Minerals Engineering 69 (2014) 120–132

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Adsorption of O-isopropyl-N-ethyl thionocarbamate

on Cu sulfide ore minerals
Alan N. Buckley a,⇑, Gregory A. Hope b, Kenneth C. Lee c, Eddie A. Petrovic d, Ronald Woods b
a
School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
b
School of Biomolecular and Physical Sciences, Griffith University, Nathan, QLD 4111, Australia
c
Orica Mining Chemicals, 16-20 Beauchamp Road, Matraville, NSW 2036, Australia
d
Orica Mining Chemicals, 1 Nicholson Street, Melbourne, VIC 3000, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption of the flotation collector O-isopropyl-N-ethyl thionocarbamate on air-exposed Cu metal,
Received 18 May 2014 cuprite, chalcocite, covellite, cubanite, chalcopyrite, bornite and pyrite at pH 6 has been investigated
Accepted 1 August 2014 primarily by X-ray photoelectron spectroscopy. It was found that CuI oxide and sulfide surfaces condi-
tioned in the collector solution were hydrophobic, regardless of whether the collector adsorbed as the
anion (IPETC), in protonated form (HIPETC), or as multilayer CuIPETC patches. The CuI native oxide layer
Keywords: on the metal was largely unaffected by the adsorbed collector. For surfaces at which chemisorption
Thionocarbamate flotation collectors
occurred, interaction of the S in the collector was directly with Cu in the metal or mineral surface, rather
Copper sulfide ore minerals
XPS
than via O. Apart from chalcocite, the main species adsorbed from the collector solution on to CuI oxide
Adsorption surfaces were different from those adsorbed on the sulfide minerals, in that the N was predominantly
deprotonated in the former and protonated in the latter. On chalcocite, comparable amounts of IPETC
and HIPETC were adsorbed. Adsorbed HIPETC was in good electrical contact with the surface of cubanite,
chalcopyrite and bornite, presumably because of direct interaction with the mineral rather than adsorp-
tion on top of chemisorbed IPETC or FeOOH. Collector coverage of the Cu minerals correlated with the
availability of CuAOHsurf with which HIPETC could react. Coverage by collector adsorbed as HIPETC on
pyrite surfaces was low, but not negligible, nevertheless conditioned abraded pyrite surfaces were not
obviously hydrophobic.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
The structure of O-isopropyl-N-ethyl thionocarbamate, also
known (more correctly) as O-isopropyl-N-ethyl thiocarbamate, is
shown in Fig. 1 in its protonated, molecular form (HIPETC). The col-
lector is commonly referred to as IPETC, though more specifically,
IPETC represents the deprotonated, anionic form.
When IPETC was initially used for sulfide mineral flotation
under the name Z-200, its advantages over xanthates and dithio-
phosphates were claimed to be higher selectivity against pyrite
and higher stability at low pH (Harris and Fischback, 1954). Those
advantages have since been validated, and there is general agree-
ment on the ore types that benefit from IPETC use. Avotins et al.
(1994) described the major attributes of IPETC as its hydrolytic sta-
bility, shelf life and selectivity against gangue iron sulfides. The
Orica analogue DSP 009 is described by that company as an
⇑ Corresponding author.
E-mail address: a.buckley@unsw.edu.au (A.N. Buckley).
effective collector for all forms of copper mineralisation and zinc
that offers improved selectivity over pyrite. Notwithstanding the
consensus on the ores for which IPETC should be used, since the
mid-1960s there have been numerous studies of the interaction
of dialkyl thionocarbamates with Cu metal, Cu sulfide minerals
and pyrite, but agreement has yet to be reached on the extent of
adsorption, the collector species adsorbed and the mechanism of
their adsorption.
Finkelstein and Goold (1972) reported that the adsorption of Z-
200 on sulfide minerals was low, and they were unable to obtain IR
spectra from surface extracts to identify the adsorbed species. The
fraction of a theoretical monolayer abstracted from solution in
15 min at pH 8 was 0.16 for chalcocite, 0.11 for chalcopyrite,
0.05 for covellite, 0.04 for bornite and 0.03 for pyrite. These esti-
mates were surprising, in that adsorption by pyrite did not appear
to be markedly less than adsorption by covellite or bornite. Less
surprising was the microflotation data for IPETC reported by
Ackerman et al. (1999), which showed that at pH 5, recovery of
chalcopyrite, chalcocite and covellite was above 90%, while that

