Minerals Engmeering, Vol. 13, No. 10-11, pp.

1097-1106, 2000
Pergamon 2000 Published by Elsevier Science Ltd
All rights reserved
0892-6875(00)00093-5 0892-6875/00/$- see front matter

THE CYANIDE LEACHING OF GOLD

IN SOLUTIONS CONTAINING SULFIDE*

M.I. JEFFREY and P.L. B R E U E R

Department of Chemical Engineering, Monash University, Vic, 3800.

Email: matthew.j effrey@eng.monash.edu.au
(Received 20 April 2000; accepted 13 June 2000)

ABSTRACT

A large proportion of the gold processed in the 21"' century will be recovered from sulfide ores.
Since the sulfide minerals are to some extent soluble in cyanide solutions, there will always be some
sulfur species present in the leach solution. It has been shown that soluble sulfide hinders the rate of
gold leaching, forming a protective layer of the type AulSx. Electrochemical studies of the
constituent half reactions: gold oxidation; and oxygen reduction, were consistent with this view. The
effect of sulfide and cyanide concentrations on the leaching reaction were investigated, and it was
shown that the sulfur formed is chemically attacked by cyanide, resulting in higher leach rates at
higher cyanide concentrations. The effect of lead was also studied and is discussed in detail. 2000
Published by Elsevier Science Ltd. All rights reserved.

Keywords
Cyanidation; leaching; hydrometallurgy; gold ores

INTRODUCTION

For the past 100 years, the cyanidation process has been the most important process in the extraction of
gold from its ores. Patented by MacArthur et al. (1888), the process relies on the fact that gold dissolves in
aerated cyanide solutions to produce the gold cyanide complex. The stoichiometry by which this reaction
occurs is known as the Elsner (1846) equation.

4Au + 8CN- + O 2 + 2 H 2 0 --> 4Au(CN)~ + 4 O H - (1)

In this century a large proportion of the gold processed will be recovered from sulfide ores. Since the
sulfide minerals are to some extent soluble in cyanide solutions, there will always be some sulfur species
present in the leach solution. During industrial operations, it is generally believed that the presence of such
species results in a high consumption of cyanide and oxygen. However from the results of kinetic studies, it
has been argued that sulfur species also directly affect the gold leaching reaction. For instance, Weiselbaum
et al. (1989) and Fink and Putnam (1950) showed that the addition of trace amounts of sodium sulfide to

* Presented at Hydromet 2000, Adelaide, Australia, April 2000

1097
1098 M. 1. Jeffreyand P. l.. Brcuer

the cyanide solution dramatically hindered gold leaching. It was suggested that the sulfide ions passivate
the surface of the gold by forming a passive layer of Au2S (Weichselbaum et al. 1989). Similar results were
obtained by Lorenzen and van Deventer (1992), who studied the kinetics of gold leaching in the presence
of reactive sulfide minerals such as pyrrhotite. One complication with these previous studies is that high
purity gold was utilised, for which the leaching is hindered by a film of AuCN (Jeffrey & Ritchie 2000c).
However most naturally occurring gold contains silver, for which the cyanide leaching reaction occurs at a
high rate (Jeffrey & Ritchie 2000b). The present study aims to establish the effect of sulfur species on the
leaching of gold containing 5 % silver.

EXPERIMENTAL

All experiments were carried out using solutions prepared from analytical grade reagents and doubly
distilled water. Unless specified, the solutions contained 5 mM (245 ppm) sodium cyanide. Such a
concentration was chosen as it represents a typical cyanide concentration for Australian gold processing
plants treating sulfidic ores. The pH was adjusted to 10.0 using sodium hydroxide, and at this pH, any S2-
present will be converted to HS-. For the electrochemical experiments, 0.2 M sodium perchlorate was
added as background electrolyte. Linear sweep voltammetry was conducted using a Pine RDE4
potentiostat. All experiments were performed at a rotation rate of 300 rpm and a scan rate of 1 mV s -~,
unless otherwise specified. All potentials were measured relative to the saturated calomel electrode (+0.242
V vs. SHE), but are reported relative to the SHE. A platinum wire was used as the counter electrode. Mass
changes were measured using the rotating electrochemical quartz crystal microbalance (REQCM), which is
described elsewhere (Jeffrey et al. 2000). Prior to each experiment, gold was electroplated onto the quartz
electrode at 25 A m 2 from a solution containing 0.02 M potassium dicyanoaurate, 0.23 M potassium
cyanide, 0.086 M potassium carbonate, and 0.5 mM silver nitrate. This resulted in a deposit containing
approximately 5 % silver by mass (which for simplicity will be referred to as gold), thus ensuring that the
experiments more closely mimicked industrial conditions.

