International Journal o f Mineral Pr,ocessing, 4(1977) 227--239 227

© Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

AN ELECTROCHEMICAL INVESTIGATION OF PYRITE FLOTATION

AND DEPRESSION

N.D. JANETSKI', S.I. WOODBURN' and R. WOODS 2

1Chemistry Department, Ballarat College o f Advanced Education, Vic. 3350 (Australia)
2CSIRO Division o f Mineral Chemistry, Port Melbourne, Vic. 3207 (Australia)
(Received October 26, 1976; revised and accepted January 18, 1977)

ABSTRACT

Janetski, N.D., Woodburn, S.I. and Woods, R., 1977. An electrochemical investigation of
pyrite flotation and depression. Int. J. Miner. Process., 4: 227--239.

The oxidation of ethyl xanthate on pyrite electrodes, and the influence of the flota-
tion depressants hydroxide, cyanide, and sulphide, have been investigated using cyclic
voltammetry. A layer of a hydrated iron oxide has been identified on pyrite surfaces.
Xanthate does not interact with this layer but is oxidized to dixanthogen at positive
potentials. An increase in pH results in an increase in the background current due to
oxidation of the mineral, and at p H = l l this reaction becomes faster than xanthate oxida-
tion. Cyanide interacts with the electrode to form a surface species which inhibits xan-
thate oxidation. Sulphide gives rise to an anodic wave preceding the wave due to xanthate
oxidation. The flotation and depression of pyrite are interpreted in terms of mixed-
potential mechanisms.

INTRODUCTION

P y r i t e is a c o m m o n c o n s t i t u e n t o f b a s e - m e t a l ore deposits, a n d t h e flota-

t i o n a n d d e p r e s s i o n o f this m i n e r a l is i m p o r t a n t in the e x t r a c t i o n o f the
valuable c o m p o n e n t s . F o r e x a m p l e , p y r i t e is f l o a t e d w h e n it c o n t a i n s pre-
cious metals such as gold, a n d w h e n it needs t o be s e p a r a t e d f r o m o x i d e
minerals such as cassiterite a n d scheelite. It is generally d e p r e s s e d d u r i n g the
f l o t a t i o n s e p a r a t i o n o f sulphidic ores c o n t a i n i n g lead, zinc, c o p p e r , or
nickel. P y r i t e is also r e c o v e r e d b y f l o t a t i o n f o r use as a s o u r c e o f s u l p h u r
f o r acid m a n u f a c t u r e .
T h e f l o t a t i o n o f m i n e r a l sulphides, a n d t h e m o d u l a t i o n o f f l o t a t i o n o f
these materials, has b e e n t h e s u b j e c t o f investigation over m a n y y e a r s
( S u t h e r l a n d a n d Wark, 1 9 5 5 ; G a u d i n , 1957). Detailed studies involving
p y r i t e , h o w e v e r , are relatively limited. T h e c h e m i s t r y o f p y r i t e f l o t a t i o n ancl
d e p r e s s i o n has r e c e n t l y b e e n r e v i e w e d b y Ball a n d R i c k a r d (1976).
A l k y l x a n t h a t e s are the m o s t i m p o r t a n t c o l l e c t o r s f o r t h e f l o t a t i o n o f
sulphide minerals. T h e p r o d u c t s o f the i n t e r a c t i o n o f these c o m p o u n d s with
228