http://dx.doi.org/10.1016/j.mineng.2014.08.002
0892-6875/Ó 2014 Elsevier Ltd. All rights reserved.
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132
S which results in a metal thiol compound being formed on the min-
O N
H Mnþ þ nðTCÞ ! MðTCÞn
Fig. 1. Structure of O-isopropyl-N-ethyl thionocarbamate.
of bornite and pyrite was 50–90%. At pH 8.5, the recovery of chal-
cocite and covellite was above 90%, but that for chalcopyrite was
only just below 90%, while recovery for bornite was lower and pyr-
ite 59%.
The mechanism of IPETC adsorption remains unresolved,
despite the research effort. From an IR spectroscopic study of O-
butyl-N-ethyl thionocarbamate, its Cu salt, and its interaction with
chalcopyrite and a Cu metal film, Bogdanov et al. (1976) concluded
that the thionocarbamate attached to the surface of a Cu film in
ionic (deprotonated) form, but by ‘chemisorption’ in molecular
(protonated) form to the surface of chalcopyrite. In each case, it
was deduced that both the S and N of the collector formed a bond
with the same Cu atom. For pyrite, both chemisorption and phys-
ical adsorption were deduced. On the other hand, Glembotskii
(1977) argued that in the dialkyl thionocarbamates, both the elec-
tron density on the hetero atom, and its steric accessibility,
decreased in the order S > O > N. Accordingly, if the chemisorption
of the collector to Cu in the surface of Cu sulfides was going to
involve a hetero atom in addition to the S, it was more likely to
be the O rather than the N. Adsorption on pyrite, by contrast,
would be predominantly physical in nature.
Ackerman et al. (1984) noted that while the S was the most acces-
sible and most reactive atom in a dialkyl thionocarbamate molecule,
the N must also be accessible for chelate ring formation. Thus, it was
implicitly assumed that if a heteroatom other than S was involved in
the interaction, it would be the N rather than O. Furthermore,
Ackerman et al. (1999) claimed that for sulfide flotation, ‘‘the most
effective collectors, in terms of high flotation recoveries and rates
with good pyrite rejection, are those compounds containing N and
S as functional groups for chelation’’. With an even greater emphasis
on the N in IPETC, Solozhenkin et al. (2013), in their molecular mod-
elling of the in vacuo interaction of IPETC with pyrite (analogous to
the chemisorption of IPETC on pyrite), compared monodentate
bonding of the collector N to a pyrite Fe atom with bidentate bonding
of the collector N and S to the Fe. However, they did not model biden-
tate bonding of the collector S and O to the pyrite Fe, or calculate the
energy for an HIPETC/pyrite complex.
From an in-situ FTIR investigation of the adsorption of IPETC on
chalcocite, chalcopyrite and pyrite, Leppinen et al. (1988) found
that, except at very low pH, adsorption of IPETC on chalcocite
was 3–20 times higher than on chalcopyrite (or pyrite). They con-
sidered their IR spectra obtained at pH 4 to be consistent with
CuAS bonding, but it was not clear whether there was any coordi-
nation via N. At pH 6, new bands appeared in the IR spectrum that
were thought to indicate coordination via O as well as S. They rea-
soned, like Glembotskii (1977), that steric accessibility and elec-
tron density considerations favoured additional coordination
through O rather than N, and concluded that below pH 6, IPETC
adsorbed on chalcocite through the S only, but above pH 6, adsorp-
tion was through the S and O. They found that IPETC did not
remove sulfate-like oxidation products from the surface of pyrite,
and hypothesised that this might account for the flotation selectiv-
ity against pyrite. They noted that ethyl xanthate does remove the
oxidation products from pyrite.
Yoon and Basilio (1993) claimed that thionocarbamates adsorb
on sulfide minerals via a dissolution–precipitation mechanism
121
eral surface:
MS ! Mnþ þ S0 þ ne ð1Þ
ð2Þ

