COLLOIDS

AND
Colloids and Surfaces SURFACES
ELSEVIER A: Physicochemical and Engineering Aspects 136 (1998) 51-62

The surface and solution chemistry of pyrite flotation with

xanthate in the presence of iron ions
C.L. Jiang a, X.H. Wang b, B.K. Parekh a *, J.W. Leonard a
a Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506, USA
b Betz Dearborn Inc., Paper Process Group, Jacksonville, FL 32256, USA

Received 4 February 1997; accepted 28 August 1997

Abstract

The effects of the surface and solution chemistry of the Fe( II) and Fe( III) ions on the flotation of both ore- and
coal-pyrite with xanthate have been systematically investigated based on flotation results, zeta potential measurements
and thermodynamic calculations. It was found that the presence of ferrous and ferric ions in solution significantly
depresses ore-pyrite flotation in the pH range of 6 -9.5. The effect of ferrous ions is stronger than that of ferric ions.
Coal pyrite was found to be nonfloatable above pH 6 due to the large amounts of ferrous ions resulted from pyrite
oxidation. The results of thermodynamic calculations have been found to be in good agreement with the experimental
results, indicating that the formation of ferric hydroxyl xanthate compounds are responsible for the reduced
floatabilities of pyrites when pH is greater than 6. C 1998 Elsevier Science B.V.

Keywords: Flotation: Iron ions; Oxidation; Pyrite: Xanthate

1. Introduction but some investigations attribute the ease of oxida­

Pyrite, the r» ;t common sulfide mineral, is
often associateu with other sulfide minerals as well
as coal. During the flotation of minerals, pyrite is
usually referred to as an impurity mineral and
removed from the associated sulfides or coal to
minimize its contamination of the valuable mineral
concentrate or to reduce sulfur dioxide emissions
into air. Pyrite is usually removed by the froth
flotation method using xanthate as a collector. In
coal flotation, pyrite rejection has been investigated
by reverse flotation using xanthate collectors.
However, a large xanthate requirement dosage is
a major setback for the process. The reason for
the large dosage of xanthate required is not clear,
* Corresponding author.
tion of coal-pyrite versus ore-pyrite [1].
The mechanisms of xanthate adsorption on
pyrite have been extensively studied. It is generally
accepted that the sole species of xanthate responsi­
ble for pyrite flotation is dixanthogen, independent
of solution and pyrite surface conditions [2-8].
This conclusion was based on the results of spec­
troscopic, flotation, zeta potential and electro­
chemical studies. However, the proposed
mechanisms could not explain a number of phen­
omena observed in the pyrite flotation system with
xanthate. For instance, the complete or partial
depression of pyrite was observed in the neutral
pH range; the zeta potential of pyrite became
negative below PZC in the presence of xanthate.
Fuerstenau et al. [2] studied the effect of solution
pH and different xanthate concentrations on the

0927-7757 98 SI9.00 C 1998 Elsevier Science B.V. All rights reserved.