pyrite have been identified by U.V. and I.R. spectroscopy (Fuerstenm et al.,
1968; Majima and Takeda, 1968; Allison et al., 1972) as the corresponding
dixanthogens. This conclusion is supported by measurements of the rest
potential of pyrite in xanthate solutions (Majima and Takeda, 1968; Usul
and Tolun, 1974) which show that the potential is close to that of the
xanthate/dixanthogen redox couple.
Fuerstenau et al. (1968) concluded that the dixanthogen was formed by
oxidation of xanthate by iron (III) species released from the mineral surface.
The presence of oxygen is known to be essential for the flotation of pyrite
(Plaksin and Bessanov, 1957), but the oxygen was assumed by Fuerstenau
et al. (1968) to act by maintaining the dissolved iron in the ferric state. The
oxidation of xanthate by oxygen was ruled out on the grounds that the rate
of this reaction in solution is negligible. However, subsequent workers
(Majima and Takeda, 1968; Usul and Tolun, 1974) pointed out that the in-
teraction of xanthate with oxygen can be catalyzed by the mineral surface.
The catalysis will take place by a mixed-potential mechanism involving the
reactions:
2ROCS2- -* (ROCS:)~ + 2e (1)
1/202 + H20 + 2e -~ 2OH- (2)
Electrochemical investigations (Majima and Takeda, 1968; Usul and Tolun,
1974) support this mechanism rather than one involving iron species. The
technique employed, however, did not allow kinetic analysis of the individual
processes.
The depression of pyrite has not been studied in any detail using electro-
chemical techniques. Only for the mode of action of cyanide has the process
been considered from the electrochemical viewpoint. Elgillani and
Fuerstenau {1968) related the rest potential of pyrite in xanthate and
cyanide solutions to flotation response, and concluded that the formation of
ferric ferrocyanide on the surface was probably responsible for cyanide de-
pression.
In the present communication, we present cyclic voltammetric studies of
the anodic oxidation of ethyl xanthate on pyrite and of the influence of the
flotation depressants hydroxide, cyanide, and sulphide on this process.

EXPERIMENTAL

Materials

Potassium cyanide, sodium sulphide, and the various buffer solutions

were prepared from analytical grade materials and doubly distilled water.
The buffer solutions were prepared from various combinations of potassium
orthophosphate or sodium tetraborate with sodium hydroxide in accordance
with the pH tables of Clark and Lubs (Bower and Bates, 1955). Potassium
ethyl xanthate was prepared from potassium hydroxide, ethyl alcohol, and
 229

carbon disulphide (Vogel, 1956). It was recrystallized from acetone by the

addition of ether and stored under dry nitrogen. Stock 0.1M xanthate solu-
tions in the appropriate buffer solution were prepared daily and stored under
nitrogen. The nitrogen was purified from traces of oxygen by passage over
a column of copper deposited on kieselguhr and heated to 200°C (Meyer and
Ronge, 1939).

Electrodes

Pyrite electrodes were prepared from hand-picked specimens cut into

rectangular prisms approximately 7 X 3 X 15 mm avoiding, as far as possible,
inclusions, cracks, or voids. The mineral specimens originated either from
Spain or from Gumeracha, South Australia. A copper wire was attached to
one end of the prism by means of conducting epoxy cement prepared by
saturating an epoxy resin (Epirez, Epimount) with finely powdered graphite.
It was found that 60--70% graphite was required to provide a suitable com-
promise between the conductive and adhesive properties of the resulting
cement. In one case, a commercial silver epoxy cement (Epo-tek 410E,
Epoxy Technology Inc., Watertown, Mass., U.S.A.) was employed. Before
cementing the copper wire to the surface, the specimen was rough ground
in order to make the contact resistance as low as possible. The copper wire
was threaded through a length of glass tubing and the mineral and the ad-
jacent I cm of tubing e m b e d d e d in mounting epoxy. After curing, the
lower face of the pyrite was exposed by grinding away the epoxy. The elec-
trode surface was prepared on successively finer grades of silicon carbide
paper. The pyrite surface was renewed between each electrochemical exper-
iment by grinding on 600 grade paper. No differences in the results of the
electrochemical experiments were observed between electrodes prepared
from the different sources of pyrite or with different compositions of con-
ducting cement.

Electrochemical measurements

Electrochemical experiments were carried out at 25°C using a conventional

H-cell. Potentials were measured against a saturated calomel reference elec-
trode (SCE) and adjusted to the standard hydrogen electrode {SHE) scale,
on the basis that the SCE has a potential of 0.245 V to the SHE (Bates,
1964). A Princeton Applied Research Model 170 Electrochemistry System
was used for programming and controlling the electrode potential and re-
cording current-potential relationships.

