Minerals Engineering 18 (2005) 855–865

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A review of pyrrhotite flotation chemistry in the processing

of PGM ores
a,*
J.D. Miller , J. Li a, J.C. Davidtz b, F. Vos b

a
Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT 84112, USA
b
Department of Materials Science and Metallurgical Engineering, University of Pretoria, Pretoria 0002, South Africa

Received 20 January 2005; accepted 26 February 2005

Abstract

The chemistry of pyrrhotite flotation using xanthate collectors is reviewed with respect to the processing of PGM ores and the
recent results from captive bubble contact angle measurements at the University of Utah are presented. In some cases a low flotation
recovery of PGM may be due to the surface state of pyrrhotite particles under conventional flotation conditions (open to air and pH
9.0).
Thermodynamically pyrrhotite is not stable and reacts relatively quickly with its environment. Natural/collectorless flotation of
pyrrhotite is observed only under a low oxidation potential in acidic solution. Its surface is easily oxidized to ferric hydroxide/oxide
under conventional flotation conditions, creating a hydrophilic state at the pyrrhotite surface and low flotation recovery even
though xanthate collectors can be adsorbed. Under these conditions, activation by copper is not easily achieved. These observations
reported in the literature have been confirmed by captive bubble contact angle measurements. Based on the analysis of previous
research, conditions for improved pyrrhotite flotation and increased PGM recovery are suggested.

2005 Published by Elsevier Ltd.

Keywords: Pyrrhotite; PGM; Flotation; Xanthate; Oxidation; Activation

1. Introduction the processing PGM ores from the Bushveld Complex in

Pyrrhotite is one of the most abundant iron sulfide
minerals. It is found in nature to be commonly associ-
ated with pentlandite, quartz, ankerite (CaFe(CO3)2),
pyrite, chalcopyrite, and other sulfide minerals. In many
flotation plants, pyrrhotite is rejected to the flotation
tailings as a waste product such as in the case of Cu–
Ni ores and massive nickel ores (Fornasiero et al.,
1995; Bozkurt et al., 1998; Chanturiya et al., in press;
Khan and Kelebek, 2004). However, a strong interest
in pyrrhotite recovery arises in certain instances. Specif-
ically, the importance of pyrrhotite flotation is evident in
*
Corresponding author. Tel.: +1 801 581 5160; fax: +1 801 581
4937.
E-mail address: jdmiller@mines.utah.edu (J.D. Miller).
South Africa.
The Bushveld complex is the worldÕs largest source of
platinum group minerals (PGMÕs). Within this deposit,
two important horizons occur known as the Merensky
reef and the UG2 reef which contain the valuable
PGM minerals. The PGMs are mainly associated with
base metal sulfides and to a lesser extent with oxides
and silicate minerals. Typically the PGM ore contains
about 1% base metal sulfide minerals. The nature of
the PGM association determines the overall flotation
efficiency.
There are three primary base metal sulfides in the
Merensky and UG2 reefs, namely pentlandite ((Fe,
Ni)9S8), chalcopyrite (CuFeS2), pyrrhotite (Fe1
xS),
with lesser amounts of pyrite (FeS2). The main sulfide
mineral in the Merensky reef is found to be pyrrhotite,

0892-6875/$ - see front matter
2005 Published by Elsevier Ltd.

doi:10.1016/j.mineng.2005.02.011
856 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865

and consequently it is important to achieve high pyrrho- hydroxide (Smart et al., 2003; Buckley and Woods,
tite recoveries during flotation. 1985; Heyes and Trahar, 1984):
In general, under conventional flotation conditions
Fe1
x S þ ð7
3xÞH2 O ¼ ð1
xÞFeðOHÞ3 þ SO2

4
open to air at pH 9.0, good chalcopyrite and pentlandite
recoveries are obtained with thiol collectors. However, þ ð11
3xÞHþ þ ð9 þ 3xÞe

