Colloids and Surfaces

A: Physicochemical and Engineering Aspects 167 (2000) 245 251

www.elsevier.nl/locate/colsurfa

Quantifying pyrite surface oxidation kinetics by contact

angle measurements
A.M. Raichur a,*, X.H. Wang b, B.K. Parekh c
a
Department of Metallurgy, Indian Institute of Science, Bangalore 560 012, India
b
BetzDearborn Inc., Jackson6ille, FL 32256, USA
c
Uni6ersity of Kentucky, Lexington, KY 40506, USA

Received 21 January 1999; accepted 18 November 1999

Abstract

Pyrite surface oxidation plays an important role in several mineral processing and hydrometallurgical systems. The
initial oxidation takes place very quickly and affects the surface characteristics of pyrite greatly. Contact angles under
different atmospheres were measured to quantify the oxidation kinetics of pyrites from various sources. The contact
angle of water droplet on pyrite in air was found to decrease with time indicating that the surface was becoming less
hydrophobic with time. Among the various pyrite samples, pyrite from coal sources oxidizes much faster than mineral
pyrite. The oxidation rate was found to be dependent on solution pH. All pyrite samples studied exhibited a high
oxidation rate in the acidic and alkaline pH range when compared to the neutral pH range. Under nitrogen
atmosphere, the oxidation rate was much slower than air but a similar trend was observed. When contact angle
measurements were done with samples immersed in n-alkanes such as hexane, the contact angle did not decrease with
time since no oxidation took place. The above studies clearly demonstrate that oxidation of pyrite surfaces makes it
less hydrophobic. 2000 Elsevier Science B.V. All rights reserved.

Keywords: Contact angle; Pyrite; Oxidation; Surface chemistry; Coal preparation

1. Introduction sulfide ores [1], sulfide mineral separation [2,3],

coal preparation [4,5], geochemistry as well as in
The surface chemistry of pyrite has been stud- acid mine drainage. Pyrite as with other sulphide
ied extensively over the years. The pyrite/aqueous minerals, is extremely susceptible to surface oxi-
interaction has been the subject of extensive re- dation. There is a vast volume of literature on
search in view of its importance in extractive pyrite surface chemistry. Several previous investi-
metallurgy, e.g. gold leaching from complex gators [610] have comprehensively reviewed
these studies. It has been demonstrated by many
* Corresponding author. Tel.: +91-80-3092513; fax: + 91-
researchers that surface oxidation takes place as
80-3349472. soon as the surface comes into contact with air/
E-mail address: amr@metalrg.iisc.ernet.in (A.M. Raichur) oxygen [1114]. Previous methods of studying

0927-7757/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 5 1 2 - 9
246 A.M. Raichur et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 245251

Table 1 the pyrite surface is presented. In this method,

List of source and type of different pyrites used in this study
both oxidation kinetics and effect of oxidation of
Sample ID Source Physical Appearance hydrophobicity of pyrite surfaces can be studied
As-Received simultaneously. Pyrites from both coal and ore
sources have been used for comparative studies.
SPPY (Mineral) Lograno, Spain 110.5 cm single
cubic crystal
PUPY (Mineral) Huanzala, Peru Large crystal lumps
ICPY (Coal) No.6 Coal, IL, Lilly pads, good 2. Experimental materials and methods
USA crystallinity
KYPY (Coal) No.9 Coal, KY, Large lumps, much 2.1. Materials
USA coal inclusion
PAPY (Coal) No.8 Coal, PA, Large lumps, much
Pyrite samples from different sources have been
USA coal inclusion
used in this investigation. A list of pyrites used in
this investigation is given in Table 1. Mineral
pyrite samples from Spain (SPPY) and Peru
surface oxidation include electrochemical tech- (PUPY), and Illinois coal-pyrite (ICPY) sample
niques like cyclic voltammetry, measured mixed were acquired from Wards Natural Science Estab-
potential as a function of time etc, oxygen uptake, lishment, NY. Two coal-pyrite samples were col-
total solubility (by measuring total iron and/or lected from the following coal seams: Kentucky
sulphate in solution), or Fe3 + uptake when Fe3 + No.9 (KYPY) and Pittsburgh No.8 (PAPY)
is used as an oxidant. Generally such methods seams. The PUPY, SPPY, and ICPY samples
provide information on the extent of pyrite oxida- were of high purity and no purification was per-
tion and are useful to subjects like acid mine formed. The coal-pyrite samples, KYPY and
drainage, pyrite ore leaching, etc. X-ray pho- PAPY, were acquired from the mines in the form
toelectron spectroscopy and Raman spectroscopy of lumps with some coal particles adhering to
have been used to study the oxidation kinetics as them. The coal was first removed and the lumps
well as the products of pyrite oxidation [1316]. were crushed manually. Large pieces were chosen
Oxidation of pyrite surfaces alters the surface for preparing pellets for contact angle measure-
properties of pyrites. In processes such as coal ments. The chemical analysis of the pyrite samples
flotation where pyrite needs to be separated, sur- is given in Table 2.
face oxidation of pyrite surface plays a major role Normal-alkanes were purchased form Aldrich
in determining the pyrite rejection efficiency at the highest purity available (99.999%). Sodium
[17,18]. nitrate, sodium hydroxide, and nitric acid, also
In this paper a new technique for quantifying obtained from Aldrich were of analytical grade.
the oxidation kinetics of pyrite surfaces using Double distilled and deionized water was used
contact angle measurements of water droplets on throughout the investigation. Unless otherwise

