Hydrometallurgy 93 (2008) 23–29

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Electrodeposition of a Silver-Gold Alloy (DORÉ) from Thiourea Solutions in the

Presence of Other Metallic Ion Impurities
M. Elena Poisot-Díaz a, Ignacio González b, Gretchen T. Lapidus a,⁎
a
Universidad Autónoma Metropolitana Iztapalapa. Depto. Ingeniería de Procesos e Hidraúlica, Apdo.Postal 55-534, 09340 México, D.F., Mexico
b
Universidad Autónoma Metropolitana Iztapalapa. Depto. Química, Apdo.Postal 55-534, 09340 México, D.F., Mexico

a r t i c l e i n f o a b s t r a c t

Article history: With the increasing complexity of gold and silver containing minerals, the thiourea system has been
Received 3 October 2007 considered a possible alternative for precious metal leaching. In the present work, direct electrodeposition is
Received in revised form 20 February 2008 proposed as a viable method to recover gold and silver values from thiourea leaching solutions. With this
Accepted 20 February 2008
purpose in mind, thermodynamic and electrochemical analyses of this complex system were undertaken. The
Available online 29 February 2008
thermodynamic reduction potentials of copper and lead ions were shown to be very close to those of gold and
silver, favoring the formation of codeposits of these metals.
Keywords:
In order to complement the thermodynamic analysis, kinetic studies were performed using potentiostatic
Doré electrodeposition
electrodeposition with anodic stripping. A vitreous carbon electrode was shown to be sufficiently inert over
Anodic stripping voltammetry
Thermodynamic analysis the entire potential range studied to allow its use for the investigation of the metal deposits formed. Regarding
Thiourea leaching solutions these deposits, it was demonstrated that the presence of a small amount of gold (10 ppm), in solutions
containing silver, favorably affects the energy and kinetics of the gold-silver alloy (doré) deposition process. In
this same manner, it was also shown that the presence of lead(II) (10 ppm), zinc(II) (10 ppm) or iron(II)
(100 ppm) favors the alloy deposition by shifting the initial reduction potential to less negative values while
maintaining the same deposition rate. On the other hand, the addition of 200 ppm of copper (II) provokes a
slight decrease in the reduction rate, although the potential at which the deposition begins is practically the
same as that observed for solutions of only gold and silver.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Industrial hydrometallurgical processes for silver and gold extrac-
tion have been dominated by cyanidation, which consists of the
dissolution of the metals in cyanide solutions (leaching), followed by
the recovery of the values by cementation with zinc powder or
adsorption on activated carbon. However, due to the continuous
exploitation of ore bodies, the quality of the precious metal content
has diminished, frequently encountering refractory mineral phases.
Because of this, in addition to environmental restrictions regarding
toxic waste handling, the search for viable and competitive alter-
natives to cyanidation, which decrease the quantity and toxicity of the
waste produced, has recently been intensified. Among these alter-
natives, thiourea is considered attractive because it is less toxic than
cyanide (Inchem, 2003), shows rapid gold and silver extraction y is
adequate for treatment of sulfide minerals (Marsden and House,
1992). The main topic of research in this system since the 1940's has
been its solution chemistry, especially the importance of the oxidizing
agent, since it affects the solution stability (Plaskin and Kozhukhova,
1941; Preisler and Berger, 1946; Gupta, 1963; Groenewald, 1977;
⁎ Corresponding author. Fax: +52 55 58044666.
E-mail address: igm@xanum.uam.mx (G.T. Lapidus).
Hiskey, 1981; Hiskey, 1984; Hiskey and Atluri, 1988; Marsden and
House, 1992; Bek and Rogozhnikov, 1997; López, 2002; Girón et al.,
2003). For this reason, the research has principally focused on the
leaching stage, relegating the study of value recovery.
In this sense, different alternatives have been studied, including
adsorption on activated carbon, solvent extraction, ion exchange
resins, aluminum cementation and electrowinning (Hiskey, 1981).