pyrrhotite recoveries are not always satisfactory even ð3Þ
under conditions where xanthate adsorption is expected
Under these conditions, the natural flotation of pyrrho-
to take place (Buswell et al., 2002a). This may be due to
tite does not occur.
the fact that significant pyrrhotite oxidation occurs dur-
Recently at the University of Utah (2004), the natural
ing milling and the fact that pyrrhotite is a very poor
hydrophobicity of pyrrhotite (provided by the Geology
catalyst for oxygen reduction as may be required for
Curator, College of Mines and Earth Sciences, Univer-
the electrochemical adsorption of xanthate (Buswell
sity of Utah; Pyrrhotite content >95%, unknown source)
and Nicol, 2002b).
was examined in air from pH 3.0 to pH 9.2 based on
With more and more attention being given to pyrrho-
captive bubble contact angle measurements. The results
tite flotation in order to improve PGM recovery (Gathje
in Fig. 1 demonstrate that the pyrrhotite surface has a
and Simmons, 2004), a review of the flotation chemistry
strong hydrophilic state at pH values above pH 4.5 (con-
literature is presented together with some recent contact
tact angle 0). When the pH is less than pH 4.5, the nat-
angle measurements.
ural hydrophobicity of pyrrhotite increases with a
decrease in pH, having a contact angle of 51 at pH
3.0. These experimental results further confirm the flota-
2. Natural or collectorless flotation tion results reported by other investigators. It is evident
that a hydrophilic surface state is stabilized at pH >4.5
The natural floatability of pyrrhotite was investigated under an air atmosphere and room temperature.
by Hodgson and Agar (1984). These researchers sug- Further, pyrrhotite is thermodynamically unstable in
gested that a stable intermediate surface state, acidic solutions (pH  4.5) without consideration of oxi-
Fe(OH)S2, formed in acidic solution for short condition- dation. Theoretical solution chemistry calculation
ing times and at low oxidation potential of 0–200 mV regarding pyrrhotite stability by formation of H2S sug-
(SHE) accounting for the natural hydrophobicity ob- gests that H2S should evolve (1 atm total pressure) un-
served under certain conditions. However, extensive oxi- der an assumption of a ferrous ion activity of 10
4
dation during long conditioning times was found to lead (M) at pH 6 7 and determined by Fe(OH)2 solubility
to poor flotation. At the same time, it was reported by product at pH P 8. Thus, it is expected that such a reac-
Heyes and Trahar (1984) that pyrrhotite displays self- tion at the pyrrhotite surface may account for the natu-
induced flotation as a result of mild oxidation. Peters ral hydrophobicity in the absence of collector as
(1977) pointed out that pyrrhotite-collectorless flotation observed below pH 5 (see Fig. 1). Although the rate of
results from elemental sulfur formation at the mineral
surface since sulfur is strongly hydrophobic and may re-
main stable for a long time, even in alkaline solutions.
Similar research (Hamilton and Woods, 1981, 1983;
Heyes and Trahar, 1984; Buckley and Woods, 1985;
Jones et al., 1992) regarding the natural hydrophobicity
of pyrrhotite attributed its collectorless flotation to the
formation of iron-deficient/sulfur-rich metastable inter-
mediates at relatively low pH and under mild oxidation
potentials, which condition may be described by the fol-
lowing reactions:
Fe1
x S þ 3yOH
¼ Fe1
ðxþyÞ S þ yFeðOHÞ3 þ 3ye
ð1Þ
and

