Hydrometallurgy 81 (2006) 142 – 151

www.elsevier.com/locate/hydromet

Leaching of gold and palladium with aqueous ozone in dilute

chloride media
J. Viñals a,⁎, E. Juan a , M. Ruiz a , E. Ferrando a , M. Cruells a , A. Roca a , J. Casado b
a
University of Barcelona, Department of Materials Science and Metallurgical Engineering, Martí i Franqués 1, E-08028 Barcelona, Spain
b
MATGAS Research Centre, Universitat Autónoma de Barcelona, E-08193 Bellaterra, Barcelona, Spain
Received 22 September 2005; received in revised form 6 December 2005; accepted 6 December 2005
Available online 24 January 2006

Abstract

The recycling of gold and palladium from metallic scraps can be carried out by ozone-leaching at ambient temperature and low
(∼0.1 M) H+ and Cl− concentrations. Rh and Pt remain un-reacted, whereas metals such as Cu, Ni, Ag, can be previously
eliminated through O2/H+ and O2/O3/H+ leaching pretreatments. Gold and palladium are dissolved in O3/Cl−/H+ with formation of
AuCl−4 and PdCl2− −
4 . Leaching studies showed a passive region, basically located at b 0.01 and b 0.05 M Cl for Au and Pd,
+ −
respectively. In the non-passive region, rates were only slightly dependent on either H and Cl . Secondary formation of chlorine or
hypochlorous acid was negligible at ≤ 0.1 M Cl−. Kinetics appeared to be controlled by mass transfer of O3(aq) to the solid–liquid
interface, showing first order dependency with respect to [O3]aq. Rates increased with temperature up to about 40 °C, but decreased
at higher temperatures due to the fall in the O3 solubility. The ozone mass transfer coefficients showed an activation energy b 20 kJ/
mol. Gold leaching rate gradually diminished for pH N 2, as consequence of the influence of the [H+] on transfer control. The
electric power consumption associated with O3 generation was in the range 4–8 kWh/kg metal leached.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Gold; Palladium; Ozone; Chloride; Recycling; Leaching; Kinetics