PII S0927-7757(97)OO25O-1
52 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
flotation of pyrite, and reported that when low
concentrations of xanthates were used, in spite of
the nature of xanthate species added (xanthate or
dixanthogen), a high or complete recovery in the
acidic region, a partial recovery under mildly alka­
line solution, and an intermediate depression or
low recovery region in neutral pH range were
observed. At high xanthate concentrations, the
depression of pyrite observed in the neutral pH
range was absent and high recovery was observed.
From these flotation results, the conclusion that
dixanthogen adsorption was primarily responsible
for the flotation of pyrite could not explain the
intermediate depression phenomena near neutral
pH solutions. Based on the work by Sheikh [9] on
the Mossbauer spectroscopy of iron xanthate, Leja
[10] suggested that ferric xanthate (FeX3) may be
responsible for the improved recoveries in acidic
solutions and Fe(OH )X2 may be the cause of low
recovery under mildly alkaline pH. It was also
suggested that the depression in neutral pH range
may be associated with the formation of
Fe(OH) + X complex which eliminated the adsorp­
tion of particular hydrophobic xanthate species on
pyrite surface.
Zeta potential measurements showed that the
surface charge of pyrite was reversed in the pres­
ence of xanthate, and it became more negative
with the higher concentration of xanthate [11-13].
Obviously, the flotation results obtained by several
investigators were contradictory to the above zeta
potential measurements [2,10.14], which suggested
that there are some other reactions taking place
on the pyrite surface and species besides dixantho­
gen being formed or adsorbed on the pyrite sur­
face. Therefore, the conclusion that dixanthogen
was the sole species on pyrite surface given by the
previous investigators was too vague, and the real
mechanism may be much more complex. Recently,
extensive studies using a number of techniques
have been conducted to delineate the principles
underlying pyrite flotation with xanthate [15-18].
It has been reported that a number of different
ferric xanthate compounds can be formed under
the conditions of pyrite flotation, and that these
compounds play a very important role in pyrite
flotation. The adsorption of xanthate in the acidic
pH region is attributed to the chemisorption of
xanthate ions and dixanthogen and the formation
of surface or bulk ferric xanthate compounds at
the high concentration of iron ions. In the alkaline
pH region, the adsorption of xanthate is attributed
to the physical adsorption of aqueous dixanthogen
and xanthate ions. The above conclusion was also
supported by other investigators in their studies
on the interaction of ethyl xanthate with pyrite
[19].
It should be pointed out that the oxidation
products such as ferric or ferrous ions were also
obviously involved in the reaction of xanthate
adsorption on pyrite surfaces. The adsorption of
xanthate is strongly related to the oxidation of
pyrite surface, depending on the solution condi­
tions. It is known that coal-pyrite differs signifi­
cantly from ore-pyrite in its oxidation behavior,
so that studying the role of oxidation products of
pyrite such as iron ions is very helpful for under­
standing the principles of pyrite flotation with
xanthate.
2. Experimental
2.1. Materials and reagents
Pyrites from both ore and coal sources were
utilized in this study in order to compare their
different physico-chemical properties of flotation.
The Peru ore-pyrite sample was obtained from
Wards Natural Science Establishment Inc.,
Rochester, NY. The coal-pyrite sample was col­
lected from the Kentucky no. 9 coal seam.
Chemical analysis results of the pyrite samples are
given in Table 1. The ore-pyrite sample was of
high purity and no further cleaning was necessary.
The coal-pyrite sample was in the form of lumps
with visibly attached coal particles. The coal pyrite