RESULTS AND DISCUSSION

Surface reactions o f pyrite

Curve 1 of Fig.1 is a voltammogram obtained when the potential of a

230

I0o F . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . J
Ex/×z ~ 2 /i~I
'~ 50

a, 0

-50 i ,
~ -I00

150
I I I I I I
-0,4 -0.2 0 0"2 0'4 0-G
Potentiat (V w SHE)
Fig. 1. Voltammograms for a pyrite electrode in orthophosphate buffer, pH=6.87, at 25°C.
Triangular potential sweeps at 5 mV s-'. Ethyl xanthate concentration 0 (curve 1) and
2.0 - 10-3M (curve 2). EX/X2 is the reversible potential of the xanthate/dixanthogen couple
(Winter and Woods, 1973).

pyrite electrode was cycled in a phosphate buffer solution of pH=6.87. The

increase in current at the cathodic potential limit of the sweep marks the
commencement of the evolution of hydrogen and of hydrogen sulphide
from decomposition of pyrite (Peters and Majima, 1968). The anodic current
at potentials above 0.35 V is due to oxidation of the pyrite surface to form
sulphate ions (Peters and Majima, 1968). A comparison with the Eh-pH
diagram for pyrite (see Fig.4) shows that the anodic reaction occurs only at
potentials considerably anodic to the reversible value. This could be due to
irreversibility of sulphate formation or to the formation of a "passive layer"
on the pyrite surface (Peters and Majima, 1968).
An anodic peak occurs on the voltammogram of pyrite at 0.03 V with a
corresponding peak at - 0 . 1 1 V on the reverse scan. The potential of each
peak was found to shift to more cathodic values by %60 mV per pH unit
when the pH was increased over the range 6,9--11.4 and the peak current
to increase when ferrous iron was added to the solution. These results are
consistent with a redox process involving oxidation of an Fe(II) to an
Fe(III) oxide or hydroxide species on the anodic scan and the reverse reac-
tion on the cathodic scan. This mechanism is substantiated by the fact that
the anodic wave commences at a potential close to the reversible potential
of the Fe(OH)2/Fe(OH)a couple at the experimental pH (Fig.2).
Markova and Cohen (1967) demonstrated that, when a platinum electrode
is inserted in a neutral solution containing ferrous ions, an iron oxide is
deposited on the surface and the electrode responds to the Fe(II)/Fe(III)
system. Fig.2A shows the voltammogram obtained when a gold electrode
was cycled over the potential range - 0 . 5 to 0.2 V in borate solution to
which ferrous iron had been added in excess of the solubility level o f ferrous
hydroxide, viz. 10 -s at pH=9.1 (Pourbaix, 1963). A gold electrode was
chosen for this experiment rather than platinum, because the latter metal
 231

0"1

0
I

-0"1

E 0"2:

0
p.

-0"1

-0"2
I I I I
-04 -0'2 0 0"2
P0tentiaL (V v.~ SHE)
Fig.2. Voltammograms for (A) gold and (B) pyrite electrodes in borate buffer, pH=9.2,
at 25°C. (A) --- borate alone, saturated with ferrous iron; (B) borate alone. Triangular
potential cycles at 40 m V s-'.EFe is the reversible potential for the Fe(OH)JFe(OH)3
couple at this p H (Pourbaix, 1963).

displays chemisorption peaks due to hydrogen adsorption in the potential

region of interest (Woods, 1971). The results of Markova and Cohen (1967)
suggest that gold will behave in an identical manner to platinum with respect
to the deposition and reactions of iron oxides on its surface. Fig.2B shows
a voltammogram obtained for a pyrite electrode cycled over the same po-
tential range in borate solution. It can be seen that the shape of the volt-
ammograms and the potentials at which the peaks appear are similar to those
for the iron oxide on gold. The feature which appears on the anodic sweep
at - 0 . 0 9 V in Fig.2A is n o t evident on the pyrite sweep presented. However,
it was observed, at the identical potential, on a number of voltammograms
for pyrite in borate solution recorded over a wider potential range. These
observations add further support to the conclusion that the peaks for pyrite
involve the oxidation and reduction of Fe(II) and Fe(III) hydrated oxides
on the mineral surface.
It was found that potential sweeps commencing at either - 0 . 5 or 0.2 V
gave rise to the oxide peaks on the initial curve, even when a fresh surface
was generated b y regrinding. This implies that pyrite oxidizes to some ex-
tent when the surface is exposed to air, acquiring an iron oxide layer. In
232