1. Introduction
Aqueous ozone may be a reasonable alternative for
the leaching of concentrates and wastes containing
precious metals, mainly due to the formation of oxygen
as reaction by-product. Another advantage is that the
ozone can be used at very low aqueous concentration
(∼10− 4 M) by injecting O2/O3 mixtures at low PO3
(b10 kPa). Major disadvantage is the electric power
consumption, 12–18 kWh/kg O3 (Gottschalk et al.,
⁎ Corresponding author.
E-mail addresses: jvinalsvinals@.ub.edu (J. Viñals),
casado.j@carburos.com (J. Casado).
0304-386X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2005.12.004
2000). This fact would limit the ozone leaching to high
price metals and/or when high costs for the detoxifi-
cation of effluents are to be expected in the
conventional processes.
Concerning gold hydrometallurgy, O3 pretreatment
was reported by Van Antwerp and Lincoln (1987) as a
means for improving gold recoveries in the subsequent
hypochlorite leaching. Patiño et al. (2003) studied a
similar pretreatment for refractory gold ores, prior to
conventional cyanidation. Direct O3 leaching for gold
was also investigated in different media. Scheiner and
Linstrom (1973) patented a process for the gold recovery
from carbonaceous ores by O3-treatment in high (1–5 M)
chloride media. However, the stoichiometry of the
 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151
reaction, the ozone consumption, and full kinetics were
not determined. Grudeva and Grudev (1991) studied a
combination of chemical and biochemical treatments for
gold bearing polymetallic ores. The final step consisted
of silver and gold thiourea leaching in presence of ozone.
Reported extractions were 60% Au and 55% Ag but in
150 days. Nobre (1993) also patented a process of gold
leaching with thiourea in presence of oxidants in which,
among others, ozone was cited. Chtytan and Babayan
(1977) studied the O3 leaching of gold and silver with
acid thiocarbamide, and Chtytan et al. (1985) in
polyacrylonitrile, in a medium of formamide and
chloroform.
Recently (Viñals et al., 2001, 2004), an O2–O3
leaching process (Metalozon) has been described. The
process consists of three consecutive steps: (1) Cu and
Ni are recovered in a first step by treatment in O2/
H2SO4(dil) (2) Ag is then selectively leached in O2/O3/
H2SO4(dil) (3) Au and Pd are recovered by treatment in
O2/O3/H2SO4(dil) in presence of dilute Cl− (∼0.1 M),
with Pt and Rh remaining in the final residue. The
residual O2 from steps 2 and 3 is recycled to step 1.
All steps are carried out at ambient temperature and
pressure, with low reagent concentrations (∼0.1 M).
The process was tested at laboratory-scale on gold
bearing electronic scrap, gold gravimetric concen-
trates, anode slimes from copper electrorefining and
waste radiographic plates. A kinetic study of the step
2 of the process has also been published (Viñals et al.,
2005). The rate of the silver leaching was limited by
mass transfer of the aqueous ozone with a first order
dependency with respect to the PO3 and [O3]aq. The
ozone consumption was about 1 mol O3/mol Ag.
The present paper is a base study for optimizing step
3 of the Metalozon process. The kinetics of the reaction
of gold and palladium with aqueous ozone, including
stoichiometry and the effects of stirring speed, ozone,
chloride and acid concentrations and temperature are
described. Some preliminary experiments on Rh and Pt
are also included in order to corroborate the selectivity
of the Au and Pd leaching.
2. Materials and methods
2.1. Materials
Metal powders (Au, Pd, Rh, Pt, N 99.9%) consist-
ing of aggregates of spheroidal grains (0.5–5 μm),
were used in most of the preliminary experiments and
in the determination of the Au and Pd stoichiometry.
Gold and palladium plates (N 99.9%) of 1 mm
thickness and 21.1 cm2 (Au) and 19.6 cm2 (Pd) of
143
total surface, were used in the kinetic experiments for
the measurement of specific rates and the mass
transfer coefficients.
2.2. Leaching experiments
The leaching apparatus was described in a previous
paper (Viñals et al., 2005). It consisted of an ozone
generator, a leaching reactor and an absorber of residual
ozone containing conc. KI solution. The leaching
reactor consisted of a stirred, thermostatted closed
vessel, with a gas entrance to the solution through a
fritted-glass diffuser, a gas exit connected to the KI
absorber and a sampling device. Volumetric flow (q) and
total pressure of the O2/O3 mixture were measured. The
•
O3 mass flow (qO3) and PO3 in the input gas were
regulated through the current intensity applied to the
ozone generator. The solubility of O3 in the leach
solutions was measured by pumping 50 cm3 solution
into an absorber flask containing KI and further titration.
Most of the experiments were carried out in the
•
following conditions: q 21.5 L/h, qO3 0.42–2.1 g/h,
PO3 1–5 kPa.
The conditions for the preliminary tests on Au, Pd,
Rh and Pd are reported with the leaching results. In
some experiments, the very low extraction levels were
determined by solution analysis in the ppb range, by
using Inductively Coupled Plasma/Mass Spectroscopy
(ICP-MS).
Stoichiometry experiments for Au and Pd were per-
formed as a follows: An excess of metal powder
(0.200 g) was placed in 550 cm3 of a previously
saturated O3/HCl solution of known concentration (O3
5.1 × 10− 4 M). The mixture was maintained hermetically
closed and stirred for different time periods (up to ∼6 h)
until ozone was completely consumed. Stoichiometry
was determined by the ratio of the moles of Au or Pd
dissolved and the initial moles of ozone in the reactor.
Kinetic experiments on Au and Pd were conducted in
500 cm3 solutions of known O3 concentration, as
described in the previous paper (Viñals et al., 2005). A
plate of constant surface area of Au or Pd was suspended
in the solution, and the leaching rate was measured by
solution sampling and analysis by AAS (Au) or ICP-
AES (Pd). The O3 saturation was practically maintained
during the experiments because the rates of metal
leached (∼ 10 − 4 mol/h) were relatively small as
compared with the rate of ozone injection (∼10− 2 mol
O3/h). In the kinetic study, the effects of H+ and Cl− were
separated by using H2SO4/NaCl solutions. The condi-
tions of each group of tests are reported together with the
leaching results.
144 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151

40 HCl 0.25M 0.2

Selected samples of affected powders and plates
HCl 1M
were observed using Scanning Electron Microscopy

% Extraction in H2SO4
H2SO4 0.25M

% Extraction in HCl
in conjunction with Energy Dispersive Spectrometry 30
(SEM/EDS). For the detection of possible Cl2 or
HClO in experiments in O3/Cl− media, UV spectra 20 0.1
of selected solutions were recorded in the range
190–500 nm. 10

3. Results and discussion

0 0
0 10 20 30 40 50 60 70
3.1. Preliminary experiments on Au, Pd, Rh and Pt Time (min)

