( + H+ - 1 1.70 [I61
AdOH), + 2H,O = ALI( + H+ -25.10 iI61
AdOH), = Au(OH),(s) 5.50 [I61
Ag+ +H?O= AgOH+H+ - 12.00 [I61
Ag+ +2H,O = Ag(OH); +2H+ - 24.01 [I61
Cd+ +HLO=CuOH+ +H+ - 7.97 12.51
CL?+ +2H>O = CUE +2H+ - 16.24 [251
CL?+ +3Hz0 = Cu(OH), +3H+ - 26.62 [251
CL?+ +4H,O = CU(OH);~ +4H+ - 39.70 [251
2Cu+ +HzO=Cu20H+ +H+ -6.71 [251
2Cu+ + 2H20 = Cu,(OH);+ +2H+ - 10.55 L251
3Cu+ +4Hz0 = Cu,(OH);+ +4H+ - 20.95 Ml
Cu+ +2Hz0 = Cu(OH),(s)+2H+ - 8.68 [161
2Cu+ +H,0=CuzO(s)+2H+ I .40 [I61
Fe++H O=FeOH++H+ - 9.50 [I61
Fe+ + 3t?1?0 = Fe(OH); +3H+ - 32.00 [I61
Fe+ +4H,O = Fe(OH):- +4H+ - 46.40 [I61
Fe+ + 2H,O = Fe(OH),(s) + 2H+ - 12.90 [I51
Fe++HzO=FeOH+H+ -2.19 [I61
Fe+ +2H,O = Fe(OH)T +2H+ - 5.70 [I61
Fe+ +4H,O = Fe(OH); +4H+ - 2 1.60 [I61
2Fe+ + 2Hz0 = Fe,(OH):+ +2H+ ~ 2.90 [I61
3Fe+ +4H,O= Fe,(OH)z+ +4H+ - 6.30 [161
Fe+ +2H,O = FeOOH(s)+3H+ - 0.50 [I61
CN- +H+ = HCN 9.21 1161
Au+ +2CNmm = Au(CN) 38.90 [I81
Ag+ + CN - = AgCN(s) 15.66 [I31
Ag+ +2CNm = Ag(CN); 20.48 [I(51
Ag+ +3CNm = Ag(CN);- 21.40 [If51
Ag+ + 4CN = Ag(CN)j - 21.90 [I61
Ag+ +CN- +H,O = Ag(CN)OH- +H+ -0.80 [I51
 Y. Zhang et al./Hydrometallurgy 46 (1997) 251-269

