PERGAMON Electrochimica Acta 44 (1999) 2625-2632

Electrochemistry of conventional gold cyanidation

L. Guzmana, M. SegarraC, J.M. ChimenosC, P.L. Cabotb, F. Espiell”? *
“Depurtment of Physical Chemistry. Universidad Mqor de Sun Andrl~. La Pa-_. Bolivia
bLCTEM, University of Barcelonu. Barcelona, Spain
CDepurmwnf of Chemicul Engineering and Metallurgy. Fuculty of Chemistry, University, of Barcelona, P7, Marii i Franqu& I, 08028
Barcelona, Spain

Received 3 August 1998; received in revised form 5 November 1998; accepted I1 November 1998

Abstract

The kinetics of conventional gold cyanidation in air has been studied using open circuit potential measurements,
voltammetry and atomic absorption spectrophotometry. The experimental results show that this is a complex
process characterized by the interdependency of the different variables (cyanide concentration, pH, temperature and
stirring speed).The measurement of the mixed potentials at which the process takes place gives valuable information
to ascertain the influence of each variable. A good correlation between mixed potential and dissolution rate, thus
having a potential interest for an industrial application, has been found. The study of the current-potential curves
for oxygen reduction on gold surface and anodic dissolution of gold in cyanide solutions gives more insight into the
control of the process: depending on the experimental conditions, gold dissolution takes place in the active region
(oxygen diffusion control) or in the potential region where dissolution of adsorbed species limits the rate of the
process. Depending also on the experimental conditions, two or four electrons are transferred per oxygen molecule.
0 1999 Elsevier Science Ltd. All rights reserved.

Key’ords: Gold; Conventional gold cyanidation; Gold anodic dissolution; Oxygen reduction on gold; Mixed potential

1. Introduction despite the intense research works in this field, gold

leaching with cyanide solutions has not substantially
The dissolution of gold in aqueous cyanide solutions changed.
is known since XVIII century. Scheele in 1783 and Thirty years ago, Habashi [I] published one of the
Bagraton in 1843 observed that gold can be dissolved most relevant articles concerning gold cyanidation. He
in cyanide solutions. Elsner in 1846 was the first in proposed that gold leaching in cyanide solutions is an
considering the vital importance of oxygen in the cya- heterogenous electrochemical process controlled by the
nidation of gold. Although Elsner’s findings were diffusion of cyanide ions and oxygen towards gold sur-
further confirmed, a practical application of this face through the Nernst boundary layer. His con-
knowledge was only developed after ca. 40 years. In elusions were based on the fact that the gold
1887, McArthur and Forrest presented the first patent cyanidation rate linearly depends on cyanide and oxy-
of gold and silver extraction with cyanide solutions gen concentrations, is a function of the stirring speed
from gold and silver-bearing minerals. Since then, and the activation energies of the process are in the
range of 8-20 kJ mol-‘, values which are typical for a
__- diffusion controlled process. In the same article,
* Corresponding author. Fax: + 34-93-402- I29 I ; e-mail: Habashi refers to the possibility of having another cya-
espiell(a angel.qui.up.es. nidation mechanism under chemical control for stirring

0013-4686/99/$19.00 c 1999 Elsevier Science Ltd. All rights reserved.

PII: SO0 I3-4686(98)00392-2
2626 L. Gu-_mcm ct al. I Elrctrochimicu ACM 44 (1998) 2625-2632