was first crushed with a hammer and the coarse
coal particles were removed manually. The selected
pyrite samples were first crushed to - 20 mesh by
jaw and roll crusher, and ground to —100 mesh
with a laboratory pulverizer. The ground samples
were dry screened to obtain -45, -74 + 45,
—100 + 74 and —150+100 pm size fractions. The
-45 pm fraction of pyrites was used for zeta
potential measurements. The prepared samples
 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
Table 1
Chemical analysis of pyrite samples used in the study
Element (%)
Fe S C
Ore-pyrite 42 49.6 <0.1
Coal-pyrite 30 39.0 4.3
Note: N denotes nondetective.
were stored in a refrigerator to minimize surface
oxidation.
Reagents used in microflotation included potas­
sium ethyl xanthate of analytical grade and methyl
isobutyl carbinol (MIBC). Sodium hydroxide,
nitric acid, potassium nitrate, ferrous sulfate and
ferric sulfate were of analytical grade. Distilled
and deionized water was used in all experiments.
All the pH adjustments were made with dilute
solutions of sodium hydroxide or nitric acid.
2.2. Flotation experiment
Flotation experiments were carried out in a glass
microflotation cell of a 2 cm diameter and 20 cm
height. Nitrogen gas was used in all flotation tests
at the flow rate of 5 ml min"1. One gram of the
pyrite sample was conditioned in a beaker with
60 ml of distilled and deionized water for 2 min at
the desired pH. The collector, ethyl xanthate, was
added and conditioned for 2 min. Additional 1 min
conditioning was done after addition of MIBC.
The slurry was immediately transferred into the
micro-flotation cell, and the total flotation slurry
volume was adjusted to 100 mi with water. The
pH of the water used during transference of slurry
and flotation was kept the same as that used
during conditioning periods to avoid the pH
change due to dilution. Another 0.5 min condition­
ing time was allowed prior to aeration. Froth was
collected for 3 min. After flotation, froth and tail­
ing were filtered, dried and weighed. The froth
weight fraction was calculated as recovery. The
pH of the tailing solution in the flotation ceil was
measured and reported as the flotation pH.
To study the effect of surface cleaning on flota­
tion, pyrite samples were pretreated by ultrasonic
treatment with a Branson ultrasonic cleaner which
53
Ca SiO, MgO A12O3 Cu Pb
0.03 <0.01 N N 2.67 0.12
6.6 2.1 0.91 0.55 0.02 <.01
had a frequency of 40 kHz. The purpose was to
remove the surface oxidation products from min­
eral surface. A beaker containing 100 ml water
and 1 g pyrite sample was put into the ultrasonic
bath and treated for 5 min. Afterwards, the water
was decanted before the treated pyrite sample was
used for flotation. Unless specified, the pyrite
samples were not pretreated by ultrasonic
treatment.
2.3. Zeta potential measurements
Zeta potential measurements were conducted
using the Zeta-Meter model 3.0 system. For each
measurement, I g of —45 pm pyrite sample was
wet ground in a mortar and pestle manually to
obtain fresh surfaces. No ultrasonic treatment for
the pyrite samples and deoxygenation of the water
solution was carried out before wet grinding. The
ground sample was transferred to a beaker contain­
ing 10"2 M KNO3 solutions and conditioned for
5 min before zeta potential measurement.
3. Results and discussion
3.1. Pyrite flotation with xanthate
Fig. 1 compares the floatabilities of ore- and
coal-pyrite as a function of solution pH in the
presence of 3.3 x 10"4 M ethyl xanthate with and
without ultrasonic treatment. Without ultrasonic
cleaning, ore-pyrite floats well both in acidic and
alkaline solutions, but a partial depression is
noticed in neutral pH values of 6-8.5. For coal­
pyrite, flotation occurs only below pH 6. However,
it was found that the partial depression of ore-
pyrite observed between pH 6 and 8.5 disappeared
54 C.L. Jiang el al.; Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62

