International Journal of Mineral Processing, 25 (1989) 153-158 153

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

Short Note

Workshop on the Flotation-Related Surface

Chemistry of Sulfide Minerals
G.W. WALKER 1., P.E. RICHARDSON l and A.N. BUCKLEY 2
~U.S. Department of the Interior, Bureau of Mines, Washington, DC 20241 (U.S.A.)
2CSIRO Institute of Energy and Earth Resources, Division of Fossil Fuels, P.O. Box 136, North
Ryde, N.S. W. 2113 (Australia)
(Received January 27, 1987; accepted after revision January 29, 1988)

ABSTRACT

Walker, G.W., Richardson, P.E. and Buckley, A.N., 1989. Workshop on the flotation-relatedsur-
face chemistry of sulfideminerals. Int.J. Miner. Process.,25: 155-158.

The nature of the sulfur-richspeciespresent on mildly oxidized surfacesof chalcopyriteand

galena and the nature of the speciesproduced by treatment with sodium sulfidewere discussedat
a workshop held at the Avondale Research Center of the Bureau of Mines. Participantsfrom the
United States,Australiaand France argued the merits of the metal-deficientlatticemodel com-
pared with the polysulfide or elemental sulfur models in explaining the collectorless flotation of
sulfide minerals. In addition, the techniques used to identify the surface sulfur species, such as
linear sweep voltammetry, AC impedance, X-ray photoelectron spectroscopy and 33S nuclear mag-
netic resonance spectroscopy, were discussed.

INTRODUCTION

The natural flotation of sulfide minerals and the involvement of elemental

sulfur in that process have been topics of considerable debate over the last
decade, but still no single interpretation has been accepted. A workshop ad-
dressing some of the surface reactions associated with the role of sulfur in the
flotation of sulfide minerals was held at the U.S. Bureau of Mines Avondale
Research Center, Avondale, Maryland, on April 2, 1986. The workshop was
made possible by the concurrent visits of Jean-Luc Cecile from the Bureau of
Geological and Mineral Research (France) and Alan Buckley and Ron Woods
from the Commonwealth Scientific and Industrial Research Organization
(Australia) to the Minerals Beneficiation group at Avondale. Roe-Hoan Yoon
(Virginia Polytechnic Institute and State University), Subhash Chander
(Pennsylvania State University),John Tosselland George Helz (University
*Current address:U.S. Army Belvoir R D & E Center, STRBE-JDR, Ft. Belvoir,V A 22060 (U.S.A.)

0301-7516/89/$03.50 © 1989 Elsevier Science Publishers B.V.

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of Maryland, College Park), and Howard Evans (U.S. Geological Survey, Res-
ton, VA ), as well as Paul Richardson, Silvia Termes and Grayson Walker (Bu-
reau of Mines, Avondale, MD) participated in the workshop.

METAL-DEFICIENT SULFIDE

Buckley outlined the case for a metal-deficient sulfide lattice being the hy-
drophobic species responsible for flotation of sulfide minerals in the absence
of collectors or sodium sulfide. He claimed that under the above conditions,
the X-ray photoelectron (XPS) spectra are inconsistent with elemental sulfur
or with a metal-polysulfide being the hydrophobic species, whereas in the pres-
ence of hydrosulfide the surface species may be a metal polysulfide or a form
of elemental ( or quasi-elemental ) sulfur (Buckley and Woods, 1984 ). The crux
of this argument is that, for a mineral such as galena, the chemical environ-
ment of the sulfur atoms remains essentially unaltered during the initial oxi-
dation of the surface. The photoelectron spectra for an air-oxidized sulfide
mineral can be interpreted by proposing that the metal atoms migrate to the
surface to form an overlayer of hydrated oxide or hydroxide, while the sulfur
atoms remain in the lattice. Consequently, the lattice becomes metal deficient.
Buckley postulated that, while the high mobility of metal atoms allows the
metal vacancies to be distributed throughout a number of atomic layers, the
metal-deficiency within the surface region nevertheless must be greater than
the nonstoichiometry observed for stable bulk phases. Under flotation condi-
tions, Buckley postulated that as the metal hydroxide or oxide forms, it dis-
solves in the typically alkaline aqueous phase, leaving at the solid-liquid
interface a metal-deficient layer that is evidently hydrophobic. Buckley as-
serted that for galena, this layer should not be described as either metal poly-
sulfide or elemental sulfur, because no sulfur environments other than galena-
like sulfide were evident from the S(2p) spectra. Termes, concurring with
Buckley, asserted that the environments of the sulfur atoms nearest to the
metal atoms would be appreciably different from those of the sulfur atoms in
the remainder of the polysulfide chain. In the case of oxidized chalcopyrite,
Buckley also referred to the chalcopyrite surface product underneath the iron
hydroxide or oxide as being an iron-deficient chalcopyrite lattice, rather than
copper polysulfide or elemental sulfur plus a stable-phase copper sulfide. In
this case, the photoelectron spectra reveal that significantly different sulfur
environments are created by the oxidation process; therefore, the formation of
a polysulfide is not inconceivable.
Woods discussed the study of reactions at sulfide mineral surfaces by cyclic
voltammetry. In commenting on his 1979 results, he pointed out that voltam-
metry may provide insufficient discrimination to differentiate between the
metal-deficient sulfide model and the stable-phase sulfide plus elemental sul-
fur model. Consequently, it is possible to reinterpret voltammograms in terms
 155