Fe1
x S þ 3ð1
xÞH2 O ¼ ð1
xÞFeðOHÞ3 þ S

þ 3ð1
xÞHþ þ 3ð1
xÞe

ð2Þ
However, pyrrhotite surfaces are oxidized rapidly upon
exposure to air, and with an increase in oxidation time
the surfaces are covered by an overlay of iron(III)
Fig. 1. Contact angle at pyrrhotite surface as a function of pH at
ambient temperature in 0.05 M Na2SO4 solution and in the absence of
collector (University of Utah, 2004).
 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
this reaction has been reported to involve a significant
induction period, additional research is warranted.
3. Flotation with thiocarbonate collectors
Thiocarbonates, particularly xanthates, are widely
used as collectors for selective and bulk flotation of sul-
fide minerals from PGM ores. It has been found that
PGM recovery in bulk flotation is limited in some in-
stances by the poor flotation response of pyrrhotite.
With more and more attention being given to pyrrhotite
recovery, the use of thiocarbonate collectors has been
examined in order to identify conditions for increased
recovery.
3.1. Ethyl xanthate
Montalti (1994) systematically investigated pyrrhotite
floatability using ethyl xanthate. The pyrrhotite sample
was from North Bend, Washington and was analyzed
by XRD to be only one phase b-Fe1
xS (Fe 47.0%
and S 32.6%) having hexagonal crystal structure with
some impurities (C 1.45% and Zn 4.64%). The zeta po-
tential of this pyrrhotite sample was measured under se-
lected conditions and the results are presented in Fig. 2.
The results show that the point of zero charge (PZC)
for this pyrrhotite mineral (sample 2 g/l, KNO3
2 · 10
3 mol/l) is around pH 6.5 and that the electroki-
netic response is not significantly affected by the pres-
ence of ethyl xanthate at low concentration. These
results might be expected if the surface is oxidized and
Fe(OH)3 is stabilized at the pyrrhotite surface since
Fe(OH)3 has a PZC of about pH 6.5.
Fig. 2. Zeta potential–pH plot for pyrrhotite in the presence of differ-
ent concentrations of ethyl xanthate of 0 mol/l (s), 5.0 · 10
4 mol/l
(m), 1.0 · 10
3 mol/l (h), [FeS] = 2.0 g/l in 2 · 10
3 mol/l KNO3
(Montalti, 1994).
857
100
90
pH 5.5
80
pH 7.0
70
Flotation Recocery (%)
60
50 pH 9.0
40
30
20
10
0
0 1 2 3 4 5 6
Ethyl Xanthate Concentration (M)
Fig. 3. Flotation recovery of pyrrhotite (conditioned 30 min) con-
tacted with various concentrations of ethyl xanthate for 15 min at pH
5.5 (s), pH 7.0 (m), and pH 9 (h), [FeS] = 3.3 g/l in 2 · 10
3 mol/l
KNO3 (Montalti, 1994).
In this study by Montalti, the effects of pH, ethyl
xanthate concentration, and collector reaction time, on
flotation recovery were determined. It can be seen
from Fig. 3 that the influence of pH and collector con-
centration is significant. The flotation recovery at
1 · 10
4 mol/l ethyl xanthate significantly increases
from 50% to 82% with a pH decrease from pH 9.0 to
pH 5.5. When the collector concentration is above
1 · 10
4 mol/l, the flotation recovery was found to be
insensitive to variations in concentration. For these
experiments, the conditioning time was 30 min, and
the reaction time for collector adsorption was 15 min.
The influence of ethyl xanthate adsorption time on
flotation recovery for different ethyl xanthate concentra-
tions was examined and the flotation recovery was
found to reach a maximum at 15 min. Of course, the ex-
tent of recovery is dependent on pH. A maximum flota-
tion recovery of 90% at pH 5.5 was achieved with an
initial concentration of 5 · 10
4 mol/l ethyl xanthate.
3.2. Butyl xanthate
Sodium n-butyl xanthate (1 · 10
4 mol/l) was used to
investigate the flotation selectivity between pentlandite
and pyrrhotite at pH 9.0 to 9.5 under potential control
(Khan and Kelebek, 2004). The results are shown in
Fig. 4. The samples employed in these tests originated
from process streams consisting mainly of pyrrhotite–
pentlandite middlings processed in a nickel–copper
plant in the Sudbury region of Canada. The middlings
were first reground in order to liberate pentlandite from
pyrrhotite using mild steel grinding media in the pH