Table 2 (continued)
Reaction log K Ref.
Cu + + 4CN = C&N),2 - 25.00 1141
CL?+ +4CNm +H?O=Cu(CN):- +CNO- +2H+ 35.20 [12,141
Cu(CN); - + CN- = Cu(CN);: 1.50 1161
C&N); - = Cu(CN), + CN- -5.34 [161
Cu(CN); = CuCN(s) + CN -4.91 [141
Fe + + 6CN = Fe(CN)i 35.40 [I61
Fe(CN$ + H+ = HFe(CN)i- 4.30 [I61
HFe(CN)i + H+ = H 2 Fe(CN)z 2.60 [I61
4Ag+ + Fe(CN)i- = Ag,Fe(CN)&) 19.21 I171
2Cu + + Fe(CN)i - = Cu, Fe(CN),(s) 17.00 iI71
2Fe+ + Fe(CN&- = Fe,(CN&) 14.14 iI71
Fe+ +6CNm = Fe(CN)- 43.60 I161
3Ag+ + Fe(CN)zm = A$,Fe(CN)&) 18.20 I171
3Cu+ + 2Fe(CN&- = Cu,[Fe(CN&,l?(s) 24.40 [I71
Fe + + Fe(CN)z = Fe,(CN), 1.55 [I61
HS- = S- +H+ - 13.90 [I61
HS- +H+ = H,S 7.02 [161
HS- +H = H,S(g) X.01 [161
Ag- +HS- = AgS- +H+ 5.30 [I61
Ag +HS- = AgHS 13.60 [I61
Ag+ +2HS = AgHS;- +H+ 8.20 [161
Ag+ + 2HSm = Ag(HS), 17.70 [I61
2Ag+ +HS- = Ag&)+H+ 36.20 [I51
CL?+ +HS- =CuS(s)+H+ 22.20 I161
2Cu+ +HS- =C$S(s)+H+ 34.60 [I61
Fe+ +HS- = FeS(s)+H+ 4.20 [161
Cu+ + Fe+ + 2HS = CuFeS,(s) + 2H+ 33.40 [81
S#- + H+ = HS,O, 1.60 [I61
HS?O+H+ = HzS201 0.60 [161
Au +2S& = Au&O& 26.00 I161
Ag + +&Of- = A&O, 8.80 [I61
Ag +2S& = Ag(S,O,):- 13.70 [161
Ag +3S,0:m = Ag(S,O,)$- 14.20 [I61
cu+ + s,o:m = cus,o, 10.40 iI61
cu+ + 2s,o:- = cu(s,o,);m 12.30 [I61
cu+ +3s,o;- =cu(s,o,,:- 13.70 [I61
Fe+ +S O- = FeS 2O+3 1.98 [I61
SO:- +;+1=HSO; 7.18 [161
HSO+H+=HzSOI 1.91 1161
Ag++SO;-=AgSO, 5.60 []I
Ag++2SO;- =Ag(SO$ 8.68 [If31
Ag++3SOfm=Ag(S0,):- 9.00 [I61
2Ag++SO:m=Ag,S0,(s) 13.82 [161
cu+ +so:- =cuso, 7.90 [161
cut +2so:- =cu(soJ- 8.78 [161
cu++3so,2~=cu(so,,:- 9.40 [I61
SOjm+H+=HSO, 1.99 [I61
Ag+ +SO;- =AgSO,- 1.30 [I61
2Ag+ +SO,2-= Ag,SO,(s) 4.83 [I61
258 Y. Zhang et al./ Hydrometallurgy 46 (1997) 251-269

Table 2 (continued)
Reaction log K Ref.

cd+ + so;- =cuso, 2.30 [16,171

4Cu2 + + SO; + 6H *O = CU,(OH)~ SO, + 6H + 68.64 [t61
Fe+ + S02- = FeSO 2.20 [I61
Fe+ + SO;-4 = FeS04+
4 4.04 [t61

specified component are plotted against the variation of the concentration or activity,
e.g., czi(metal)-[CNP]tota, or ai(metal)-pCN. These kinds of diagrams can also present
the results of the calculations concerning the kinetics of a leaching process if the
variation of metal concentrations is considered as being time-dependent.

3. Results and discussions

3.1. Au,Ag-S2 --CN p-02-H20 system

The existence of gold-sulphur species such as Au,S(s), Au,S,(s), AuS, AuS, and
AuS,O; has been reported [6,16]. However, the stability regions for these species are
not found under the conditions considered in the present work. The pe-pH and
log[CN]-pH(p0,) predominance diagrams of gold are presented in Fig. la and b,
respectively. They are not affected by increasing the total concentration of sulphur
species, as specified above, up to 1 M. The results indicate that Au(CN); is the
dominant species in a wide range of pH and potentials as long as the total concentration
of cyanide exceeds that of gold.

OO,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
1 2 p:2 4 5 6

I (b)

-1 -

-2-
Au(CN),

a.--3-
z -

(CN-kow 5ii; -
0.2 mM S-4
AW ~;.~~.~_______,.OmM
-lO- .<.-_-_____ ,OrnM AW
-5-
---------lOOmY

-2Oo-4
PH
PH

Fig. 1. Predominance of gold species (0.1 mM in total). (a) pe-pH diagram for different total concentrations of
CN-, 0.2, 1, 10 and 100 mM; (b) log[CN- ],,ta,-pH/pOz diagram.
 Y. Zhang et al. / Hydrometallurgy 46 (1997) 2.5-269 259

Fig. 2. Experimental data of gold dissolution in a solution of 4 g/l NaCN ( = 82 mM) at pH = lo- 11 under
different oxygen partial pressures, 0.01, 0.2, 0.5 and I atm.