industrial flotation plants, an oxide layer would be expected to form on

pyrite during milling, since the redox potentials reported for pyritic flota-
tion systems (Woodcock and Jones, 1970) are anodic to the region of
stability of the mineral.
The charge passed in the oxidation or reduction of the oxide layer on a
freshly ground surface was found to be 1.5 mC by integration of the charge
passed on a potential cycle. This corresponds to a layer of 2.5 nm, assuming
each Fe(II) atom in the surface layer is oxidized to Fe(III) and the structure
of the layer approximates that of Fe203. The results of Markova and Cohen
(1967) support these assumptions. The structure of Fe203 is rhombohedral,
consisting of hexagonal layers spaced 0.23 nm apart (the cell dimensions are
a.nex = 0.503 .nm, c,ne;~ = 1.375 nm -- Pearson, 1958). This suggests t h a t the
oxide on pyrite consists of a number of Fe203 layers. It should be noted,
however, that the true thickness could be considerably less than 2.5 nm since
the surface is not perfectly smooth. Indeed, Biegler et al. (1975) concluded
that the surface of pyrite treated with 600 paper was eight times that of a
polished specimen.

Oxidation o f xanthate on pyrite

Cu.we 2 of Fig.1 is a voltammogram for pyrite in a phosphate buffer con-

taining ethyl xanthate. No influence of xanthate is evident on the anodic scan
at potentials below the reversible xanthate/dixanthogen potential, only the
background currents due to reactions involving the mineral itself being ob-
served in this region. Above the reversible potential there is an increase in
current due to the formation of dixanthogen on the electrode surface, and
the current reaches a mass transport limited plateau at % 0.3 V. Stirring the
solution increased the current in the potential region where it is mass-
transport controlled. On the reverse scan the dixanthogen is reduced back to
xanthate, giving rise to a cathodic peak. The charge passed in reducing the
dixanthogen was found to be between 84 and 100% of that formed on the
anodic scan. Hence, the dixanthogen formed by electro-oxidation of xan-
thate is retained at the electrode surface, the a m o u n t diffusing into the bulk
solution being negligible.
It is apparent from the electrochemical characteristics that dixanthogen
is the only significant product of the oxidation of xanthate on pyrite, only
one anodic and one cathodic peak on voltammograms being identified with
the reactions of xanthate. The shoulder on the cathodic scan in Fig.1 is due
to the reduction of the iron oxide on the surface. The electrochemical ob-
servations substantiate previous conclusions (Fuerstenau et al., 1968; Majima
and Takeda, 1968; Allison et al., 1972) derived from spectroscopic analysis
of the products of the interaction of xanthate and oxygen on pyrite. Harris
and Finkelstein (1975) found that a small a m o u n t of ethyl monothio-
carbonate (C2HsOCOS-) was formed in addition to dixanthogen and inter-
preted this behaviour in terms of the intermediate formation of a ferric
 233