of the production of metal-deficient sulfides, rather than elemental sulfur, as

has been done to date {Buckley et al., 1985). Woods also suggested that the
currents normally ascribed to double-layer charging could arise from Faradaic
processes that change the stoichiometry of the surface layer of the sulfide min-
eral. For example, when the potential of a galena electrode is increased, an
anodic current could flow due to the removal of lead atoms; when the potential
is decreased, a cathodic current could flow as a result of the removal of sulfur
atoms. The initial oxidation of galena in acid solutions is known to result in
passivation; elemental sulfur then nucleates and active dissolution occurs. The
initial product has been identified as plastic sulfur, but the observed behavior
could equally be interpreted in terms of the formation of a highly metal-defi-
cient sulfide that decomposes to release elemental sulfur.

M E T A L POLYSULFIDE O R E L E M E N T A L SULFUR

Yoon believed that Buckley was making too fine a distinctionbetween the
terms metal-deficient sulfide latticeand metal polysulfide. In particular, he
feltthat the term "lattice"referredto bulk or long-ranged properties and ques-
tioned whether a mineral surface from which iron had been removed could still
be referred to as having latticestructure.Yoon argued that under these con-
ditions,a metal polysulfidewas a betterdefinitionor explanation of the surface
product. In contrast to Termes, Tossell doubted whether there would be a sig-
nificant differencein the electronicenvironments of the sulfur atoms within a
polysulfide ligand or chain. Therefore, Buckley's X P S results showing only
galena-likesulfur at an oxidized galena surface were not necessarilyproof that
polysulfide was not present.
Yoon noted that in some cases the amount of elemental sulfur detected by
mass spectrometry at the surface of sodium sulfide-treatedminerals was much
less than the amount of sulfur detected by UV-spectrophotometry (Luttrell
and Yoon, 1984). He asserted that much of the supposed elemental sulfur de-
tected by the lattertechnique was in fact polysulfide,and that there was no
necessary relationshipbetween the presence of elemental sulfur and flotation.
Termes suggested that dimethylformamide could be used to differentiateele-
mental sulfur from polysulfide,since in this solvent,polysulfides give rise to
an absorption band at ca. 610 nm, which is associated with the formation of
the radical ion S~-.
The structuresof a numbe r of metal polysulfidecomplexes were reviewed by
Termes. In commenting on aspects of the electronicstructure of sulfides,Tos-
sellmade the observation that although the metal-metal distances in sulfides
were often less than those in metals, this does not necessarily imply metal-
metal bonding; rather, the anion-anion interactions were more likely to be
responsible for many of the structural properties of the transition-metal
sulfides.
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Cecile noted that grinding causes a modification of the surface composition

of sulfide minerals. He also discussed the oxidation of galena and presented
evidence for the formation of elemental sulfur. However, Buckley objected to
Cecile's initial cleaning of the galena surface with argon ions, on the grounds
that ion-bombardment results in unacceptable damage to the newly exposed
surface. Cecile also presented evidence for the formation of elemental sulfur
at the surface of copper-activated sphalerite.
Further evidence for the formation of elemental sulfur on sulfide-mineral
surfaces under simulated flotation conditions was presented by Walker. In ox-
ygen-saturated electrolyte under open-circuit conditions, elemental sulfur with
a characteristic (2p)~/2 binding energy of 163.5 eV, with respect to Au (4f)7/,~
= 83.8 eV, was found on chalcopyrite and pyrite after treatment with sodium
sulfide {Walker et al., 1987). For chalcopyrite at high sulfide concentrations
(10 -~ M), only the metal-deficient type sulfide was observed, but at 10 -4 M
sulfide ion concentration, elemental sulfur equivalent to 5 atomic layers was
formed. Similar coverages were found with pyrite. These results suggest that
the use of sulfide reagents to alter flotation response in commercial plants
must be considered with caution, since the formation of elemental sulfur on a
mineral such as pyrite could initiate its flotation when its depression was
intended.
Walker also described experiments performed recently at Avondale concern-
ing the effects of sodium sulfide treatment on pyrite and chalcopyrite surfaces
under electrochemical control. In hydrosulfide solution, a thick ( ~ 3 nm) cov-
ering of sulfur can be deposited on these minerals when an applied potential is
maintained above the open-circuit potential. The outermost layers of this sul-
fur have a 2p binding energy consistent with that of bulk elemental sulfur (Ss)
and are sufficiently volatile to be lost quickly to the spectrometer vacuum at
ambient temperature. The sulfur atoms in a thinner ( ~ 1 nm) coverage have
a binding energy a few tenths of an eV less than that for bulk sulfur atoms. On
metallic gold, sulfur layers of comparable thickness are even less volatile and
have a correspondingly lower 2p binding energy, more characteristic of a metal-
sulfide structure.