range of 9.0–9.5 (nitrogen atmosphere). The case for
858 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
80 Potential Controlled:
-0.095 to - 0.005 V/SHE
70
Pentlandite Recovery %
60
50
40 Potential Uncontrolled:
0.25 to 0.30 V/SHE
30
20
10
0
0 10 20 30 40 50
Pyrrhotite Recovery %
Fig. 4. Flotation selectivity between pentlandite and pyrrhotite at pH
9.0 to 9.5; potential controlled:
0.095 to
000.5 V (SHE), potential
uncontrolled: 0.25–0.3 V (SHE); sodium isobutyl xanthate 1 · 10
4 M
(Khan and Kelebek, 2004).
potential control refers to a condition whereby the po-
tential of the pulp was initially kept at relatively low lev-
els (
0.095 to
0.055 V/SHE) by sparging nitrogen and
then at about
0.005 to 0 V/SHE for subsequent stages.
In the case of uncontrolled potential, the potential dur-
ing flotation with air continuously increased up to a
level 0.25–0.3 V as in usual practice.
Fig. 4 demonstrates that under potential control the
selective flotation of pentlandite from pyrrhotite oc-
curs with sodium n-butyl xanthate. For uncontrolled
potential less flotation selectivity was observed. These
results suggest that the relatively high potential (open
to air during conditioning) favors pyrrhotite flota-
tion in the system studied. A similar phenomenon
was observed in AlekseevaÕs research (1965), in which
the surface oxidation did not apparently depress
pyrrhotite flotation. In the presence of xanthate, using
high levels of aeration, flotation recoveries of pyrrho-
tite were improved as compared to low levels of
aeration.
The floatability of pyrrhotite has recently been
considered from contact angle measurements at the Uni-
versity of Utah (2004) using sodium isobutyl xanthate
(SIBX) as collector for solution pH values from pH
4.5 to 9.2. During these measurements, the system was
open to air. Fig. 5 suggests that the addition of collector
improves the hydrophobicity when compared with that
in the absence of collector, but the improvement de-
pends on the system pH. When the pH is above pH 5
the hydrophobicity of the pyrrhotite surface is relatively
low (contact angle 30) and not very sensitive to vari-
ation in collector concentration. At pH 4.5, the contact
angle increases greatly from 30 to 84 with the addition
of collector (1 · 10
4 M).
60 70 80
Fig. 5. Contact angle at pyrrhotite surface as a function of pH in the
absence/presence of SIBX at ambient temperature and 0.05 M Na2SO4
(University of Utah).
Even though most researchers claim that mild oxida-
tion and/or low oxidation potential favors natural and/
or collector flotation of pyrrhotite, it was reported (Rao
and Finch, 1991; Hodgson and Agar, 1991) that under a
nitrogen atmosphere pyrrhotite flotation with addition
of xanthate is not possible. In some cases, when xan-
thate is not oxidized to dixanthogen, the collector
adsorption density and degree of hydrophobicity may
be reduced.
4. Activation
In order to improve recovery in the xanthate flotation
of sulfide minerals, copper, lead, silver, and other metal
ions can be used as activators. Chang et al. (1954) con-
ducted a detailed experimental investigation of the acti-
vation and flotation of pyrrhotite with xanthates and
copper sulfate at pH 5.1. It was found that copper sul-
fate significantly improves pyrrhotite recovery. In these
experiments, the cupric ions directly exchange with fer-
rous ions at the pyrrhotite surface, the activated state
accounting for the improved flotation of pyrrhotite:
Cu2þ þ FeS ¼ CuS þ Fe2þ ð4Þ
The concentration of copper, iron, and sulfur during
activation of pyrrhotite was measured and the results
presented in Fig. 6 confirm the activation reaction given
in Eq. (4). Buswell and Nicol (2002b) electrochemically
measured the anodic decomposition rate of CuS at a
pyrrhotite surface. When the potential is above 0.4 V
(SHE), the anodic rate was found to become significant.
The standard equilibrium potential for CuS oxidation
was calculated to be 0.548 V (SHE). In the absence of
copper, one of the anodic reactions for pyrrhotite is
 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865 859