speeds over 150 min- ‘, as the gold dissolution rate is However, the rate determining step is considered to
then proportional to the square rate of oxygen press- depend on the potential [14, 151.
ure, and the activation energy is found to be 58.9 kJ Gold passivation depends on the hydroxide ion con-
mol-‘. centration. However, gold is passivated by the for-
The electrochemical nature of cyanidation, which is mation of AuzOs at sufficiently anodic
similar to a corrosion process controlled by diffusion, potentials [ 10, 1 11.
oxidizing power of oxygen and the low cyanidation On the other hand, the oxygen electroreduction can
rate of gold in the presence of added H202, have been follow different pathways depending on the experimen-
the aim of the methods and research lines on gold cya- tal conditions and the substrate nature. The current-
nidation for the last years. The features controlling dis- potential curves found by different researchers [9] have
solved oxygen and cyanide concentration during the same form: two waves are distinguished, the first
cyanidation acquire a fundamental importance. related with the oxygen reduction to hydrogen per-
Therefore, it is necessary to control cyanicides and oxide (2-electron process):
oxygen scavengers that cause the cyanide and oxygen
02 + Hz0 + 2eeHO; + OH - (4)
concentration in solution to decrease.
Habashi’s results were further confirmed using differ- and the second related with hydrogen peroxide re-
ent experimental techniques and most of the results duction to hydroxide ions (another 2-electron process):
concerning cyanidation of silver were explained as for
gold cyanidation [2]. Nevertheless, the mechanisms of HO, + Hz0 + 2e-e30H - (5)
gold and silver cyanidation appear to be somewhat The first wave is higher than the second. This can be
different. explained by considering that a significant part of the
With respect to the mechanism of gold cyanidation, formed peroxide is decomposed to oxygen, which can
some authors considered that the final product of the also be further reduced (thus increasing the current
oxygen reduction is hydrogen peroxide [1,3]: density) or by considering that oxygen reduction in the
first wave is given by two mechanisms: one in series
02 + 2HzO + 2e--Hz02 + 20H - (1) (yielding to peroxide by a 2-electron process) and
another in parallel by direct reduction to water (invol-
while some others proposed an oxygen reduction to
ving 4-electrons).
hydroxide via four electrons [4]:
The oxygen reduction can also be affected by the
crystalline orientation of the gold surface [16-211. The
02 + 2H10 + 4e--4OH _ (2)
number of electrons depends on the potential, hydro-
gen peroxide is observed as an intermediate, the reac-
Three mechanistic models for oxygen adsorption and
tion is slow and its mechanism complex, making the
subsequent reduction on different electroactive surfaces
study of each particular case necessary [19].
in alkaline solutions were reported by Yeager [5]. The
If we consider the electrochemical nature of gold dis-
‘end-on’ adsorption model, M-O-O, is the pathway
solution in aerated alkaline cyanide solutions, it is im-
that Favours the two-electron reduction of oxygen to
portant to study in-depth some aspects of the anodic
hydrogen peroxide. Many studies have shown that the
dissolution of gold and of the cathodic reduction of
‘end-on’ adsorption mechanism prevails on Au [2,6-81.
oxygen. The study of the mixed potentials at which the
Griffith’s and bridge models involve the dissociative in-
process takes place depending on the experimental con-
teraction, which is sufficiently strong to weaken the O-
ditions gives very important information on the pro-
0 bond. On Ag, a four-electron oxygen reduction
cess and the dependence of the mechanism involved
appears to take place according to the bridge
with the different variables. Thus, the influence of
model [2,6, 71.
these variables and their relationship with the mixed
For the last years, the anodic dissolution of gold in
potentials of gold on the process of conventional gold
alkaline cyanide solutions has been studied using
cyanidation have been studied using open circuit po-
chronoamperometry, voltammetry and RDE [9915].
tential measurements, voltammetry and atomic absorp-
Three anodic peaks are obtained in the corresponding
tion spectrophotometry.
voltammograms 191.
The formation of adsorbed species such as AuCN
has been claimed in the active dissolution region [lo],
the process being determined by the dissolution of the 2. Experimental
intermediate adsorbed [ll]. Some authors suggest the
following rate determining step [12, 131: Gold of electrolytic purity (999.5/1000) was used for
all the experiments. It was melted in a magnesite cupel
AuCN ;&-AuCNads + e- (3) at 1050°C for 30 min and the resulting button was
 L. Gu:man et al. I Electrochimica Acta 44 ( 1998) 2625-2632 2621