Electrowinning, however, has been used only for recovery from high
concentration solutions, once the solutions have been purified by one
of the other four methods. For example, in the process of adsorption of
the gold thiourea complexes on activated carbon, an additional stage
(stripping) is necessary before the solution is subjected to electro-
winning for the recovery of metallic gold. For the utilization of ex-
tractants to recover gold and coexisting ions, Songling et al. (1993),
suggests up to four extraction stages to obtain 98.1% of the gold; the
concentrated solution is subjected to stripping and metallic gold is
obtained by a pyrometallurgical process. Silver cementation using
aluminum has the disadvantage that the resultant solution has a high
concentration of aluminum (III) ions (Teutli et al., 1990), causing an
accumulation of this ion in the leaching solution which must be
purged before the solution can be recycled back into the process.
In order to implement a separation process which precludes
additional concentration and purification stages, electrolysis has been
proposed as a direct recovery method. With this in mind, gold

0304-386X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.02.015
24 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29
electrodeposition from synthetic solutions has been investigated
using stainless steel and gold electrodes (Zhang et al., 1996; Juárez and
Dutra, 2000). These authors analyzed the effect of the gold-thiourea
complex and thiourea concentrations, as well as that of temperature,
stirring velocity and solution pH. However, neither of these articles
reported the influence on the electrowinning process of other ions
that are present in real leaching solutions, such as copper, iron, lead or
zinc.
In this work, due to the complexity and instability of thiourea-
containing solutions, a thermodynamic analysis was initially under-
taken to examine the possibility of obtaining a selective gold-silver
(doré) electrodeposit from solutions containing copper, iron, lead or
zinc in concentrations similar to those found in pregnant leaching
solutions. Employing the Medusa© program (Puigdomenech, 2004),
potential-pH diagrams were constructed, in order to determine the
predominant species in acidic thiourea solutions with different metal
ions and to predict the thermodynamic conditions that favor a
selective doré deposit. These diagrams were elaborated varying the
species concentration.
Because the thermodynamic analysis does not consider kinetic
aspects, such as the substrate material or the nature of the solution,
cyclic voltammetric and potentiostatic pulse studies with anodic
stripping analysis were undertaken, firstly, screening different sub-
strate materials (titanium, stainless steel 304, and vitreous carbon) in
order to select the most adequate to study the electrodeposition from
acidic thiourea solutions. Secondly, the potential range was deter-
mined for selective electrowinning of doré, in the presence of copper,
iron, lead and zinc ions.
2. Experimental methodology
Systematic thermodynamic (Predominance diagrams) as well as
kinetic (voltammetric) studies were performed on solutions that are
similar in composition to those obtained in real leaching systems. The
first step (thermodynamic study) was accomplished through the use
of the Chemical Equilibrium Software MEDUSA©, whose algorithms
are based on the Free Energy minimization reported by Eriksson
(1979). The data for complex formation were taken from the Critically
Selected Stability Constants (database 46, version 6.0) published by
the National Institute of Standards and Technology (2001) and others
from the literature. These were complemented with the program
database (HYDRA). The MEDUSA© program generates bidimensional
potential-pH diagrams (E-pH), specifying as parameters the reagent
concentration, solution pH and potential ranges, in which the desired
species exists. In this manner, it is possible to construct a graphical
representation of the thermodynamic behavior of complex thiourea
solutions which provides a solid basis for the analysis of the behavior
observed in kinetic studies.
The second stage of this work corresponds to the cyclic
voltammetry and chronoamperometric studies, which consisted of
two parts; in the first, three commercially viable electrode materials
were tested: titanium, stainless steel 304 and vitreous carbon. Of
these, the one with the lowest electroactivity in the acidic thiourea
medium was deemed the most adequate for the study of silver
electrowinning. The objective of the second part of this work was to
determine the effect of foreign ions on the formation process of the
selective deposit of doré.
A typical three electrode system was employed for electrochemical
measurements, with a mercury sulfate reference electrode (Hg/
Hg2SO4 with a K2SO4 saturated solution, E' = 0.64 V vs. Standard
Hydrogen Electrode (SHE)), a graphite bar as the auxiliary electrode
and planar disks as the working electrode with a geometric area of
0.08 cm2 for titanium and 0.20 cm2 for both the stainless steel 304 and
the vitreous carbon. All of the potentials reported in this work are
referred to the SHE scale. All solutions were prepared with deionized
water (10 MΩ− 1 cm− 1) and analytical grade reagents. The metallic ions
were added as nitrates. The solutions without metal ions used for
the experiments were the following: Solution 1, 0.01 M H2SO4 and
Solution 2, 0.2 M thiourea in 0.01 M H2SO4. For the solutions con-
taining one or more metallic ions, solutions were prepared with the
same base conditions as Solution 2 and the following ion concentra-
tions: 0.93 mol m− 3 silver(I) (100 ppm), 0.05 mol m− 3 gold(I) (10 ppm),
3.15 mol m− 3 copper(II) (200 ppm), 1.79 mol m− 3, iron(II) (100 ppm),
0.05 mol m− 3 lead(II) (10 ppm) and 0.15 mol m− 3 de zinc(II) (10 ppm).