Fig. 6. Concentration of Fe, Cu, and S in solution during the reaction Fig. 7. Contact angle at pyrrhotite surface with and without copper
of pyrrhotite with copper sulfate solution at pH 5.1 (Chang et al., activation as a function of pH in the presence of SIBX (1 · 10
4 M) at
1954). ambient temperature and 0.05 M Na2SO4 (University of Utah, 2004).

found at a much lower potential of about 0.1 V (SHE).

Based on these results it seems that copper stabilizes the
pyrrhotite surface.
In contrast, the role and effectiveness of copper ions
for the activation of pyrrhotite in alkaline solutions is
not fully understood, and the conclusions are controver-
sial. Fundamental research (Nicol, 1984) demonstrated
that copper activation is not possible since copper is
essentially insoluble above pH 8 and thus not available
for reaction at the pyrrhotite surface. Furthermore, pyr-
rhotite particles are likely to be well oxidized and cov-
ered with ferric hydroxide/oxide, which may inhibit
any reaction with the underlying mineral surface. In
contrast, other studies (Kelebek et al., 1996; Leppinen,
1990; Senior et al., 1995) have shown that pyrrhotite
recoveries are significantly improved in alkaline solu-
tions with the addition of copper sulfate. Copper was
Fig. 8. Contact angle at pyrrhotite surface with and without lead
detected on concentrate particles from actual flotation
activation as a function of pH in the presence of SIBX (1 · 10
4 M) at
circuits operating at pH 9 (Yoon et al., 1995), indicating ambient temperature and 0.05 M Na2SO4 (University of Utah, 2004).
that pyrrhotite was effectively activated.
Recent experiments for activation of pyrrhotite by
cupric ions (sulfate) and lead(II) ions (nitrate) at an ini- 5. Other factors
tial concentration of 1 · 10
4 m sodium isobutyl xan-
thate in 0.05 M Na2SO4 have been carried out with In an actual flotation system, it is expected that the
contact angle measurements at the University of Utah situation becomes much more complicated since pyrrho-
(2004), Figs. 7 and 8. These results show that when tite particles coexist and/or are in contact with other
the pH is greater than pH 7 the presence of these metal minerals/materials. Under the various conditions, a pyr-
ions does not influence the contact angle at the pyrrho- rhotite particle may act as an anode or cathode, which
tite surface. When the pH is reduced to pH 5, these me- may lead to hydrophobic or hydrophilic surface states.
tal ions significantly increase the contact angle, from 28 From a review of the literature, there are such other fac-
to 84 for copper and from 28 to 51 to 73 for lead, tors influencing pyrrhotite floatability, including:
depending on concentration. It should be noted that Pyrrhotite-grinding media: the contact of pyrrhotite
copper activation is insensitive to concentration varia- with mild steel when being ground was found to have
tions under the conditions studied and that the contact a deleterious effect on its floatability (Admas et al.,
angle is greater than that obtained with lead activation. 1984). The reduced floatability was attributed to the
860 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
formation of an iron hydroxide coating on the pyrrho-
tite particles, which is not only hydrophilic, but also
inhibits xanthate adsorption.
Pyrrhotite–pyrite: when pyrrhotite particles are con-
tacted/associated with pyrite particles during flotation,
pyrrhotite recovery can be improved. This phenomenon
is attributed to a shift of oxygen reduction from sites on
pyrrhotite to pyrite, which consequently reduces iron
hydroxide formation on pyrrhotite and promotes its flo-
tation (Nakazawa and Iwasaki, 1985, 1986).
Pyrrhotite–chalcopyrite: similar to pyrite influence,
chalcopyrite acts as the cathode and pyrrhotite acts as
the anode. The presence of chalcopyrite accelerates the
oxidation reaction of xanthate on pyrrhotite (i.e. effec-
tive collector adsorption) and increases pyrrhotite float-
ability. At the same time, a lower floatability of
chalcopyrite was observed either due to iron hydroxide
formation on its surface (as a cathode for oxygen reduc-
tion) or to a shift of increased xanthate adsorption by
pyrrhotite. An XPS study confirmed that the increased
floatability of pyrrhotite is not due to activation of cop-
per ions but rather the absence of iron hydroxide on the
pyrrhotite surface (Cheng and Iwasaki, 1992, 1994).
6. Discussion
6.1. Pyrrhotite characteristics
Pyrrhotite, Fe1
xS, is nonstoichiometric and of vari-
able composition with a density which varies from
4.58 to 4.65. Accordingly, it has some unusual charac-
teristics. First, the amount of sulfur varies from 50 to
55 atoms of sulfur per 50 atoms of iron. That is, the x
value varies from 0 to 0.2 (when x = 0, the pyrrhotite
mineral is called troilite). Secondly, it has two symme-
tries for its crystal structure: when pyrrhotite is relatively
low in sulfur or x is close to 0, the mineral structure is
hexagonal or prismatic; when pyrrhotite is high in sulfur
its structure is monoclinic. Thirdly, pyrrhotite magne-
tism is very low when x is 0 (hexagonal) at 20 C, only
having a magnetic susceptibility of 1 · 10
5 e.m.u./g.
When x is close to 0.2 (monoclinic), its magnetism in-
creases to 13.1 e.m.u./g. So, next to magnetite, the sulfur
rich monoclinic pyrrhotite is the most common mag-
netic mineral. The bonding difference between troilite
and monoclinic pyrrhotite mineral samples has recently
been discussed based on XPS measurements (Skinner
et al., 2004).
In nature, pyrrhotite minerals occur with significant
variation in structure and/or composition. Generally, a
mixture of hexagonal (relatively iron-rich, h-Po) and
monoclinic (relatively sulfur-rich, m-Po) phases is pre-
dominant according to the literature. Arnold (1967)
made the analysis of 82 terrestrial pyrrhotite samples.
Seventy percents were a mixture of h-Po and m-Po,
10% contained hexagonal pyrrhotite only, and 9% con-
tained monoclinic pyrrhotite only. The remaining sam-
ples, 8% contained troilite, stoichiometric FeS.
6.2. Stability of pyrrhotite
Thermodynamically, pyrrhotite is not stable in aque-
ous solutions under conventional flotation conditions
(pH 9.0, open to the air atmosphere, and 25 C), which
is evident from the Eh–pH diagram in Fig. 9 (Garrels
and Christ, 1990). At low levels of dissolved sulfur and
iron pyrrhotite is stable between pH 7 and pH 9 at a po-
tential less than
0.35 V (SHE). It is expected that pyr-
rhotite is oxidized finally to hematite and sulfate under
conventional flotation conditions.
Kinetically, Montalti (1994) examined the dissolved
iron concentration from pyrrhotite, chalcopyrite, and
pyrite in a neutral solution (pH 6.9) with variation in
the oxidation potential as shown in Fig. 10. It is evident
that the rate and extent of iron release from pyrrhotite is
much greater than that from chalcopyrite and pyrite. It
was found that the rate of pyrrhotite dissolution at