cold-laminated to a thickness less than 50 pm. Plates 140 ,

were cut with a surface area ca. 0.3 cm’. To obtain a ‘;ul 120 -
good reproducibility of the reaction rate measure- “E
ments, it was necessary to heat the plate in a bunsen 5 100 -
E
flame just before the experiment in order to remove t 80 -
hydrocarbons adsorbed on the gold surface [22]. 2
Sodium cyanide was of analytical grade and distilled E 60 -
water, filtered through a Millipore Mini-Q system oc
“3 40 -
prior to the solution preparation, was used in all ex- ‘0
periments. The pH was corrected by the addition of .B 20 -
Q
drops of 0.1 M sodium hydroxide solution. 0’
The dissolution rate measurements of the gold plates 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5
were carried out in a 500 ml cylindrical reactor, mag-
PH
netically stirred, with two holes in the cover for insert-
ing a thermo-regulator and a holder for the metal Fig. I. Effect of pH on the conventional cyanidation of gold.
Experimental conditions: 0.02 M NaCN, po? = 0.21 atm, 400
plate, so that it could be removed from the reactor
min - 1, 25°C.
after a given reaction time. These plates were immedi-
ately washed with distilled water, dried at 110°C and
weighed. During the experiments, samples of 2 ml were cathodic sweeps were also started just after the immer-
also taken at different dissolution times and their gold sion of gold into the electrolyte. Certain experiments
concentration was analyzed by atomic absorption spec- were conducted in the presence of Tl(1) salts to study
trophotometry. In all cases the weight loss of the met- its effect on the oxygen reduction rate.
allic plate was proved to be equal to the amount of
gold found in the solution. The plots of gold concen-
tration versus reaction time were always linear, thus 3. Results and discussion
confirming that the metal dissolution took place under
steady-state conditions. 3.1. Effkct of’pH, cyanide concentration, temperature
The electrochemical experiments were carried out and stirring speed on the conventional gold cyanidation
with a 1286 Solartron potentiostat commanded by the rate
CorrWare for Windows 1.2 Corrosion software. A 500
ml cylindrical cell immersed in a thermostatic bath at The influence of pH on the kinetics of gold cyanida-
25°C was used, with five holes in the cover for insert- tion at atmospheric pressure has been determined
ing a pH-meter (optionally), the working electrode, an under the following conditions: 0.02 M NaCN, 400
Ag/AgCl/KCI (3 M) reference electrode connected via min-’ and 25°C. The corresponding results are shown
a Luggin capillary (all the potentials given in this work in Fig. 1. As shown in Fig. 1, the gold dissolution rate
are referred to such a reference electrode), the Pt wire slightly increases until pH 12. A further increase in pH
counter electrode and a gas inlet for nitrogen or argon leads to a sudden decrease in the cyanidation rate,
sparging. The working electrode was made of a gold probably due to a change in the mechanism of the pro-
plate joined to a copper wire by a cold soldering and
further inlaid in epoxy resin. Prior to the electrochemi-
140 ,
cal experiments, the electrode surface was grounded 120 -
5 n..---.-.- _..__
------.._______
and polished with alumina to a 1 urn finish and further
rinsed with distilled water in an ultrasonic bath. An r‘ii loo -
, a

electrode section of 0.16 cm’ was exposed to the sol- tE 0

!
ution. The mixed potentials (E,,,) were measured in the 80-
aerated and magnetically stirred solutions. The station-
s
e 60- ,
ary values were taken as those which varied less than 3 s i
mV/lO min [23]. The anodic sweeps of the gold vol-
3 40 - ?”
tammograms were obtained, just after its immersion ,$ 20 - ;’
into the electrolyte, in the deaerated and magnetically
stirred alkaline solutions, with cyanide, in the potential
0 5 10 15 20 25 30 35 40 45 50 55
range from -0.8 to +0.8 V and a sweep rate of 1 mV
S - ‘. The cathodic reduction of oxygen was studied in NaCN concentration I mM
the aerated and magnetically stirred alkaline solutions Fig. 2. Effect of cyanide concentration on the conventional
in the absence of cyanide, in the potential range of cyanidation of gold. Experimental conditions: pH 11.5,
+ 0.1 to -1 V and a sweep rate of 1 mV s- ‘. The ~0, = 0.21 atm, 400 min-‘. 25°C.
2628 L. Gunman et al. 1Electrochimica Acfa 44 ( 1998) 2625-2632