An AUTOLAB PGSTAT 30 potentiostat, connected to a PC with GPES
(General Purpose Electrochemical System) software, was used to
register and process the potential-current data.
2.1. Selection of the appropriate electrode
In order to perform a study on metal electrodeposition, the first
step should include voltammetric examination of different electrode
materials, in the absence and presence of metal ions, to insure that the
electrode does not produce an electrochemical response in the same
potential range as the gold and silver electrodeposition processes.
Cyclic voltammograms were performed on each electrode material
with the following three solutions: Solution 1: 0.01 M sulfuric acid;
Solution 2: 0.2 M thiourea in 0.01 M sulfuric acid and Solution 3: 0.2 M
thiourea in 0.01 M sulfuric acid with 0.93 mol m− 3 (100 ppm) silver(I)).
The three solutions were used to study the electroactivity of three
distinct materials: titanium, stainless steel 304 and vitreous carbon.
All of the voltammograms were obtained without agitation by ini-
tiating the sweep from the open circuit potential (OCP) in the
negative-going direction until the desired potential was reached (E-λ),
after which the direction of the potential sweep was reversed in order
to analyze the oxidation of the products formed in the negative-going
sweep as well as possible oxidation of the substrate material itself. At
this point, due to the nature of the solutions, only the peaks obtained
in the positive-going sweep were analyzed, since they provide in-
formation on the electroactivity of the electrode.
Titanium and stainless steel electrodes were found to be un-
suitable for the study of the oxidation of precious metal electro-
deposited from thiourea solutions because they are oxidized in the
relevant potential range (Fig. 1), obviously these materials could be
used as cathode materials where only reduction occurs.
The behavior of vitreous carbon electrode for each of the three
solutions is shown in Fig. 2. It may be observed in Fig. 2(i) and (ii) that
there are no evident redox responses for Solutions 1 and 2. However,
the voltammogram corresponding to the silver solution, Fig. 2 (iii),
presents a fine oxidation peak, characteristic of a metal oxidation,
which in this case would be for metallic silver. As a result, the vitreous
carbon electrode was found to be suitable for the studies of the metal
electrodeposits.
3. Results and discussion
3.1. Thermodynamic analysis
In this part, the characteristics of the solution components are
analyzed from a thermodynamic perspective, employing Pourbaix
diagrams and distributions diagrams, in order to determine pre-
dominant zones of the different species formed in the redox process.
The stability of thiourea was examined using the redox reactions
reported in the literature (Preisler and Berger, 1946; Gupta, 1963;
Krishnan and Reddy, 1970; Groenewald, 1975; Groenewald, 1977;
Hiskey, 1981; Hiskey, 1984; Kirchnerová and Purdy, 1980; Grigorova
and Wright, 1986; Hiskey and Atluri, 1988; Yan et al., 1996).
Fig. 3 shows the species distribution diagram for thiourea solutions
with 0.01 M sulfate ion, where the oxidation of the thiourea to
elemental sulfur and cyanamide is observed at 0.32 V in an acid
solution (pH = 2). The maximum concentration of formamidine di-
sulfide (Tu2+2 ), the first oxidation product of thiourea, is reached at a
 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29
Fig. 1. Typical cyclic voltammograms obtained on a: a) titanium electrode and
b) stainless steel electrode, initiating the sweep in the negative-going direction.
Solution concentrations: (i) 0.01 M sulfuric acid (Solution 1), (ii) 0.01 M sulfuric acid and
0.2 M thiourea (Solution 2), (iii) 0.01 M sulfuric acid, 0.2 M thiourea and 0.93 mol m− 3
(100 ppm) silver(I) (silver solution). All solution were adjusted to pH = 2 with the
addition of sulfuric acid. Sweep velocity = 20 mV/s.
potential of 0.4 V. However, this concentration is always less than that
of other species formed as secondary oxidation products (cyanimide,
CYAN and sulfur, S). Although it exists, it is never predominant in this
system. This small amount of Tu2+ 2 is sufficient to oxidize gold and
silver minerals, which allows thiourea to complex with metallic ions.