200 mV (SHE) decreases with an increase in reaction
time and that the dissolution rate becomes quite slow
after 3 h. It is expected that a portion of the dissolved
iron precipitated from the solution as Fe(OH)3, covering
the sample surface, and contributing to the decrease in
dissolution rate.
Because of the variation of pyrrhotite in composition
and crystal structure, each pyrrhotite sample may have a
different nature, which is supported by the following re-
sults. Khan and Kelebek (2004) and Buswell and Nicol
(2002b) examined the kinetics of pyrrhotite decomposi-
tion by electrochemical measurements—cyclic voltam-
Fig. 9. Stability regions of iron oxides and sulfides in water at 25 C,
1 atm. with Sum S = 1 · 10
6 mol/l and Sum Fe = 1 · 10
6 mol/l
(Garrels and Christ, 1990).
 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
Fig. 10. Concentration of iron in solution (pH 6.9) as a function of
time for various sulfide minerals at several Eh: chalcopyrite Eh
+200 mV (s), pyrite +200 mV (n), pyrite Eh +0 mV (j), pyrite Eh

200 mV (d), pyrrhotite Eh
200 mV (h) (Montalti, 1994).
metry. KhanÕs results for a Sudbury pyrrhotite, as pre-
sented in Fig. 11, demonstrate that when the potential
is below 0.5 V (SHE) the initial rate of pyrrhotite oxida-
tion (anodic current density) is quite slow even though
there is a peak for the oxidation in the potential region
from
0.05 V to 0.18 V (SHE). The maximum current
density for this peak is 0.2 mA/cm2 at pH 9.2 and oxy-
gen concentration of 0.1 mg/l in the absence of collector.
This peak was attributed to the following anodic
reaction:
Fe1
x S þ 3yOH
¼ Fe1
ðxþyÞ S þ yFeðOHÞ3 þ 3ye

When the positive potential scan reaches 0.5 V (SHE), a
new anodic current peak appears and reaches its maxi-
Fig. 11. Cyclic voltammogram of FeS electrode at pH 9.2, a scan rate
10 mv/s, DO = 0.1 mg/l, X = 0.0 (Khan and Kelebek, 2004).
DO = dissolved oxygen, X = sodium n-butyl xanthate.
861
Fig. 12. Cyclic voltammograms for FeS electrode in deoxygenated
Na2B4O7 (0.05 M) solution at pH 9.3, a scan rate 20 mV/s (Buswell,
2002).
mum current density at 0.75 V (SHE). This anodic
process is considered to involve oxidation of pyrrhotite
to sulfate in addition to the formation of ferric
hydroxide:
Fe1
x S þ ð7
3xÞH2 O ¼ ð1
xÞFeðOHÞ3 þ SO2

4
þ ð11
3xÞHþ þ ð9 þ 3xÞe

ð3Þ
In contrast, the results from electrochemical measure-
ments (pH 9.3 and 0.05 M Na2B4O7) by Buswell and Ni-
col (2002b) show that pyrrhotite from an RSA mineral
dealer is much more active than the Sudbury pyrrhotite
sample used by Khan and Kelebek (2004), see Fig. 12.
These results suggest that when the potential exceeds
ð1Þ

0.4 V (SHE), the initial rate of pyrrhotite oxidation
(anodic current density) becomes significant. The anodic
current density varies from 1.0 to 2.0 mA/cm2 at a po-
tential 0–0.2 V (SHE).
6.3. Flotation response
It is evident that pyrrhotite is susceptible to oxidation
in aqueous solution, an important factor which influ-
ences its flotation recovery since the oxidation products
at particle surfaces inevitably influences surface hydro-
phobicity. The kinetics of pyrrhotite oxidation and the
oxidation products at the surface depend on:
(i) surface area of pyrrhotite;
(ii) oxidation potential/oxygen pressure;
(iii) solution pH;
(iv) temperature;
(v) time.
As a consequence all these factors will influence the
natural/collectorless flotation of pyrrhotite.
862 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
As shown in Figs. 9–12, pyrrhotite tends to be ther-
modynamically and kinetically unstable. It is generally
accepted that during the flotation process in acidic solu-
tion under low oxidation potentials, such as sparging
nitrogen, the surface products of pyrrhotite oxidation
are rich sulfur intermediates and/or elemental sulfur,
which accounts for the naturally hydrophobic pyrrhotite
surface. In alkaline solutions and under relatively high
oxidation potentials—open to the air atmosphere, the
surface is covered by ferric oxides and/or ferric hydrox-
ide, resulting in a hydrophilic surface state.
It is generally thought that thiocarbonate collectors
adsorb at sulfide mineral surface due to an electrochem-
ical reaction involving the formation of a dimer such as
shown by the following half cell reaction for the
dixanthogen formation:
2ROCðSÞS
¼ ROCðSÞS–SðSÞCOR þ 2e

The standard potential of the xanthate/dixanthogen pair
in reaction (5) was reported to be
0.128 V/SHE and

0.06 V/SHE (Buswell et al., 2002a; Buswell and Nicol,
2002b; Winter and Woods, 1973). Of course, the stan-
dard potential depends on the length of the hydrocarbon
chain of the collector molecule (Plessis, 2004). Such a
reaction is expected at the pyrrhotite surface coupled
with reduction of oxygen:
1=2 O2 þ H2 O þ 2e
¼ 2OH