cess. As conventional cyanidation is usually performed cI 4.90

at pH values between 10 and 12, it can be observed -7
u, 4.70
that in this pH range the gold dissolution rate does Z
not essentially change, having a mean value of 120 z 4.50
urn01 me2 s-‘. 1
The effect of cyanide concentration was determined
by measuring the gold dissolution rate at pH 11.5, 400
min- ‘, 25°C and cyanide concentrations in the range
of 2-5 mM. As shown in Fig. 2, cyanide concentration
strongly affects gold dissolution rate. At low cyanide
concentrations, the cyanidation rate is proportional to
the initial cyanide concentration. When it reaches
values over 0.012 M, the cyanidation rate increases 4.0 4.5 5.0 5.5 6.0
until a near constant value of 121.5 urn01 me2 s-’ for
In [stining speed / min-‘]
a 0.0125 M NaCN concentration. The change in the
cyanidation rate can be explained by the change in the Fig. 4. Effect of stirring speed on the gold cyanidation rate.
mechanism as cyanide is involved directly both in the Napierian logarithm of the reaction rate against Napierian
adsorption step and in the gold complexation to lead logarithm of the stirring speed. Experimental conditions: 0.02
finally to dissolved Au(CN)F. M NaCN, pH 11.5, ~0, = 0.21 atm, 25°C.
The effect of temperature has been studied at 0.02
M NaCN, pH 11.5 and 400 min-‘. From the obtained established by Habashi. Our different result may be
data the activation energy was calculated by plotting attributed to the different stirring mechanism
the logarithm of the dissolution rate versus the inverse employed, which can produce different electrolyte
of temperature (Fig. 3). The value thus calculated was rates. It was observed that when the stirring speed was
8.8 kJ mol-’ thus suggesting that the process is diffu- 420 min-‘, convection is so turbulent that some
sion-controlled. bubbles appear that cause the dissolution rate to
The influence of the stirring speed on the kinetics of decrease.
gold cyanidation at atmospheric pressure has been
measured at 0.02 M NaCN, pH 11.5 and 25°C. A 3.2. E&t of cyanide concentration and pH on the
direct proportionality between dissolution rate and mixed potentials
stirring speed was observed. When plotting the logar-
ithm of the dissolution rate versus the logarithm of the The mechanism of gold cyanidation depends on the
stirring speed (Fig. 4) a slope of 0.57 was found. potential at which the process takes place. As a conse-
These results indicate that under these conditions the quence, it depends mainly on the complex behaviour
process is diffusion-controlled, in agreement with the of the anodic dissolution of gold [9]. Therefore, it is
activation energy data reported above. This diffusion necessary to know the potentials at which during gold
control is also maintained over 150 min- ‘, limit value leaching the different systems evolve. The potential, in
this case, is given by the mixed potential of cyanida-
tion E,,, and it is expected to depend on cyanide con-
centration and pH.
In general, the mixed potentials of cyanidation have
been measured under the same experimental conditions
as those used in obtaining the cyanidation rates.
The effect of cyanide concentration on the mixed po-
tential for the gold dissolution process was studied
using pH 11.5 solutions, a stirring speed of 400 min-’
and 25°C. The corresponding results are plotted in
Fig. 5.
At low cyanide concentrations, E,,, is inversely pro-
portional to the cyanide concentration, while for cya-
nide concentrations in the range 0.01-0.0125 M, E,,,
3.0 3.1 3.2 3.3 3.4 3.5
changes rapidly to more negative values. For cyanide
WOO/l I K-’ concentrations higher than 0.0125 M the mixed poten-
Fig. 3. Effect of temperature on the gold cyanidation rate. tial also diminishes, but more slowly.
Arrhenius plot. Experimental conditions: 0.02 M NaCN, pH Fig. 5 also shows the influence of cyanide concen-
11.5, ~0, = 0.21 atm, 400 min-‘. tration on the cyanidation rate and the corresponding
 L. &,-man et al. 1 Electrocltimica Ada 44 (1998) 2625-2632 2629

