Electrochimica Acta 45 (2000) 2729 – 2741

www.elsevier.nl/locate/electacta

An electrochemical study of galena concentrate in

^ perchlorate medium at pH 2.0: the influence of chloride ions
Irma Cisneros-González, Mercedes T. Oropeza-Guzmán, Ignacio González *
Departamento de Quı́mica, Uni6ersidad Autónoma Metropolitana Iztapalapa, Apartado Postal 55 -534, 09340 Mexico, D.F., Mexico

Received 13 October 1999; received in revised form 10 January 2000

Abstract

An electrochemical study of galena flotation concentrates in solutions of perchlorate and chloride ions at pH 2 has
been carried out, through the use of carbon paste electrodes and cyclic voltammetry. The analysis of the voltammetric
results indicates that in perchlorate solutions the galena is oxidized forming several products dependent on the applied
potential. When the potential is below to 0.54 V/saturated calomel electrode (SCE), Pb(II) and elementary sulfur are
formed. Galena oxidation to higher oxidation state of sulfur (e.g. thiosulfate and sulfate) requires a higher
overpotential (E\0.8 V vs. SCE), in the presence of perchloric acid, while in chloride medium a considerable lower
overpotential is needed. From this reaction, the Pb(II) reacts with the chloride ions in order to form a lead – chloride
complex that could precipitate depending on the concentration of chloride in solution and also could remain adsorbed
on the galena particle surface. In the chloride media, the galena is reduced into metallic lead and hydrogen sulfide.
© 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Galena; Carbon paste electrode; Leaching; Lead chloride; Electrochemistry; Mineral sulfide oxidation

1. Introduction cal reaction, taking place at the surface. Kobayashi et

During galena leaching, oxidation products affect the
kinetics of the reaction. In a recent review of published
kinetic studies through 1990, Kobayashi et al. [1] dis-
cuss the relationship between the leaching process and
parameters such as particle size, temperature and ferric
chloride and sodium chloride concentrations. This arti-
cle also reviews the difference between leaching in dilute
ferric chloride ( B0.1 M FeCl3) and in more concen-
trated solutions. The kinetic models for galena leaching
describe diffusion of the PbCl2 species through the
initially formed coating of elemental sulfur or a chemi-
* Corresponding author. Tel.: +52-5-8044671; fax: +52-5-
8044666.
E-mail address: igm@xanum.uam.mx (I. González)
al., however, believe that in order to define a dissolu-
tion mechanism, the influence of ferric chloride and
sodium chloride concentrations on the system must be
described.
The overall leaching process involves electron trans-
fer reactions that are evaluated by means of electro-
chemical studies. Although many electrochemical
studies of galena in acidic medium have been published
[2 – 7], a number of aspects concerning the processes
involved remain poorly defined. The majority of these
studies report the process on solid galena electrodes
carried out in perchloric acid solutions since this
medium avoids formation of complex metal cations and
can dissociate itself completely to form very stable
perchlorate ions [7]. However, even when perchloric
acid is used as an oxidizing agent, galena chemical