Under more oxidizing conditions, thiourea is oxidized completely to
its secondary products.
In Figs. 4–6, the potential-pH diagrams are shown for different
solutions of thiourea, with 0.01 M sulfate (pH = 2), containing the
following metallic ions: silver, gold and copper, respectively (see
Fig. 2. Typical cyclic voltammograms obtained on a vitreous carbon electrode, initiating the
sweep in the negative-going direction. Solution concentrations: (i) 0.01 M sulfuric acid
(Solution 1), (ii) 0.01 M sulfuric acid and 0.2 M thiourea (Solution 2), (iii) 0.01 M sulfuric
acid, 0.2 M thiourea and 0.93 mol m− 3 (100 ppm) silver(I) (silver solution). All solution were
adjusted to pH = 2 with the addition of sulfuric acid. Sweep velocity = 20 mV/s.
25
Fig. 3. Distribution diagram for a solution of 0.2 M (200 mol m− 3) thiourea (Tu) with
0.01 M (10 mol m− 3) sulfate. Thiourea actually is initially oxidized to its dimer,
formamidine disulfide (Tu2+ 2+
2 ) and finally to sulfur (S) and cyanamide (CYAN); the Tu2
species is never present at more than 20% and, therefore, does not appear in the
corresponding predominance diagram.
below). It is important to emphasize that when thiourea forms me-
tallic complexes, its oxidation potential shifts to more positive values.
When iron, lead or zinc is present in solution, no predominant zones
are observed for the cationic complexes of these metal ions with
thiourea. The E-pH diagrams, which are similar to those for these
ions in sulfuric acid, are not included here. The order of deposi-
tion potential for these metal-thiourea complexes or metallic ions
is arranged as follows: AuTu+2 b AgTu+3 b Pb2+ b CuTu+4 b Fe 2+ b Zn2+ (see
Table 1).
In Fig. 4, at potential above 0.6 V the soluble species Ag+ pre-
dominates. As the potential diminishes, the reduction pair Ag(I)/Ag(0)
is perceivable. This behavior is expected since the thiourea is com-
pletely degraded, according to Fig. 3. At lower potential, the silver
thiourea complexes may be observed, AgTu+ (i) and AgTu3 +. Silver
reduction occurs at a potential of −0.03 V.
A similar behavior is observed with Au(I), as shown in Fig. 5, where
at the potentials between 0.5 and 1.0 V, the formation of Au(0) is
identified. At the potentials less than 0.5 V, a small predominance
zone appears for the soluble gold-thiourea complex, AuTu+2, followed
by the reduction pair Au(I)/Au(0) at approximately 0.38 V.
Fig. 4. Potential versus pH diagram (PTD) for a solution of 0.2 M (200 mol m− 3) thiourea
with 0.01 M (10 mol m− 3) sulfate and 100 ppm (0.93 mol m− 3) silver(I).
26 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29
Fig. 5. Potential versus pH diagram for a solution of 0.2 M (200 mol m− 3) thiourea with
0.01 M (10 mol m− 3) sulfate and 10 ppm (0.051 mol m− 3) gold(I).
In the same manner, the potential-pH for the Cu(II), Cu(I) and Cu(0)
system is presented in Fig. 6. It may be observed at acidic pH values
less than 2 and very positive potentials, the existence of Cu2+.
However, as the potential is decreased below 0.5 V, the cupric ion is
reduced to Cu(I) which is stabilized by thiourea, forming the complex
CuTu+4. In this manner, the predominance zone for this species is
extended to very alkaline values of pH, because the thiourea stabilizes
the copper(I) in solution. At negative potentials of approximately
−0.38 V, the reduction pair Cu(I)/Cu(0) may be observed. At alkaline
values of pH and positive potentials, the typical potential-pH for
copper may be recognized (Pourbaix, 1996), in which the cuprous ion
is never stable in solution, but forms cuprous oxide and eventually
cupric oxide at higher potentials.