140 I I 475
cyanidation rate
‘;., 120 -
/.-*-"'m
.-. - ..--Q -500
Z 9
5 loo -
E .’
t 80 - :* .*
s!
@ 60- : *
’ :
s mixed potential
;:
$j 40- 0--o. : .’
. . .. .
mixed potential P 20- ,’*. . 425
a ‘.0.4&_0 ‘.m
01 ’ la
01 1 -700
10.0 10.5 11.0 Ii.5 12.0 12.5 13.0 13.5 14.0
0 10 20 30 40 50 60

NaCN eoncentfation I mM PH

Fig. 7. Effect of pH on the dissolution rate and the mixed po-

Fig. 5. Effect of CN- on the dissolution rate and the mixed
tential of conventional gold cyanidation. Experimental con-
potential of conventional gold cyanidation. Experimental con-
ditions: 0.02 M NaCN, pal = 0.21 atm, 400 min-‘, 25°C.
ditions: pH 11.5,po, = 0.21 atm, 400 min-‘, 25°C.

mixed potential. It is clear that there is a decay in the

cyanidation rate between 0.01 and 0.015 M NaCN. min-’ and 25°C. From Fig. 7 it follows that when pH
This dramatic decay suggests a change in the nature of increases, En, becomes slightly more cathodic until pH
the process. In addition, a correlation of the cyanida- 12.5 is approached. Further, En, shifts to more positive
tion rate with E, is also apparent (Fig. 6). Therefore, values, thus clearly indicating a change in the nature
it is possible to establish an equation that relates the of the process in both pH ranges, above and under pH
cyanidation rate with E,,,: 12.5.
rd = - 113 - 0.38E,,,
As shown in Fig. 7, the cyanidation rates clearly cor-
(6)
relate with the corresponding E,,,: the cyanidation rate
where Yd (dissolution rate) iS giVerI in urn01 m -2 S- ’ presents a dramatic decrease where E, starts to
and E,,, in mV versus Ag/AgCl/KCI (3 M). Eq. (6) increase to more positive potentials. Thus, the I$,,
suggests that it is possible, in practice, to determine the values strongly depend on pH and cyanide concen-
cyanidation rate by measuring a simple and direct vari- tration and denote the best conditions for a rapid cya-
able such as the mixed potential. Note, however that nidation by dividing cyanidation in two different
Eq. (6) was obtained under particular stirring con- categories with very different rate constants. As E,,, is
ditions and therefore, a calibration experiment should correlated with the active-passive state of the metal,
be performed under the particular conditions of the the two different conditions denoted by the sudden
practical application. change in E,,, have to be ascertained from the response
Fig. 7 shows the effect of pH on E,,, during gold of the metal as a function of potential, the active-pas-
cyanidation in 0.02 M NaCN, a stirring speed of 400 sive properties of gold under the relevant conditions
have been examined by the corresponding gold voltam-
mograms, both in the gold dissolution region and in
the oxygen reduction region.
120 .
3.3. Voltctmmetric experinzents
100 -
80- The anodic sweep of gold voltammogram in oxygen-
free cyanide solutions were obtained for different cya-
80. nide concentrations and pH. NaCN concentrations of
40. 0.01 and 0.02 M were used because they correspond to
two different regions in the cyanidation rate and E,
20 . curves (see Fig. 5). The voltammograms obtained at a
I speed rate of 400 min- ‘. 25”C, 1 mV s-’ and different
OL
pH are exemplified in Figs. 8 and 9.
-700 800 -500 400 -300
In the anodic dissolution of gold, three zones can be
E, ImV observed: the active region (current increase ca. -0.6
Fig. 6. Relation between cyanidation rate and mixed potential V), a region with smooth changes in current (after the
of gold conventional cyanidation. Experimental conditions: first peak) and the passive region (after the current
pH 11.5, po? = 0.21 atm, 400 min-‘, 25°C. decay ca. 0.7 V).
2630 L. Guman et al. 1 Electrochimica Actct 44 (1998) 2625-2632

