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Hydrometallurgy 89 (2007) 189 195

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Dissolution kinetics of galena in acetic acid solutions

with hydrogen peroxide
Salih Aydoan a,, Ali Aras a , Gkhan Uar a , Murat Erdemolu b
a
Seluk University, Department of Mining Engineering, 42075 Konya, Turkey
b
Inn University, Department of Mining Engineering, 44280 Malatya, Turkey
Received 23 May 2007; received in revised form 12 July 2007; accepted 13 July 2007
Available online 20 July 2007

Abstract

The kinetics of leaching lead from galena in acetic (ethanoic) acid solutions with hydrogen peroxide are investigated with
regard to stirring speed, temperature and concentration of HAc and H2O2 concentration. Oxidation of galena with H2O2 to produce
lead sulphate which dissolves by complexing Pb2+ with acetate anion (PbCH3COO+ and Pb(CH3COO)2). Results indicate that the
rate of galena dissolution is controlled by a surface chemical reaction with an apparent activation energy is 65.6 kJ mol 1 in the
temperature range 3070 C. Both HAc and H2O2 affect the rate of extraction of lead as an acetate complex. The order of reaction
was 0.79 and 0.31 for H2O2 and HAc concentrations, respectively.
2007 Elsevier B.V. All rights reserved.

Keywords: Galena; Leaching; Kinetics; Acetic acid; Hydrogen peroxide; Shrinking core model