RESULTS AND DISCUSSION

Kinetic aspects of gold leaching in solutions containing hydrosulfide ions

The REQCM was used to study the leaching of gold in air saturated 5 mM cyanide solutions in the
presence and absence of hydrosulfide ions. Shown in Figure 1 are the kinetic plots, which show the change
in mass as a function of time. It can be seen that the mass of the electrode, m, decreases as the metal is
leached, and this decrease can be related to the dissolution rate through Eq 2,

1 dm (2)
r - - -

M A dt

where r is the leaching rate (mol m 2 s ~), M is the atomic mass of gold (196.97 g mol-l), A is the area of
the gold electrode (m2), and t is the time elapsed (s). Thus, the slope of the kinetic plot is a measure of the
leaching rate.

It can be seen from Figure 1 that the leaching behaviour of gold in the absence of hydrosulfide is
significantly different to that in its presence. Clearly, gold leaches much more readily when hydrosulfide is
not present. At steady state, the leaching rate for gold is calculated to be 4.7x10 5 m o l m -2 s -~, which is
more than seven times higher than the rate calculated for gold in the presence of hydrosulfide, 0.62x10 -5
mol m 2 s-~.

To establish the role of hydrosulfide ions in the cyanide leaching process, a gold sample was exposed to
HS at different stages of the leaching reaction. In one experiment, the gold was initially leached in a
solution containing 1 mM hydrosulfide and 5 mM cyanide. After 250 seconds of leaching, the gold was
removed from solution and thoroughly rinsed with distilled water, before being placed into a 5 mM cyanide
solution in the absence of hydrosulfide. As can be seen from Figure 2, the leaching rate of gold pretreated
in this way is significantly lower than the leaching rate of a clean gold surface. It is thus clear that the
 Cyanide leachingof gold in solutionscontainingsulfide 1099

surface of the gold is passivated when it is exposed to the hydrosulfide solution, and this passivation
remains when the gold is transferred to a hydrosulfide free solution. These results also confirm that the
main effect of hydrosulfide is not to consume oxygen or cyanide. In a second experiment, a fresh gold
sample was allowed to leach in a solution in the absence of HS- for 250 seconds. At this point,
hydrosulfide was added to the solution, and the mass response of the electrode is shown in Figure 2. It can
be seen that when the gold is exposed to hydrosulfide, the leaching reaction is almost instantaneously
hindered. Such a result clearly shows that the passivation of the gold surface by 1 mM hydrosulfide is a
rapid process.

0 ~ o ~ 0 mM sulfide
....... , .. . ......... 1 mM sulfide
- ~eelileolel
-10 ~m=Qe~tm~Je~l~,...itBmoo~l~l~ee~elbo~Beol
~ =

ol
=. -20
E
<3
-30

-40

-50 , , , , I , , , . , l ~ = ~ = l n ~ = I
0 100 200 300 400 500
tls
Fig. 1 Kinetic plots of gold leaching in aerated 5 mM cyanide in the presence and absence of 1 mM HS-.

i exposure to sulfide:
0 before leaching
i. - - , ~ c h l n g

-10

o~
-20
E
<3
-30
~P ~w~ Q b ~ b q
-40

Ii
-50 i n n I , I I ' I . , , , I , t , , I a , ~ , I I I I , I . . . . I , , , ,

0 50 100 150 200 250 300 350 400

t/s

Fig.2 Kinetic plots showing the leaching kinetics of gold exposed to HS- at different stages of the
process. The dotted line shows the leaching in the absence of HS- after being pre-passivated by
leaching in a solution containing 5 mM cyanide and 1 mM HS- for 250 s.
11O0 M. 1. Jeffreyand P. L. Breuer