0013-4686/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 0 ) 0 0 3 9 2 - 3
2730 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
dissolution has not yet been reported in these kinds of
studies [3–6]. This is probably due to a slow kinetics of
this process.
Gardner [3] and Paul and Nicol [5,6] performed the
most complete voltammetric studies in perchloric acid.
Galena dissolution occurs as elemental sulfur forms
beginning at 0.5 V. Paul and Nicol [5,6] propose that
dissolution proceed either by the reaction of active sites
on the galena surface, due to impurities present, or by
dislocations of the crystal network. Gardner [3] found
that sulfur produced during galena oxidation is in
crystalline form with sufficient porosity so that subse-
quently galena layers continue to oxidize. These studies
establish dissolution conditions for galena in HClO4,
yet the influence of chloride ions on the dissolution
mechanism remains unclear.
Systematic comparison of mineral oxidation pro-
cesses using solid electrodes is troublesome since polish-
ing makes surface reproducibility difficult. Carbon
paste electrodes (CPE) are a suitable alternative to solid
electrodes for mineral studies as the particle size used is
similar to that employed in chemical leaching processes
and the surface available for electrochemical studies is
quite consistent [8,9]. An electrochemical study of
galena concentrate was performed using carbon paste
electrodes in perchlorate and chloride solution to deter-
mine the effect of chloride ion incorporation on galena
dissolution.
2. Experimental
2.1. Materials and reagents
The galena flotation concentrate used to make the
electrodes was a product of a common flotation process
and supplied by Servicios Industriales Peñoles (Monter-
rey, México). A typical analysis (wt.%) is 45.75% Pb,
14.8% S, 4.75% Zn and 5.25% Fe and the particle size
was −200 mesh. Previous studies showed the presence
of impurities of sphalerite and pyrite in this galena
concentrate [9]. These impurities do not present a gal-
vanic effect in the galena electrochemical behavior [9].
All chemicals used were A.R. grade. Specific resistance
of the water used to make up solutions was always 18.2
MV cm − 1. Electrolytes of perchlorate and chloride
were at pH 2 and deaerated with nitrogen before
experimentation.
2.2. Apparatus and procedure
A Pyrex electrochemical cell designed to work at
room temperature and inert atmosphere was used. The
cell employed the conventional three-electrode system.
The voltammetric response was obtained using an
EG&G PAR 273 potentiostat coupled to a personal
computer. The electrode system consisted of a working
electrode made of carbon paste-mineral (CPE-PbS)
80:20 wt.% with silicon oil as a binder [9].
Synthetic graphite powder (Alfa Aesar, Johnson
Matthey), −200 mesh, high purity, 99.999%, was used
to prepare the working electrode by mixing a total of
0.8 g graphite powder with 0.2 g of galena flotation
concentrate in an agate mortar. A total of 0.8 ml silicon
oil (Sigma) was added to the resulting powder and
carefully mixed to obtain a homogeneous paste. The
paste was placed in a 7-cm long, plastic tube (0.2 cm
inner diameter); equipped with a plunger to eliminate
reacted paste (approximately 0.5 cm). The plunger
manually ejected reacted paste onto an emery paper to
renew the surface for each experiment. A platinum
wire, silver soldered to a copper wire, provided the
electrical contact to the graphite paste. A carbon rod
(Alfa Aeser, Johnson Matthey, 99.9995%) was used as a
counter electrode and a saturated calomel electrode
(SCE) as a reference. The potentials given in this work
refer to the SCE scale. All measurements were per-
formed at room temperature.
Calculation of current densities passing through the
CPE-mineral electrodes requires estimation of the sur-
face area of the electrode. However, several characteris-
tics of the CPE-electroactive species make estimation of
the geometric area unreliable. A more realistic estima-
tion of surface area is the evaluation of the cross-sec-
tional area of mineral particles, which depends on the
weights of mineral and carbon added. The mineral
carbon paste prepared in this work was completely
homogeneous so that geometric areas, calculated from
the mineral carbon paste in contact with the electrolyte,
are directly proportional to the real active area. The
current densities were calculated based on this geomet-
ric area (3.14×10 − 2 cm2).
3. Results and discussion
3.1. Galena in perchlorate medium
Two typical voltammograms obtained on carbon
paste electrodes with galena concentrate in perchlorate
solution pH 2.0 are shown in Fig. 1. Sweep potential
was initiated in both the positive and negative direc-
tion. Both sweeps originated from the open circuit
potential (OCP) of 0.1 V, with a range of 1.0 and −1.0
V at 100 mVs − 1. When the sweep potential was ini-
tiated in the negative direction (Fig. 1), a reduction
process with a small associated current appeared (D in
the figure). This process was energetically favored when
the sweep potential was inverted (the reduction current
was greater in the inverse than in the direct sweep). A
small oxidation peak (E) associated with the above
reduction process was later observed. As the sweep
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
potential became more positive, it observed an increase
in the oxidation current (A), which did not reach a
maximum over the range studied. The small reduction
process (D) obtained in the direct sweep is associated
with galena reduction.
In the voltammogram initiated in the positive direc-
tion (Fig. 1), a less prominent oxidation process (A%)
appeared. As the sweep potential was inverted, reduc-
tion oxidation processes, (B%, C%, D% and E%) which were
not observed in the negative sweep, appeared in the
−0.4 to −1.0 V range. These processes correspond to
the reduction–oxidation of chemical species produced
during the galena oxidation process.
Calculating the area below the curve for the pro-
cesses associated with galena oxidation gives a charge
of 977 mC for process A and 168 mC for process A%. The
large difference between the current and charge magni-
tudes for the oxidation process in the voltammogram
initiated in the negative direction is not due to the
oxidation of products formed during reduction (D)
since the value of the cathodic process charge is only
−49 mC. This significant increase in charge and current
magnitude is attributable to surface activation of the
electrode induced during the cathodic sweep, making
galena oxidation more evident.
In order to identify the nature of the species pro-
duced (soluble or insoluble) in galena oxidation and
reduction processes, voltammetric measurements were
performed in stirred and unstirred perchlorate solu-
tions. Figs. 2 and 3 show comparisons of the resulting
voltammograms in which the sweep potential was ini-
Fig. 1. Cyclic voltammograms obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2. Scan
rate 100 mVs − 1. Potential scan was initiated in: the negative direction (black line), positive direction (gray line).
2731
tiated in the negative and positive direction, respec-
tively. When the sweep potential was carried out in the
negative direction (Fig. 2), the current associated with
the galena reduction process (D) was 0.38 mA cm − 2
for the unstirred and 0.51 mA cm − 2, for the stirred
solution at −1.0 V, suggesting that the galena reduc-
tion process was affected by diffusion of chemical spe-
cies to the interface. This last reduction process was
associated with oxidation (E in the figure), which in-
creased when the solution was stirred (Fig. 2). The
charge associated with the galena oxidation process (A)
increased slightly from 977 mC for the unstirred solu-
tion to 1079 mC when the solution was stirred. Thus,
once the galena surface is activated, its oxidation pro-
cess is not controlled by diffusion.
When the sweep was initiated in the positive direc-
tion (Fig. 3), however, stirring favored the oxidation
process A% since the values of the charge differed con-
siderably (298 mC for the stirred and 168 mC for the
unstirred solutions). It was also observed that the re-
duction and oxidation process (B%, C%, D% and E%, in
Fig. 3) of the unstirred voltammogram, were absent
when the solution was stirred. These results suggest
that, when the oxidation potential reaches 1.0 V, the
species produced during galena oxidation are soluble
and are eliminated from the interface with stirring and
are undetectable in the inverse sweep. Since the prod-
ucts are eliminated from the interface, galena oxidation
increased when the solution was stirred. This fact could
indicate that accumulation of the products formed in
oxidation process in the interface could provoke
2732 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741