Fig. 1. Effect of ultrasonic surface cleaning on the flotation of
ore- and coal-pyrite as a function of pH in the presence of
3.3 x 10'4 M ethyl xanthate and 50 mg 1"1 MIBC. Particle size,
-74 + 45 pm. Solid line, pyrite cleaned by ultrasonic treatment;
dotted line, without ultrasonic treatment.
Fig. 2. Flotation recovery of ore-pyrite of different particle sizes
as a function of pH in the presence of 3.3 x 10 4 M ethyl xan­
thate and 50 mg l1 MIBC.

after ultrasonic surface cleaning. Similar results

was observed for coal-pyrite, where recovery was
improved to 60% in the alkaline solutions below
pH 9.5, These results showed that ultrasonic treat­
ment cleans the pyrite surface and improves flota­
tion of both ore- and coal-pyrite. It is should be
pointed out that even after ultrasonic treatment,
the coal-pyrite has lower floatability than ore-
pyrite above pH 6.
The flotation of various particle size ore-pyrites
as a function of solution pH in the presence of
3.3 x 10’4 M ethyl xanthate is given in Fig. 2. It
can be seen that for all the particle sizes studied,
ore-pyrite exhibits complete flotation in the acidic
solution below pH 6. However, above pH 6 the Fig. 3. Flotation recovery of coal-pyrite of different particle
coarser particle fraction (-100 + 74 pm) floats sizes as a function of pH in the presence of 3.3 x 10 4 M ethyl
completely up to pH 11. The intermediate size xanthate and 50 mg I 1 MIBC.
fraction (-74 + 45 pm) exhibits partial flotation in
the neutral pH range, which is in good agreement dent on solution pH. All the coal-pyrite size frac­
with previous studies [2,5]. Flotation of fine ore- tions tested exhibit good flotation below pH 6.
pyrite fraction (-45pm) decreases sharply at However, at around pH 6, the recoveries of the
pH 6, and ultimately ceases in the alkaline solu­ coal-pyrite decrease drastically. These results
tions. The flotation behavior of coal-pyrite differs shows that the flotation of coal-pyrite with xan­
considerably from that of ore-pyrite. As shown in thate is favored only in the acidic solution. The
Fig. 3, the floatability of coal-pyrite is almost results are in agreement with the results obtained
independent of particle size, but strongly depen- by Chernosky and Lyon [20],
 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
3.2. Effect of iron ions on pyrite flotation
The role of iron ions in the flotation of pyrite
by xanthate has not been studied thoroughly. Since
pyrite is composed of ferrous disulfide and suscep­
tible to oxidation when it is exposed to air and
water, the following stoichiometric reactions char­
acterize the oxidation of pyrite [21]:
FeS2+7/2O2 + H2O=Fe2 + +2SO5- +2H\
Fe2 + + l/4O2 + H + = Fe3 + +1 /2H2O,
Fe3 + + 3H2O = Fe(OH )3(s) + 3H +.
Pyrite oxidation can also occur in the presence of
ferric ions:
FeS2 + 14Fe3 + + 8H2O = 15Fe2 +
+ 2SO2+16H + . (4)
Since the oxidation of pyrite can take place within
a very short time of exposure to air and water,
during the flotation processes the ferrous and ferric
irons are ubiquitous on the pyrite surface and in
the solution, which may considerably influence the
flotation behavior of pyrite by xanthate.
The effect of ferric ions on the flotation behavior
of ore-pyrite as a function of pH was examined in
three different cases where pH adjustment and the
addition of ferric ions and xanthate were per­
formed in different order The results of these
experiments for particle size fraction of
— 150+ 100 pm are shown in Fig. 4. Complete
flotation of pyrite is observed up to pH 10 with
3.3xl0"4M ethyl xanthate. However, when
2 x 10“3 M Fe3 + ions are added and conditioned
at pH 3 before the addition of xanthate, flotation
recoveries are high both in the acidic and alkaline
regions, while partial flotation is observed in the
intermediate pH range, indicating reactions
between ferric ions and xanthate.
The sequence of the reagent addition and pH
adjustment remarkably affects the flotation
response of pyrite in the neutral pH region. In the
presence of 2 x 10~3 M Fe3+ ions, when the solu­
tion pH is first adjusted before xanthate addition,
the depression is much more significant in the
neutral pH range than that obtained in the reverse
order (i.e. xanthate is first added before pH is
55
(1)
(2)
(3)
Fig. 4. Effect of pH and reagent addition order on the flotation
of ore-pyrite in the absence and presence of 2 x 10"3 M Fe3*
ions using 3.3 x I0"4 M ethyl xanthate (EX) and 50 mg l1