hydroxyxanthate. Fig.1 shows that xanthate has no discernible effect on

the small peak due to the surface iron oxide, and hence the quantity of
ferric xanthate formed by interaction of xanthate with this oxide must be
very small.
Because steady-state measurements of xanthate oxidation result in the
buildup of thick layers of dixanthogen which inhibit further reaction, linear
potential sweep voltammograms are preferred for mechanistic studies of this
reaction. This approach was previously found to be appropriate for studying
the same process on platinum, gold, and galena electrodes (Woods, 1971).
A Tafel relationship was found to be obeyed over an order of magnitude of
current at the f o o t of the anodic wave on pyrite. The Tafel slope was found
to be 85+2 mV, and the current was linearly dependent on xanthate concen-
tration. A similar Tafel slope and reaction order was observed for xanthate
oxidation on gold (Woods, 1971), and the behaviour was interpreted in terms
of a t w o step reaction with chemisorption of a xanthate intermediate:
C2HsOCS2 - ~ (C2HsOCS2)ad s + e (3)
2(C2HsOCS:)ads ~- (C2HsOCS2)2 (4)
In order to account for the Tafel slope, it was necessary to assume the xan-
thate adsorbed according to a Temkin isotherm and the kinetics to be deter-
mined by the second step (Woods, 1971). The theoretical Tafel slope under
such conditions is 59 mV (Woods 1971); the higher experimental slope could
be due to the kinetics being influenced by both reactions 3 and 4.
Biegler et al. (1975) have shown that pyrite is a relatively active electro-
catalyst for oxygen reduction. They found the oxygen reduction wave at
pH=6.6 to commence at % 0.3 V. Xanthate oxidation is rapid at this poten-
tial (see Fig.l). Thus, an isolated pyrite particle in a solution containing both
xanthate and oxygen will exhibit a mixed potential at which oxygen is re-
duced and xanthate oxidized. This process results in a hydrophobic layer of
dixanthogen being formed on the pyrite surface and renders the mineral
floatable.

Influence of pH

Control of the solution pH is one of the most widely applied methods for
the modulation of mineral flotation. In the present system, a change in pH
was found to have little influence on the kinetics of xanthate oxidation on
pyrite (Fig.3); this is to be expected since dixanthogen formation does not
involve either hydrogen or hydroxyl ions. However, the current due to the
oxidation of pyrite itself increases as the pH is increased (Fig.3), i.e. the
oxidation wave shifts to less anodic potentials. At p H = l l . 4 , oxidation of the
mineral surface occurs at lower potentials than xanthate oxidation. Under
these conditions, the mixed potential system becomes one of pyrite oxida-
tion and oxygen reduction, the oxidation of xanthate is suppressed, and the
mineral will remain hydrophilic.
234

0 ..,// pH ~ 6

~ o ~ ~

0 05 - /

°'i
0 o5
/ pH I1 4

L
0 0g 04 O~
Peter)haL (v v$ SHE)

Fig.3. V o l t a m m o g r a m s for a pyrite electrode in solutions at different pH at 25°C. Linear

potential sweeps at 5 m V s -J. Ethyl xanthate concentration 0 (---) and 5.0 - 10-3M ( - - ) .

+ Z-
O'B

Ve z÷ \
0"4 +SO;-~ o~

o.o . \ \

ge e+ + H2
-0'4

-0"8 Fe + H2S ~---...~\

Fe + H S -
-1"0 h I I , L L I J
0 2 4 G 8 I0 i2 14
pH

Fig.4. E h - p H diagram for pyrite in aqueous solutions. Dashed line is the reversible xanthate/
dixanthogen potential for 25 mg 1-1 of potassium ethyl xanthate. Plotted points s h o w the
potentials at which 10 p A c m -2 was observed for: ×, the reduction of oxygen on pyrite,
o, the oxidation of pyrite. T h e r m o d y n a m i c data for the F e - - S - - H 2 0 systere from Bouet
and Brenet (1963), o x y g e n reduction currents from Biegler et al. (1975).
 235