Fig. 2. Cyclic voltammograms obtained for a carbon paste electrodes (CPE) − galena electrode immersed in 1 M NaClO4, pH 2.
Scan rate 100 mV s − 1, the potential scan was initiated in negative direction. Effect of solution stirring: stirring (black line), no
stirring (gray line).

diminution of the galena dissolution. The small ca-
thodic currents associated in the voltammogram of
galena initiated in negative direction indicate the stabil-
ity of the galena in the perchlorate medium used in this
study.
3.1.1. Reduction process of galena
To identify the galena reduction processes, a voltam-
metric study was carried out in the negative direction
changing the cathodic switching potential (E − l ), as
shown in Fig. 4. When E − l \ − 0.8 V, only one reduc-

Fig. 3. Cyclic voltammograms obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2. Scan
rate 100 mV s − 1, the potential scan was initiated in positive direction. Effect of solution stirring: stirring (black line) no stirring
(gray line).
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
tion current appeared not associated with an oxidation
process When E − l 5 −0.8 V, however, an autocata-
lytic process occurred (the reduction current is less for
the direct than for the inverse scan). This process (D in
Fig. 4) could be identified with a high negative overpo-
tential that initiated galena reduction and this is associ-
ated with a small oxidation peak (E).
The reduction process can be attributed to galena
reduction according to Eq. (1).
PbS+2e − +2H+ “Pb0 +H2S(aq)
E*= −0.501 V vs. SCE
The equilibrium potential, E*, associated with reac-
tion (1) was calculated from corresponding thermody-
namic constants of solubility [11] and E 0 [12],
considering the specific chemical conditions: pH 2. This
E* value is similar to the value calculated starting from
the data reported by Sivenas and Foulkes ( −0.55 V vs.
SCE) [4].
In this work, the equilibrium potentials have been
evaluated taking into account the corresponding nor-
mal potential (E 0) for each reaction, and considered
10 − 6 M for the soluble species formed on the interface
which was not present in the bulk solution. This con-
vention is often chosen when considering the corrosion
of metals or the leaching of mineral ores [10].
A negative overpotential, higher than − 0.20 V, rela-
tive to the equilibrium potential, was required to carry
out the reduction associated with Eq. (1) on the CPE-
mineral (Fig. 4). Once this reduction begins, the process
requires less energy, explaining the autocatalytic pro-
Fig. 4. Cyclic voltammograms obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2. Scan
rate 100 mV s − 1. The potential scan was initiated in negative direction. The negative switching potential (E − l ) was varied: − 0.4
V (black line), − 0.6 V (thin line),–1.0 V (gray line).
2733
cess observed and the crossover of the anodic and
cathodic branches. The galena reduction is controlled
by the chemical species diffusion to the interface ac-
cording to Eq. (1). Thus the oxidation (peak E in Fig.
4) corresponds to the oxidation of Pb (0) to Pb (II).
The difference in current densities, with and without
stirring, is caused by removal of hydrogen sulfide
formed at the interface in reaction (1), so that the only
reaction occurring is the oxidation of metallic lead to
Pb2 + in stirring solution (see peak E Fig. 2). In the
unstirred solutions, hydrogen sulfide remains at the
(1) interface where it reacts with Pb2 + to form lead sulfide,
which rapidly passives the electrode surface, resulting in
a diminished oxidation process, (peak E in Fig. 2).
3.1.2. Oxidation process of galena
To evaluate the oxidation processes of galena, a
voltammetric study was performed in the positive direc-
tion, changing the anodic switching potential (E + l )
(Figs. 5 and 6). For E + l 5 0.2 V, (Fig. 5) no oxidation
process was observed. At 0.4 V beginning the oxidation
process A%, and a reduction process, B%, was observed.
In order to compare the variation of the reduction
process, in Fig. 5, a voltammogram initiated in negative
direction was also included. This comparison shows an
overlap between the reduction process of galena (D%)
and process associated with B% (Fig. 5).
When the switching potential reached 0.6 V (Fig. 6),
an oxidation process (A%), and reduction peak, (B%)
were observed. If E + l was increased to 0.8 V (Fig. 6),
galena oxidation was altered, since the reduction peak,
2734 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741