MIBC. Particle size, -150+100pm. Conditioning time and
reagent addition order: (■) Fe3+ (2 min) at pH 3-*pH adjust­
ment (2 min)-*EX (2 min); (□) Fe3* (2 min) at pH 3-*EX
(2min)-*pH adjustment (2min): (▼) Fe3* (2min) at
pH 11 -*EX (2 min)-*pH adjustment (2 min).
adjusted). The partial depression in both cases
commences at about pH 6, corresponding well
with the flotation behavior for coal-pyrite and fine
size ore-pyrite as shown previously in Figs. 2 and
3. These data indicate that a different reaction
mechanism between xanthate and ferric ions is
involved in this pH region. The depression of
pyrite below pH 3 was attributed by Fuerstenau
et al. [2] to the decomposition of xanthic acid into
disulfide and alcohol. However, in the absence of
ferric iron no depression was observed below
pH 3 — the enhancement of the decomposition of
xanthate by ferric iron or the formation of ferric
xanthate would be more likely responsible for the
depression [15-17]. It can be seen from the figure
that in alkaline solutions of pH 9-10 the presence
of ferric iron does not substantially affect the
flotation of pyrite by xanthate, showing that the
adsorption of xanthate species is dominant.
It can also be seen from Fig. 4 that when Fe3 +
ions are added first to the solution of pH 11 before
addition of ethyl xanthate followed by adjusting
the solution to the desired flotation pH, the flota­
tion behavior of ore-pyrite is almost identical to
56 C.L. Jiang et al. / Colloids Surfaces A: Pliysicochem. Eng. Aspects 136 (1998) 51-62
that in the absence of ferric ions. This may be due
to the fact that nearly all the ferric ions are in the
stable precipitate form of ferric hydroxides at such
a high initial pH of 11. Extremely low concen­
tration of free ferric ions is available to react with
xanthate. It demonstrates that once ferric ions are
precipitated at high pH in the solution, their effect
on the adsorption of xanthate on pyrite surface is
negligible.
It was found from our studies that ferrous ions
also play a significant role in flotation of ore-pyrite
in the neutral to weakly alkaline solutions. The
effect of ferrous ion on the flotation recovery of
ore-pyrite as a function of solution pH in the
presence of 3.3xlO~4M ethyl xanthate and
50 mg 1 ~1 MIBC is shown in Fig. 5. It can be seen
that in the presence of ferrous ions, irrespective of
reagent addition order complete flotation is
observed below pH 6. Interestingly, partial flota­
tion is again observed around the neutral pH
region of 6-9. Flotation recovery shows improve­
ment between pH 9 and 11. Similar to the data
obtained with ferric ions, the region of partial
flotation is broader when xanthate is added before
Fig. 5. Effect of pH and reagent addition order on the flotation
of ore-pyrite in the absence and presence of 2 x 10" 3 M Fe2*
using 3.3xl()"4M ethyl xanthate and 50mgl“‘ MIBC.
Particle size. —150+100 pm. Conditioning time and reagent
addition order: (Fi) Fe2* (2 min) at pH3.O-3.5-pH
adjustment-EX (2 min): (▼) Fe2 + (2 min) at pH 3.0 3.5-EX
(2 min)—pH adjustment (2 min).
pH adjustment than that when pH is first adjusted
and followed by xanthate addition. Unlike ferric
ions, in the acidic media below pH 6 the presence
of 2xlO-4M ferrous ion does not affect the
flotation of pyrite. Since the solubility of ferrous
xanthate is high [15], it indicates that in the acidic
pH region no significant reaction between ferrous
ions and xanthate occurs during normal flotation
conditions, and if any, the reaction must be very
weak. However, the drastic decrease of floatability
of pyrite at around pH 6 suggests that ferrous ion
is involved in the reaction with xanthate to form
a weakly hydrophobic compound on pyrite sur­
faces and in the solutions.
Fig. 6 shows the effect of different ferrous ion
concentrations on the flotation behavior of ore
pyrite as a function of pH in the presence of
3.3 x 10-4 M ethyl xanthate. Even at a very high
ferrous ion concentration of 1 x 10"2 M complete
flotation of pyrite remains unchanged below pH 6.
Near pH 6 the pyrite flotation is sharply reduced.
Above pH 6 complete depression of ore pyrite
occurs as the ferrous ion concentration increases
from 2 x 10“3 M to 1 x 10~2 M. Compared with
the flotation curve of pyrite in the presence of
Fig. 6. Effect of different concentrations of ferrous ions on the
flotation of orc-pyrite as a function of solution pH in the pres­
ence of 3.3 x 10 '4 M ethyl xanthate and 50 mg I "1 MIBC.
Particle size, 150+ 100 pm. Conditioning time and reagent addi­