3.1.1. Gold
No leaching of Au in O3/H2SO4 (25 °C, 1 h) was
detected and no surface change was observed using
SEM. However, it is well known that the action of
gaseous O3 on gold surface produces nanolayers of
Au2O3 (King, 1995; Krozer and Rodahl, 1997). In
aqueous media, however, nanolayers of gold(III)-
hydroxyl species such as Au(OH)3 seem more probable,
because these were reported during the anodic oxidation
of gold in H2SO4(dil) (Gmelin Handbook of Inorganic
and Organometallic Chemistry, 1992). Treatment in O3/
HCl removes these layers showing linear leaching rates
(Fig. 1). No significant [HCl] effect was observed in a
wide range of concentrations (0.1–2 M).
3.1.2. Palladium
The behavior of Pd was similar to Au. However, in
O3/H2SO4 some leaching was detected by ICP-MS
solution analysis, although the levels were extremely
low, even with 0.5–5 μm particles (∼0.05% in 1 h).
These low values ensure a practical selectivity of the
silver leaching in analogous conditions (Viñals et al.,
2005). On the other hand, the curve obtained in O3/
H2SO4 (Fig. 2) suggests the formation of a passive
surface. Although no product layer was observed using
50
40 HCl 0.1M
Fig. 2. O3 leaching of Pd powder in different media. (12 mg Pd/300 cm3
solution, 20 °C, q: 21.5 L/h, PO3: 4.95 kPa, 700 min− 1).
SEM, PdO was reported as the most stable oxide during
the anodic passivation of this metal (Gmelin Handbook
of Inorganic and Organometallic Chemistry, 1989). The
leaching in O3/HCl was N103 times faster than in O3/
H2SO4, showing linear rates. As in gold, no significant
effect of the HCl concentration was observed in the
range 0.25–1 M (Fig. 2).
3.1.3. Rhodium
The behavior of Rh in O3 leaching was different from
those of the Au and Pd. Rhodium reacts very slowly but
at linear rates in O3/H2SO4, as observed through ICP-
MS. In addition, the presence of the Cl− does not
significantly increases the leaching rate (Fig. 3).
Moreover, temperature has a significant positive effect
(Fig. 3), in spite of diminishing O3, for instance, by 50%
from 20 to 40 °C. On the other hand, an increase of
[H2SO4] leads to a continuous decrease in the leaching
rate, which is nearly imperceptible at 5 M H2SO4,
presumably as consequence of the fall in the O3
0.1
HCl 0.25M, 20°C
H2SO4 0.25M, 20°C
H2SO4 0.25M, 40°C
% Extraction

HCl 1M
HCl 2M
(gAu/m2)

30 0.05

20

10

0 0
0 20 40 60 80 100 0 20 40 60 80
Time (min) Time (min)

Fig. 1. O3/HCl leaching of Au plates. (21.1 cm2 plate/500 cm3 Fig. 3. O3 leaching of Rh powder in different media. (12 mg Rh/300 cm3
solution, 25 °C, q: 21.5 L/h, PO3: 4.95 kPa, 700 min− 1). solution, q: 21.5 L/h, PO3: 4.95 kPa, 700 min− 1).
 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151 145

solubility. However, even at 40 °C and in dilute H2SO4, 20 100 min-1

the leaching rate of rhodium can be considered 300 min-1

negligible as compared from the data of Ag in O3/ 500 min-1

16
H2SO4, and the data obtained in the present study for Au 500 min-1 bis

(mole Au/m2)x100
and Pd in O3/Cl− media. 12
700 min-1
700 min-1 bis
900 min-1
3.1.4. Platinum 8
900 min-1 bis
No significant attack and surface change was detected
(by SEM) on Pt in O3/H2SO4 (0.25 M H2SO4, 25 °C, 3 h),
4
or in O3–HCl (0.1–2 M HCl, 25 °C, 3 h). Leaching in
O3/H2O2/HCl showed significant rates, but only at
high HCl concentration (6 M). However, chlorine 0
0 20 40 60 80 100
evolved under these last conditions, and, consequently,
Time (min)
no environmental advantage over the classical leaching
processes was observed. Fig. 5. Effect of stirring speed on gold leaching. (25 °C, H2SO4 0.01 M,
NaCl 0.05 M, PO3 4.95 kPa).
3.2. Kinetics of gold and palladium leaching
of the metal, the ozonization of the aqueous Pd(II)
3.2.1. Stoichiometry chloride complexes can produce oxidation to PdCl62−,
Fig. 4 shows the results of the stoichiometry although the kinetics is not instantaneous (Zamashchi-
experiments. Results indicate a molar ratio of metal kov and Pryadko, 1985).
leached/O3 consumed, close to 0.67 and 1 for Au and
Pd, respectively. Thus, the overall reactions can be 3.2.2. Effect of the stirring speed
written as: Figs. 5 and 6 show the results obtained for gold and
palladium, respectively. Leaching showed practically
Au þ 3=2O3 þ 3Hþ þ 4Cl− →AuCl−4 þ 3=2O2 linear rates, as expected for the constant surface area of
þ 3H2 O ð1Þ the solid. For Pd plates, however, an initially slow rate
was detected in all the leaching experiments. This was
Pd þ O3 þ 2Hþ þ 4Cl− →PdCl2−
4 þ O2 þ H2 O ð2Þ attributed to the presence of an initially passive surface
due to contact with the atmospheric O2. Therefore, rate
Formation of Pd(II) was also reported when Pd reacts
constants were computed from ≥ 5 min points.
with H2O2 in HCl media (Zhang and Zheng, 2003),
On the other hand, rates increase with increasing
along with PdCl42− the predominant species for high
stirring speed, indicating a probable kinetic control due
Cl− / PdII ratio (Gmelin Handbook of Inorganic and
to transfer of aqueous ozone.
Organometallic Chemistry, 1989). However, in absence
Therefore, data treatment was similar to that used in
the previous paper (Viñals et al., 2005). Assuming that
2
Au 15
Pd 300 min-1
mole metal / mole O3