Fig. 5. Cyclic voltammograms obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2. Scan
rate 100 mV s − 1. The potential scan was initiated in positive direction, the switching potential was varied: 0.2 V (gray line), 0.4 V
(thin line). In order to compare the reduction process, cyclic voltammogram obtained when the potential scan is initiated in negative
direction (black line) is also shown.

B%, associated with reduction of the corresponding in more negative potentials (C%). In the same time the
products moved toward less negative potentials, and current density of peak E% increased considerably. The
the peak became wider. Other process seems to overlap presence of different stages in the reduction of products

Fig. 6. Cyclic voltammograms obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2. Scan
rate 100 mV s − 1. The potential scan was initiated in positive direction, the switching potential was varied: 0.4 V (black line), 0.6
V (gray line), 0.8 V (thin line).
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741 2735

formed during the oxidation process indicates that oxi-
dation occurs in at least two stages. Initially, when
E + l B0.8 V, PbS could be oxidized to form a sulfur
layer, and as the potential increases, the sulfur achieved
higher oxidation states (see below).
3.1.2.1. Galena oxidation in lower positi6e potentials. In
order to evaluate where the change in galena oxidation
state occurs, the effect of different anodic switching
potentials (at increments of 20 mV) in a small potential
range, 0.52 V to 0.58 mV, was studied. The fixed E − l
selected ( −0.65 V) avoids galena reduction. Fig. 7
shows an oxidation process above 0.52 V corresponding
to galena oxidation, A% and in the reverse scan a
reduction process appears. At lower E + l, only an
autocatalytic process is observed while at higher E + l, a
cathodic peak, B% (Epc = −0.65 V) is well defined. This
process corresponds to the reduction of species formed
during the oxidation process. At switching potential
E + l of 0.54 V the oxidation charge, 21.61 mC, is very
close to the charge of the reduction process, 22.42 mC.
Thus, the reaction occurring for E]0.54 V could be
associated with reaction below:
PbS −2e − “Pb2 + +S0 E* = −0.043 V vs. SCE
(2)
The corresponding reduction reaction (B%) is:
Pb2 + +2e − “Pb0 E*= − 0.547 V vs. SCE
E* values were calculated from corresponding ther-
modynamic constants of solubility [11] and E 0 [12]. The
values of E* for Eq. (2), is similar to that calculated
from the data reported by Nicol [5] ( − 0.08 V). The E*
determined by Eq. (3) is close to that data calculated
from Sivenas [4] ( − 0.546). It is important to note that
the experimental potentials where processes 2 and 3
were observed differ from respective E*.
The mineral sulfide oxidation requires a very high
overpotential, as has been previously reported [3 – 5]. In
the galena oxidation here an E* of − 0.043 was found
with its oxidation beginning at 0.54 V; meanwhile the
overpotential required for the reduction of Pb2 + is not
high.
The sulfur formed on the galena surface in the posi-
tive scan direction is not reduced in the reverse scan. At
the same time, as the lead reduction process is more
important (process B%), the associated oxidation process
(E%) is also more important and corresponds to the
inverse of the reaction (3). This process (E%) is charac-
terized by a narrow oxidation peak, and is modified for
the presence of the H2S formed at the interface during
the reduction process of galena (compare thick gray
curve in Fig. 6 with dotted curve in Fig. 7). The current
of oxidation associated with E% in Fig. 6 is small in
comparison with the corresponding in Fig. 7, where
galena reduction was avoided.
(3)
3.1.2.2. Galena oxidation in higher positi6e potentials.
The change in the galena oxidation process, observed