Interaction between gold and hydrosulfide ions in non cyanide solutions

The interaction between hydrosulfide ions and a gold surface can be simply studied using standard
electrochemical techniques. However in this instance, cyanide and oxygen must be excluded from solution;
otherwise the electrochemical reactions of hydrosulfide will be masked by gold oxidation to gold cyanide
and oxygen reduction. The cyclic voltammogram which results when gold is electrochemically polarised in
the presence ofhydrosulfide ions is shown in Figure 3.

0.8
A2

0.4
A1

N 0.0

.~ -0.4

-0.8

-1.2 . . . . ' . . . . i . . . . , . . . . I . . . . i . . . . i . . . .
-800 -600 -400 -200 0 200 400 600

EImV
Fig.3 Cyclic voltammogram of gold in 1 mM HS-. The potential scan rate used was 25 mV s -].

Clearly there are two anodic and two cathodic peaks, marked A 1, A2, C1 and C2. Similar results have been
obtained at pH 9.2 by Hamilton and Woods (1983), and it is generally agreed that peaks A2/C2 are due to
bulk deposition and removal of sulfur onto and from the gold substrate respectively. Peaks A1 and C 1 are
most relevant to the cyanidation process, as the mixed potential of gold leaching in oxygenated cyanide
solutions is about 400 mV. It has been suggested that peak A1 is a result of the underpotential deposition
of a monolayer of sulfur onto the gold surface, with peak C1 representing the reduction of this monolayer
(Hamilton & Woods 1983). Hence it would appear that during gold cyanidation in the p~ebcnce of
hydrosulfide, the surface is protected by a monolayer of sulfur. Briceno and Chandler I lou{~ have
suggested that this monolayer is a two dimensional chemisorbed sulfur layer of the type AuJ.'-;~. It is not
surprising that such a film causes passivation of the gold in cyanide solutions.

Effect of hydrosulfide ions on the anodic and cathodic half reactions

The leaching of gold in aerated cyanide solutions is an electrochemical reaction involving the oxidation of
gold to gold cyanide, and the reduction of oxygen, as shown in Eqs 3 and 4 respectively. Hence useful
information can be obtained by using standard electrochemical techniques to study the constituent half
reactions.

Au + 2 C N - ~ A u ( C N ) j + e- (3)
02 + 2 H 2 0 + 4e- --~ 4 O H - (4)
Figure 4 shows the voltammograms for gold oxidation in oxygen-free cyanide solutions in the presence and
absence ofhydrosulfide ions. It is clear that hydrosulfide ions have a dramatic effect on the electrochemical
 Cyanide leachingof gold in solutionscontainingsulfide 1101

behaviour of gold. In the absence of HS-, the oxidation of gold proceeds rapidly, reaching a diffusion
limiting plateau at approximately 200 mV. However in the presence of hydrosulfide ions, gold is almost
completely passive in cyanide solutions, even at very high overpotentials. This suggests that the sulfur
which is formed on the gold surface is highly protective. Such a result is consistent with the observed slow
leaching kinetics in the presence ofhydrosulfide ions.

12 . . . I "- - "'S ; : ,.z_;.

10 , ,, O m M s u l f i d e

6
E
<
--- 4
m

__j .p

. , , , I , , , , I . . . . I . . . . I . . . . I T I f I I f I I I

-600 -400 -200 0 200 400 600 800

EImV

Fig.4 Linear sweep voltammograms showing gold oxidation in 5 mM cyanide in the presence and
absence of I mM HS-.

Figure 5 shows the effect ofhydrosulfide on the reduction of oxygen on gold in the absence of cyanide. It is
clear that in the absence of HS-, oxygen reduction occurs readily at potentials more negative than -100
mV. However, in the presence of hydrosulfide ions, oxygen reduction is signifcantly hindered, and only
occurs at potentials negative of -300 mV. In this instance oxygen reduction may occur on the sulfur
surface, although due to the high resistance of sulfur, there is a considerable iR drop. This also contributes
to the slow leach kinetics in the presence of hydrosulfide.