1. Introduction In hydrometallurgical processes, carboxylic acids have

Short-chain or low molecular weight carboxylic acids
(LMWCA) having 15 C atoms per molecule are usually
referred to as an aliphatic mono-carboxylic acids. These
may affect mineral weathering rates by at least three
mechanisms (Drever and Stillings, 1997): by changing
the dissolution rate far from equilibrium through
decreasing solution pH or forming complexes with
cations at the mineral surface; by affecting the saturation
state of the solution with respect to the mineral; and by
affecting the speciation in the solution of ions.
Corresponding author.
E-mail address: saydogan@selcuk.edu.tr (S. Aydoan).
0304-386X/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2007.07.004
been proposed as an alternative, and probably less
expensive, leaching agent (Panias et al., 1996; Ambikadevi
and Lalithambika, 2000). Organic acids such as oxalic,
citric, ascorbic, acetic, fumaric and tartaric acid, have
been used for their ability to solubilize iron and other metal
oxides. Of the above organic acids, oxalic (Baumgartner
et al., 1983; Cornell and Schindler, 1987; Blesa et al.,
1987; Taxiarchou et al., 1997; Ubaldini et al., 1996) citric
(Waite and Morel, 1984) and ascorbic acids (Afonso et al.,
1990; Parida et al., 1997) are the most used carboxylic
acids, due to their effectiveness as solvent reagents.
Generally, the studies carried out were mainly focused on
the dissolution of iron oxides and aluminum oxide; together
with those on the dissolution of non-oxide minerals
such as feldspar (Drever and Stillings, 1997) hornblende
(Zhang and Bloom, 1999) and apatite (Goyne et al., 2006).
190 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195
There are hardly any studies aimed at leaching
sulphide minerals using organic acids. Evans and Masters
(1976) developed a method for leaching finely divided
galena bearing material to convert lead to soluble lead
acetate with concurrent conversion of sulphur to elemen-
tal state. The method involves forming slurry consisting
of the material dispersed in an aqueous medium contain-
ing free acetate ions and having a pH below 5.1, at a
temperature of 60 to 120 C under oxygen pressure.
Geisler and Puddington (1996) is described a method for
dissolving galena by in-situ leaching with acetic acid and
acetate solution in the presence of an oxidant such as
oxygen gas. Accordingly, the experiments conducted by
Greet and Smart (2002) demonstrated that EDTA readily
dissolves lead hydroxide, lead carbonate, lead sulphate,
and lead hydroxy-carbonate all typical galena
oxidation products.
This present study aims to examine the effectiveness
of acetic acid to leach galena in aqueous oxidizing
conditions and dissolve lead. For this purpose, galena
was leached with acetic acid in the presence of hydrogen
peroxide, and effects of some parameters such as stirring
speed, temperature, acetic acid and hydrogen peroxide
concentrations on the kinetic parameters of galena
dissolution were investigated.
2. Materials and methods
A galena concentrate sample obtained from the
Koyulhisar complex sulphide ore concentrator in Sivas
province of Turkey was used. The sample was sieved
into three size fractions but experiments were performed
only with the 4575 m fraction which contained
79.0% Pb, 14.61% S, 2.97% Fe, 1.90% Zn and 0.50%
Cu.
The dissolution experiments were carried out in a
glass reactor of 1 L, equipped with a Teflon coated
mechanical stirrer, maintained in a constant temperature
bath. The ranges of dissolution parameters chosen were
0600 min 1 for stirring speed, 303343 K for
temperature, 0.12.0 mol/L for hydrogen peroxide
concentration and 0.55.0 mol/L for acetic acid
concentration. For each experiment, 1 g of galena was
stirred in 500 mL of H2O2/HAc mixture for up to 90 min
and sampled at various time intervals. Lead in the
solution was determined using flame atomic absorption
spectrophotometer (GBC Scientific Equipment, SensAA
Model, Australia). For calculation of the fraction of lead
extracted, the equation incorporating correction factors
to account for volume losses during sampling was used.
Distilled water and reagent grade chemicals were used to
prepare all the solutions.
3. Results and discussion
3.1. Dissolution of galena
The oxidation and dissolution mechanisms of galena
still remain uncertain with a wide variety of possible
mechanisms having being proposed in the literature.
Surface species found on galena during oxidation and
dissolution have been studied using many techniques
(Gerson and O'Dea, 2003). It has been assumed that
complexation takes place at the surface of hydrous
galena sulphides. The adsorption of H+ ions onto a
surface of S atom in the aqueous phase is found to be
favorable whereas the adsorption onto a surface Pb atom
is not favorable. On exposure to air and aqueous
solution, hydroxides form on galena surface, often with
a lead deficient sulphide beneath the hydroxides. On
oxidation of galena in air, a metal deficient sulphide is
formed, covered with a layer of lead hydroxide, oxide
and carbonate. On further exposure to air, basic sulphate
and lead sulphate are also observed. An ion exchange
process between protons and lead ions is assumed to
occur at the surface resulting in the formation of a lead
deficient surface.
It has been reported by Hsieh and Huang (1989) that as
the dissolution rate is much higher under acidic conditions
as compared to alkaline conditions, a protonated surface,
PbSH22+, initiates the dissolution process: In the presence
of oxygen,
2solid 2O2 PbS2 d 2O2solid Pb
PbSH2 2 2
1
SO2
4 2H
Pb2 SO2
4 PbSO4solid 2
Accordingly, Jennings et al. (2000) have stated that the
formation of PbSO4 prevents Pb2+ from undergoing
hydrolysis and generating acid,
Pb2 2H2 OPbOH2solid 2H 3
Instead, the overall reaction for galena weathering by
H2O2 is presented as,
PbS 4H2 O2 PbSO4solid 4H2 O 4
Hydrogen peroxide, H2O2, is a strong oxidant and
environmentally safe reagent as apart from water no