nation which, on the other hand, we do not suspect

because of the purity of the reagents employed.
As shown in Fig. 8 three peak potentials are found
at -0.45, +0.3 and +0.63 V versus Ag/AgCl for 0.01
M NaCN and pH 10. The second peak potential is
normally higher than the first, thus meaning that the
gold dissolution rate is significantly higher in the po-
tential range corresponding to the second anodic peak.
The first and third peaks are highly dependent on pH,
but the second is only slightly dependent on it. All of
them move in the negative direction when pH
increases. The first peak appears to be related to the
-0.5 I formation of adsorbed species such as AuCN or
-0.8 -0.6 -0.4 a.2 0 0.2 0.4 0.6 0.8 1
AuCN- [lo, 12,13,25]. In the potential region corre-
EIV sponding to the first and second peaks, a net quantity
of cyanide-containing species covers the metal surface.
Fig. 8. Current-potential curves for anodic dissolution of
gold in deaerated alkaline cyanide solution at different pH. Poskus and Agafonovas [25] have shown by the radio-
Experimental conditions: 0.01 M NaCN. 400 min-‘, 25’C, active labelling (14C) method that in the potential
sweep rate I mV s-‘. regions of the first and second peaks, the amount of
cyanide-containing species on the surface increases
smoothly when the potential moves in the positive
The height of the first peak, that is the peak at ca. direction, without sharp increases or decreases. In ad-
-0.5 V, depends on the cyanide concentration, pH and dition, the amount of cyanide-containing species on
stirring speed. The curves shown in Figs. 8 and 9 were the surface increases with the cyanide concentration in
performed at a stirring rate of 400 min-’ using cya- the bulk solution. The presence of a smoothly increas-
nide concentrations as low as 0.01 and 0.02 M. In a ing quantity of such species in the potential region of
review by Nicol [24], the effect of heavy metal micro- the first and second anodic peaks together with the
impurities was shown to be a dramatic increase in the existence of significant anodic currents, can be
height of the first peak. Note that the current density explained as the net result of its continuous formation
in the potential range from -0.6 to -0.4 V for the on the metal surface and its further dissolution and
curve at pH 12.8 in Fig. 9 is less than 1 mA cm-l, transport to the electrolyte. The third peak corre-
that is comparable to that reported by Nicol [24] for sponds to Auz03 formation [lo, 1 l] and overlaps with
0.1 M KOH + 0.1 M KCN. Our results are then con- the second peak when pH increases.
sistent with those of Nicol’s review and they are not The anodic voltammograms for 0.02 M NaCN are
considered to be the result of heavy metal contami- quite similar to those obtained for 0.01 M NaCN
(compare Figs. 8 and 9). However, the second anodic
peak in Fig. 8 is deconvoluted in two peaks, 0.15 and
0.38 V at pH IO in Fig. 9. Also at pH 10, a first peak
is found at -0.45 V and the most anodic peak at
+0.65 V. As in the case of 0.01 M, the potential of
the first and that of the most anodic peak are highly
dependent on pH. They are shifted to the cathodic
direction when pH increases and thus, the most anodic
peak also overlaps with the previous anodic peak.
A number of voltammograms corresponding to the
oxygen reduction are depicted in Fig. 10. Oxygen dis-
solved in the electrolyte came from air saturation
(po2 = 0.21 atm). Two waves can be observed, which
are related with the oxygen reduction via 2 and 4
electrons [9]. The difference between the first and the
-0.8 -0.8 8.4 -0.2 0 0.2 0.4 0.6 0.8
second waves increases with pH. This means that the
EIV reduction of oxygen to peroxide is favoured by a pH
Fig. 9. Current-potential curves for anodic dissolution of increase, probably due to the formation of some kind
gold in deaerated alkaline cyanide solution at different pH. of specimen on the gold surface that causes the re-
Experimental conditions: 0.02 M NaCN, 400 min-‘, 25’C, duction of oxygen to peroxide faster, but inhibits a
sweep rate I mV s-‘. further peroxide reduction.
 L. Gurmun ei al. / Elwtrochimicu Acta 44 (1998) 2625-2632 263 I