Assuming that the pregnant solutions originating from a leaching
stage has the following composition: 0.2 M thiourea, 0.01 M sulfuric
acid, 100 ppm silver(I), 10 ppm gold(I), 200 ppm copper(I), 100 ppm
iron(II), 10 ppm lead(II) and 10 ppm zinc(II), a one dimensional cut of
the diagrams presented in Figs. 4–6, in addition to those from the
diagrams for iron(II), lead(II) and zinc(II) [not shown], was prepared at
pH 2 in order to evaluate the thermodynamic reduction potentials
(Table 1). The first metal which is reduced from its thiourea complex is
Fig. 6. Potential versus pH diagram for a solution of 0.2 M (200 mol m− 3) thiourea with
0.01 M (10 mol m− 3) sulfate and 200 ppm (3.10 mol m− 3) copper(I).
gold at 0.38 V, followed by silver at −0.03 V and copper at −0.39 V.
However, if free lead(II) is found in solution, this could affect the co-
deposition of gold and silver at −0.26 V. As for iron(II) and/or zinc(II),
presumably they will not compete with the co-deposition of gold and
silver because their reduction potentials are extremely negative,
−0.55 V and −0.89 V, respectively.
It is essential at this point to emphasize that the thermodynamic
studies do not consider the overpotentials required for the electro-
crystallization of the metals on the different substrates. For this
reason, a systematic cyclic voltammetry and chronoamperometric
study is necessary to corroborate the previous results and principally
to determine the effect of co-existing ions on the selective doré
electrodeposit and to identify the potential range in which these
deposits take place.
3.2. Influence of other metallic ions on the doré deposit
Potential pulse studies with anodic stripping analysis were then
undertaken to identify the potential intervals in which a selective
deposit of precious metals can be obtained in the presence of other
metal ions. In the determination of the potential to selectively deposit
doré (Ag-Au), it is important to separate and quantify only the charge
associated with the metal deposition. When the deposition potential
behavior is monitored in voltammetric studies, there are several
phenomena, such as diffusive, adsorptive, charge transfer and, in the
case of the metallic ions, electrocrystallization processes, which sim-
ultaneously affect the measured current, making it difficult to identify
the reduction potential. In contrast, the oxidation peaks present only
the energetic contributions related to the redissolution of the metallic
species. These energetic contributions will be different for each me-
tallic species, allowing the identification of potentials zones where the
selective deposit or a co-deposit of two or more metals is occurring
(Reyes, 2002).
The method of anodic stripping is a combination of a concentration
(pre-electrolysis or cathodic-deposition) step, in which the metal ion
concerned is reduced by controlled-potential electrolysis by deposi-
tion as metal onto a solid microelectrode, and a following step con-
sisting of an anodic dissolution, or stripping process, in which the
metal is oxidized. The concentration step is carried out for a constant
time under reproducible conditions and the stripping process is, in
most cases, performed in some voltammetric scanning procedure. The
resulting “stripping voltammogram” shows peaks, the heights or the
areas under these peaks are generally proportional to the amount of
the deposited metal. The sensitivity of this technique is remarkable:
high dilute solutions in the range of 10− 6 to 10− 9 mol L− 1 and less can
be analyzed with excellent precision and selectivity (Barendrecht,
1967).
In this case, a reduction potential was applied during 15 seconds;
immediately after, the reduced metal is oxidized with a potential scan
in the positive direction (velocity = 20 mV s− 1) was performed without
stirring, obtaining a current-potential curve from which the area of
the oxidation peak is determined. This value is plotted as a function of
Table 1
Reduction potential for each metal at pH = 2, extracted from the Potential versus pH
diagrams (Figs. 4–6 and diagrams [not shown] for iron(III), zinc(II) and lead(II))
Complex or metallic ion Reduction Potential / V vs. SHE
AuTu2 + 0.38
AgTu3 + −0.03
H+ −0.1
Pb2+ −0.26
CuTu4 + −0.39
Fe3+ −0.55
Zn2+ −0.89
 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29
the reduction potential applied. The anodic charge is associated with
the oxidation peak of the deposited mass obtained with the negative
potential application. When this procedure is carried out at different
deposit potentials, the anodic charge may be plotted with respect to
the deposit potential.
The relation between the potential and the anodic charge is a
straight line, whose slope is modified only when the nature of the
deposit is altered (Reyes, 2002). Therefore an increase in the slope
implies the addition of another component in the formed deposit or a
change in its stoichiometry.