other reaction products generated during the dissolution
of sulphide minerals. The oxidative action of hydrogen
 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195
peroxide in acidic solutions is based on its reduction
according to,
H2 O2 2H 2e 2H2 O E 0 1:77V 5 Regardless of very low solubility of PbSO 4
Hydrogen peroxide can also act as a reducing agent,
undergoing oxidation:
H2 O2 O2 2H 2 6
Overall reaction can be written:
2H2 O2 O2 2H2 O 7 number of acetate ligands in the nth lead species. The
By decomposition of hydrogen peroxide, oxygen is
adsorbed on the mineral surface whereby electron
transfer takes places in the solution. The potential
value of 1.77 V is adequate to oxidize almost all of the
metal sulphides (Aydoan, 2006).
The net results of the oxidation of sulphides, despite
the consequences of details of the dissolution mechanism
for galena, are (1) to get the metal ion into solution or into
the form of an insoluble compound stable under surface
conditions, (2) to convert the sulphur to sulphate ion, and
(3) to produce relatively acid solutions. Discussion of
such reaction for lead minerals can be refined by the use
of EhpH diagrams (Fig. 1), which serves only to
express the relationships quantitatively (Krauskopf and
Bird, 1994). Of the four lead minerals shown in Fig. 1,
galena is the most stable at low values of Eh, regardless
Fig. 1. EhpH diagram for lead minerals at 298 K and 1 bar. Total
carbonate = 10 3 mol/L and total dissolved sulphur = 10 2 mol/L,
(Krauskopf and Bird, 1994).
191
of activity. When conditions are oxidizing, anglesite is
the most stable in an acid environment and cerussite in
most alkaline conditions.
(Ksp = 1.82 10 8), acetic acid (CH3COOH) and acetate
(CH3COO) rapidly form complexes with lead ions. The
lead acetate complexes formed have stoichiometries which
can be described by the following generalized reaction;
Pb2 nAc PbAcn 2n 8
where Ac is the acetate ion (CH3COO) and n is the
degree of association of lead is defined in terms of average
ligand number, nav, calculated from the following
expressions:
Pn h i
2n
mHAc  HAc  Ac   n Pb Ac n
nav 1 9
mPb2 mPb2
where mHAc represents the stoichiometric concentration of
acetic acid, [HAc] and [Ac] are the calculated acetic acid
and free acetate concentrations, respectively, and mPb2+
represents the total stoichiometric metal concentration
(Bnzeth and Palmer, 2000).
The leaching solutions after removal of un-dissolved
solids were analysed for SO42 ion by adding 0.1 mol/L Ba
(NO3)2 solution instead of BaCl2 which is generally used
for sulphate precipitation. Nitrate salt was employed to
avoid precipitation of PbCl2 (Ksp = 1.78 10 5). It was
observed that BaSO4 (Ksp = 1.08 10 10), as identified by
chemical analysis, precipitated without delay.
In the literature, there are some studies both on the
oxidation of galena (Wittstock et al., 1996) and the
dissolution of lead sulphate in acetate medium (Giordano,
1989). The thermodynamic stability constants at 298 K
for the complexes PbCH3COO+ and Pb(CH3COO)2 are
log K1 = 2.4 and log K2 = 3.4, respectively, as calculated
by Giordano (1989). He found that lead hydrolysis is
significant in those experiments conducted at 343 and
353 K; however hydrolyzed lead is not detected at 298, 313
and 328 K. The author concludes that lead acetate
complexes predominate over Pb2+ and PbOH+ at tempera-
tures between 298 and 358 K in solutions which are slightly
acid and have free acetate concentrations N 0.01 m.
3.2. Effects of parameters
The effect of stirring on the dissolution rate was
determined at 323 K in solutions containing 3 mol/L
HAc and 0.5 mol/L H2O2. Interestingly, for this reactive
sulphide at low pulp density, there was no significant
192 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195
Fig. 2. Effect of temperature on galena dissolution (no stirring; HAc:
3 mol/L; H2O2: 0.5 mol/L).
effect of stirring on the rate of dissolution. In previous
studies, it was reported that oxygen derived from the
decomposition of H2O2 caused self mixing with mineral
particles (Aydoan, 2006; Adebayo et al., 2006;
Antonijevi et al., 1997, 2004). But in this study, no
oxygen gas emission was observed yet the dissolution
rate was high without stirring except for simply shaking
to homogenize the solution prior to the sampling.
The effect of temperature on dissolution was carried
out in the 303343 K temperature range again in
solutions containing 3 mol/L HAc and 0.5 mol/L H2O2.
It was observed that fast leaching rates occurred within
the first 20 min. (Fig. 2). The fraction of lead extraction
after 20 min was 0.69, 0.77 and 0.85 at 323, 333 and
343 K, respectively. After that time, the leaching slows
down or stops suggesting that the lead sulphate produced
Fig. 3. Effect of H2O2 concentration on galena dissolution (no stirring;
HAc: 3 mol/L; temperature: 323 K).
Fig. 4. Effect of HAc concentration on galena dissolution (no stirring;
H2O2: 0.5 mol/L; temperature: 323 K).
immediately precipitates at the un-reacted galena
surface, inhibiting further attack of hydrogen peroxide.
In order to determine the effect of hydrogen peroxide
concentration, the experiments were performed by varying
the initial H2O2 concentration in the range of 0.12.0 mol/
L at 323 K in solutions containing 3 mol/L HAc. Only 40%
of lead was extracted using 0.1 mol/L H2O2 within 90 min,
while the extraction was almost completed by leaching
with 0.5 mol/L H2O2. It was observed that as the H2O2
concentration increased, oxidation of galena together with
dissolution of lead sulphate significantly accelerated
(Fig. 3). However, the rate drastically decreased when
using 1 and 2 mol/L H2O2 after 20 min of leaching,
suggesting the same phenomenon observed during leach-
ing at higher temperatures, e.g., fast precipitation of lead
sulphate inhibits further oxidation of unreacted galena.
Fig. 5. Variation in surface chemical reaction model equation with time
at various temperatures (symbols as in Fig. 2).
 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195 193