Table 2
Chemical analysis of the pyrite samples

Sample ID Major element (%) Impurities (wt.%)

Fe S S/Fe C Ca Si Cu Pb Zn

PUPY 42.0 49.6 2.05 B0.1 0.03 B0.01 2.67 0.12 0.06
SPPY 44.6 53.6 2.09 B0.1 B0.01 B0.01 0.31 0.75 1.27
ICPY 42.0 50.2 2.08 0.81 0.12 B0.01 0.04 0.20 B0.01
KYPY 30.0 39.0 2.26 4.33 6.60 B0.01 0.02 B0.01 B0.01
PAPY 33.0 44.9 2.37 3.00 3.80 B0.01 0.01 0.09 B0.01
 A.M. Raichur et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 245251 247

Water droplets were placed using a calibrated

syringe. The size of the water droplet was main-
tained constant at 2 ml. The ionic strength of the
water was maintained constant at 0.01 M NaNO3.
The contact angles on both the sides of the
droplets were measured. An average value of 6
droplets has been reported here. It should be
noted that all the data reported could be repro-
duced with an error of less than 4%. The standard
deviation (S.D.) in measuring single contact angle
was about 9 2. All measurements were carried
out at 259 2C.

3. Results and discussion

As described in Section 2, contact angle mea-

surements were made both in the presence of air
Fig. 1. The apparent contact angle of water droplet on Illinois and nitrogen. It was found that when the contact
coal-pyrite (ICPY) surfaces as a function of contact time
under different environment as indicated. Relative humidity in
angle was measured in air or under nitrogen
air/under nitrogen ca. 100%. atmosphere, both the contact angle and size of
water droplet placed on the pyrite surface de-
creased rapidly with contact time as shown in Fig.
stated, all pH adjustments were made using 1. The water droplet eventually disappeared after
sodium hydroxide and nitric acid. a certain amount of time. The contact angle mea-
sured under such dynamic conditions may not
2.2. Methods necessarily represent the true surface hydropho-
bicity of clean unoxidized pyrites. Because of this,
Contact angle measurements were done using a the measured contact angle of the water droplet
Rame-Hart contact angle goniometer Model 100- on the pyrite surface has been defined as appar-
00. Samples of approximately 1 1 0.5 cm size ent contact angle to distinguish it from the con-
were selected and were first mounted using epoxy tact angle of an unoxidized pyrite surface.
resin. The mounted specimens were polished using The change in contact angle with time under air
60, 240, 500, 1000 and 4000 grit silicon carbide and nitrogen may be attributed to two reasons:
papers sequentially. Final polishing was done on a evaporation and surface oxidation/dissolution.
microcloth using an aqueous suspension of 0.05 Since the evaporation of water solution at con-
micron Micropolish Alumina-B. After polishing, stant temperature is mainly determined by the
the samples were washed thoroughly with double partial pressure of water vapor, i.e. the relative
distilled water and then quickly transferred to the humidity and the ionic strength, the evaporation
contact angle goniometer for measurements. rate should have been the same at different pH
When measuring contact angles under organic values and under different atmospheres as long as
non-polar liquids, the polished sample was di- the relative humidity and ionic strength are con-
rectly immersed into the organic liquid contained stant. It is also known that contact angle is inde-
in the quartz cell. The quartz cell was then placed pendent of the drop size provided the drop size is
onto the specimen stage to make measurements. small enough to eliminate the gravity and line
Latex gloves were used throughout the experi- tension effects. The droplet size of our measure-
ments in order to avoid contamination of the ment was 2 ml, corresponding to an equivalent
surfaces. sphere of 1.67 9 10 2 cm in diameter. Within this
248 A.M. Raichur et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 245251