Fig. 7 presents the response voltammetrics for a solution
containing 0.2 M thiourea in 0.01 M sulfuric acid with 100 ppm
silver(I), using a vitreous carbon electrode. The formation of an
oxidation peak is observed for values of Edep more negative than
− 0.36 V; the more negative the deposition potential limit, the
oxidation peak shifts to more positive potentials and the magnitude
of current is larger. It is important to note that the integrated charge
(area under the curve) takes into account the oxidation of all of the
deposited metal and therefore is a valid technique to quantify the
deposition which occurred when a negative potential is applied; in
contrast, methods such as peak height measurement, only show a
partial picture, and are dependent upon peak width. The variation of
the area under the curve of the oxidation peak with respect to the
negative deposition potential (Edep) is plotted for silver(I) in Fig. 8(a),
where two linear correlations may be observed. Considering the
composition of the solution, the sharpness of the peak and the linear
correlations, these correlations can be attributed to the redissolution
of silver deposited on the surface of the electrode during the
application of the deposition potential. Since at each value, the
potential was imposed for 15 seconds, the associated charge can
be considered proportional to the velocity of the reduction process or
processes involved. The first slope (m = − 1.1 C m− 2 V− 1) should
correspond to the oxidation kinetics of the silver reduced as
a function of the deposition potential. At values more negative than
- 0.61 V, the slope gradually decreases until practically zero value and
the reduction rate becomes constant; this is probably due to the onset
of mass transport limitation, which completely controls the process
at potentials more negative than − 0.79 V. The addition of 10 ppm gold
(I) to the silver solution, Fig. 8(b), causes the reduction of the metallic
species to shift 125 mV less negative and the slope to increase (− 1.6 C
m− 2 V− 1). It is highly improbable that this effect is caused solely by
gold deposition because its concentration is very small (10 ppm).
Therefore, the gold must be catalyzing silver reduction by promoting
Fig. 7. Typical responses to an oxidative potential scan (sweep velocity = 20 mV/s) for
different previous reduction potentials (Edep), indicated in the figure. Cyclic voltammo-
grams obtained on a vitreous carbon electrode. Solution concentration: 0.2 M thiourea
in 0.01 M sulfuric acid (pH = 2) and 100 ppm silver(I).
27
Fig. 8. Integrated charge (Qa) associated with the oxidations peak as a function of the
previous reduction potential (Edep), from stripping voltammograms obtained on a
vitreous carbon electrode at 20 mV/s for solutions of 0.2 M thiourea in 0.01 M sulfuric
acid which contain: (a) ■ ■ 100 ppm silver(I), (b) □ □ 100 ppm silver(I) and 10 ppm gold
(I), (c) Δ Δ 100 ppm silver(I), 10 ppm gold(I) and 10 ppm de zinc(II), (d) ○ ○ 100 ppm silver
(I), 10 ppm gold(I) and 100 ppm iron(II).
a co-deposition of the two species or the formation of a silver-gold
alloy on the surface of the electrode (Hultren et al., 1963; Reyes,
2002). When the potential deposition is more negative than
− 0.335 V, the slope diminishes (− 0.4 C m− 2 V− 1), indicating a
modification in the electrodeposition process; this is possibly related
to a partial depletion of the gold near the electrode and silver
deposition on the gold-silver alloy. At potentials more negative than
− 0.69 V, mass transport limitations become important.
On the other hand, when 10 ppm zinc(II) is added to the solu-
tion containing 100 ppm silver(I) and 10 ppm gold(I), Fig. 8(c), the
initiation of gold and silver reduction reaction shifts to a potential
100 mV less negative, in comparison to the reduction potential with-
out zinc(II), (Fig. 8(b)). In the presence of zinc(II), the charge versus
potential shows two linear dependence, the first with a slope of −1.8 C
m− 2 V− 1, slightly larger than that observed in the solution with only
gold and silver. From the thermodynamic studies previously shown,
zinc deposition commences at very negative potentials (−0.89 V, see
Table 1), which eliminates the possibility of zinc-silver-gold deposit;
however the zinc probably catalyzes the deposition of the silver-gold
alloy by lessening the energy required for reduction process, this effect
could be associated to the modification to the interface substrate-
Fig. 9. Integrated charge (Qa) associated with the oxidations peak as a function of the
previous reduction potential (Edep), from stripping voltammograms obtained on a
vitreous carbon electrode at 20 mV/s for solutions of 0.2 M thiourea in 0.01 M sulfuric
acid which contain: (a) ■ ■ 100 ppm silver(I), (b) □ □ 100 ppm silver(I) and 10 ppm gold
(I), (c) ▲ ▲ 100 ppm silver(I), 10 ppm gold(I) and 200 ppm copper(I), (d) ⁎ ⁎ ⁎ 100 ppm
silver(I), 10 ppm gold(I) and 10 ppm lead(II).