where TC is the thionocarbamate anion. The coupled reactions
would occur at a potential greater than or equal to the thermody-
namic potential for the (bulk) metal thionocarbamate formation.
Those authors pointed out that, since their proposed mechanism
involved an electrochemical step followed by a chemical reaction,
it was best described as an EC mechanism (Zanello, 2003). Yoon
and Basilio argued that dissolution–precipitation was more likely
than chemisorption for thionocarbamate collectors because of the
very high pK values for the metal thionocarbamates. Nevertheless,
even when the production of S0 in Eq. (1) is interpreted as the for-
mation of a metal-deficient (or S-rich) sulfide surface layer, there
appears to be a dearth of convincing experimental support for dis-
solution–precipitation as an alternative to chemisorption.
Rather than precipitation as CuIPETC, Woods and Hope (1999)
and Hope et al. (2000) provided evidence for chemisorption of
IPETC on Cu metal. They investigated the interaction of IPETC with
an electrochemically roughened Cu metal electrode by means of
in-situ and ex-situ surface-enhanced Raman scattering (SERS)
spectroscopy. The SERS spectra from emersed electrodes that had
been held in de-aerated IPETC solution of pH 6 at a potential below
that at which multilayer CuIPETC would be formed were broadly
similar to the spectrum for CuIPETC, in which the IPETC ligand
was deprotonated. The similarity of the spectra suggested that
any interaction between the O or N of IPETC and surface Cu was
similar to that in the bulk complex. The spectra were consistent
with the collector being chemisorbed through the S to surface Cu
atoms in the anodic process shown in Eq. (3).
Cu þ HIPETC ! CuIPETC þ Hþ þ e ð3Þ
In the flotation of a Cu sulfide, an anodic process analogous to
Eq. (3) could be coupled with the cathodic reduction of oxygen,
but IPETC interaction would not necessarily be represented by such
a mechanism for mineral surfaces that had been exposed to air
before contact with collector.
In the present investigation, the unresolved and contentious
issues concerning the interaction of IPETC with Cu sulfides and
pyrite have been addressed. In particular, specific answers have
been sought to questions concerning (a) the identity of the collec-
tor species adsorbed on the minerals of interest, (b) the adsorption
mechanisms of the collector species, and (c) whether there is a cor-
relation between the collector species adsorbed and observed flo-
atability. Characterisation of collector species adsorbed at
conditioned mineral surfaces was performed by means of X-ray
photoelectron spectroscopy (Buckley, 2010).
2. Experimental details
2.1. IPETC collector and mineral specimens
Commercial DSP 009 collector supplied by Orica Mining Chem-
icals was used without purification. According to the SDS informa-
tion, DSP 009 consists of at least 95% O-isopropyl ethyl
thionocarbamate (MW 147.24), with less than 2% 1,3-diethyl thio-
urea and less than 2% isopropyl alcohol. Manufacturers of IPETC
collector claim no more than 1% diethyl thiourea, no more than
2% isopropanol and 1% maximum moisture. The collector is
described as being slightly soluble in water. The pH of the undi-
luted DSP 009 was near 7, consequently with decreasing concen-
tration, the pH of the diluted collector approached that (5.5) of
122 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132
the water in equilibrium with air used for dilution. All conditioning
was carried out at the unadjusted pH of the collector solution, and
with physical agitation to simulate the turbulent environment in a
flotation cell. A freshly diluted collector solution was prepared
before each conditioning. Collector concentrations between 104
and 102 M were used, with conditioning periods between 1 and
10 min.
Fairthorne et al. (1996) confirmed that IPETC, with a pKa of 12,
was present in molecular form in near-neutral aqueous solution,
and had a solubility at pH 7.7 of 2.6  102 mol dm3 at 25 °C. That
solubility is slightly higher than the 5  103 mol dm3 value
determined by Poling (1976) for Z-200. Poling had noted that
because Z-200 was an oily liquid with limited solubility in water,
it was often added at the grinding circuit. Livshits et al. (1968)
had measured the pKa of Z-200 to be 11.52 ± 0.06.
The chalcocite and covellite investigated were from Butte, Mon-
tana, USA, the chalcopyrite was from Kadina, Yorke Peninsula,
South Australia, the cubanite was from the Henderson #2 mine,
Chibougamau, Quebec, Canada, and the bornite was from Kipuchi,
Zaire. The cuprite was a crystalline specimen from the Red Dome
Mine, Chillagoe, Queensland, Australia, and its interaction with
dialkyl dithiophosphate collectors has been studied previously
(Buckley et al., 2009). The pyrite was from a 2.3 cm cube from
Navajún, La Rioja, Spain.
Mineral particle surfaces produced during plant-scale commi-
nution (prior to flotation collector addition) typically display frac-
ture and abrasion characteristics, depending on the degree of
hardness and brittleness of the particular mineral. To emulate
those characteristics in this investigation, mineral surfaces were
prepared by fracture or abrasion in air, and as the composition of
abraded and fracture surfaces can be subtly different, collector
interaction with both is of relevance. Also, provided mineral spec-
imens are of adequate purity and do not fracture along a pre-oxi-
dised interface, fracture surfaces are inherently cleaner than
abraded surfaces, and subsequent surface characterisation is less
complicated by extraneous contamination. Either P1200 silicon