Fig. 7. Cyclic voltammetry curves obtained for a carbon paste electrodes (CPE)-galena electrode immersed in 1 M NaClO4, pH 2.
Scan rate 100 mV s − 1. The potential scan was initiated in positive direction, the switching potential was varied in a small range:
0.52 V (black line), 0.54 V (gray line), 0.56 (thin line), 0.58 V (dotted line). The fixed E − l selected ( −0.65 V) avoids the galena
reduction.
2736 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
above 0.8 V, is likely due to the oxidation of galena to
another species with a greater oxidation state of sulfur.
There are different chemical species with higher oxida-
tion state of sulfur (e.g. thiosulfate, tetrathionate,
sulfite, and sulfate). The appropriate identification of
these species is not easy due to the complex chemistry
of S-H2O system.
In many electrochemical studies of sulfide minerals, it
has been reported that thiosulfate and sulfate are com-
monly formed chemical species during the anodic disso-
lution of the sulfide minerals [13,14]. Gardner and
Woods [3] and Nicol [5] reported the formation of
thiosulfate during galena oxidation at higher potentials
in perchloric media. For this reason, the formation of
the S2O23 − and SO24 − species was suggested for the
electrochemical oxidation of galena for potentials
higher than 0.8 V.
The reaction involved in the galena dissolution for
El ] 0.8 could be described as follows
2PbS +3H2O“2Pb2 + +S2O23 − +6H+ +8e −
E*=0.077 V vs. SCE (4)
The value of E* for Eq. (4) is similar as that evalu-
ated for data from Gardner, 0.036 V versus SCE, [3].
The reaction (4) also requires a very high positive
overpotential to be performed. It seems that the thio-
sulphate begins to form at 0.8 V. This higher overpo-
tential may provoke the S2O23 − formed at the interface
to be oxidized to sulfate species, because the E* of Eq.
(5), is less positive than the overpotential required for
reaction (4):
S2O23 − +5H2Ol2SO24 − +10H+ +8e −
E*=0.229 V vs. SCE (5)
In this way, for E\0.8 V, the abrupt change in the
oxidation behavior of galena is probably due to the
presence of thiosulfate and sulfate adhered at the inter-
face. Furthermore, the presence of Pb2 + in the oxida-
tion process could induced the precipitation of
PbS2O3(s) or PbSO4(s). The formation of these precipi-
tates could provoke a surface passivation of the galena.
This is not observed in the voltammograms in Figs. 5
and 6. The voltammogram obtained in stirring solution
(Fig. 3) confirms this contention.
Therefore, the reaction that abruptly modifies the
reduction process (B%), shown in the inverse scan, in
Fig. 6 could correspond to a greater level of Pb2 + in
the interface and in other hand, the reduction of thio-
sulfate may be associated with peak C% formed at the
interface during the inverse sweep. This hypothesis
should be corroborated by other techniques.
3.2. Galena in chloride medium
The anodic behavior of galena in chloride solutions is
complicated by the number of possible competitive
reactions and by the formation of solid products that
can adhere to the galena particle interface. To elucidate
the sequence of electrochemical reactions which occur
in CPE-galena chloride solutions at pH 2, a cyclic
voltammetry study was performed.
Fig. 8 compares voltammograms of CPE-galena ob-
tained in perchlorate and chloride solutions for a po-
tential range between 1.0 and − 1.0 V, and 100 mV
s − 1. The potential scan for the chloride solution was
initiated at an OCP of 0.05 V in the positive direction.
The comparison demonstrates that the presence of
chloride favors galena oxidation since a lower potential
is required for oxidation in the chloride than in the
perchlorate solution. Nonetheless, the oxidation process
(peaks H%%Cl and H%Cl) indicates a complex process,
which appears to be associated with passivation of the
galena surface. This passivation is broken at the same
potential where galena oxidation occurs in perchlorate
solutions. When the potential was inverted, a very
narrow cathodic peak, B%Cl appeared, indicating the
reduction of a species adhering to the electrode. When
the scan potential is inverted again to the positive
direction, three anodic peaks (E%Cl, F%Cl, and G%Cl) at the
peak potentials of − 0.503, −0.479 and − 0.240 V,
respectively, were observed. The disappearance of peak
B%Cl in voltammetric measurements initiated in the nega-
tive direction (data not shown) showed that this peak
corresponds to the reduction of species formed during
the oxidation process.
To determine the processes occurring in each of the
anodic and cathodic peaks appearing in the voltam-
mogram in chloride medium and to detect any correla-
tion between these, a study was performed at different
anodic switching potentials.
3.2.1. Influence of anodic switching potential (E + l)
The voltammetric curves obtained by varying the
anodic switching potential in the range between 0.116
and 0.668 V are shown in Fig. 9. The sweep potential
was initiated at 0.05 V, continued in the positive direc-
tion to the selected positive switching potential (E + l ),
then taken to −1.0 V, and again inverted.
In Fig. 9a (E + l = 0.116), a reduction process, D%Cl
associated with galena reduction was observed. The
peaks of oxidation E%Cl and F%Cl, corresponding to the
oxidation of species (Pb0), produced in the galena re-
duction process are observed with the same current
density (0.649 and 0.652 mA cm − 2). The presence of
chloride provides better differentiation of the galena
reduction process compared to reduction in the pres-
ence of perchlorate ions (Fig. 1).
When E + l was 0.23 and 0.36 V, Fig. 9b,c, respec-
tively, the galena oxidation process, H%%Cl, began. The
products of this oxidation provoke a disturbance of the
cathodic peak D%Cl (Fig. 9b) and one peak (B%Cl in Fig.
9c) appears. The reduction process widens as E + l
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
Fig. 8. Cyclic voltammograms obtained at pH 2, scan rate 100 mV s − 1, for carbon paste electrodes (CPE)-galena electrodes. The
potential scan was initiated in positive direction. The electrode was in presence of different solutions: in 1 M NaClO4 (black line),
1 M NaCl (thin line).
becomes more positive (Fig. 9c), apparently due to the
presence of various reduction stages, such as galena
reduction, D%Cl, and reduction of products obtained
during the oxidation process, C%Cl and B%Cl. The current
densities of oxidation peaks E%Cl and F%Cl are also
altered.
For E + l =0.36 V (Fig. 9c), the peak current density
for peak E%Cl increases (1.02 mA cm − 2) while decreas-
ing for peak F%Cl (0.48 mA cm − 2). The current density
ratio of E%Cl/F%Cl is 0.5, contrasting with the equivalent
current density values obtained for these peaks when
the switching potential was 0.116 V. It was also ob-
served that a peak G%Cl, begins to form ( −0.266 V) with
a current density of 0.104 mA cm − 2.
For E + l ]0.43 V (Fig. 9d), the galena oxidation
process suffers a considerable modification forming an
insoluble product, which adheres to the non-oxidized
galena. This product modifies the reduction stages and
a narrow reduction peak, B%Cl appears. The current
density of peak E%Cl continues to increase (1.31 mA
cm − 2), and that of peak F%Cl remains relatively un-
changed ( −0.554 mA cm − 2). This great difference in
current density values and the proximity of their peak
potentials cause these two peaks to appear as stacked
one on top of the other. In addition the current density
of peak G%Cl becomes greater (0.162 mA cm − 2), Fig. 9d.
As E + l increases (Fig. 9e), oxidation peak H%Cl in-
creases until it reaches a maximum and then it de-
creases rapidly. This is characteristic of a partial
passivation process (the current does not drop to zero).
This could indicate that the insoluble product formed is
2737
porous and this product should be PbCl2 (see below),
which is then reduced in peak B%Cl. The current densities
of the reduction peak B%Cl increases as E + l increases
(Fig. 8) indicating greater galena oxidation. This oxida-
tion – reduction alters the oxidation processes, E%Cl, F%Cl
and G%Cl, so that formation of these oxidation peaks,
depends on the switching potential, E + l.
3.2.2. Influence of the cathodic switching potential
To establish the relationship among the peaks E%Cl,
F%Cl and G%Cl, voltammetric measurements were carried
out at a fixed anodic switching potential of 1.0 V to
produce various oxidation products. The cathodic
switching potential (E − l ) was varied in the range from
− 0.544 to −0.74 (Fig. 10).
From Fig. 10 it was determined that peaks E%Cl and
F%Cl are associated with the products formed in the
reduction process, occurring at potentials less negative
than − 0.6 V. These oxidation processes are related to
interface oxidation of Pb0, derived from the reduction
of oxidation product of galena (e.g. PbCl2). The peak
G%Cl is related to reduction peak B%Cl. Voltammograms
initiated in the negative direction demonstrate that
different processes are carried out in the reduction, and
oxidation peak F%Cl is observed at less cathodic poten-
tials ( −0.46 V), (data not shown).
Voltammetric measurements performed in stirred so-
lutions (Fig. 11), indicate that the species produced in
peak H%Cl is partially soluble and is also related to the
oxidation products of peak E%Cl, since it disappeared in
2738 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741