28 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29

Table 2 the other hand, the essential finding of this study is the existence of a
Comparison of the energetic conditions for the metallic or alloys deposition from potential window of approximately 300 mV in which doré may
aqueous solutions containing 0.2 M thiourea in 0.01 M sulfuric acid and the different
metallic ion concentration
selectively be obtained without a copper codeposit, although a minor
lead co-deposit is inevitable.
Metallic ion E(1)(therm)/V E(2)(exp)/V Alloy or E(2)exp/V vs Slope(3)
vs SHE vs SHE codeposit SHE alloy C m− 2 V− 1 4. Conclusions
observed or codeposit

Gold (I) 10 ppm 0.36 ⁎ Doré −0.210 −1.6 In the present work, direct electrodeposition is proposed as a
Silver (I) 100 ppm − 0.03 −0.360
method to recover gold and silver values from thiourea leaching
Zinc (II) 10 ppm − 0.89 ⁎ Doré −0.135 −1.8
Iron (III) 100 ppm − 0.55 ⁎ Doré −0.210 −1.3 solutions, in order to diminish the number of unit operations and
Copper (I) 200 ppm − 0.36 −0.56 Doré −0.210 −1.2 stages in the industrial flow diagram and maximize the recirculation
Cure-Doré −0.410 −1.3 of the reactants. With this purpose in mind, thermodynamic analysis
Lead (II) 10 ppm − 0.26 −0.460 Pb-Doré −0.160 −1.6 and kinetic studies of this complex system were undertaken. The
(1)
Thermodynamic potential evaluated from Potential-pH diagrams. results obtained show that the thiourea is stabilized by the formation
(2)
Experimental potential corresponding to the initiation of metal or alloy deposition of metallic complexes, shifting its oxidation towards more positive
evaluated from potentiostatic deposition/anodic stripping study.
(3) potentials; thiourea was found to form stable complexes only with
Change of metallic or alloy deposition amount as a function of potential deposition.
⁎ Electrodeposition potentials were not detected. gold, silver, and copper under leach conditions. The reduction
potentials of copper and lead metals were shown to be very close to
those of gold and silver, favoring the formation of codeposits of these
metals with the doré.
solution of the zinc solutions. The second slope presents the same For the cyclic voltammetry studies with anodic stripping analysis,
behavior as that displayed by the gold-silver solution. it was demonstrated that the presence of a small amount of gold, zinc,
In Fig. 8(d), the effect of adding 100 ppm of iron(II) to the solution iron and lead, in the solutions containing silver, favorably affects the
of 100 ppm silver(I) and 10 ppm gold(I) is shown. Two linear regions energy of the deposition process, producing a gold-silver alloy (doré).
with different slopes may be appreciated. In the potential range On the other hand, copper ions limit the potential range where the
between −0.210 and −0.285 V, the presence of iron causes the doré to selective doré deposit is formed.
deposit 25 mV less negative and the slope is slightly diminish (m =
−1.3 C m− 2 V− 1) with respect to the solution with only gold and silver. Acknowledgements
At more negative potentials, the silver deposition on the gold and
silver alloy takes place, since the slope decreases to the same value M. Elena Poisot-Díaz thanks the Consejo Nacional de Ciencia y
(m = −0.4 C m− 2 V− 1) observed in the silver-gold solutions (Fig. 8(b)). Tecnología (CONACYT) for her PhD scholarship and grant #54436.