tion order: (□ and ▲) Fe2* (2 min) at pH 3.O-3.5—EX
(2 min)—pH adjustment (2 min).
 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
2xlO_3MFe2+,a much smaller increase in flota­
tion at around pH 11 is still observed in the
presence of 1 x 10~2 M Fe2+. This reveals that the
detrimental effect of ferrous ions on pyrite flotation
with xanthate is more predominant in the neutral
pH range than in the highly alkaline pH range.
From Fig. 6 it can also be seen that the recovery
versus pH curve at lxlO~2M Fe2+ becomes
almost identical to the flotation curve of coal­
pyrite as illustrated in Fig. 3. It suggests that the
flotation of coal-pyrite with xanthate may be
strongly controlled by the presence of ferrous
species produced by surface oxidation. These
results demonstrate that apart from ferric ions, the
ferrous ions play a more important role in influ­
encing the adsorption of xanthate on pyrite in the
intermediate depression region.
3.3. Zeta potential measurements
The zeta potentials of ore- and coal-pyrite as a
function of solution pH are given in Fig. 7, which
shows PZC’s of ore- and coal-pyrite at pH 7.5 and
9, respectively. The effect of ferric and ferrous ion
on the zeta potential of ore-pyrite is shown in
Fig. 8. In the presence of 2 x 10 3 M ferric ions,
the PZC of the ore-pyrite nearly remains the same
at around pH 7.5, except that the surface becomes
Fig. 7. The zeta potentials of ore- and coal-pyrite as a function
of solution pH.
57
Fig. 8. The zeta potentials of ore-pyrite as a function of solution
pH in the absence and presence of 2 x 10“3 M Fe3 + and Fe2+.
more positively charged below pH 7.5. It is obvious
from Fig. 8 that the surface electrical properties of
ore-pyrite are principally determined by the pres­
ence of ferric ions. Unlike ferric ions, the addition
of ferrous ions shifts the PZC of ore-pyrite from
pH 7.5 to 9, and the magnitude of the zeta poten­
tial of ore-pyrite is also lowered. A number of
studies have been performed on the electrokinetic
behavior of ore-pyrite in the past. It has been
reported that even a modest degree of oxidation
of pyrite surface will produce a pyrite surface
which behaves like iron oxide with a PZC at
around pH 7 [19,22]. The iron ions produced by
oxidation form ferric hydroxide precipitation on
pyrite, the surface is postulated to acquire the
electrokinetic features of the iron hydroxide.
Comparing Fig. 7 with Fig. 8, it is clear that the
zeta potential behavior of coal-pyrite is analogous
to that of ore-pyrite in the presence of ferrous ions
with the same PZC at pH 9. It demonstrates that
the surface charge property of coal-pyrite is mainly
controlled by ferrous ions. This conclusion can be
proved by the fact that the flotation behavior of
coal-pyrite is extremely similar to ore-pyrite in the
presence of high concentrations of ferrous ions
(Fig. 6).
Fig. 9 shows the zeta potential of ore-pyrite as
a function of pH in the absence and presence of
58 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51 62
Fig. 9. The zeta potentials of ore-pyrite as a function of solution
pH in the absence and presence of two different concentrations
of ethyl xanthate.
two different concentrations of ethyl xanthate. In
the presence of 6.6xlO“4M ethyl xanthate, the
zeta potential of ore-pyrite becomes negative in
the whole pH range, and no PZC can be observed.
Similar results have been reported previously
[11,12,23]. These results indicate that some other
reaction products besides dixanthogen, which were
identified by Wang and Forssberg [17] to be ferric
xanthate compounds, have been absorbed on
pyrite surface. As shown in the figure, the magni­
tude of zeta potential is nearly independent of the
solution pH. which indicates that the xanthate
species is potential-determining ions. At a lower
ethyl xanthate concentration of 3.3 x 10“4 M, the
zeta potential is reversed to negative in the pH
range of 4.5-6. At pH >6 there is little difference
from that obtained in the absence of xanthate, and
the same PZCs are observed at pH 7.5. This shows
that xanthate cannot adsorb readily onto pyrite
above pH 6 at low concentrations.
Fig. 10 shows the zeta potential results of coal­
pyrite as a function of pH in the absence and
presence of 6.6 x 10“4 M ethyl xanthate. The addi­
tion of xanthate only slightly decreases the zeta
potential values of coal-pyrite below pH 8 and no
great difference occurs at higher pH, showing that
the adsorption of xanthate is only favored below