-1

-2
0 mM sulfide
.......... 1 mM sulfide

o~"
..-/
~.r"
,.~*"~ '~' " " ~

E
'< -3
,m
../...o
-4 .t,

-5

-6 . . . . I . . . . I . . . . I . . . . I . . . . I . . . . I . . . . I . . . .

-800 -700 -600 -500 -400 -300 -200 -100 0

EImV

Fig.5 Linear sweep voltammograms showing oxygen reduction in the presence and absence of 1 mM
HSL
1102 M.I. Jeffreyand P. L. Breuer

Effect o f c y a n i d e concentration on the leach kinetics

Figure 6 shows the effect of cyanide concentration on the kinetics of gold leaching in the presence of
hydrosulfide. It can be seen that at a cyanide concentration of 20 mM the gold leaching reaction is still
passive. However, at 40 mM cyanide, gold leaching is slow for an initial period but then proceeds to leach
at a much more rapid rate. It would thus appear that under some experimental conditions, the sulfur can be
removed from the gold surface; most likely as SCN-, as shown in Eq 5.

S + C N - --+ S C N - (5)
0

-10

-20

-30

~- -40
E
<l -50 %
.......... 4 0 m M c y a n i d e ", %%
%%
-60 %
%%
%
-70

-80 ,,, I .... I .... I .... I .... I .... I .... 700

0 100 200 300 400 500 600

time I s

Fig.6 Effect of cyanide concentration on the kinetics of gold leaching in solutions containing 1 mM HS-.

It is thus not surprising that gold is less passive at higher cyanide concentrations, since the rate of AulS
dissolution to form SCN- would be dependent on [CN-]. In addition, once the sulfur has been removed
from the surface, the gold may react with HS- to reform AulSx or w.ith CN- to leach as Au(CN)2-. It would
be expected that at high cyanide concentrations, the probability of forming Au(CN)2- instead of AulSx
would be increased, hence resulting in a higher steady state leach rate. Conversely at low cyanide
concentrations, the re-passivation of the gold surface by HS- would be more likely to occur, resulting in a
lower leach rate (as shown in Figure 6).

The effect of cyanide concentration on the rate at which S is leached off the gold surface can be further
quantified by studying the dissolution of gold which had been prepassivated by a solution containing HS-.
It can be seen from Figure 7 that at each cyanide concentration, the leach rate (slope of the data) increases
with time. Such a result is consistent with the sulfur film on the gold surface becoming less protective with
time. In this instance, there is no HS- in solution and hence once the sulfur is attacked by cyanide, the
passivation cannot be reformed. In a similar manner to the results shown in Figure 6, the leaching of a
sulfur passivated gold sample is a function of cyanide concentration. These results are consistent with the
film of sulfur being attacked by cyanide to form soluble thiocyanate, as shown in Eq 5.

Effect o f h y d r o s u l f i d e concentration on the leach kinetics

Figure 8 shows the effect of sulfide concentration on the kinetics of gold leaching in 5 mM cyanide
solutions. It is clear that at very low hydrosulfide concentrations (0.01 mM) no passivation of the gold
surface was evident in the time frame of interest. Obviously, under these conditions, the formation of Au[Sx
is a slow process, and hence does not hinder gold leaching. For solutions containing 0.1 mM hydrosulfide it
can be seen from Figure 8 there are two distinct regions in the kinetic plot. For the first 300 s of leaching,
 Cyanide leaching of gold in solutions containing sulfide 1103

the reaction is slower than for 0.01 mM HS-, but is much more rapid than for solutions containing 1 mM
HS-. Such a result suggests that some sulfur is deposited on the gold surface, but the rate at which this
occurs is low. For t > 300 s, it can be seen from Figure 8 that the leach rate steadily drops with time, and
after 600 s o f leaching, the reaction rate is approaching that for solutions containing 1 mM HS . This
suggests that in solutions containing 0.1 mM HS-, at least 600 s is required for a highly protective film o f
AulS x to form on the gold surface. In comparison, passivation is almost instantaneous for solutions
containing 1 mM HS-.