dimension, the contact angle is independent of studies and the contact angle changes rapidly as
size. This means that while evaporation may de- the volume of the droplet decreases, the reduction
crease the size of the droplet, it will not change of the apparent contact angle must be essentially
the contact angle. Since the humidity and ionic due to surface oxidation. This is supported by the
strength have been maintained constant in our results of the contact angle measurements under
different environments. As shown in Fig. 1, for
almost the same pH, the contact angle decreases
rapidly when it is measured in air or under nitro-
gen, the rate being proportional to the partial
pressure of oxygen. Oxygen essentially does not
dissolve in n-alkanes, and water and n-alkanes are
completely immiscible. Thus the problems of wa-
ter evaporation/diffusion and surface oxidation
can be minimized or eliminated. As can be seen,
the contact angle of a water droplet under n-hex-
ane remains constant within the time length stud-
ied. The change of contact angle in air suggests
that pyrite surfaces are readily oxidized. Since the
contact angle decreases with time, it indicates that
the surface becomes more hydrophilic after oxida-
tion. Therefore, measuring the apparent contact
angle as a function of time can be used to quanti-
tatively characterize the pyrite surface oxidation
kinetics and its effect on hydrophobicity.
Fig. 2 shows the apparent contact angles mea-
Fig. 2. The apparent contact angle of water droplet on Illinois sured on ICPY surfaces in air as a function of
coal-pyrite (ICPY) surfaces as a function of contact time. contact time. It can be seen that the apparent
Water droplet pHs are indicated in the figure. Relative humid-
ity ca. 100% in air.
contact angle decreases with increasing contact
time. More importantly, the rate of reduction of
the apparent contact angle was different for dif-
ferent solution pHs, as shown in Fig. 3. The
decreasing rate of the apparent contact angle of
ICPY is high at the two extreme pHs and shows a
minimum around the neutral pH. Similar results
were obtained for other pyrites studied as shown
in Fig. 4. The rate constants for ore-pyrites
(SPPY and PUPY) and coal-pyrites (PAPY and
KYPY) showed a very similar variation with solu-
tion pH with a minimum reduction rate around
neutral to slightly alkaline pH. However, the rate
at which the contact angle decreased was less than
ICPY. The variation of the rate constant for
Illinois No.6 coal was almost independent of the
solution pH. The low rate constant exhibited by
coal indicates that coal oxidizes at a slower rate
than the coal-pyrites.
Fig. 3. The rate constant of the apparent contact angle reduc- Similarly the oxidation kinetics of pyrite sur-
tion in air as a function of solution pH for different pyrites. faces under a nitrogen atmosphere was studied
 A.M. Raichur et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 245251 249

apparent contact angle on coal-pyrite ICPY de-

creased at a slower rate than in air but showed a
similar change with solution pH, i.e. a minimum
around neutral pH. The change of the apparent
contact angle of the ore-pyrite SPPY also showed
a very similar variation with pH with a minimum
in the slightly alkaline pH solution. However, the
coal-pyrites KYPY and PAPY exhibited a slightly
different behavior. A minimum in the reduction
rate was observed in the acidic pH range. But the
variation of the rate constant with solution pH in
the slightly acidic and alkaline pH range was
essentially the same as that observed in air.
The change of surface hydrophobicity of pyrites
can be explained in terms of electrochemical stud-
ies. Electrochemical studies in our laboratory
have shown that surface oxidation of pyrite takes
place even in an oxygen deficient atmosphere. As
Fig. 4. The rate constant of the apparent contact angle reduc- shown in Fig. 6, a sharp reduction peak appears
tion in air as a function of solution pH for different pyrites. on the first negative going scan. The studies (not
shown here) demonstrate that the reduction peak
is observed in the first negative-going scan at both
the stationary and rotating electrode, regardless of
the direction of the initial potential scan. Further-
more, the charge passed under the peak is the
same if the positive potential limit is less than 600

Fig. 5. The rate constant of the apparent contact angle reduc-

tion under nitrogen atmosphere as a function of solution pH
for different pyrites.

and the results are given in Fig. 5. The decreasing

rate of the apparent contact angle under a nitro-
gen atmosphere was slower than in air for all the Fig. 6. Cyclic voltammograms of freshly polished Illinois
pyrites. This is obvious because under a nitrogen coal-pyrite (ICPY) electrode at pH 2.5. Solid line: rotation
atmosphere, most of the oxygen is removed. The (500 rpm); dashed line: stationary.
250 A.M. Raichur et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 245251

mV versus SCE. This suggests that the surface 2. The results indicated that the surfaces of the
oxidation products formed during electrode pol- coal-pyrites oxidized at a much faster rate in
ishing are insoluble. Therefore, when a small air than ore-pyrites or coal.
droplet of water is placed on the pyrite surface in 3. The oxidation rate for pyrites was found to be
air, surface oxidation takes place as soon as water dependent on the solution pH. A minimum in
is in contact with the pyrite surface by reactions oxidation rate was observed in the neutral pH
as the one below [19]: range.
4. The reaction products formed on the surface
FeS2 +H2O+ 1/2O2 Fe(OH)2(s) + S 02 of pyrite in the presence of air make the
surface less hydrophobic as indicated by the
No tests were done to identify the type of decreasing contact angle.
reaction products formed on the surface after the 5. This was confirmed by measuring contact an-
water droplet had disappeared. The above reac- gles under hexane where there is no air, i.e. no
tion has been shown to indicate the fact that the oxidation occurs and hence the contact angle
reaction products of pyrite with air and water is stable over the time length studied.
contain iron oxides/hydroxides and sulfur. Since
the above reaction consumes water, the size of the
water droplet decreases as the reaction proceeds. Acknowledgements
It has been shown that iron hydroxides formed
in-situ are present on the outer surface of pyrite The authors wish to acknowledge the financial
[1618]. The pyrite surface will be hydrophilic support provided by the Department of Energy
unless these iron hydroxides are removed to ex- under grant number DE-FG22-90PC90295.
pose the sulfur-rich inner surface. Therefore, the
reduction of the contact angle in air is due to
increased hydrophilicity. This means that upon References
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