carbide paper or 0.3 lm alumina powder moistened with distilled
water was used in the preparation of surfaces by abrasion.
2.2. Assessment of hydrophobicity of conditioned metal and mineral
specimens
A conditioned Cu metal or mineral surface was assessed as
hydrophobic if the water used to rinse any adhering collector solu-
tion from the specimen, when it was emersed at the end of the
conditioning period, did not leave a film that wet the surface. For
abraded surfaces, a contact angle greater than 50o for any adhering
droplets of water could usually be determined by visual examina-
tion. Mineral fracture surfaces were typically too rough to make
such a visual assessment. However, any fine particles, which had
been broken off the edges of mineral specimens by agitation during
the conditioning period, accumulated at the liquid/air interface
when those particles had been rendered hydrophobic. For fracture
surfaces of some minerals, such behaviour provided an alternative
indicator of hydrophobicity.
2.3. X-ray photoelectron spectroscopy (XPS)
2.3.1. Acquisition and processing of XPS data
X-ray photoelectron spectra were collected from a surface of
single piece mineral or Cu metal specimens of size approximately
5 mm  5 mm  1 mm mounted in electrical contact with the
sample stub. Each fracture surface, or surface abraded until rela-
tively smooth to the unaided eye, was rinsed with pure water if
conditioned in collector solution and characterised by XPS at ambi-
ent temperature. XPS data were obtained on an ESCALAB 250Xi
spectrometer using monochromatised Al Ka X-rays focused to a
spot size of 0.5 mm, and an electron analyser pass energy of
20 eV for narrow range scans. The magnetic lens mode of the ana-
lyser was used in all cases. Included in the binding energies
employed for calibration were 83.96 eV for Au 4f7/2 of metallic gold
and 932.6 eV for Cu 2p3/2 of Cu metal. The pressure in the analysis
chamber was better than 5  107 Pa during spectral acquisition.
The data were collected and processed under Thermo Scientific
Avantage 4.58 and 4.54 software. The elemental composition
(excluding H) of the 2–4 nm surface layer characterised by XPS
was estimated, where appropriate, from the Cu 2p3/2, Fe 2p3/2, S
2p, O 1s, N 1s and C 1s peak intensities above a Shirley background
in each narrow range spectrum, and the theoretical photo ionisa-
tion cross-sections incorporated in the Avantage software. The esti-
mated composition could contain a small systematic error arising
from 2p3/2 peak background selection.
In most cases, photoelectron spectra were obtained initially
without the use of a flood-gun, and subsequently under the influ-
ence of flood-gun electrons with the specimen earthed (suite 2) or
the specimen floating (suite 3). However, the frozen DSP 009 spec-
imen required the flood-gun and spectra were determined with the
specimen floating. With the specimen holder floating, in minimis-
ing peak broadening from a non-uniform potential within the spec-
imen surface layer, the low energy electrons ‘over-compensate’ for
charging and the measured photoelectron binding energies are
typically lower than their correct energies by a value approaching
the energy of the electrons. The measured binding energies were
corrected by assuming that they all experienced the same shift,
and adjusting them so that the hydrocarbon C 1s binding energy
was 285.0 eV. Where appropriate, spectra in the figures have been
shown with binding energy adjusted in that way. Whenever the
flood-gun was used, the possibility of beam damage by the low
energy electrons was monitored, but in all cases, spectra were
obtained as quickly as possible at the expense of signal-to-noise
in order to minimise any damage arising from the secondary elec-
trons associated with the X-ray photoemission.
2.3.2. Collector coverage information from Cu L3M4,5M4,5 kinetic
energies
It is argued that just as the onset of molecular Cu or Ag xanthate
or dithiophosphate adsorption on Cu or Ag sulfide can be detected
from the initial appearance of a significantly lower kinetic energy
peak in the X-ray excited Cu L3M4,5M4,5 or Ag M4N4,5N4,5 spectrum
(Buckley and Woods, 1993, 1995), so the onset of Cu thionocarba-
mate adsorption on a Cu sulfide should be able to be detected from
the initial appearance of a Cu L3M4,5M4,5 peak at 915 eV. Cu 2p or
Ag 3d binding energy shifts are too small to differentiate the chem-
isorbed monolayer from any adsorbed multilayer CuI or AgI thio-
late. Unlike the situation for Cu thiolate adsorption, there should
be no change in the Cu L3M4,5M4,5 spectrum when a thiol collector
is chemisorbed on a Cu sulfide mineral surface. Since the main Cu
L3M4,5M4,5 peak for CuI in an oxide and sulfide lattice is at a com-
parable kinetic energy (916.6 and 917.2 eV, respectively), the
chemisorption of IPETC on the native oxide layer of Cu metal
should also give rise to no noticeable change in the Cu L3M4,5M4,5
spectrum, as an additional, low intensity component near 917 eV
would not be resolved from the main oxide peak at 916.6 eV. The
relevant, previously observed Cu L3M4,5M4,5 peak kinetic energies
are summarised in Table 1.
2.3.3. Interpretation of N 1s spectral components
The N 1s spectra from HIPETC (Section 3.1) and multilayer CuI-
PETC (Section 3.3) confirmed the assignment of components at
400.0 ± 0.2 and 398.6 ± 0.3 eV to protonated and deprotonated
thionocarbamate N, respectively. These binding energies are close
to those observed for protonated and deprotonated N in analogous
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132 123