reaction products are crucial for a complete understand-

ing of the system. In order to elucidate the reaction
mechanism of galena dissolution with hydrogen perox-
ide in acetic acid solutions, the shrinking core model was
utilized (Habashi, 1999). According to the shrinking core
model, if the reaction of galena can be represented as,

Afluid bBsolid Fluid products Solid products 10

and the rate of the reaction is controlled by surface

chemical reaction, then the integral rate equation is
constituted as follows:

Fig. 6. Arrhenius plot of the data presented in Fig. 5.
To establish the effect of acetic acid, four different
HAc concentrations were examined in the range of 0.5
5.0 mol/L at 323 K in solutions containing 0.5 mol/L
H2O2. Increasing the HAc concentration up to 3 mol/L
increased the rate of sulphate dissolution (Fig. 4). But a
further increase in HAc concentration caused a decrease
in the dissolution rate. The slower kinetics with 5 mol/L
acetic acid is likely due to the increased viscosity and
lower mass transport of H2O2 through the solution and
surface layer. This effect could also rationalize why the
reaction order of HAc is unusually low. The change in
the rate at higher reagent concentrations has been
claimed to be due to the larger quantity of solid lead
sulphate produced.
kc MB CA
1  1  X1=3 t kr t 11
qB ar0
where X is the fraction reacted, kc is the kinetic constant,
MB is the molecular weight of the solid, CA is the
concentration of the dissolved lixiviant A in the bulk of
the solution, a is the stoichiometric coefficient of the
reagent in the leaching reaction, r0 is the initial radius of
the solid particle, t is the reaction time, B density of the
solid and kr is the rate constant calculated from Eq. (11).
Eq. (11) was applied to the data obtained from each
temperature which gives a straight line (Fig. 5). The rate
constants were calculated as slopes of the straight lines.
By using these values, the Arrhenius equation k = AeE/RT,
(plotted in Fig. 6), gives an activation energy of 65.6 kJ
mol 1 that supports the proposed surface chemical
reaction as the rate controlling step. The activation
energies of galena dissolution reported by various authors
are summarized in Table 1 and compares favourably.

3.3. Dissolution kinetics

Understanding the mechanism of a leaching system is

the main consideration, while a knowledge of the
kinetics of the rate controlling processes and solid