In Fig. la, a dotted line represents the operational correlation between pe and pH
when oxygen is used as a principal oxidant having a partial pressure of p0, = 0.2 atm
(i.e., 1 atm of air). Even at [CN]/[Att] = 2, this line is still well under the stable domain
of Au(CN), that steadily increases by increasing the cyanide concentration. On the
other hand, it is found that the variation of pH (between 8 and 14) and oxygen partial
pressure (from lo- to 1 atm) makes no significant difference as shown in Fig. lb.
where p0, = - log(oxygen activity) = - log PO,. This indicates that oxygen partial
pressure should not affect the stability of Au(CN& under the given conditions. In
practice, however, the cyanide leaching of gold is very difficult at p0, < 0.01 atm due
to the slow kinetics, as shown in Fig. 2. In other words, the calculation results presented
in Fig. 1 are in practice not valid if p0, < 0.01 atm within a finite leaching time.
Fig. 3a shows that the stability domain of the solid silver sulphide, Ag,S(s), lies
within that of native silver. The potential range of dominating Ag, S(s) is too low to
affect the domains of cyanide complexation of silver, as emphasized by Wang and
Forssberg [8]. In their pe-pH diagrams of silver, however, Wang and Forssberg
presented some questionable results at high potentials demonstrating the dominance of
AgO in an unexpectedly large region. By referring to the literature listed by them
[8,16], it is found that, for the reaction:
Agf+ H,O e AgO + 2H++ e- (16)
an erroneous value of log K = - 12.7 was used for the equilibrium constant. The value
of log K = - 30.12, as used by Xue and Osseo-Assare [7], is the correct one. As shown
in Fig. 3a, Ag,O,(s) is the dominant solid species of silver at high potentials, which is
in general agreement with the pe-pH diagram for the Ag-HCN-H,O system presented
by Osseo-Assare et al. [6,7]. At a very low concentration of cyanide, Ag,O(s) is more
stable under ambient oxygen partial pressure, p0, around 0.2 atm (Fig. 3b), while Ag(s)
is more stable under much lower oxygen pressure, p0, < 10P4 atm at pH = 11 (Fig.
3~). However, the variation of oxygen pressure does not affect the predominance of the
soluble silver cyanides.
260 Y. Zhang et al. / Hydrometallurgy 46 (1997) 251-269

-20 I I I"' 8' I ("I I"2 4" I I") II

0 2 4 6 8 10 12 14
PH 0 2 4 6 8 10 12 14
PH
w o_ (d) I,0 F __----,
Ash*. Ag(CN),-
;
-I-
/'
/
/
/

0.8

0.4

Fig. 3. Predominance/distribution of silver species (0.1 mM in total). (a) pe-pH predominance diagram for
different total concentrations of CN-, 0.2, I, IO and 100 mM; (b) log[CN- ]tOta, -pH predominance diagram at
p0, = 0.7; (c) log[CN- Itotal-pOz predominance diagram at pH = 11; (d) Distribution of different Ag species
vs. total concentrations of CN- at pH = 11 and pOz = 0.7.