the stirred solutions. The peak C%Cl could be associated
with the higher oxidation sulfur species (e.g. thiosul-
fate) as suggested by the results obtained in perchlorate
medium, discussed earlier. It was also observed that
stirring does not favor the oxidation process, as it did
in the perchlorate solutions, since oxidation peak H%Cl
appears at more positive potentials than in the un-
stirred solutions (0.445 V in stirred and 0.427 V in
unstirred solutions). Peak B%Cl is observed at the same
potential as in the voltammograms of the unstirred
solutions ( −0.642 V in stirred and −0.641 V in un-
stirred solutions). However, the current obtained is
small ( −0.52 mA cm − 2), as compared to that ob-
served in unstirred solutions ( −1.62 mA cm − 2). This
indicates that during the H%Cl oxidation process; both
porous and insoluble species is produced, as well as a
soluble species. It is likely that the soluble species is
formed first, from which a precipitate results. Varying
chloride ions in the system further indicated the occur-
rence of this mechanism. The oxidation peak H%Cl was
similar for voltammograms carried out in unstirred 2
M chloride, and in stirred 1 M chloride solutions. The
charge associated with the peak were also similar in
value (1.45 mA cm − 2 in unstirred 2 M chloride solu-
tions and 1.29 mA cm − 2 in stirred 1 M chloride), as
shown in Fig. 12.
Peak F%Cl was observed at the same potential in
unstirred and stirred solutions ( −0.487 V in unstirred
and −0.488 V in stirred); however, stirring caused the
peak current to increase from 0.47 (unstirred) to 0.79
mA cm − 2 (stirred). The disappearance of peak E%Cl in
the stirred solution voltammogram allowed unob-
structed observation of peak F%Cl.
From the above observations, the reactions associ-
ated with peaks H%Cl, E%Cl, F%Cl, B%Cl and D%Cl were
determined. The equilibrium potential (E*) for each