-10

-20

<1 -30 "".. "'"'-..

.......... 20 mM cyanide " ' , *o
%,

-40 "o
t~

-50 ! ,i ,i , i, l ~ , ~ n l ~ n ~ l v l l I I , , , , I , , , ,

0 100 200 300 400 500 600

time I s

Fig.7 Effect o f cyanide concentration on the kinetics of pre-passivated gold in the absence o f HS-. The
gold was pre-passivated by leaching in a solution containing 5 mM cyanide and 1 mM HS- for
250 s.

sulfide concentration
0
'~,~ ..... 0.01 mM
"~<~;. ..... . .... 0 1 mM
"~'~ ............. . ......... 1 mM
-10
%~ II~l*'l,e
%%

-20

E
-30

-40

, . . . . , , . .
-50
0 100 200 300 400 500 600
tls

Fig.8 Effect o f H S concentration on the leaching o f gold in 5 mM cyanide solutions.

l 104 M. 1. Jeffreyand P. L. Breuer

Effect of lead

It has been suggested that the addition of lead can overcome the detrimental effects of sulfide ions
(Weichselbaum et al. 1989), and hence its effect was studied in detail. In the first set of experiments, 5 ppm
lead(II) was added to a solution containing 5 mM cyanide and 1 mM hydrosulfide. This caused the
immediate precipitation of lead sulfide which results in a fall in the sulfide concentration to 0.98 mM.
Obviously such a decrease will not affect the leach rate, and when the kinetics were measured for this
solution, it was found that the gold was passive. The solution was then allowed to stand, and the leach was
measured at various time intervals, with the results being shown in Figure 9. It was observed that after 2
hours, the solution became clear; Figure 9 shows that once this had occurred, the gold leach rate was
significantly higher (there was no passivation of the surface). These results are consistent with hydrosulfide
ions no longer being present in solution. In comparison, for cyanide/hydrosulfide solutions not containing
lead, the leach rate was found to be low even after standing the solution for prolonged periods. It is thus
believed that lead catalyses the oxidation of hydrosulfide ions, presumably forming thiocyanide (which
does not passivate the gold surface).

0 0 ppmlead
. 5 ppmlead * .
~r

"7
V) 4

fi
"3 3
E
..,.... ~r
2
o

~ * 0 0
, , , , I , , , , I . . . . I , , , I ] I I I/ /' I , , , , / . . . .

0 1 2 3 4 ~ / 23 24 25
t/h

Fig.9 Effect of lead on gold leaching in hydrosulfide containing solutions. The abscissa shows the time
elapsed since preparing the solution.

The effect of lead on the passivation caused by hydrosulfide ions was also studied, since it is well known
that lead affects the surface of gold during cyanidation (Jeffrey & Ritchie 2000a). This was accomplished
by exposing the gold to a solution containing lead prior to and after passivation in the hydrosulfide
containing solution. Figure 10 shows these results.

In the first experiment, a gold sample was exposed to a hydrosulfide containing solution for 2000 s, and
then rinsed and placed into cyanide solution containing 2 ppm lead in the absence of HS-. It should be clear
that the addition of lead increases the leaching rate to some extent. However the rate measured (2xl 0 -3 mol
m -2 s-J) was significantly slower than that for a clean gold surface in a solution containing 5 mM cyanide
and 2 ppm lead (5.5x10 -5 mol m -2 s-I). This suggests that the process by which lead disrupts the sulfur film
on the gold surface is slow. In the second experiment, a gold sample was leached in the lead containing
solution for 400 s, after which it was rinsed and placed into a hydrosulfide containing cyanide solution.
Clearly the gold in this instance is passive, despite the fact that the lead is retained on the surface during
rinsing. It is also interesting to note that the leach rate is actually lower than that for of a fresh gold sample
in cyanide solutions containing hydrosulfide. Such a finding suggests that in this instance lead hinders the
 Cyanide leachingof gold in solutionscontainingsulfide 1105

leaching reaction. It is believed that in the presence of hydrosulfide ions, the lead present on the gold
surface is oxidised to form PbS (E of this reaction is -0.93 V) (Antelman & Harris, 1992). The leach
results are thus consistent with PbS causing further passivation of the gold surface.