For the pyrrhotite–xanthate system under practical flo-
tation conditions, the pyrrhotite surface can be oxidized
to hydroxides and/or oxides which inhibit pyrrhotite flo-
tation. However, in some cases, the pyrrhotite was
found to be floatable. Thus, Khan and Kelebek (2004)
suggested that xanthate can form thermodynamically
stable Fe(II)/Fe(III) hydroxyl xanthates in alkaline solu-
tions at potentials lower than the stability domain of
dixanthogen (Harris and Finkelstein, 1975; Wang
et al., 1989). During the initial stage of adsorption, xan-
thate electrostatically interacts with ferrous ion on the
surface.
þ þ
Po½FeðOHÞ þ X
! Po½FeðOHÞ X
! Po½FeðOHÞX
This species is considered to be metastable and has a
low level of hydrophobicity, but it is considered to be a
favorable site to accommodate more xanthate and/or
dixanthogen. More stable iron compounds can follow:
Po½FeðOHÞX þ OH
! Po½FeðOHÞ2 X þ e

Further adsorption of xanthate can lead to dixantho-
gen formation:
Po½FeðOHÞ2 X þ X
! Po½FeðOHÞ2 X–X þ e

Po½FeðOHÞ2 X–X þ X
! Po½FeðOHÞ2 X–X2  þ e

ð10Þ
Bozkurt et al. (1998) examined the IR spectra of pyrrho-
tite with isobutyl xanthate adsorption (1 · 10
5 M, 9.2)
(see Fig. 13). The bands in the spectra are well defined at
1265, 1048, and 1026 cm
1, which are characteristic of
coupled S–C–S and C–O–C stretching vibrations in dix-
anthogen. These results are similar to those reported by
Leppinen et al. (1989), Leppinen (1990), and Valli and
Persson (1994). It appears from Fig. 13 that the adsorp-
tion density of dixanthogen at the pyrrhotite surface is a
little greater for pyrrhotite alone (A) than for the pyr-
rhotite in direct contact with pentlandite (C). Additional
studies by Rao and Finch (1991) established that the to-
tal xanthate adsorption was slightly greater in the pres-
ence of air than with nitrogen. At the same time, the
amount of adsorbed dixanthogen was found to be greater
than adsorbed xanthate in the presence of air. Impor-
ð5Þ tantly, these researchers observed that dixanthogen was
not produced in the nitrogen environment. These results
may help explain the fact that at a relatively low potential
the selective flotation of pentlandite from pyrrhotite is
possible, as presented in Fig. 4, or that a nitrogen
environment (very low potential) inhibits pyrrhotite flo-
atability with xanthates. Also noting a high level of aera-
tion or oxidation potential for improved pyrrhotite
flotation (Khan and Kelebek, 2004; Alekseeva, 1965), it
is expected that the oxide or hydroxide product layer
ð6Þ from pyrrhotite oxidation may have a high electric resis-
tance (average resistivity for natural pyrrhotite: 1 ·
10
5 X/m, average resistivity for hematite: 1 · 10
1 X/
m, Shuey, 1975) and/or that xanthate oxidation may have
significant over-potentials on the surface of hydroxide–
oxide products. The high oxidation potential might be
needed to oxidize xanthate to dixanthogen and would
favor flotation of oxidized pyrrhotite particles. In con-
ð7Þ
ð8Þ
ð9Þ
Fig. 13. FTIR spectra of pyrrhotite at xanthate concentration of
5 · 10
5 mol/l and pH 9.2 in the cases of single mineral (A), mixed
minerals (B, solution contact with pentlandite), and mixed minerals
(C, direct contact with pentlandite) (Bozkurt et al., 1998).
 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
trast, it was reported that pyrrhotite was effectively de-
pressed and selective flotation of pentlandite and chalco-
pyrite from pyrrhotite was achieved (Khan and Kelebek,
2004; Kelebek, 1993) as a result of selective oxidation of
pyrrhotite at relative high levels of potentials through
pre-aeration of slurries.
Even though adsorption of xanthate and/or dixanth-
ogen can occur on the oxidized pyrrhotite particles, the
hydrophobicity is not great, and a low flotation recovery
for pyrrhotite is frequently found under the traditional
flotation conditions as used in the PGM industry. These
phenomena indicate that adsorbed collector covers only
a part of the oxidized pyrrhotite particles, a state which
needs to be examined in future research.
6.4. Summary
It can be noted from review of the literature and re-
cent results at the University of Utah that the pyrrhotite
flotation system is very complicated, resulting from var-
iation in the pyrrhotite composition/structure, pyrrho-
tite and thiocarbonate oxidation, Eh/pH, minerals
contacted/associated with it, and activation reactions.
The following chemical factors appear to have a signif-
icant influence on pyrrhotite hydrophobicity and its
recovery by flotation.
Oxidation potential: it has been seen in the above sec-
tions that pyrrhotite is thermodynamically and kineti-
cally unstable and is easily oxidized to ferric