Fig. 9. Cyclic voltammograms for carbon paste electrodes (CPE)-galena in 1 M NaCl at pH 2. Scan rate 100 mV s − 1. The potential
scan was initiated in positive direction and the switching potential E + l was varied: (a) 0.116 V, (b) 0.23 V, (c) 0.36 V, (d) 0.43 V,
(e) 0.668 V.
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741 2739

Fig. 10. Cyclic voltammograms for carbon paste electrodes (CPE)-galena in 1 M NaCl, at pH 2 scan rate 100 mV s − 1. The scan
was initiated in positive direction, positive switching potential was fixed (+1.0 V), scan potential was inverted and the switching
potential E − l was varied, (a) − 0.544 V, (b) − 0.58 V, (c) −0.63 V, (d) −0.74 V.

reaction was evaluated from thermodynamic constants 3.2.2.1. Peak D%Cl. Peak D%Cl corresponds to the galena
(solubility constants and normal potential taken from reduction reaction when the sweep is initiated in the
[11,12]). The concentrations of species formed at the negative direction.
interface were considered as 1 ×10 − 6 M, as was de-
scribed above. The E* values were compared with the
PbS+2e − + 2H+ l Pb0 + H2S(aq)
data obtained in other studies and the differences were
minimal. E*= −0.501 V vs. SCE

Fig. 11. Cyclic voltammograms for carbon paste electrodes (CPE)-galena in 1 M NaCl, at pH 2 scan rate 100 mV s − 1. The potential
scan was initiated in positive direction. Effect of the stirring solution: stirring (black line), without stirring (gray line).
2740 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741

3.2.2.2. Peak E%Cl. This oxidation peak represents oxida- drop of overpotential required for initiated galena oxi-
tion of metallic lead obtained in the galena reduction dation in chloride media, in comparison with the over-
reaction and is only observed in unstirred chloride potential required in presence of perchlorate.
solutions where hydrogen sulfide is not eliminated from
the interface. 3.2.2.5. Peak H%Cl.
H2S(aq) +Pb lPbS +2H +2e
0 + − PbS+ 2Cl − “ PbCl2(s) + S0 + 2e −