0 0 ppm lead
.......... 2 ppm lead

-10
BI~BUm I

-j_
-20

""'..,...
-30

-40

-50
0 200 400 600 800 1000
tls

Fig. 10 Effect of lead on the passivation of gold by hydrosulfide. The first set of results (marked 1) were
obtained for gold which had been pre-passivated in 1 mM HS- for 2000 s, and then leached in 5
mM cyanide in the presence and absence of lead. The second set of results (marked 2) were
obtained for gold which had been leached in the presence and absence of lead for 400 s, and then
placed in a solution containing 5 mM cyanide and 1 mM HS-.

CONCLUSIONS

It has been shown that the presence of hydrosulfide in cyanide leach solutions results in the formation of a
passive layer of sulfur on the gold surface which significantly reduces the gold leach rate. These results
were confirmed using electrochemical techniques, and it was shown that the presence of hydrosulfide
hinders both the gold oxidation and oxygen reduction half reactions. It was also shown that the sulfur
formed is chemically attacked by cyanide, resulting in higher leach rates at higher cyanide concentrations.
The effect of lead on the gold/cyanide/hydrosulfide system was studied, and it was shown that the main
role of lead is to catalyse the oxidation ofhydrosulfide ions.

ACKNOWLEDGEMENTS

Some of the initial research in this project was carried out as part of a PhD program at the AJ Parker CRC
for Hydrometallurgy. The authors acknowledge the support for the CRC program by the Australian
Government, and in particular, the guidance provided by lan Ritchie during these studies.
1106 M.I. Jeffreyand P. L. Breuer

REFERENCES

Antelman, M.S. and Harris, F.J., The Encyclopedia of Chemical Electrode Potentials, 1982, Plenum Press,
New York.
Briceno, A. and Chandler, S., Oxidation ofhydrosulphide ions on gold. Part I: A cyclic voltammetry study.
Journal of Applied Electrochemistry, 1990, vol. 20, 506-511.
Elsner, L., Uber das verhalten verschiedener metalle in einer wassrigen losung von cyankalium. Journal
fuer Praktische Chemie, 1846, voi. 37, 441-446.
Fink, C.G., Putnam, G.L., The action of sulphide ion and of metal salts on the dissolution of gold in
cyanide solutions. Mining Engineering, 1950, vol. 187, 952-955.
Hamilton, I.C. and Woods, R., An investigation of the deposition and reactions of sulphur on gold
electrodes. Journal of Applied Electrochemistry, 1983, vol. 13,783-794.
Jeffrey, M.I., Zheng, J. and Ritchie, I.M., Development of a Rotating Electrochemical Quartz Crystal
Microbalance for the Study of Metal Leaching and Deposition. Measurement Science and Technology,
2000, vol. 11,560-567.
Jeffrey, M.I. and Ritchie, I.M., The leaching of gold in cyanide solutions in the presence of impurities I.
The effect of lead. Submitted to Journal of the Electrochemical Society, 2000a.
Jeffrey, M.I. and Ritchie, I.M., The leaching of gold in cyanide solutions in the presence of impurities II.
The effect of silver. Submitted to Journal of the Electrochemical Society, 2000b.
Jeffrey, M.I. and Ritchie, I.M., The leaching of gold in cyanide solutions under conditions of high purity.
Submitted to Journal of the Electrochemical Society, 2000c.
Lorenzen, L., van Deventer, J.S.J., Electrochemical interactions between gold and its associated minerals
during cyanidation. Hydrometallurgy, 1992, vol. 30, 177-194.
MacArthur, J.S., Forrest, R.W. and Forrest, W., 'Improvements in obtaining gold and silver from ores and
other compounds', British Patent 14174, 1888.
Weichselbaum, J., Tumilty, J.A. and Schmidt, C.G., The effects of sulfide and lead on the rate of gold
cyanidation. In The Aus.l. M M Annual Conference Perth/Kalgoorlie. Aus.I.M.M., Melbourne, 1989, pp.
221-224.

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