Electrochemistry Communications 8 (2006) 1661–1664

www.elsevier.com/locate/elecom

An in situ chronoamperometry/synchrotron radiation grazing

incidence X-ray diffraction study of the electrochemical oxidation
of pyrite in chloride media
a,*
Roland De Marco , Stuart Bailey b, Zhong-Tao Jiang a, Jono Morton a, Ryan Chester a

a
Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology, GPO Box U 1987, Perth, WA 6845, Australia
b
Western Australian Corrosion Research Group, Department of Applied Chemistry, Curtin University of Technology,
GPO Box U 1987, Perth, WA 6845, Australia

Received 12 July 2006; accepted 24 July 2006

Available online 28 August 2006

Abstract

The influence of chloride on the electrochemical oxidation of pyrite has been studied using a combination of chronoamperometry
(CA) and in situ synchrotron radiation grazing incidence X-ray diffraction (SR-GIXRD). The SR-GIXRD data revealed that the elec-
trochemical oxidation of pyrite at 0.4 V vs. a psuedo stainless steel reference electrode induced the formation of crystalline FeSO4,
Fe(OH)SO4 Æ 2H2O and Fe(OH)2 with an almost total extinction of the underlying pyrite. Similar patterns of oxidation were observed
at 0.5 and 0.6 V vs. a pseudo stainless steel reference electrode; however, there was little or no oxidation products evident at 0.7 and 0.8 V
vs. a pseudo stainless steel reference electrode. Significantly, in all cases, there was a significant build up in the quantity of amorphous
reaction products, as evidenced by an elevation in intensity of the amorphous bump at low 2-theta, and this observation was supported
by the visual appearance of the oxidised electrode at 0.7 and 0.8 V vs the pseudo stainless steel reference electrode which showed a ‘‘fools
gold’’ appearance. These CA/SR-GIXRD outcomes suggest that oxidation of pyrite in chloride media under alkaline conditions may
mildly passivate the electrode, and this may have important ramifications for the processing of pyritic ores in the hydrometallurgical
industry.
Ó 2006 Elsevier B.V. All rights reserved.

Keywords: Electrochemical oxidation; Chronoamperometry; Pyrite; Synchrotron radiation grazing incidence X-ray diffraction

1. Introduction A common mineral sulfide in gold and base metal con-

In the processing of refractory gold and base metal ores,
it is common to subject the concentrate to an oxidative
pressure acid leach (PAL) prior to metal ion collection
[1–4], with the primary purpose of the oxidative leach being
to destroy and oxidise any encapsulating mineral sulfides
that otherwise reduce the metal ion recovery during the col-
lection stage.
*
Corresponding author. Tel.: +61 8 9266 7265; fax: +61 8 9266 2300.
E-mail address: r.demarco@exchange.curtin.edu.au (R.D. Marco).
centrates is pyrite or FeS2, and the waters often employed
in the pulping with PAL come from groundwater sources
close to the mine site, which are saline. Accordingly, this
study has focussed on the oxidation of FeS2 in saline media
under these conditions with a view to gleaning important
mechanistic information about the oxidation of FeS2 under
gold processing conditions.
The aqueous electrochemistry of FeS2 in a variety of
acids (viz., H2SO4 [5–7], HClO4 [8–10], HCl [11,12] and
HNO3 [6,13]) is very well known, and a range of oxidation
intermediates such as SO2 2
4 , S2 O3 and S were implicated in
the reaction mechanism.