1.2 - 1.0
Au + 2 CN--t Au( + e-
:
- pH 10,l
---- PH 11.5
____--
b,, 12;s
........ ...... pH ( 3

-7

“._

-0.2 0 0.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2

-1.2 -1 -0.8 -0.6 -0.4

E IV E IV

Fig. IO. Current&potential curves for cathodic reduction of Fig. 12. Current-potential curves for anodic dissolution of
oxygen on gold in alkaline media at different pH. gold and cathodic reduction of oxygen in alkaline solutions.
Experimental conditions: po: = 0.21 atm. 400 min -I, 25°C Experimental conditions: 400 mm’, 25’C, sweep rate I mV
sweep rate I mV s-‘. These curves have been corrected for s-‘. Anodic curve: 0.02 M NaCN, deaerated. Cathodic
the background currents measured in the absence of air dis- curves: (a) pal = 0.21 atm, pH 11.5, (b) po, = 0.21 atm. pH
solved. 13, (c)pa? = 0.21 atm, pH 11.5, 0.5 mM TI (I).

According to the theory of mixed potential, cyanida- of TI(1) (curve c), while the number of electrons
tion takes place at the potential at which cathodic and exchanged in the oxygen reduction in conventional
anodic currents are equal. This fact is represented by gold cyanidation (curve CI) corresponds to a value
the intersection of anodic and cathodic curves shown higher than 2 electrons per oxygen molecule, but lower
in Fig. I I. Under these conditions (pH I 1.5, 400 min- than 4 electrons. As the cyanidation rate in the pre-
I. 25 C). E is ca. -600 mV, gold cyanidation takes sence of Tl(I) in this pH range is significantly higher
place in td”e active zone of the first peak of anodic dis- than in its absence [22] and the effect of T](I) ions on
solution of gold and the cyanidation rate is limited by the adsorption of CN-containing species cannot
the oxygen transportation to the gold surface. The cya- explain the catalytic effect of TI(I) ions on dicyanoau-
nidation rate could then be increased by a faster oxy- rate reduction [26], the number of electrons exchanged
gen supply. seems to be very important in the cyanidation process
Fig. 12 shows the effect of the addition of small itself. However, the effect of TI(I) on the rate can not
amounts of T](I) salts on the cathodic reduction of be connected only with the changes of the number of
oxygen. Four electrons are transferred in the presence electrons in the cathode process, because a significant
effect of Tl(1) on the extent of gold passivation has
9 , 1
been demonstrated 1241.
At 0.02 M NaCN, and pH between IO.5 and 12, the
0 -
gold cyanidation would then correspond to an
7 -
exchange of more than 2 electrons per oxygen mol-
TE 6 - ecule. The explanation of the fact that the number of
v 5- exchanged electrons is found between 2 and 4, would
2
.4- lie in the fact that oxygen reduction takes place by the
two consecutive reactions. Eqs. (4) and (5) indicated
F3-
-
before, the second being slower than the first as per-
2 -
oxide reduction is more selective with respect to the
1 different crystalline orientations of gold [ 161. This leads
i,E#n ( \.
0 to the accumulation of peroxide on the gold surface
0.8 -0.6 -0.4 a.2 0 0.2 0.4 0.0 0.8 and a part of it can be removed from the gold surface
E IV towards the solution by diffusion and stirring, dimin-
ishing the number of exchanged electrons per oxygen
Fig. I I. Current-potential curves for anodic dissolution of
gold and cathodic reduction of oxygen in alkaline solutions. molecule.
Experimental conditions: pH 11.5, 400 min-‘, 25 C, sweep According to the previous discussion, the gold cyani-
rate I mV 5-l. Anodic curve: 0.02 M NaCN. deaerated. dation in 0.02 M NaCN at pH between 10.5 and I2
Cathodic curve: pal = 0.21 atm. appears then to be controlled by oxygen diffusion, the
2632 L. Gunman et al. 1 Electrochimica Acta 44 (1998) 2625-2632