By comparing Figs. 1 and 3, it is found that the dominance region of soluble silver
cyanide, Ag(CN), is smaller than that of Atr(C This region covers only the
high-pH part of the dotted line that presents the conditions at p0, = 0.2 atm (Fig. 3a).
As either pH or cyanide concentration decreases, the precipitation of AgCN(s) is
pronounced (Fig. 3b). At pH > 12, AgCN(s) may be dissolved as AgOHCN-. In order
to avoid any precipitation, more than 0.35 mM CN- may be required to dissolve 0.1
mM Ag at pH = 11, as shown in Fig. 3d. However, Ag(CN)i- can be dominant only at
a relatively high total concentration of cyanide, e.g., [CN] > 100 mM for 0.1 mM Ag.
It is important to note that the results presented in Fig. 3a-d are based on an
assumption, suggested by Wang and Forssberg [S], that the sulphide ions should be
completely oxidized into more stable species with higher oxidation state, e.g., SO:-, as
described in Eq. (7). It has been found, however, that the experimental results do not
confirm the above prediction. As shown, e.g., in Fig. 4, the overall dissolution of silver
is always less than 30%, which produces max. 0.03 mM Ag, after leaching with an
 Y. Zhang et al. / Hydrometallurgy 46 (1997) 251-269 261

8
A

Au Ag NaCN(gI1)

0 ?? 6
0 ?? 4
n A 2

1:

Fig. 4. Experiment data of gold and silver dissolution in the solutions of different NaCN concentrations (2. 4
and 6 g/l) at pH = 10-l 1 and p0, = 0.7.

alkaline solution of 6 g/l NaCN (122 mM CN- in total) even for 10 h. For comparison,
the dissolution of gold is more than 90% after 6 h. Besides, the concentration of silver in
the solutions even decreases after 2 h. leaching even though the bulk concentration of
free CN- is still relatively high (> 50 mM). This is evidence of precipitation of some
silver compound(s). Fig. 5a presents a solubility diagram of several silver compounds in
cyanide solutions at pCN (- log[CNP],,,) = O-15 and pH = 11. Among them, Ag,S
appears to be the only one that may precipitate under the given conditions as long as the
oxidation of sulphide is limited by kinetics. For a short leaching time, the non-oxidized
sulphide tends to cause the precipitation of soluble silver cyanide as follows,

2Ag(CN)j;- I)- + S2-0 Ag,S(s) + 2nCN- (7)

The re-dissolution of Ag,S(s), i.e., the back reaction in Eq. (171, would be difficult
owing to its kinetic limitation even though the oxidation of free S*- tends to be
complete after a long time of leaching. Fig. 5b-d present the calculation results based on
an assumption that part of the sulphide would not be oxidized. By comparing Fig. 5b
with Fig. 3b, it is evident that the dominance region of Ag(CN), is much smaller when
the oxidation of sulphide described by Eq. (7) is incomplete. Ag,S(s) should then be a
predominant solid compound of silver instead of Ag(s), AgCN(s) and Ag,O(s), even in
the presence of much higher concentration of CN-, when the oxidation of sulphide is
suppressed. The oxidation kinetics of sulphide ligand, which, in large quantity, results
from the dissolution of copper and iron sulphides, therefore controls the dissolution/pre-
cipitation of Ag,S(s). Fig. 5c presents a 3-dimension diagram where the precipitation of
Ag, S(s) is plotted as a function of total concentrations of CN- and non-oxidized S-.
For 0.1 mM Ag, precipitation of Ag,S(s) may take place even with 0.001 mM of
non-oxidized S2- as long as CN- is less then 10 mM. As shown in Fig. 5d, the
concentration of free CN- should be at least 30 mM for the dissolution of 0.1 mM Ag at
pH = 11 when the molar ratio silver to the non-oxidized sulphide is 2:l.
262 Y. Zhang et al./ Hydrometallurgy 46 (1997) 251-269

P
1
F -3 A9,W
0
3 i

-go 3 6 9 12 15 0 2 4 6 8 10 I2
PCN PH

_._
-6 -5 -4 -3 -2 -1 0 -
-t%Wl,,,
Fig. 5. Calculations of the silver species (0.1 mM in total) in the presence of non-oxidized S2-. (a) solubility
of silver and its compounds vs. concentration of free CN- at pH = 11 and p0, = 0.7; (b) log[CN- Itotal-pH
predominance diagram at p0, = 0.7 and [S*- ]to,a, = 0.05 mM; (c) fraction of Ag,S(s) vs. total concentrations
of CN- and S*- at pH = 11 and p0, = 0.7; (d) distribution of different Ag species vs. total concentrations of
CN- at pH = 11 and p0, = 0.7 in the presence of 0.05 mM S*- (non-oxidized).