Table 1
Previously reported Cu L3M4,5M4,5 peak kinetic energies.

Cu environment Example Cu L3M4,5M4,5 kinetic energy Reference

(eV)
CuI coordinated by O in lattice Cuprite 916.6 Buckley et al. (2009)
CuI coordinated by O in lattice and S by chemisorbed Thiol chemisorbed on Cu in 917 Buckley et al. (2009)
collector cuprite
CuII coordinated by O in adsorbed molecule Multilayer Cu hydroxamate 915.0 ± 0.5 Hope et al. (2011)
CuI coordinated by S in lattice Chalcocite 917.2 ± 0.1 Buckley and Woods (1993)
CuI coordinated by S in lattice and S in chemisorbed Thiol chemisorbed on Cu in 917.2 ± 0.3 Buckley and Woods (1993)
collector chalcocite
CuI coordinated by S in adsorbed molecule Multilayer Cu thiolate 915.0 ± 0.2 Buckley et al. (2009) and Buckley and Woods
(1993)

materials, and their assignments are not contentious. However, the (a) (b)
origin of an unresolved component near 401 eV required to fit
some spectra is less clear cut. A component between 400.8 and
401.4 eV in the N 1s spectrum determined with the flood-gun off
and the specimen earthed has been interpreted as arising from
charge-shifted protonated N in adsorbed HIPETC in poor electrical
contact with the surface. The justification for this assignment is the
absence of this 401 eV component, with a concomitant increase
in the intensity of the 400 eV component, when the flood-gun
is on while the specimen is floating (e.g., Section 3.4.3), or the shift-
ing of the 401 eV component by the energy of the flood-gun elec-
trons when the specimen is earthed (e.g., Section 3.4.5).
Accordingly, the observation of such a component is considered a 291 288 285 282 291 288 285 282
diagnostic indicator, along with a more intense N 1s component
Binding Energy (eV) Binding Energy (eV)
at 400 eV and a C 1s component near 288.4 eV from HIPETC in
good electrical contact with the specimen surface, for the presence (c) (d)
of multilayer adsorbed HIPETC.