E*= −0.501 V vs. SCE E*=0.2783 V vs. SCE (8)

The presence of chloride ions considerably diminishes
the overpotential required for galena reduction in com-
parison with that required in perchlorate medium.
3.2.2.3. Peak F%Cl.
2Cl − +Pb0 −2e − lPbCl2(s)
E*= −0.51 V vs. SCE
As shown in Fig. 11, this reaction exists both in
stirred and unstirred solutions. In stirred solutions it is
the predominant reaction since, as hydrogen sulfide is
eliminated from the interface, all the lead present reacts
with the chloride ions.
3.2.2.4. Peak H%%Cl.
PbS+2Cl − “PbCl2(aq) +S0 +2e −
E*=0.0131 V vs. SCE
The experimental potential where the galena oxida-
tion begins (E\ 0.23) was not so far from equilibrium
potential of reaction (7), indicating a very important
3H2O+ 4Cl − + 2PbSl
2PbCl2(s) + S2O23 − + 6H+ + 8e −
E*=0.289 V vs. SCE (9)
Identification of the experimental potential zones
where these reactions occur is complicated by the high
intrinsic solubility of PbCl2 (as neutral species, 1 mM),
(6) as well as the nature of the PbCl2 precipitate formed at
the interface.
For E] 0.36 V, the PbCl2(aq) increases at the inter-
face, provoking the formation of PbCl2 precipitate on
the galena surface. The nature of the chemical reactions
involved requires a small overpotential in order to
induce reaction 8. At the potentials region E* where a
PbCl2 is formed as oxidation product of galena, the
simultaneous transformation of sulfur to thiosulfate
occurs according with the similar equilibrium potential
(7) for both transformation, Eqs. (8) and (9).
From this discussion it can be assumed that peak H%Cl
could be identified by the simultaneous reactions 8 and
9.

Fig. 12. Cyclic voltammograms for carbon paste electrodes (CPE)-galena in aqueous pH 2 scan rate 100 mV s − 1, in presence of
different electrolytes: 1 M chloride with stirring (thin line), 2 M NaCl without stirring (gray line), 1 M NaCl without stirring (black
line).
 I. Cisneros-González et al. / Electrochimica Acta 45 (2000) 2729–2741
Finally the nature of the electrochemical behavior of
peak B% allows to identify with reaction 6.
3.2.2.6. Peak B%Cl.
PbCl2(s) +2e − lPb0 +2Cl −
E*= −0.51 V vs. SCE
The reduction of adhered (PbCl2(s)) precipitate does
not require an important potential compare E*, with
experimental potential beginning of reduction PbCl2(s).
4. Conclusions
According to Paul et al. [5], galena dissolution in
perchlorate medium occurs at 0.35 V and the dissolu-
tion products are Pb(II) and elemental sulfur. Using
carbon paste electrodes, Albergh et al. [8] reported
galena dissolution at 0.65 V and they proposed that not
only elemental sulfur, but also a compound of sulfur
having a greater oxidation state (e.g. thiosulfate and
sulfate), are also products of the reaction depending on
the potential imposed. In this work, it was found that
galena flotation concentrate is oxidized in perchlorate
medium to form different products. When the potential
is less than 0.8 V, Pb(II) and elemental sulfur are
formed. At El ]0.8 V, sulfur is probably oxidized to
either thiosulfate or sulfates. It was also observed that
when a negative sweep potential was previously applied
to the galena electrode the oxidation process became
more evident.
In chloride medium galena is reduced to form metal-
lic lead and hydrogen sulfide. It is important to men-
tion that the chloride medium allowed a clearer
differentiation of the galena reduction process than
reduction in the presence of perchlorate media.
Galena oxidation is energetically favored in chloride
medium since a lower potential is required for its
oxidation in the presence of chloride than in the pres-
ence of perchlorate. Lead reacts with the chloride ions
forming a chloride complex and due to its high intrinsic
solubility value (1 mM), the complex formed first must
be a PbCl2(aq). The PbCl2(aq) is soluble, but when a
2741
critical chloride concentration is achieved, it precipi-
tates as PbCl2(s) and adheres to the electrode surface.
Acknowledgements
Financial assistance was received from CONACyT
(Project 400200-5-4250PA). The authors would like to
thank Ing. Pablo González from Servicios Industriales
Peñoles. I. Cisneros-González also acknowledges
CONACyT for scholarship support.
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