Table 1
Reported activation energies for leaching of galena with different
leaching media
Leaching reagent Activation energy Reference
(kJ mol 1)
Ferric fluosilicate 62.1 Chen and Dreisinger
(1994)
Ferric chloride 4045 Dutrizac (1986)
Cupric chloride 33 Dutrizac (1989)
Ferric nitrate 47 Fuerstenau et al.
(1987)
HCl 64.4 Nunez et al. (1988)
HClO4 71.5
Fig. 7. Determination of reaction order for galena dissolution with
HBr 66.5
respect to H2O2 and HAc concentrations.
194 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195
To establish the order of reaction with respect to
reagent concentration, the dissolution data obtained
from Figs. 3 and 4 were used in Eq. (11) to determine
rate constants. By constructing the plots of ln kr versus
ln [H2O2] and ln [HAc], the order of reaction was found
proportional to 0.79 and 0.31 power of H2O2 and HAc
concentrations (Fig. 7).
4. Conclusions
The dissolution of galena with hydrogen peroxide in
acetic acid solutions assumes that galena oxidizes with
hydrogen peroxide to form solid lead sulphate which
further dissolves with acetate anion to give a lead acetate
complex in solution. This study concludes that the
leaching kinetics of galena follows the shrinking core
model with the surface chemical reaction as the rate
controlling step. Increasing the hydrogen peroxide and
increasing the acetic acid concentration up to 3 mol/L
accelerates galena dissolution. The activation energy
was found to be 65.6 kJ mol1 in the temperature range
303343 K, supporting a surface chemical reaction
controlled dissolution. Empirical orders of the galena
dissolution reaction with respect to hydrogen peroxide
and acetic acid concentrations are 0.79 and 0.31,
respectively.
Acknowledgement
This study was supported by The Research Founda-
tion of Selcuk University.
References
Adebayo, A.O., Ipinmoroti, K.O., Ajayi, O.O., 2006. Leaching of
sphalerite with hydrogen peroxide and nitric acid solutions. Journal
of Minerals and Materials Characterization and Engineering 5 (2),
167177.
Afonso, M.S., Morando, P.J., Blesa, M.A., Banwart, S., Stumm, W.,
1990. The reductive dissolution of iron oxides by ascorbate. Journal
of Colloid and Interface Science 138, 7482.
Ambikadevi, V.R., Lalithambika, M., 2000. Effect of organic acids on
ferric iron removal from iron-stained kaolinite. Applied Clay Science
16, 133145.
Antonijevi, M.M., Dimitrijevi, M., Jankovi, Z., 1997. Leaching of
pyrite with hydrogen peroxide in sulphuric acid. Hydrometallurgy
46, 7183.
Antonijevi, M.M., Jankovi, Z., Dimitrijevi, M., 2004. Kinetics of
chalcopyrite dissolution by hydrogen peroxide in sulphuric acid.
Hydrometallurgy, 71, 329334.
Aydoan, S., 2006. Dissolution kinetics of sphalerite with hydrogen
peroxide in sulphuric acid medium. Chemical Engineering Journal
123, 6570.
Baumgartner, E.C., Blesa, M.A., Marinovich, H.A., Maroto, A.J.G.,
1983. Heterogeneous electron transfer as a pathway in the
dissolution of magnetite in oxalic acid solutions. Inorganic
Chemistry 22, 22242226.
Bnzeth, P., Palmer, D.A., 2000. Potentiometric determination of
cadmium-acetate complexation in aqueous solutions to 250C.
Chemical Geology 167, 1124.
Blesa, M.A., Marinovich, H.A., Baumgartner, E.C., Maroto, A.J.G.,
1987. Mechanism of dissolution of magnetite by oxalic acid-
ferrous ion solutions. Inorganic Chemistry 26, 37133717.
Chen, A.A., Dreisinger, D.B., 1994. The ferric fluosilicate leaching of
lead concentrates. I. Kinetic studies. Metallurgical and Materials
Transactions. B, Process Metallurgy and Materials Processing
Science 25, 473480.
Cornell, R.M., Schindler, P.W., 1987. Photochemical dissolution of goe-