1.5
600 min-1
(mole Pd/m2)x100

Pd Pd(II) 10 900 min-1

1 1000 min-1

0.5 Au Au(III) 5

0
0 1 2 3 4 5 6 0
Time (h) 0 10 20 30 40
Time (min)
Fig. 4. Plot of mole of metal leached/mole of O3 consumed at different
times. (0.200 g metal powder, 550 cm3 HCl 1M, [O3]initial 5.1 × 10− M, Fig. 6. Effect of stirring speed on palladium leaching. (25 °C, H2SO4
20 °C, 700 min− 1). 0.1 M, NaCl 0.1 M, PO3 4.95 kPa).
146 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151

12 Au 1.3x10-4 M
30
Pd
2.6x10-4 M
k (m/s)x105

8 25
4.4x10-4 M

(mole Au/m2)x100
20
5.3x10-4 M
4
15 6.0x10-4 M

0 10
0 200 400 600 800 1000 1200
Stirring speed (min-1) 5

0
Fig. 7. Mass transfer coefficients of the aqueous ozone as a function of 0 50 100 150
the stirring speed. (Conditions as in Figs. 5 and 6).
Time (min)

the reaction rate was basically limited by mass transfer
in the aqueous ozone and considering the different
stoichiometries for the two processes, the rates of Au
and Pd leaching in fixed hydrodynamic conditions and
temperature, can be written as:
1 dNAu
− ¼ ð2=3Þkt ½O3
sat
A dt
1 dNPd
− ¼ kt ½O3
sat
A dt
Where A is the surface area (m2), Ni the mole of
metal, [O3]sat the ozone concentration in the bulk
solution (mol/m3), and kt (m/s) the mass transfer
coefficient for aqueous ozone. In this formulation, the
effects of Cl− and H+ ions are considered to have little
significance over a wide range, as shown in the
preliminary experiments.
Fig. 7 shows a plot of the mass transfer coefficients,
calculated from the specific rates and Eqs. (3) and (4),
under different stirring conditions. For both metals, the
values obtained for the O3 mass transfer coefficients
were close, increasing with the stirring speed. This is
Fig. 9. Gold leaching data for different ozone concentrations. (25 °C,
H2SO4 0.01 M, NaCl 0.05 M, 900 min− 1).
consistent with the kinetic control assumed to be
present.
3.2.3. Effect of ozone concentration
ð3Þ The effect of ozone concentration was studied at
900 min− 1, 25 °C and in the range [O3] 1.3 × 10− 4–
6.0 × 10− 4 M. These leach solutions were prepared by
saturation at different PO3. The measured O3 solubility
ð4Þ
in dilute H2SO4/NaCl media and in dilute H2SO4 were
similar (Fig. 8).
Figs. 9 and 10 show the leaching data and Fig. 11 is a
plot of the specific rates against the ozone concen-
tration. Rates were practically proportional to the
[O3], in agreement with the expected first order
dependency.
3.2.4. Effect of chloride concentration
The effect of the chloride concentration on the
leaching rate is shown in Figs. 12 and 13.
The plot of the specific rates vs chloride
concentration is presented in Fig. 14. For both
metals, there is a threshold [Cl−] at which there is a