Fig. 10. The zeta potential of coal-pyrite as a function of solu­
tion pH in the absence and presence of 6.6x10 4M ethyl
xanthate.
PZC or in the acidic solutions. It should be noted
that coal-pyrite floats by xanthate at an equivalent
level to ore-pyrite in acidic media, and it is expected
that the adsorption of xanthate on coal-pyrite
should also be strong in acidic medium. However,
the change of zeta potential values for coal-pyrite
in the presence of xanthate is much smaller than
ore-pyrite. Larger amounts of oxidation products
such as ferric and ferrous irons in solution and on
coal-pyrite surface may result in these differences.
The effect of ferric ions on the zeta potentials
of ore-pyrite in the absence and presence of xan­
thate as a function of pH is presented in Fig. 11.
It can be seen that in the presence of 2 x 10“3 M
ferric ions and 6.6xlO"4M ethyl xanthate, the
zeta potential of ore-pyrite shows less positive
charge below pH 7.5, compared with that in the
presence of ferric ion alone. At pH >7.5, there is
no noticeable difference between the two curves.
Therefore, in the presence of ferric ions, the
adsorption of xanthate on pyrite surface is favored
in the acidic solutions below PZC.
The effect of ferrous ions on the zeta potentials
of ore-pyrite in the presence of xanthate is shown
in Fig. 12. The PZC of ore-pyrite in the presence
of ferrous ion is at pH 9. However, in the presence
of both 2 x 1()“3 M ferrous ion and 6.6 x IO“4 M
 C.L. Jiang el al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
Solution pH
Fig. 11. Effect of Fe' + ions on the zeta potential of ore-pyrite
as a function of solution pH in the absence and presence of
6.6 x 10 4 M ethyl xanthate.
Fig. 12. Effect of Fe2 * ions on the zeta potentials of orc-pyrite
as a function of solution pH in the absence and presence of
6.6 x 10 4 M ethyl xanthate.
ethyl xanthate, a surface charge reversal is
observed at pH 6. It is obvious that a different
reaction mechanism is involved below and above
pH6. At pH <6 the zeta potential of pyrite is
negative and similar to the results in the presence
of only xanthate (Fig. 9). At pH>6 the zeta
potential curve is identical to that in the presence
59
of only ferrous ion. These results indicate that
unlike ferric ion, ferrous ions do not undergo
significant reaction with xanthate on ore-pyrite
surface in the acidic solution of pH <6, and the
flotation of pyrite in this region is mainly due to
the adsorption of xanthate on surface. At pH >6,
the adsorption of xanthate species is apparently
reduced. These results are in excellent agreement
with the flotation results in the presence of ferrous
ions (Fig. 6).
3.4. Thermodynamics of pyrite-xanthate system
The oxidation products such as ferric and fer­
rous ions formed on the surface play an important
role in influencing the surface electrical properties
and flotation of pyrite with xanthate. The different
flotation and surface properties of ore- and coal­
pyrite may result from differences in their chemical
composition and oxidation behavior [14,32]. It
can be expected that coal-pyrite in coal deposits
could have been exposed to a more oxidizing
environment than ore-pyrite. A higher degree of
oxidation might have occurred even in the interior
of the coal-pyrite, thereby producing larger quanti­
ties of ferric or ferrous iron on the surface than
ore-pyrite. Lai et al. [24] and Khan et al. [25]
studied the surface oxidation of pyrites by XPS,
and they found that the iron atoms showed a
much higher oxidation state on coal-pyrite than
on ore-pyrite. This is consistent with the poor
floatability of coal-pyrite in the presence of xan­
thate even with ultrasonic surface cleaning
(Fig. 1).
Based on the flotation and electrokinetic studies,
the role of iron ions in the flotation of pyrite with
xanthate can be explained in terms of the solution
chemistry of the iron-xanthate-water system. The
thermodynamic equilibrium calculations were per­
formed with the help of the computer program
SOLGASWATER [26]. The stability constants of
the species considered in this study were obtained
from the literature [15,16,27-30], and ire listed
in Table 2. The calculated results are presented
in Figs. 13 and 14 in terms of distribution
[log(concentration) versus pH] diagram at
Eh = 0.177V and at 298.15 K, where Eh is the
redox potential versus standard hydrogen electrode
60 CL. Jiang et al. i Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62