The electrochemical explanation of the depression of pyrite by alkali is

also illustrated by kinetic data considered in relation to the Eh--pH diagram
for the system (Fig.4). The horizontal dashed line represents the reversible
potential of the xanthate/dixanthogen couple for 25 mg 1-1 of potassium
ethyl xanthate. It can be seen that in basic solutions the potentials at which
dixanthogen is formed are outside the stability region of pyrite. However,
the rate of oxidation of the mineral is slow; the circles represent the poten-
tials at which a current of 10 p A cm -2 was observed (cf. Fig.3). The crosses
represent the potential at which the rate of oxygen reduction from air-
saturated solution on pyrite is 10 g A cm-2; these data have been interpolated
from the results of Biegler et al. (1975). It can be seen that, at the lower pH
values, pyrite oxidation occurs only at potentials much more anodic than the
xanthate/dixanthogen reversible potential. At these pH values oxygen reduc-
tion is rapid at the xanthate/dixanthogen potential, and hence a mixed-
potential system will operate and this will involve dixanthogen formation.
At a pH between 10.5 and 11, the rates of pyrite oxidation and oxygen
reduction are equal and opposite at a potential cathodic to that for xanthate
oxidation. Hence, only the mineral will be oxidized at the mixed potential
and flotation will be depressed. These observations are in good agreement
with the findings of Sutherland and Wark (1955) that the critical pH for
pyrite flotation is 10.5 for a 25 mg 1-~ potassium xanthate solution.
The cathodic shift in the pyrite oxidation curve was found to be 68 mV
per pH unit over the pH range 6.8--12. A cathodic shift in the xanthate oxi-
dation wave of 85 mV can be achieved by increasing the xanthate concen-
tration by an order of magnitude. Thus, it is apparent that the effect of
increasing the solution pH can be counteracted by an increase in xanthate
concentration. For equal shifts, and hence equal flotation response:
[C2HsOCS2-]/[OH-] 0.s = constant (5)
This is the modified form of the Barsky relationship which Gaudin (1957)
derived from data relating critical pH for flotation with collector concentra-
tion for a number of different sulphide minerals and flotation collectors.
Note that the original Barsky rule (Sutherland and Wark, 1955) will be
obeyed by those systems in which the shifts in the mineral and collector
oxidation waves are identical. Thus, the electrochemical approach to sul-
phide flotation explains the Barsky relationship and deviations from it.

Influence of potassium cyanide

Investigations were carried o u t to determine the influence of potassium

cyanide on the electrochemical reactions occurring on pyrite in the absence
and presence of ethyl xanthate. A shift in the oxidation wave of pyrite to
cathodic potentials, similar to that observed with hydroxide, would be ex-
pected if pyrite dissolved to form an iron cyanide complex. This is n o t ob-
served; on the contrary, the presence of cyanide actually shifts the wave
slightly in the anodic direction.
236

No additional features appeared on the voltammogram for pyrite when

cyanide was present in solution. However, the small peak identified with the
oxidation of iron(II) to iron(III) oxide was progressively diminished as the
cyanide cohcentration was increased. The peak was eliminated in the pres-
ence of 3 • 10 -3 M potassium cyanide. This behaviour would be explained by
either dissolution of the surface oxides by complexing with cyanide, or their
conversion to an insoluble surface iron species which does not change its
valence state within the potential limits of the potential sweep. The fact that
the oxidation of pyrite is inhibited rather than enhanced, when cyanide is
present, rules out the former and supports the latter hypothesis.
The effect of cyanide on xanthate oxidation is shown in Fig.5. On in-
creasing the concentration of cyanide at constant pH and xanthate concen-
tration, the xanthate wave is shifted to more anodic potentials. At sufficient-
ly large concentrations of cyanide, the xanthate oxidation curve merges with
the background current due to the anodic reactions of the mineral itself.

50 x TO~4 M
25

,t,/"/
50 × 10 . 4 N

::~ 0

i//
F
75
50 I ×104~

5°
75- /

50 / /
i" 0
25

0 i I .. i 1
02 04
Poten%ia[ (V vs S H E )

Fig.5. Voltammofftams for a pyrite electrode in borate buffer, pH=9.2, containing dif-
ferent potassium cyanide concentrations at 25°C. Ethyl xanthate concentration 0 (---)
and 4 - 10-3M ( - - ) .