10
H2SO4 0.01M, NaCl 0.05M 8 5.3x10-4 M
5.2x10-4 M
8 H2SO4 0.1M, NaCl 0.1M 3.3x10-4 M
[O3] (mole/L)x104

(mole Pd/m2)x100

6 2.0x10-4 M
6 H2SO4 0.25M (Viñals et al., 2005) 1.5x10-4 M

4
4
2
2
0
0 0 5 10 15 20 25 30 35 40 45
0 1 2 3 4 5 6 Time (min)
PO3 (kPa)
Fig. 10. Palladium leaching data for different ozone concentrations.
Fig. 8. Ozone solubility for different partial pressures. (25 °C). (25 °C, H2SO4 0.1 M, NaCl 0.5 M, 900 min− 1).
 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151
5
4
Rate (mole/m2.s)x105
3 Au
Pd
2
1 the values at 25 °C can be estimated, resulting in:
0 rate at 0.05 M Cl− and 0.01 M [H+] would be very small
0 2 4 6
[O3] (mole/L)x104
Fig. 11. Plot of the specific rates against the ozone concentration.
(25 °C, 900 min− 1) (Au: H2SO4 0.01 M, NaCl 0.05 M. Pd: H2SO4
0.1 M, NaCl 0.1 M).
change from passive to non-passive behavior. Under
the conditions studied (25 °C, H2SO4 0.01 M) the
passive region is located at b0.01 M Cl− for gold
and b0.05 M for palladium.
However, the passive behavior of Pd in the O3/Cl− /
+
H system is more complex than that observed for
gold, and further studies using XPS-Auger would be
necessary to investigate the nature of the oxide layers
and their growth rates. Whereas for gold the [Cl−] was
the only determinant parameter, for palladium the
passive region also depends on the temperature and
possibly on the [H+], for [H+] b 0.01 M. The borders
of the passive region for Pd were not extensively
studied. Fortunately, the passive region is located at
highly diluted concentrations and low temperatures.
Conditions such as T ≥ 20 °C, [Cl− ] ≥ 0.05 M and
[H+ ] ≥ 0.01 ensure reactive palladium during the
ozone leaching.
In the non-passive region, the leaching rate for
both metals was not very sensitive to Cl− concen-
tration, although a maximum rate was found on
about 0.05 M Cl−, with a slight decrease at higher
concentrations. This latter effect can mainly be
attributed to a slight decrease in ozone solubility (From
5.9 × 10− 4 mol/L at 0.01 M Cl− to 4.9 × 10−4 mol/L at
0.5 M Cl−).
The use of HCl solutions instead of the H2SO4/
NaCl solutions was studied for gold (Fig. 1). The
specific rates obtained at 0.1, 1 and 2M HCl were in
the same range (3 ± 0.3 × 10− 5 mol/m2 s) that in
H2SO4/NaCl (Fig. 14).
On the other hand, the secondary formation of
chlorine or hypochlorous acid during the O3/Cl −
leaching was also checked. Yeatts and Taube (1949)
147
indicated that chlorine can be formed in ozone/chloride
solutions in acid media, according to:
O3 þ 2Cl− þ 2Hþ →Cl2 þ H2 O þ O2 ð5Þ
d½Cl2
=dt ¼ k 1 ½O3
½Cl−
þ k 2 ½O3
½Cl−
½Hþ
: ð6Þ
From the reported kinetic constants at 0 °C and 9.5 °C,
k1 ∼ 10− 3 L/mol s and k2 ∼ 10− 2 L2/mol2 s. Reaction
8 (∼10− 8 mol/L s) in the leach solutions of the present
paper. But, for instance, at 0.5 M Cl− and 0.5 M H+ the
rate could reach values of about 10− 6 mol/L s. More
recent works (Hoigne et al., 1985; Levanov et al., 2002,
2003, 2005) confirm the ∼10− 3 L/mol s second order
rate constant as well as the catalytic effect of the H+.
In order to verify the possible formation of
chlorine, UV spectra of different leach solutions
were recorded (Fig. 15). For dilute Cl− concentration
(≤0.1 M), only the peaks of ozone (260 nm) (Alder
and Hill, 1950) and Cl− (195–200 nm) were detected.
However, on increasing Cl− concentration to 0.5 M, a
peak of hypochlorous acid (230 nm) (Zimmerman and
Strong, 1957) appeared together with the peak of
ozone. No molecular chlorine (310 nm) was found
even at 0.5 M Cl−, because in acid medium and for
very dilute (total) chlorine solutions, the hydrolysis
equilibrium to hypochlorous acid is strongly displaced.
Thus, the reaction of the ozone under the conditions
tested was of the type:
O3 þ Cl− þ Hþ →HClO þ O2 ð7Þ
Formation of some hypochlorous acid was not a
serious inconvenient for the leaching, because it was
30
0.001 M
0.01 M
25
0.05 M
(mole Au/m2)x100
20 0.05 M bis
0.1 M
15 0.5 M
10
5
0
0 50 100 150
Time (min)
Fig. 12. Gold leaching data for different chloride concentrations.
(25 °C, H2SO4 0.01 M, PO3 4.95 kPa, 900 min− 1).
148 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151

0.01 M
0.03 M
9 0.05 M
0.05 M bis
0.1 M
0.1 M bis
(mole Pd/m2)x100

0.2 M
6 0.3 M
0.4 M
0.4 M bis
0.5 M
3

0
0 10 20 30 40
Time (min)

Fig. 13. Palladium leaching data for different chloride concentrations. Fig. 15. UV spectra for different ozone solutions (25 °C, H2SO4 0.1 M,
(25 °C, H2SO4 0.01 M, PO3 4.95 kPa, 900 min− 1). O3 5.4 × 10− 4 M).

also consumed during the attack of the metals. Therefore,
the global leaching rate was practically unaffected
(Fig. 14). However, from the environmental point of
view, optimum conditions are achieved operating at
low [Cl−] and [H+], which minimize this secondary
reaction.
3.2.5. Temperature effect
Temperature effect was studied in the range 12–
80 °C, [H2SO4] 0.01 M, at a fixed PO3 4.95 kPa. [Cl−]
was 0.05 M for gold and 0.1 M for palladium, except
in the experiment at 12 °C in which Pd was passive
under the former conditions. At 12 °C, the test for Pd
was performed in [H2SO4] 0.05 M, [Cl−] 0.5 M.
5
For both metals, the specific rates (Fig. 16) increase
with increasing temperature up to a maximum rate at
about 40 °C, decreasing at higher temperatures. These
results can be attributed to two overlapped and contrary
effects: The increase of the rate constants and the
diminution of the O3 solubility when temperature
increases.
In order to determine the mass transfer coefficients at
different temperatures, the O3 solubility in the leaching
media was measured. Fig. 17 shows a plot of the ln
[O3]sat vs the reciprocal of the absolute temperature.
Solubility decreases exponentially from 7.5 × 10− 4 M at
12 °C to 1.6 × 10− 4 M at 80 °C, and is nearly identical at
4.5
4