hydroxide/oxide, or intermediate compounds, depend-
ing on the oxidation potential level and solution pH.
If the flotation process is operated under conventional
conditions, it is unavoidable that the product from pyr-
rhotite oxidation is ferric hydroxide/oxide precipitating
at particle surfaces, rendering the pyrrhotite surface
hydrophilic and causing its low flotation recovery even
though adsorption of xanthates and formation of di-
xanthogen occurs. In this regard, appropriate control
of the oxidation potential should be important during
flotation process for improved flotation recovery. First,
the oxidation potential/oxygen level during milling
should be controlled to protect pyrrhotite from oxida-
tion. Second, in order to assure formation of dixantho-
gen, relatively high oxidation potential (0–0.2 V/SHE)
should be maintained during a short conditioning stage
prior to flotation.
pH: the pH effect has been shown to be very impor-
tant as is evident from the results for pyrrhotite natural
floatability, collector flotation, and activation. These re-
sults demonstrate that under the traditional flotation
conditions, such as at pH 9–9.5, no natural pyrrhotite
floatability is observed (contact angle is zero); pyrrhotite
floatability with collector is low; and activators (copper
and lead) lose their effectiveness in most cases, precipi-
tating as hydroxides. Significantly improved pyrrhotite
flotation can be achieved at pH < 5.
863
Activation: according to the literature, the effective-
ness of copper for pyrrhotite activation in alkaline solu-
tions is controversial. Some researchers claim that
copper activation is not possible since copper ions are
essentially insoluble in alkaline solution and thus not
available for reaction. Furthermore, pyrrhotite particles
are likely to be well oxidized and covered with ferric
hydroxide/oxide, which may inhibit any activation reac-
tion with the underlying mineral surface.
Other studies have shown that pyrrhotite flotation
recovery is significantly improved with addition of cop-
per sulfate in alkaline solutions, and that copper has
been detected on concentrate particles from actual flota-
tion circuits. These results obviously indicate that pyr-
rhotite may be activated by copper ions.
The recent results of contact angle measurement at
the University of Utah support the first observation.
Addition of copper ions or lead ions did not improve
the hydrophobicity of pyrrhotite in neutral and alkaline
solution, although some positive effect was observed be-
low pH 7.
7. Conclusions
The flotation recovery of PGMs is dependent on
the pyrrhotite flotation recovery since PGMs are nat-
urally associated with this sulfide mineral. Pyrrhotite
is not stable and is easily oxidized to ferric hydrox-
ide/oxide under conventional flotation conditions,
open to air at pH 9.0. The products from pyrrhotite
oxidation cover the pyrrhotite particles, rendering
the particle surface hydrophilic and causing a
lower flotation recovery of pyrrhotite under most
circumstances.
Under low oxidation potential in acidic solutions,
pyrrhotite displays a distinct natural floatability. In the
presence of xanthate, however, if the potential is too
low to oxidize xanthate to dixanthogen, pyrrhotite flota-
tion is inhibited. It is evident that appropriate control of
oxidation potential should be important during the flo-
tation process.
Generally, activation of pyrrhotite by copper and
lead is significant in acidic solutions, but in some cases
has been found to be negligible in neutral and alkaline
solutions.
Based on this review of the literature, it seems that
improved pyrrhotite flotation to increase PGM recovery
might be achieved in at least two ways:
• Development of new collectors for improved pyrrho-
tite hydrophobicity in air at pH 9.0.
• Control of Eh/pH to minimize oxidation of pyrrho-
tite and still achieve collector adsorption with activa-
tion as might be necessary.
864 J.D. Miller et al. / Minerals Engineering 18 (2005) 855–865
Research in both these areas is in progress. The use of
trithiocarbonates for pyrrhotite flotation is one example
of collector development as an alternative to the tradi-
tional xanthate collectors. With regard to oxidation po-
tential control, the use of inert gas flotation for the
processing of PGM ores has been demonstrated (Gathje
and Simmons, 2004) and is being evaluated further.
Acknowledgments
Support for the PGM flotation research program at
the University of Utah and the University of Pretoria
by the National Science Foundation (NSN Grant
INT—0352807) and industrial participants, Impala
Platinum, Newmont, BOC, and Bateman, is recognized
with appreciation.
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