3.2. Cu-Fe-S2- -CN ---O,-H,O system

For the cyanide leaching of gold or silver, the predominance diagrams that include
copper and/or iron sulphides are not meaningful since the dissolution equilibria of
FeS,(s) and CuFeS,(s), as given in Eqs. (5) and (61, are not required in the process. Fig.
6 shows the solubility of these two minerals in alkaline cyanide solutions, in comparison
with those of gold, silver and other sulphide compounds. Thermodynamically, they are
much more stable than both native gold and silver at pCN = 5-9. However, Fe&(s) and
CuFeS,(s) tend to be very soluble at pCN = 2-3 and pH = 10-l 1, which have been
considered to be the optimal operating conditions for gold/silver cyanidation with
respect to the leaching kinetics. In other words, it is not the dissolution thermodynamics
but kinetics that limits the cyanidation of copper and iron. Compared with the slow
dissolution of the sulphide minerals, the reactions between the dissolved species in a
 Y. Zhang et al. / Hydrometallurgy 46 (1997) 251-269 263

0 3 6 9 12 15
PCN

Fig. 6. Solubility of gold, silver and some sulphide compounds vs. concentration of free CN- at pH = 11 and
po, = 0.7.

solution system can be assumed to be at equilibrium. The equilibria included are:

complexation, precipitation and some of the possible redox reactions of metal cations
and ligands except for the oxidation of sulphide.
Fig. 7a and b present log[CN]-pH diagrams of copper and iron, respectively. As
shown, the domains of soluble cyanide complexes of copper or iron are located in higher
pH ranges with the respective cyanide concentrations.
In literature there have been some arguments on the stability of the different cyanide
complexes of copper. According to Osseo-Assare et al. [6], Cu(CN); and Cu(CN):-
are stable while CuCN(s) is not found at [Cu] = 0.1 mM and [CN] = 1 mM. According
to Wang and Forssberg [8], CuCN(s1 is the most stable species in the entire pH range
and it could be dissolved with increasing cyanide concentration to form Cu(CN):- at

FeOOH(s)

:I./
0 2 4 6
PH
8 IO 12 14
:L.lm
0 2 4 6
PH
8 10 12 I

Fig. 7. Predominance diagrams at ~0, = 0.7, [Cultota, = [Fe]t,t,, = 0.5, [S*- lfola, = 10 mM. (a) log[CN- I,,_-
pH diagram of copper species; (b) log[CN- ]tOtal
-pH diagram of iron species.
264 Y. Zhang et al./Hydrometallurgy 46 (1997) 251-269

IO
A Co

0 0 Fe

1;

Fig. 8. Experimental data of copper and iron concentrations in a solution of 4 g/l NaCN at pH = 10-l 1 and
po, = 0.7.