Thus, the presence of cyanide results in an inhibition of the electrochemical

oxidation of xanthate. On decreasing the pH of the solution at constant
xanthate and cyanide concentrations, the anodic shift in the xanthate oxida-
tion curve was progressively reduced. This observation is in accord with the
conclusion (Sutherland and Wark, 1955) that the cyanide ion is the active
depressant and that the undissociated acid (pK=9.3) is inactive.
The inhibition of xanthate oxidation is best explained by the presence of
a surface iron cyanide species. From thermodynamic considerations and
redox and zeta potential measurements, Elgillani and Fuerstenau (1968)
 237

concluded that ferric ferrocyanide was formed on a pyrite surface in the

presence of cyanide and was responsible for the depression of flotation of
this mineral. Such a species could be formea by reaction of the iron oxide
layer with cyanide. This would account for the fact that cyanide is a much
more efficient depressant when the mineral is extensively oxidized (Bail and
Rickard, 1976). The results of Elgillani and Fuerstenau suggest that the
potential of pyrite in the presence of xanthate and cyanide will be higher
than the xanthate/dixanthogen potential. However, the presence of the sur-
face cyanide species inhibits xanthate oxidation. Furthermore, this species
is probably hydrophilic and hence could diminish the effect of any dixan-
thogen formed.

Influence of sodium sulphide

The voltammetric behaviour of a pyrite electrode in potassium ethyl

xanthate solution containing various concentrations of sodium sulphide is
shown in Fig.6. It can be seen that an additional anodic wave is observed,
due to the oxidation of the dissolved sulphide species present (HS- at the
experimental pH) and that the wave appears at potentials cathodic to
xanthate oxidation. The wave commences at a b o u t - 0 . 3 V and reaches a
mass-transport controlled current plateau at % 0.0 V. Thus, for a pyrite
particle in a solution containing sulphide, xanthate, and oxygen, a mixed
potential will be set up which involves oxidation of HS- ions and reduction
of oxygen. The mixed potential will be cathodic to the xanthate/dixanthogen
potential, and hence dixanthogen will not be formed and the mineral will

0'15

o o, I-
0

i o,b
- o
.f~-=~,o M

0 V i I I
-0'Z 0 0"2 01.4
Potential ( v vl SHE)

Fig.6. V o l t a m m o g r a m s f o r a p y r i t e electrode in borate b u f f e r , p H = 9 . 2 , containing

4.0 • 10-3M ethyl xanthate alone ( ~ ) and with (--) the indicated concentrations o f
s o d i u m s u l p h i d e a t 25°C. Linear potential sweeps a t 20 m V s-~.
238

not be rendered floatable. This conclusion is in agreement with measurements

of pyrite rest potentials (Abramov, 1967) which became more cathodic when
sulphide was present in solution.

CONCLUSIONS

Ethyl xanthate is oxidized on pyrite to form diethyl dixanthogen. In the

presence of xanthate and oxygen a mixed potential is set up involving the
formation of dixanthogen on the pyrite surface, and this renders the mineral
floatable.
Pyrite depression by hydroxide, cyanide, and sulphide results from dif-
ferent mechanisms, but each can be explained by a mixed-potential hy-
pothesis. Increase in pH results in a greater ease of oxidation of the mineral
surface, and at high pH this reaction replaces xanthate oxidation as the
dominant anodic process. The presence of sulphide in solution introduces an
anodic process which will occur in preference to xanthate oxidation. Cyanide,
on the other hand, reacts with the mineral surface to form an insoluble iron
cyanide complex which inhibits the oxidation of xanthate.

ACKNOWLEDGEMENT

One of us (N.D.J.) wishes to acknowledge the receipt of an Australian

Government Colleges of Advanced Education Postgraduate Award.

REFERENCES

Abramov, A.A., 1967. Reasons for the depression effect of sodium sulphide on pyrite
flotation. Soy. J. Non-Ferrous Metals, 8: 21--23.
Allison, S.A., Goold, L.A., Nicol, M.J. and Granville, A., 1972. A determination of the
products of reaction between various sulphide minerals and aqueous xanthate solution,
and a correlation of the products with electrode rest potentials. Met. Trans., 3:
2613--2618.
Ball, B. and Rickard, R.S., 1976. Chemistry of pyrite flotation and depression. In:
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