thite in acid/oxalate solutions. Clays and Clay Minerals 35, 347352.
Drever, J.I., Stillings, L.L., 1997. The role of organic acids in mineral
weathering. Colloids and Surfaces. A, Physicochemical and
Engineering Aspects 120, 167181.
Dutrizac, J.E., 1986. The dissolution of galena in ferric chloride media.
Metallurgical Transactions. B, Process Metallurgy 17, 517.
Dutrizac, J.E., 1989. The leaching of galena in cupric chloride media.
Metallurgical Transactions. B, Process Metallurgy 20, 475483.
Evans, D.J.I., Masters, I.M., 1976. Treatment of lead sulphide bearing
material. United States Patent No 3,933,973.
Fuerstenau, M.C., Nebo, C., Elango, B.V., Han, K.N., 1987. The kinetics
of leaching galena with ferric nitrate. Metallurgical Transactions. B,
Process Metallurgy 18, 2530.
Geisler, R.A., Puddington, I.E., 1996. Treatment of lead sulphide
bearing minerals. United States Patent No 5,523,066.
Gerson, A.R., ODea, A.R., 2003. A quantum chemical investigation
of the oxidation and dissolution mechanisms of galena. Geochi-
mica et Cosmochimica Acta 67, 813822.
Giordano, T.H., 1989. Anglesite (PbSO4) solubility in acetate
solutions: the determination of stability constants for lead acetate
complexes to 85C. Geochimica et Cosmochimica Acta 53,
359366.
Goyne, K.W., Brantley, S.L., Chorover, J., 2006. Effects of organic
acids and dissolved oxygen on apatite and chalcopyrite dissolu-
tion: implications for using elements as organo-markers and oxy-
markers. Chemical Geology 234, 2845.
Greet, C., Smart, R.St.C., 2002. Diagnostic leaching of galena and its
oxidation products with EDTA. Minerals Engineering 15, 515522.
Habashi, F., 1999. Kinetics of Metallurgical Processes, 2nd edition.
Metallurgies Extractive Quebec, Quebec, Canada.
Hsieh, Y.H., Huang, C.P., 1989. The dissolution of PbS(s) in dilute
aqueous solutions. Journal of Colloid and Interface Science. 131,
537549.
Jennings, S.R., Dollhopf, D.J., Inskeep, W.P., 2000. Acid production
from sulfide minerals using hydrogen peroxide weathering. Applied
Geochemistry 15, 235243.
Krauskopf, K.B., Bird, D.K., 1994. Introduction to Geochemistry, 3rd
edition. McGraw-Hill International Editions, New York, USA.
Nunez, C., Espiell, F., Garcia-Zayas, J., 1988. Kinetics of non-
oxidative leaching of galena in perchloric, hydrobromic, and
hydrochloric acid solutions. Metallurgical Transactions. B, Process
Metallurgy 19, 541546.
Panias, D., Taxiarchou, M., Paspaliaris, I., Kontopoulos, A., 1996.
Mechanisms of dissolution of iron oxides in aqueous oxalic acid
solutions. Hydrometallurgy 42, 257265.
Parida, K.M., Das, J., Data, P., 1997. Application of statistical design of
experiments in the study of dissolution of goethite (-FeOOH) in
hydrochloric acid in the presence of ascorbic acid. Hydrometallurgy
46, 271275.
 S. Aydoan et al. / Hydrometallurgy 89 (2007) 189195
Taxiarchou, M., Panias, D., Paspaliaris, I., Douni, I., Kontopoulos, A.,
1997. Removal of iron from silica sand by leaching with oxalic acid.
Hydrometallurgy 46, 215227.
Ubaldini, S., Piga, L., Fornari, P., Massida, R., 1996. Removal of iron
from quartz sands: a study by column leaching using a complete
factorial design. Hydrometallurgy 40, 369379.
Waite, T.D., Morel, F.M.M., 1984. Photo-reduction dissolution of
colloidal iron oxide: effect of citrate. Journal of Colloid and Interface
Science 102, 121137.
195
Wittstock, G., Kartio, I., Hirsch, D., Kunze, S., Szargan, R., 1996.
Oxidation of galena in acetate buffer investigated by Atomic Force
Microscopy and Photoelectron Spectroscopy. Langmuir 12,
57095721.
Zhang, H., Bloom, P.R., 1999. Dissolution of hornblende in organic acid
solutions. Soil Science Society of America Journal 63, 815822.