3.5
4
Rate (mole/m2.s)x105
Rate (mole/m2.s)x105

3 2.5

2
2
1.5
Au
Au
Pd 1
1 Pd
0.5

0 0
0 0.1 0.2 0.3 0.4 0.5 0 20 40 60 80 100
[Cl-] (mole/L) Temperature (°C)

Fig. 14. Plot of the specific rates against the chloride concentration. Fig. 16. Specific rates at different temperatures. (PO3 4.95 kPa,
(25 °C, PO3 4.95 kPa, H2SO4 0.01 M, 900 min− 1). [H2SO4] 0.01 M, [Cl−] 0.05 M for Au and 0.1 M for Pd, 900 min− 1).
 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151 149

-6.5
Arrhenius plot was not completely linear indicating
2.6 2.8 3 3.2 3.4 3.6 3.8
some mixed transfer-chemical control at low tempera-
tures, but in any case, with a predominant transfer
-7
y = 2.0365x - 14.369
component. At b25 °C, the rough activation energy of
∼35 kJ/mol (∼8 kcal/mol) for both Au and Pd would be
ln [O3] (mole/L)

-7.5 consistent with this.

3.2.6. Effect of H2SO4 concentration

-8
[Cl-] 0.05M
[Cl-] 0.1M
-8.5
-9
1000/T (K-1)
Fig. 17. O3 solubility in H2SO4 0.01 M at PO3 4.95 kPa.
0.05 and 0.1 M Cl−. From this plot, the ΔHdis o
of the
ozone can be evaluated, resulting in − 17 kJ/mol. These
data agree with those in the literature in pure water
(− 16.3 kJ/mol, Briner and Perrottet, 1939), indicating
that there was no significant effect of the added ions in
the solution enthalpy of ozone. Since this value
corresponds to an intrinsic thermodynamic property,
ozone as the major oxidant species was confirmed in
these diluted chloride media.
Fig. 18 is the Arrhenius plot of the mass transfer
coefficients obtained from the specific rates and the
measured O3 solubility. In the same figure, the data of
the silver leaching in aqueous ozone but in the absence
of Cl− were also plotted. The non-specific behavior of
the ozone for these metals is clearly evident, as expected
from the non-specific character of the mass transfer
kinetics. In the range 25–80 °C, activation energies of
11 and 17 kJ/mol (3–4 kcal/mol) were obtained for Au
and Pd, respectively, which confirmed the rate control
by transfer of the aqueous ozone. However, the
This effect was studied at 25 °C, PO3 4.95 kPa, Cl−
0.1 M, 900 min− 1, and in the range 0.01–1 M H2SO4
for both metals. Specific rates were not particularly
sensitive in this concentration interval. Therefore, mass
transfer coefficients very close to those presented in the
previous figures were obtained. However, the leaching
of gold at very low [H+] was also investigated. Fig. 19
shows the specific rates at different pH values. For pH
N 2, leaching rate progressively diminishes and is nearly
insignificant at pH 6. This response was nearly identical
to that observed in silver leaching under analogous
conditions, but in absence of Cl− (Fig. 19). Therefore,
the decrease of the leaching rate when pH increases,
should be attributed to a gradual change of the kinetic
control from the O3 transfer to the H+ transfer.
The effect of [H+] when pH increases, can be
explained by means of a classical corrosion mechanism,
through an electrochemical process with separate
cathodic (+) and anodic (−) areas:
ðþÞO3 þ H2 O þ 2e→O2 þ 2OH− ð7Þ
ð−ÞAu þ 3H2 O→½AuðOHÞ3
s þ 3Hþ þ 3e ð8Þ
½AuðOHÞ3
s þ 3Hþ þ 4Cl− →AuCl−4 þ 3H2 O ð9Þ
6
Au
5 Ag (Viñals et al., 2005)
Rate (mole/m2.s)x105

-8.1
2.8 3 3.2 3.4 3.6
4
-8.6
ln k (m/s)

3
-9.1

-9.6 2
Au
Pd 1
-10.1 Ag (Viñals et al., 2005)