Table 2 Consequently, the conclusion that dixanthogen is

Stability constants, components and species in Fe-EX H2O the only species responsible for pyrite flotation
system does not hold. The presence of the metal xanthate
Log Kf Matrix species such as ferric dihydroxy xanthate is more
likely to determine the flotation behavior of pyrite
Components in neutral to weakly alkaline solution. Wang [31]
H* 0.00 1 0 0 0
1 0 0
conducted FTIR studies of xanthate adsorption
E" 0.00 0
Fe2 + 0.00 0 0 1 0 on pyrite surfaces in neutral pH solutions, and
EX’ 0.00 0 0 0 1 reported that Fe(III )-xanthate compounds are
Aqueous species formed and adsorbed on the surfaces of pyrite.
HEX 1.65 1 0 0 1
*) The results demonstrated that Fe(III) xanthate
(EX )2(aq) -2.57 0 _2 0
-13.00 0 -1 0 0
compounds are strongly bonded to the pyrite
Fe'*
FeOH2 ’ -15.19 -1 -1 1 0 surfaces.
Fe(OH)\ -18.67 _ -) -1 1 0 The results obtained from the thermodynamic
Fe(OH h(aq) -25.58 -3 -1 1 0 calculations satisfactorily explain the flotation
Fe(OH) 4 - 34.60 -4 -I 1 0 behavior of pyrite. Freshly ground coarse size
FEOH * -9.50 -1 0 1 0
-20.60 _2 0 1 0
(-100 + 74 pm) ore-pyrite, which has a smaller
Fc(OH )2(aq)
Fe(OH) 3 - 32.00 -3 0 1 0 surface area and less oxidation products, shows
Fe.(OH )J -, -28.15 _2 _ *> 2 0 complete flotation over the entire pH range, as
FejOH)5\ -45.13 -4 -3 3 0 can be seen in Fig. 2. For the fine size fraction of
Solid species ore-pyrite ( — 45 pm), a larger surface area is
FeOH).((s) -19.00 -3 -1 1 0
Fe(OH),(s) -12.90 _2 0 1 0 exposed and results in more oxidation products
Fe( EX )3(s) 11.80 0 -1 1 3 such as ferric or ferrous ions on the pyrite surfaces.
Fe( EX )2(s) 7.11 0 0 1 2 Therefore, at pH >6 xanthate is mainly consumed
(EX )2( 1) 2.37 0 0 2 due to the formation of less hydrophobic ferric
FE(OH)EX(s) -2.50 -1 0 1 1
*> dihydroxy xanthate, Fe(OH )2EX(s), which leads
FeOH(EX),(s) 3.50 -1 -1 1
Fe(OH)2EX(s) - 5.80 -1 1 1 to the poor floatability of fine ore-pyrite.
The above conclusion also corresponds very well
Note: EX. ethyl xanthate: E . electron. with the flotation results of coarse size ore-pyrite
(-150+100 pm) in the presence of large quantity
(SHE). It was shown that this redox potential of ferrous iron as shown in Fig. 6. In the presence
value corresponded to that under normal pyrite of large amount of iron ions, the quantities of
flotation conditions [15-18]. In the presence of dixanthogen and xanthate are extremely small at
3.3xlO"4M ethyl xanthate and 2xlO_4M of pH 6-9.5, as shown in Figs. 13 and 14, thus dixan­
total iron ions (Fig. 13), liquid dixanthogen. thogen and xanthate species, which are responsible
(EX )2( 1), is the predominant species of xanthate for the flotation of pyrite, are insufficient to main­
in acidic solution. In the weakly acidic pH range tain high level flotation at this pH range. This is
of pH 4.5-5 ferric monohydroxo ethyl xanthate, also supported by the zeta potential data. As
FeOH(EX)2( 1), is formed. While in the neutral shown in Fig. 12, for the ore-pyrite-xanthate
to weakly alkaline pH solutions of pH 5-9.5, system and in the presence of ferrous ions, the
the insoluble ferric dihydroxy xanthate, surface is negatively charged due to the adsorption
Fe(OH )2EX(s), becomes stable, and liquid dixan­ of xanthate below pH 6. above which the surface
thogen disappears. At pH >9 the xanthate ion is is positively charged, indicating that the xanthate
the main species. At a higher iron ion concen­ adsorption on surface at pH >6 is very weak.
tration of 1 x 10“- M (Fig. 14). liquid dixanthogen It has been shown that the flotation behavior of
species disappears over the entire pH range. It coal-pyrite for different particle sizes by xanthate
can be seen that in acidic solution below pH 4, is extremely similar to that of fine ore-pyrite as
the ferric xanthate. Fe(EX)3(S), is formed. well as ore-pyrite in the presence of high concen-
 C.L. Jiang et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 51-62
pH
Fig. 13. Log(concentration) pH distribution diagram for
iron ethyl xanthate-water system at £h=O.177V in the pre­
sence of 3.3x10 4 ethyl xanthate at a total concentration
of 2 x 10 3 M Fe ions.
pH
Fig. 14. Log(concentration) pH distribution diagram for
iron ethyl xanthate-water system at £h=O.I77V in the pre­
sence of 3.3 x 10 4 M ethyl xanthate at a total concentration
of 1 x 10 2 M Fe ions.
trations of ferrous ions. The high degree oxidation
of coal-pyrite produces large amounts of iron ions,
especially ferrous ions, which exist both on the
pyrite surface and in the solution. The particle size
independence of coal-pyrite flotation with a critical
flotation pH of 6 suggests that the oxidation of
coal-pyrite surface is very severe, and the ferrous
ions have a determining role in the flotation of
61
coal-pyrite with xanthate in neutral to weakly
alkaline solutions.
4. Conclusions
Ferric and ferrous ions have a strong depressing
effect on ore-pyrite when xanthate is used as a
collector in the neutral to weakly alkaline pH
range (pH 6-9.5). The complete or partial depres­
sion of pyrite is mainly attributed to the reactions
between xanthate and ferrous/ferric ions to form
the poorly hydrophobic ferric dihydroxy xanthate
on the surfaces and in solution. The flotation
results showed that ferrous ions depress the pyrite
near this pH range more remarkably than ferric
ions.
The flotation of ore-pyrite with xanthate
strongly depends on both solution pH and particle
size. Coarse size ore-pyrite shows better flotation
properties than the fine sizes. The flotation beha­
vior of coal-pyrite strongly depends on the solution
pH but not the particle size. High flotation recov­
ery can be obtained only in acidic solutions of
pH <6 for coal-pyrite. Depending on the degree
of surface oxidation, ferric xanthate compounds
are also responsible for the flotation of pyrite in
addition to dixanthogen. Zeta potential measure­
ment and flotation test demonstrate that using
xanthate as collector, the fl Hation behavior is
largely controlled by ferric ions for orepyrite and
by ferrous ions for coal-pyrite.
Acknowledgment
The authors wish to acknowledge the support
of the United States Department of Energy under
grant number DE-FG22-90PC90295.
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