1388-2481/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2006.07.036
1662 R.D. Marco et al. / Electrochemistry Communications 8 (2006) 1661–1664
A previous in situ Raman spectro electrochemical study
of the electrochemical oxidation of pyrite in acidic media
comprising chloride [14] confirmed the presence of S,
HSO 2
4 and SO4 as products of the oxidation of FeS2.
Previous work [15–20] has demonstrated the power of
the surface analysis technique of grazing incidence X-ray
diffraction (GIXRD) in studies of the in situ surface chem-
istry of solid–liquid interfaces. Significantly, a marriage of
the GIXRD structural chemistry technique with an elec-
trode kinetic method such as cyclic voltammetry (CV),
amperometry, potentiometry, etc. [15–20] provides a pow-
erful research tool for elucidation of the mechanistic chem-
istry of electrochemical surfaces and interfaces.
In situ GIXRD measurements may be undertaken using
a laboratory-based diffractometer [15–17]; however, the
quality of data is inferior due to attenuation of the incident
X-ray beam by the liquid in the experimental cell. Clearly,
the use of high brilliance synchrotron radiation (SR)
enhances substantially the signal-to-noise ratio of the
in situ SR-GIXRD technique [18–20].
Although there have been several in situ GIXRD studies
of the electrochemical oxidation or reduction of electrode
surfaces [15,16,21,22], this research has primarily focussed
on model systems such as the electrochemical oxidation
of single crystals of silver [15,16], or the underlayer deposi-
tion of Cu onto single crystal gold [21,22].
In this study, we study for the very first time the elec-
trochemical oxidation of a technologically important
material (i.e., FeS2) using a specially developed in situ
CA/SR-GIXRD technique to elucidate the mechanistic
chemistry of oxidation of FeS2 in the presence of chloride,
with a view to providing a reaction model that is pertinent
to the hydrometallurgical processing of gold and base
metal ores.
2. Experimental
This in situ CA/SR-GIXRD study of the pyrite electrode
was performed on Beamline 20B at the Photon Factory in
Tsukuba Japan using the ‘‘BIGDIFF’’ diffractometer and
an in situ electrochemical cell that has been described else-
where [18–20]. This instrument employs a Si(1 1 1) channel
cut monochromator set at a wavelength of 1.000 Å, and
parallel beam optics which provided an incident beam with
dimensions that are 100 lm and 2 mm in the vertical and
horizontal directions, respectively. SR-GIXRD patterns
were recorded using Fuji imaging plates for a data collec-
tion time of 20 min, at an angle of incidence of 0.6°. Under
these conditions, total external reflection of the incident X-
ray beam occurs, and the technique is surface sensitive.
A specially designed Perspex flow-cell [18–20] – also
incorporating a 20 lm thick film of an X-ray transparent
Kapton window-was attached to the goniometer head of
the diffractometer at Beamline 20B. The flow-cell was con-
nected to a recirculating electrolyte reservoir containing
0.1 M NaCl in 0.01 M NaHCO3/0.01 M Na2CO3 adjusted
to pH 10.5 (representative of the cyanide leaching solu-
tion), which was run at a pump speed of 55 revolutions
per minute using a Masterflex peristaltic pump. The stain-
less steel inlet and outlet pump tubing connectors of the
cell were made the counter and pseudo reference elec-
trodes, and these along with the working electrode were
connected to a Princeton Applied Research PARSTAT
2263 portable potentiostat. It must be noted that the elec-
trolyte was pumped into the cell during the chronoampe-
rometry and/or cyclic voltammetry experiments, so as to
enable expansion of the electrolyte thickness to several mil-
limetres beneath the flexible Kapton window, and the elec-
trolyte distance to the counter and reference electrodes was
minimized by using the inlet and outlet pumping connec-
tors, thereby minimizing the solution resistance and allow-
ing potentiostatic control of the cell; however, this thick
layer of electrolyte totally obscured the synchrotron beam,
necessitating the use of a stop-flow method during the col-
lection of SR-GIXRD patterns. Importantly, a cessation
of the peristaltic pump caused a slight reduction in the
pressure within the cell, and this caused a slight suctioning
of the electrolyte, thereby minimizing the electrolyte thick-
ness to a few microns and the concomitant attenuation of
the X-ray beam by the electrolyte. Clearly, a cyclic voltam-
mogram of the pyrite electrode (not shown), albeit exhibit-
ing systematic oscillations due to pulsations from the
peristaltic pump, was fortuitously similar to the one
observed in a previously recorded voltammogram for a
pyrite electrode against a saturated calomel electrode
[14], both in terms of the currents and potentials, and this
allowed the measurement of very similar chronoampero-
grams compared to those obtained in the previous study
(again, apart from the oscillations ascribed to pump pulsa-
tions). Chronoamperometry experimental control and data
acquisition were performed using a personal computer
running the Power Step software, and chronoampero-
grams were collected at the nominal applied potential over
a period of several minutes, with intermittent interruption
and measurement of the corresponding SR-GIXRD
patterns.
3. Results and discussion
A previous in situ chronoamperometry/Raman spectros-
copy study [14] on the electrochemical oxidation of pyrite
in the presence of chloride under acidic conditions revealed
the formation of copious amounts of elemental sulfur.
Notably, as amorphous phases of iron oxide and iron
hydroxide are poor Raman scatterers, it is possible that
these phases formed, but were undetectable using in situ
Raman spectroscopy.
Figs. 1 and 2 present the SR-GIXRD diffraction pat-
terns for a freshly polished pyrite electrode as a function
of electrode polarization at 0.5 and 0.8 V, respectively, as
well as an overlay of the typical diffraction patterns
observed at 0.4, 0.6 and 0.7 V, respectively (see Fig. 3). A
few observations are clearly evident: (1) there is a general
build-up in the intensity of the amorphous hump at 2h
 R.D. Marco et al. / Electrochemistry Communications 8 (2006) 1661–1664 1663

60000 V 0.4
V 0.6
V 0.7
50000

40000

Intensity
30000

20000

10000
18 28 38 48 58 68
2-theta / degrees

Fig. 1. A 3D stack of in situ SR-GIXRD data for a pyrite electrode
subjected to chronoamperometry at 0.5 V (versus a stainless steel pseudo
reference electrode) in 0.1 M NaCl and 0.01 M NaHCO3/0.01 M Na2CO3
adjusted to pH 10.5. Note, the SR-GIXRD diffraction patterns were
collected at a = 0.6° and k = 1.000 Å.
Fig. 3. An overlay of SR-GIXRD diffraction patterns for a pyrite
electrode subjected to chronoamperometry at 0.4, 0.6 and 0.7 V (versus a
stainless steel pseudo reference electrode) in 0.1 M NaCl and 0.01 M
NaHCO3/0.01 M Na2CO3 adjusted to pH 10.5. Note, the SR-GIXRD
diffraction patterns were collected at a = 0.6° and k = 1.000 Å, and the
following phase assignments: (1) = FeSO4; (2) = Fe(OH)SO4 Æ 2H2O;
(3) = Fe(OH)2; (4) = FeS2.