-10.6 0
1000/T (K-1) 0 2 4 6
pH
Fig. 18. Arrhenius plot of the rate constants. (PO3 4.95 kPa, Au: H2SO4
0.01 M, Cl− 0.05 M, 900 min− 1. Pd: H2SO4 0.01 M, Cl− 0.1 M, Fig. 19. Gold and silver specific rates at different pH values. (25 °C,
900 min− 1. Ag: H2SO4 0.25 M, 700 min− 1). PO3 4.95 kPa. Au: Cl− 0.1 M, 900 min− 1. Ag: 700 min− 1).
150 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151
The transfer of Cl− cannot be a controlling step, since
the non passive region for gold appeared at [Cl−] ≥
10− 2 M, and the typical [O3] was about 10− 4 M.
Therefore, under stationary state conditions, the rate of
gold leaching can be related to the rates of the O3 and
H+ transfer, as:
Rate ¼ 2=3k O3 ½O3
Aþ ¼ 1=3k Hþ ½Hþ
A− ð10Þ
Where kO3 and kH+ are the mass transfer coefficients
for O3 and H+, and A+, A−, the cathodic and anodic
surface areas, respectively. Considering that the total
area, A, is the sum of the cathodic and anodic areas, the
rate equation can be written as:
2 A kO3 kHþ ½O3
½Hþ