NEW EXPERIMENTAL METHODS AND RECENT RESULTS

Termes and Buckley, in collaboration with Professor R.D. Gillard of the

University of Cardiff, Wales, UK (1987), have recently published an article on
an XPS study of the differentiation of sulfur atoms in platinum and copper
polysulfide complexes. Each polysulfide ligand in the [Pt(Ss)3] 2- complex
contains three structurally distinct types of sulfur atoms. The XPS. results
showed clearly that at least two, and possibly three, distinct electronic envi-
ronments for the sulfur atoms were present. For the [ Cu3 (S4)s ] 3- complex,
two different types of sulfur atoms were distinguished. These results support
 157

the earlierstatements of Buckley and Termes, who suggested that the sulfur
atoms within a polysulfidechain should be distinguishableby XPS.
Tossell has made calculations of core ionization potentials for S~- anions
and S~- ...Mg. For the isolatedanion, the ionization potential of the interior
sulfur atoms exceeds that of the exterior sulfur atoms by about 2.2 eV and for
the S~- ...M g that difference was reduced by ~ i eV, depending on the S~- ...
M g distance.These results,in contrast with his earlierprediction,also indicate
that the different sulfurs in a polysulfide should be distinguishableby XPS.
Tossell et al. (1987) have also calculated 33S nuclear magnetic resonance
( N M R ) chemical shifts for S~- anions and found that a difference of ~ 100
p p m existsbetween the interiorand exteriorsulfurs,which suggests that N M R
should also be a useful tool for studying polysulfide systems.
Chander described A C impedance measurements at surfaces and their ad-
vantages over cyclicvoltammetry, such as a smaller amplitude of the excitation
signal and a time scale close to that involved in flotation.This technique can
be employed to study reaction kinetics under redox conditions, which closely
resemble flotation (Chander and Briceno, 1987). He conceded that, at the
present time, interpretationof the data even for model systems such as sulfur
on metallic gold was far from straightforward. However, the A C impedance
technique promises to be a useful, in situ technique that complements other
electrochemical and ultra-high-vacuum methods used to study sulfidemineral
surfaces. As an illustration,the resultsobtained with the A C impedance tech-
nique show that underpotential deposition of sulfideions occurs on gold,which
is consistent with X P S and linearpotential sweep results.

REFERENCES

Buckley, A.N. and Woods, R., 1984. An X-ray photoelectron spectroscopicinvestigationof the
oxidation of galena.Appl. Surf.Sci.,17" 401-414.
Buckley, A.N., Hamilton, I.C.and Woods, R., 1985. Investigationof the surfaceoxidationof sul-
phide minerals by linearpotentialsweep volt~mmetry and X-ray photoelectronspectroscopy.
In: K.S.E. Foresberg (Editor),Flotationof Sulphide Minerals.Elsevier,AmsterdAm, pp. 41-
60.
Cecile,J.-L.,1985. Application of X P S in the study of sulphide mineral flotation- a review. In:
K.S.E. Forssberg (Editor),Flotationof Sulphide Minerals.Elsevier,AmsterdAm, pp. 61-80.
Chander, S. and Briceno,A., 1987.Kineticsof pyriteoxidation.116th A I M E Meet.,Denver, Colo.,
S M E Preprint # 87-150, Feb. 24-27.
Luttrell,G.H. and Yoon, R.-H., 1984. Surface studiesof the collectorlessflotationof chalcopyrite.
ColloidsSurf.,12: 239-254.
Terrnes, S.C.,Buckley, A.N. and Gillard,R.D., 1987. 2p Electron binding energiesfor the sulfur
atoms in metal polysulfides.Inorg.Chim. Acta, 126: 79-82.
Tossell,J.A.,Lazzeretti,P. and Vaughan, D.J., 1987. Calculationof33S N M R chemical shielding
for the polysulfurions S~-, S~ + ,and for S 2-, H2S, S02 and SO~-. J. Magn. Reson., in press.
Walker, G.W., McCarron, J.J.and Buckley, A.N., 1987.X P S investigationof the effectsof sodium
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sulfide treatments on chalcopyrite and pyrite. Presented at 116th AIME Meeting, Denver,
Colo., Feb. 24-27.