cipitation rate for iron–hydroxide–sulfate phases, and these

phases are accordingly crystalline, while the higher overpo-
tentials (i.e., 0.6, 0.7 and 0.8 V) are inducing such high rates
of oxidation and nucleation in the pyrite oxidation reaction
that the products are non-crystalline and undetectable by
SR-GIXRD.
According to a previous in situ Raman experiment [14],
the SR-GIXRD electrochemical oxidation reaction results
can be explained by the following reactions, viz.

FeS2ðsÞ ! Fe3þ
ðsaÞ þ 2SðsÞ þ 3e ð1Þ
FeS2ðsÞ þ 16OH
ðaqÞ ! Fe3þ
ðsaÞ þ 2SO2
4 ðaqÞ þ 8H2 OðlÞ þ 15e
ð2Þ
FeS2ðsÞ þ 16OH
ðaqÞ ! Fe2þ
ðsaÞ þ 2SO2
4 ðaqÞ þ 8H2 OðlÞ þ 14e
ð3Þ
Fig. 2. A 3D stack of in situ SR-GIXRD data for a pyrite electrode
subjected to chronoamperometry at 0.8 V (versus a stainless steel pseudo In alkali aqueous media, it is very likely that hydroxide
reference electrode) in 0.1 M NaCl and 0.01 M NaHCO3/0.01 M Na2CO3 ions react with released Fe2+ and Fe3+ along with sulfate
adjusted to pH 10.5. Note, the SR-GIXRD diffraction patterns were
to produce the observed oxidation products, viz., FeSO4,
collected at a = 0.6° and k = 1.000 Å.
Fe(OH)SO4 Æ 2H2O and Fe(OH)2. The elemental sulfur
product detected previously in in situ Raman studies [14]
is either an instrumental artefact due to photo-oxidation
angles between 15° and 30°, particularly at the higher of FeS2 to Fe2+ and/or Fe3+ and S by the UV laser of
applied potential of 0.8 V; (2) the electrochemical oxidation the Raman spectrometer, or it is non-crystalline and
products (viz., FeSO4 at 2h angles of 22.1 and 37.0°, as well avoided detection by SR-GIXRD. Note, the visual ‘‘fools
as Fe(OH)SO4 Æ 2H2O at 2h angles of 22.1, 35.4 and 37.0°, gold’’ appearance of the oxidised pyrite surface became
and Fe(OH)2 at 2h angles of 23.8, 24.0, 35.4, 38.4 and 57.0 more prominent as a function of oxidation potential, and
are prevalent at 0.4 and 0.5 V; (3) unreacted pyrite peaks at this is most likely ascribed to non-crystalline iron-oxide/
2h angles of 21.2, 37.2, 39.0, 47.5, 51.0, 53.5 and 68.8 are iron-hydroxide phases that avoided detection by SR-
prevalent at 0.7 V; (4) the oxidised pyrite electrode at GIXRD.
0.8 V is almost totally devoid of any crystalline phases. In summary, these CA/SR-GIXRD outcomes demon-
Clearly, the electrochemical oxidation reactions at low strate that oxidation of FeS2 in the presence of chloride
overpotentials (i.e., 0.4 and 0.5 V) are inducing a slow pre- under alkaline conditions encapsulates the pyrite surface
1664 R.D. Marco et al. / Electrochemistry Communications 8 (2006) 1661–1664
in oxidation products of iron-hydroxide-sulfate phases,
and this might passivate the pyrite surface.
4. Conclusions
The results of this study demonstrate the power of in situ
CA/SR-GIXRD as a research tool for the elucidation of
the oxidation chemistry of technologically important mate-
rials such as FeS2.
In this study, in situ CA/SR-GIXRD has shown that the
surface is encapsulated by a scale of FeSO4, Fe(OH)-
SO4 Æ 2 H2O and Fe(OH)2. Accordingly, it is possible that
the groundwater used in the hydrometallurgical processing
of gold and base metal concentrates may passivate the pyr-
ite, and this may call for the use of additives to prevent the
formation of these detrimental phases (e.g., iron complex-
ing agents such as Tiron).
Acknowledgements
The SR-GIXRD work was performed at the Australian
National Beamline Facility (ANBF) with support from the
Australian Synchrotron Research Program, which is
funded by the Commonwealth of Australia under the Ma-
jor National Research Facilities Program. We also thank
Drs. Garry Foran and James Hester at the ANBF for sup-
port on the SR-GIXRD work. One of us (Mr. Ryan Chet-
ser) is grateful to Curtin University for a University
Postgraduate Scholarship, while Mr. Jono Morton
acknowledges the support of the Australian Research
Council for an Australian Postgraduate Award Industry
scholarship.
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