higher pH value. They claimed that Cu(CN); and Cu(CN)i- were less stable because
neither of these two species was present at [Cu] = 0.1 mM and [CN] = 5 mM in their
predominance diagrams. However, these calculations are rather doubtful since no
experimental confirmation was made, such as to show the stability of CuCN(s) in the
alkaline solutions. Experimentally, CuCN(s) is always prepared from neutral or dilute
acid solutions [3,4]. Fig. 7a shows that CuCN(s) dominates only at lower range of pH
(< 9). At higher range of pH, Cu(OH),(s) is found dominant when the CN/Cu ratio is
not sufficiently high. This has been confirmed by the experiments in the present study
where a blue precipitate Cu(OH),(s) was obtained after adding a solution of copper
nitrate into alkaline solutions of cyanide. The precipitate obtained was found to be
neither white in color to indicate the formation of CuCN(s), nor black as CuO(s), as
suggested by others [6,8]. When the CN/Cu ratio is high, each of three soluble cuprous
cyanide complexes, Cu(CN);, Cu(CN)t- and Cu(CN)i- successively becomes a
dominant species with increasing cyanide concentration and/or pH value of the solution
system.
According to Osseo-Assare et al. [6], high solubility of iron minerals in cyanide
solutions should be expected and Fe(CN)i- should be predominant under the conditions
used in cyanidation processes. Considering the cyanide consumption, Wang and Forss-
berg suggested an oxidation roasting of iron sulphides before cyanidation of the ore [8].
In the present study, however, the concentration of iron in cyanide solutions has been
always found much lower than that of copper as shown in Fig. 8, though the dissolution
of iron minerals should be higher than that of copper minerals according to Eqs. (5) and
(6). Fig. 7b indicates that, under the conditions used in the oxidizing environment, all
iron species should thermodynamically dominate in Fe(II1) form. As shown, Fe(CN)z-
is the only dominant cyanide complex of iron. When CN- concentration is reduced
during cyanidation, FeOOH(s) tends to precipitate.
Fig. 9a and b show that the domain of the soluble copper complexes may not be
affected by iron dissolution but that Fe(CN)i- may be transformed to FeOOH(s) by
 Y. Zhang et al./ Hydrometallurgy 46 (19971 251-269 265

(a) 0~ P-4OL
,
I
CWM2(sl ,
-1 - , -1 Fe01
Cu(CN),+ ,

0 -1 0

Fig. 9. Predominance diagrams for pH = 11, p0, = 0.7, and [CN- llora, = 100 mM, where a broken line
represents the dissolution of CuFeS,. (a) log[Cu- ],,t,, -log[Fe- la,,,, diagram of copper speciea: (b)
log[CN- lfnta,-log[Fe],,,,, diagram of iron species.

copper dissolution. In other words, FeOOH(s) precipitates thermodynamically prior to

Cu(OH),(s) when CN- concentration is decreased.

3.3. Au-Ag-Cu-Fe-S2 --CN --O,-H,O system

The predominance diagrams for gold species are not affected by dissolution of copper
and iron while those for silver are greatly changed when the precipitation of Ag,S(s) is
involved. Fig. 1Oa shows that the predominance of silver cyanidation is limited by
dissolution of copper/iron sulphide minerals in a solution containing 122 mM CN-- (6
g/l NaCN), 0.1 mM Ag and 0.05 mM S2- at pH = 11. According to Fig. lob, Ag,S(s)
starts to precipitate when the dissolution of CuFeS,(s) proceeds to produce nearly 10
mM Cu as well as 20 mM S2-, of which only 0.05 mM is assumed as not being
oxidized. Nearly 0.8 fraction of Ag is expected to precipitate as Ag,S(s) with increasing
the dissolution of CuFeS,(s). When the dissolution of CuFeS,(s) proceeds to produce
about 20 mM Cu (Fig. lob and c), the precipitation of Ag,S(s) is reduced to less than
0.7 fraction because of the precipitation of FeOOH(s) that releases cyanide ions to retain
the silver cyanidation. As it is enhanced again by further dissolution of CuFeS,(s), the
precipitation of Ag,S(s) appears to be maintained at 0.82 fraction when Cu(OH),(s)
starts to precipitate (Fig. 10b and d). This is in good agreement with the experimental
data, e.g., in Fig. 4.
The precipitation of different metal-containing species is expected to take place as the
concentration of free CN- decreases. In the case of complete oxidation of sulphide (Fig.
1 la>, the different metal species start to precipitate in the order of FeOOH(s) >
Cu(OH),(s) > AgCN(s) > Ag,O(s) > Au(s). In the case of an incomplete oxidation of
sulphide (Fig. 11 b), however, the precipitation order is Ag 2 S(s) > FeOOH(s) >
Cu(OH),(s) > Au(s). In other words, as sulphide ore is leached by a cyanide solution,
the reactions between different metal cations and cyanide are in competition with each
266 Y. Zhang et al./Hydrometallurgy 46 (1997) 251-269