In Fig. 9(c), the anodic charges corresponding to the voltammo-
grams for a solution containing 100 ppm silver(I), 10 ppm gold(I) and Appendix A
200 ppm copper(I), are shown as a function of the deposition
potential, Edep. Here again, two regions can be appreciated (Fig. 9 Formation constants used in the MEDUSA program for the silver(I)-
(c)), similar to that observed in the Fig. 8(a,b,c,d); the first is Tu, gold(I)-Tu, copper(I)-Tu, iron(II)-Tu, lead(II)-Tu y zinc(II)-Tu
comparable to that displayed by the gold-silver alloy with a slope of systems (where, Tu corresponds to the thiourea molecule) (Puigdo-
−1.2 C m− 2 V− 1; while at potentials between −0.285 V and −0.410 V, menech, 2004; National Institute of Standards and Technology, 2001).
the slope of deposition is similar (m = −0.5 C m− 2 V− 1) to that obtained
in presence of zinc(II) and iron(II), however the charge involved is
lower to that involved for “doré” deposition in the solution free of EQUILIBRIUM REACTION LOG β
copper(II) (Fig. 9(b)). This diminution can be related to the presence of Ag+ + Tu f AgTu+ 7.59
specific adsorbed copper complexes (Vázquez-Arenas et al., 2007) on Ag+ + 2Tu f AgTu+2 10.35
the electrode surface modifying the silver deposition on the gold- Ag+ + 3Tu f AgTu+3 12.87
Ag+ + 4Tu f AgTu+4 13.57
silver deposit, and initiation the copper co-deposition for potentials
2Ag+ + 3Tu f Ag2Tu+3 20.7
more negative than −0.410 V, which is related to the increase of the Au+ + 2Tu f AuTu2 21.96
slope (−1.3 C m− 2 V− 1). Cu+ + 2Tu f CuTu+2 12.3
Finally, in Fig. 9(d), the accumulated charges associated to the Cu+ + 3Tu f CuTu+3 14.3
oxidation peaks as a function of the negative potential limit, Edep is Cu+ + 4Tu f CuTu+4 15.5
Zn2+ + Tu f ZnTu2+ 0.5
shown for a solution containing 100 ppm silver(I), 10 ppm gold(I) and
Zn2+ + 2Tu f ZnTu2 2+ 5.76
10 ppm de lead(II). It may be clearly appreciated that the energetic is Zn2+ + 3Tu f ZnTu3 2+ 6.10
slightly favored by the presence of lead ions, shifting by the 75 mV the Pb2+ + Tu f PbTu 2+ 0.4
onset of deposition toward less negative potentials and maintaining Pb2+ + 2Tu f PbTu2 2+ 1.1
Pb2+ + 3Tu f PbTu3 2+
the slope in the first potential region to −1.6 C m− 2 V− 1. At potentials 1.5
Pb2+ + 4Tu f PbTu4 2+ 1.7
more negative than −0.310 V, the behavior is practically the same as
that observed without lead, Fig. 9 (b) (Oo and Tran, 1991). ELECTROCHEMICAL REACTION STANDARD POTENTIAL (SHE scale)
A summary of the thermodynamic predictions for metal deposi- 2+
2Tu f Tu2 +2e- E0 = 0.420 V
tion and a comparison with the results of the potentiostatic 2+
Tu2 →S0 + CN∙NH2 + Tu + 2H++2e- E0 = 0.5 V
deposition/anodic stripping experiments are presented in Table 2, S0 + 4H2O→HSO-4 + 7H+ + 6e- E0 = − 0.339 V
where Eexp corresponds to initial metal or alloy deposition potential. It Ag+ +e- f Ag0 E0 = 0.800 V
Au+ +e- f Au0 E0 = 1.692 V
is possible to observe that the electrocrystallization overpotentials
Cu+ +e- f Cu0 E0 = 0.520 V
(Eexp- Etherm) to deposit silver, copper and lead are approximately Zn2+ + 2e- f Zn0 E0 = − 0.762 V
equal to 200 mV. On the contrary, with this method, no deposit or Fe3+ + 3e- f Fe0 E0 = − 0.037 V
redissolution of zinc or iron was detected. It is important to emphasize Fe2+ +2e- f Fe0 E0 = − 0.447 V
at this point that the electrocrystallization overpotential is dependent Fe3+ +e- f Fe2+ E0 = 0.771 V
Pb2+ +2e- f Fe0 E0 = − 0.126 V
upon the solution composition as well as the substrate material. On
 M.E. Poisot-Díaz et al. / Hydrometallurgy 93 (2008) 23–29 29

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