Rate ¼ : ð11Þ
6 kO3 ½O3
þ 3kHþ ½Hþ

For pH ≤ 2, [H+] H [O3], and the rate depends
basically on the [O3], as was confirmed from the
leaching data. But for pH N 2 rates would also depend
on the [H+], as was also experimentally observed
(Fig. 14).
3.3. Electric power consumption
The power consumption during ozone production
was determined for different ozone partial pressures. For
the used laboratory-scale generator (Ervin–Sander), the
specific consumption was only slightly dependent of the
PO3, showing values of 14–17 kWh/kg O3 in the range
2–5 kPa (Viñals et al., 2004). Data of similar magnitude
were reported for the industrial generators (12–18 kWh/
kg O3, Gottschalk et al., 2000), which can operate up to
about 9 kPa. Considering the kinetic characteristics of
the O3 leaching of the studied metals, the most effective
variable for maximizing the leaching productivity is the
ozone concentration. Consequently, optimal conditions
are at the maximum technically feasible PO3. For
suspended metallic plates, the specific rates at 9 kPa
can be extrapolated to about 45 g/m2 h for gold and about
25 g/m2 h for palladium and silver. The associated power
consumption would be in the range of 4–8 kWh/kg of
leached metal.
4. Conclusions
1. Gold and palladium can be leached in aqueous ozone
at ambient temperature and low H + and Cl −
concentrations (∼0.1 M). Under these conditions,
rhodium and platinum remain stable.
2. The global leaching reactions can be written as:
Au þ 3=2O3 þ 3Hþ þ 4Cl− →AuCl−4 þ 3=2O2
þ 3H2 O
Pd þ O3 þ 2Hþ þ 4Cl− →PdCl2−
4 þ O2 þ H2 O
However, gold and palladium present a region of
passive behavior, located at Cl− b 0.01 M for Au and
Cl− b 0.05 M for Pd.
3. In the non-passive region, rates are only slightly
dependent on either H + (for pH b 2) and Cl −
concentrations. Kinetics is controlled by mass
transfer of O3(aq) to the solid–liquid interface,
showing first order dependency with respect to
[O3] aq and PO 3. Gold leaching rate gradually
decreases for pH N 2, as consequence of the influence
of the [H+] in the mass transfer control.
4. Secondary formation of chlorine or hypochlorous
acid was not significant for Cl− ≤ 0.1 M, but for
0.5 M Cl− , ozone reacts partially in these leaching
media forming hypochlorous acid:
O3 þ Cl− þ Hþ →HClO þ O2
5. Leaching rates of gold and palladium increase with
temperature up to about 40 °C, but decrease at higher
temperatures as consequence of the fall in the O3
solubility. The ozone mass transfer coefficients show
an activation energy of b20 kJ/mol.
6. The electric power consumption is in the range 4–
8 kWh/Kg of leached metal.
Acknowledgements
The authors wish to thank “Fundación Domingo
Martínez” and “Carburos Metálicos (Air Products)” for
their financial support of this research and the
permission for publishing this paper. The support of
the “Serveis Científico-Tècnics de la Universitat de
Barcelona” is also gratefully acknowledged.
References
Alder, M.G., Hill, G.R., 1950. The kinetics and mechanism of
hydroxide ion catalyzed ozone decomposition in aqueous solution.
J. Am. Chem. Soc. 72 (9), 1884–1886.
Briner, E., Perrottet, E., 1939. Determination des solubilitiés de l´
ozone dans l´eau et dans une solution aqueouse de chlorure de
sodium; calcul des solubilitiés de l´ozone atmosphérique dans les
eaux. Hel. Chim. Acta 22, 397–404.
Chtytan, G.S., Babayan, G.G., 1977. Recovery of gold and silver in an
acid thiocarbamide solution under the action of ozone, In: Mal´
tsev, Y.A. (Ed.), Mater. Vses. Mezhvuz. Konf. Ozonu, 2nd ed.
Moskovskii Gos. Univ., Moscow, pp. 17–18 (in Russian).
 J. Viñals et al. / Hydrometallurgy 81 (2006) 142–151
Chtytan, G.S., Arakelyan, R.A., Bagdasaryan, A.B., Durgaryan, A.,
1985. Gold recovery from ore concentrates by leaching with
polyacrylonitrile. Arm. Khim. Zh. 38 (11), 730 (in Russian).
Gottschalk, C., Libra, J.A., Saupe, A., 2000. Ozonization Water and
Waste Water. Wiley-VCH, Weinheim, Germany.
Griffith, W.P., Swars, K. (Eds.), 1989. Gmelin Hanbook of Inorganic
and Organo-metallic Chemistry, 8th ed. Pd Sup., vol. B2. Springer-
Verlag, Berlin, Germany.
Grudeva, V., Grudev, S., 1991. In: Smith, R.W., Misra, M. (Eds.),
Proc. Mineral Bioprocessing Conference. TMS, Warrendale, PA,
pp. 153–161.
Hoigne, J., Bader, H., Haag, W.R., Staehelin, J., 1985. Rate constants
of ozone with organic and inorganic compounds in water-III.
Inorganic compounds and radicals. Water Res. 19 (8), 993–1004.
Kein, R. (Ed.), 1992. Gmelin Hanbook of Inorganic and Organo-
metallic Chemistry, 8th ed. Au Sup., vol. B1. Springer-Verlag,
Berlin, Germany.
King, D.E., 1995. Oxidation of gold by ultraviolet light and ozone at
25 °C. J. Vac. Sci. Technol., A, Vac. Surf. Films 13 (3, Pt. 2),
1247–1253.
Krozer, A., Rodahl, M., 1997. X-ray photoemission spectroscopy
study of UV/ozone oxidation of Au under ultrahigh vacuum
conditions. J. Vac. Sci. Technol., A, Vac. Surf. Films 13 (3, Pt. 2),
1247–1253.
Levanov, A.V., Antipenko, E.E, Zosimov, A.V., Lunin, V.V., 2002.
Interaction of ozone with sodium chloride—a possible additional
source of chlorine in the atmosphere. NATO Sci. Ser. IV: Earth
Environ. Sci. 16, 159–162.
Levanov, A.V., Kuskov, I.V., Zosimov, A.V., Antipenko, E.E, Lunin,
V.V., 2003. Acid catalysis in reaction of ozone with chloride ions.
Kinet. Catal. 44 (6), 740–746.
Levanov, A.V., Kuskov, I.V., Koiaidarova, K.B., Zosimov, A.V.,
Antipenko, E.E, Lunin, V.V., 2005. Catalysis of the reaction of
ozone with chloride ions by metal ions in acidic medium. Kinet.
Catal. 46 (1), 138–143.
151
Nobre, G.H., 1993. Leaching of gold using thiourea. British Patent
9201457.
Patiño, C.F., Salinas, R.E., Carrillo, P., Raul, F., Hernandez, A.H.,
Mendez, B., 2003. The use of ozone to improve cyanidation
process for silver and gold extraction from a refractory ore. Proc.
27th Conference, IPMI, Pensacola, FLA, pp. 50–62.
Scheiner, J.B., Linstrom, R.E., 1973. Recovery of gold from ores. US
Patent 3764650.
Van Antwerp, W.P., Lincoln, P.A., 1987. Precious metal recovery
using U.V.ozone. US Patent 4642134.
Viñals, J., Roca, A., Cruells, M., Juan, E., Casado, J., 2001. Procedure
for selective leaching of metals. ES Patent 200101826.
Viñals, J., Juan, E., Roca, A., Cruells, M., Casado, J., 2004. In:
Gaballah, I., Mishra, B., Solozabal, R., Tanaka, M. (Eds.), The
Metalozon Process for the Recovery and Recycling of Precious
Metals. Proc. Global Symposium on Recycling, Waste Treatment
and Clean Technology, vol. II. TMS, Warrendale, PA, pp.
1859–1869.
Viñals, J., Juan, E., Roca, A., Cruells, M., Casado, J., 2005. Leaching
of metallic silver with aqueous ozone. Hydrometallurgy 76,
225–232.
Yeatts, L.R.B., Taube, H., 1949. The kinetics of the reaction of ozone
and chloride ion in acid aqueous solution. J. Am. Chem. Soc. 71,
4100–4105.
Zamashchikov, V.V., Pryadko, O.N., 1985. Kinetics and mechanism of
oxidation of palladium(II) chloride complexes by ozone in aqueous
solutions. Ukrainskii Khimicheskii Zhurnal 51 (4), 371–376 (in
Russian).
Zhang, F., Zheng, Y., 2003. Production of palladium chloride from
sponge palladium. CN Patent 1421359.
Zimmerman, G., Strong, F.C., 1957. Equilibria and spectra of aqueous
chlorine solutions. J. Am. Chem. Soc. 79 (9), 2062–2066.