(a) O. /
(b) 1.0
,
Ag,S(s) >
F
-1-
/ 0.8 r

(c) I.0 -Y
Fe(CN), 1 FeOOH(s)
I
I
0.6 r I
I
I
0.6 I
I
n !
,
0.4 I
I
I
I
0.2 I
I
I

0.0
.6 -5 -4 -2 -1 0

(d) 1.0r-

Fig. 10. Influence of dissolution and iron sulphides in a solution of 4 g/l NaCN at pH = 11,
of copper
PO, = 0.7 and [Ag- Itotal= 0.1 mM in the presence of 0.05 mM S2- (non-oxidized); (a) log[Cu- Itotal-
Iog[Fe - It,,ta,predominance diagram of silver species. (b) distribution of silver species vs. dissolution of
CuFeS*; (c) distribution of iron species vs. dissolution of CuFeS,; (d) distribution of copper species vs.
dissolution of CuFeS,.
 Y. Zhang et al./Hydrometallurgy 46 (1997) 251-269 267

(b) 1.0: ______-~~_.-------

/.
I /

Fig. 11. Precipitation of different metal species vs. concentration of free CN- at pH = 11, p0, = 0.7,
= 0.1 mM, D&,tal = [Feltotal = 0.5 mM, and IS- Itala, = 10 mM. (a) In case of
[Au- I,,,,, = [AgeItotal
complete oxidation of S2-; (b) in case of 0.05 mM S*- non-oxidized.

other. When the oxidation of sulphide is incomplete, silver cyanides appear to be the
least stable complexes owing to the precipitation of Ag,S(s). This is probably one of the
main reasons that the overall dissolution of silver is always low. Moreover, the
quantitative precipitation of FeOOH(s) during leaching may cause surface coverage
around gold/silver grains, which prevents the complete cyanidation of gold and silver.

4. Conclusions

The chemistry of cyanide leaching of gold/silver in Cu/Fe sulphide minerals can be

described by thermodynamic calculations only under proper consideration of practical
conditions and limitations of this method. The calculation results should be experimen-
tally verified. The disagreements between the computational and experimental results
should be noted and explained if possible. In the present study of the cyanide leaching
268 Y. Zhang et al./ Hydrometallurgy 46 (1997) 251-269

process, it is essentially important to specify and consider the kinetically limited

reactions. The present recalculations can be summarized to explain the experimental
results with the following specific characteristics:
* The presence of soluble sulphides can thermodynamically result in the precipita-
tion of Ag,S(s), which suppresses the recovery of silver through the cyanide leaching
process.
- The cyanide complexation of Cu and/or Fe does not affect the recovery of gold
thermodynamically through cyanide leaching since the cyanide complexes of Cu and Fe
are much less stable than ALI(C The cyanidation competition between these metals
results in precipitation of FeOOH(s) and Cu(OH),(s) in turn. It is possibly the coating of
these precipitates on gold grains that prevents the complete cyanidation of gold.
0 The cyanide complex of Fe is much less stable than those of Cu because of the
precipitation of FeOOH(s) prior to Cu(OH),(s) when free CN- is consumed during
leaching. Therefore, the dissolution of Cu consumes more cyanides than that of Fe.
Besides, it is the reduction of Cu(I1) to form stable Cu(I)-CN complexes that enhances
the oxidation of HCN, thus resulting in the permanent consumption of HCN.
- The cyanidation competition between Ag and Cu/Fe is thermodynamically
negative toward the recovery of silver in the presence of sulphide, which results in
precipitation of Ag,S(s) prior to FeOOH(s1 and Cu(OH),(s). In order to increase the
recover of silver, therefore, it is essential to oxidize the sulphide as completely as
possible.

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