activation energy of the process being 8.8 kJ mol-‘, A linear correlation between gold cyanidation rate
with an exchange of more than 2 electrons per oxygen and mixed potential has been obtained, which permits
molecule. At ca. pH 12.5 the cyanidation rate suddenly the introduction of a rapid test to control gold cyani-
diminishes (Fig. 7). This fact cannot be explained only dation for practical purposes.
by a change in the number of electrons exchanged, but
it is necessary to consider another process accounting
for the slowing down of gold dissolution rate. It is
shown to depend on the OH- concentration (Fig. 7) References
and thus OH- adsorption can account for the slowing
down of gold dissolution. Poskus and Agafonovas [II F. Habashi. Montana Bur. Mines Geol. Bull., 59 (1967).
have found that OH- ions influence the adsorption of I21J.B. Hiskey, V.M. Sanchez, J. Appl. Electrochem. 20
cyanide on gold only for OH- concentrations higher ( 1990) 479.
than 0.1 M [25]. We therefore suggest that, apart from 131 L. Elmer, J. Prak. Chem. 37 (1846) 441.
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from pH greater than ca. 12. For pHs greater than this 171 P. Fischer, J. Heitbaum, J. Electroanal. Chem. 112
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adsorbed species. 1101 K.J. Cathro, D.F.A. Koch, J. Electrochem. Sot. 11 I
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1111 D.M. Mac Arthur, J. Electrochem. Sot. 119 (1972) 672.
4. Conclusions 1121 D.W. Kirk, F.R. Foulkes. J. Electrochem. Sot. 127
(1980) 1993.

Gold cyanidation is an electrochemical corrosion 1131 C.P. Thurgood, D.W. Kirk, F.R. Foulkes. W.F.
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feature which can be analyzed in depth by means of W.F. Graydon, J.
1141 D.W. Kirk, F.R. Foulkes,
electrochemical techniques. One of the most significant Electrochem. Sot. 125 (1978) 1436.
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indicates the nature of the process involved. Thus, Electrochem. Sot. 127 (1980) 1962.
when the different variables cause the mixed potential 1161 R.R. Adzic, N.M. Markovic, J. Electroanal. Chem. 138
vary between -0.5 and 0 V versus Ag/AgCl/KCl (3 (1982) 443.
M), the process is controlled by the chemical dissol- 1171 R.R. Adzic, N.M. Markovic, V.B. Vesovic. J.
ution reaction of the adsorbed species, as it corre- Electroanal. Chem. 165 (1984) 105.

sponds to the regions of slow dissolution rates. On the 1181N.M. Markovic, R.R. Adzic, V.B. Vesovic, J.
Electroanal. Chem. 165 (1984) 121.
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1191 S. Strbac. N.A. Anastasijevic. R. R Adzic. J. Electroanal.
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the gold anodic dissolution, gold cyanidation is con-
1201 S. Strbac. R.R. Adzic. J. Electroanal. Chem. 337 (1992)
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The dramatic decrease in cyanidation rates observed
1231 G.P. Power, J.M. Ritchie, Electrochim. Acta 26 (1981)
when increasing pH or decreasing cyanide concen-
1073.
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~41 M.J. Nicol, Gold Bull. 137 (1980) 105.
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