3. Results

Conditioned surface elemental concentrations (excluding H),

peak intensity ratios, as well as N 1s fitted components and line-
widths, are listed in the Supplementary Data. Also included with
the Supplementary Data is the detailed reasoning leading to the
deduction, from the photoelectron spectra shown in Figs. 2–8, of
collector species adsorbed at each conditioned surface. The reason-
ing is similar to that described in Section 3.3 for CuIPETC adsorbed
on a Cu metal surface conditioned in 0.01 M DSP 009. For other
conditioned surfaces, only a summary of the species adsorbed is
provided in this section.
3.1. XPS characterisation of frozen commercial IPETC collector
DSP 009 (95% HIPETC) is a liquid with a sufficiently high
vapour pressure to require cooling for a small droplet of it to be
retained as a specimen in the UHV of a photoelectron spectrome-
ter. When such a specimen was cooled to 150 K under dry nitro-
gen gas, the only foreign element detected was a low concentration
of Si, most probably from the droplet substrate. The principal com-
ponent in the O 1s spectrum was at 533.4 eV and accounted for 86%
of the intensity. An obvious shoulder on the low binding energy
side of the main peak could be fitted with a component at
532 eV to account for the remaining intensity. A binding energy
of 533.4 eV is near to that expected for HIPETC, as a value of
533.7 eV has been reported for an O adjacent to a C@O group in
a polymer (López et al., 1991), a close analogy to an O adjacent
to the C@S in HIPETC. For the carbonyl oxygen in an ester, López
et al. (1991) reported an O 1s binding energy of 532.2 ± 0.2 eV, so
the minor component in the spectrum from DSP 009 would be con-
sistent with some isopropyl monothiocarbonate (carbonothioic
acidoisopropyl ester) produced by IPETC decomposition:
291 288 285 282 291 288 285 282
Binding Energy (eV) Binding Energy (eV)
Fig. 2. C 1s spectrum from (a) frozen HIPETC; (b) multilayer CuIPETC on Cu metal;
(c) Cu metal native oxide conditioned 10 min in 104 M collector; (d) chalcocite
conditioned 10 min in 104 M collector with flood-gun on and specimen floating.
C3 H8 OCðSÞNHC2 H5 þ H2 O ! C3 H8 OCðOÞSH þ C2 H5 NH2 ð4Þ
The C 1s spectrum (Fig. 2a) could be fitted with four components
of linewidth less than 1.2 eV; a major component assigned to a
binding energy of 285.0 eV accounting for slightly more than half
the intensity, and three components each accounting for about
14% of the intensity at 286.1, 286.85 and 288.4 eV. The main com-
ponent at 285.0 eV would have arisen from the three C atoms at
the ends of the molecule, as well as the majority of the C in the
impurities. The other components, in increasing binding energy,
can be attributed to the ethyl C bonded to N, the isopropyl C bonded
to O, and the C bonded to N, S and O. The assignment of the ethyl C
atom bonded to N is on the basis of the observed binding energy of
285.6 eV for poly(ethyleneimine), [ACH2CH2NHA]n, (Beamson and
Briggs, 1992) while the assignment of the isopropyl C atom bonded
to O is supported by the measurements carried out by López et al.
(1991). The assignment is also supported by the 13C NMR spectra
124 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132

for HIPETC dissolved in chloroform (Woods and Hope, 1999). (a) (b)
Observed values for the C 1s binding energy in thiourea,
H2NAC(@S)ANH2, have been 288.0 and 288.1 eV (Lee and
Rabalais, 1977; Srinivasan and Walton, 1977). The highest binding
energy component at 288.4 eV from C bonded to the S, O and pro-
tonated N is observed at a significantly lower binding energy
(287.4 eV) in the deprotonated adsorbate (Section 3.3). It would
appear that the C bonded to the S and two O atoms in any mono-
thiocarbonate decomposition product must have had a 1s binding
energy close to that (288.4 eV) for the C bonded to N, S and O in
IPETC.
The N 1s spectrum determined at the outset (Fig. 3a) comprised
a single peak at 399.9 eV of width 1.1 eV, but it was slightly 172 168 164 160 156 172 168 164 160 156
broader (1.25 eV) at the end of the spectral suite. This binding Binding Energy (eV) Binding Energy (eV)
energy was close to the value expected on the basis of those
(399.2 and 400.1 eV) observed for the N in lactams (cyclic
(c) (d)
ACAC(@O)ANHACA) and amides, 399.6–399.9 eV (e.g., Salyn
et al., 1978; Jansen and van Bekkum, 1995), and was consistent
with a N that was protonated (ANHA). As discussed further below,
any ethyl amine retained as a result of IPETC decomposition, reac-
tion (4), must have been of negligible concentration, as a compo-
nent constrained to be at the binding energy expected for amine
(399.1 eV) could not be fitted with intensity greater than zero.
The S 2p spectrum (Fig. 4a) could be fitted predominantly with a
doublet at a 2p3/2 binding energy of 162.2 eV and with a relatively
narrow component linewidth (1.0 eV). Near the start of the spec-
tral suite, a minor doublet of similar linewidth accounting for 5%
of the overall S 2p intensity at 163.8 eV was required for an ade- 172 168 164 160 156 172 168 164 160 156
quate fit. This minor doublet is expected to have originated from an Binding Energy (eV) Binding Energy (eV)
impurity or decomposition product (Section 3.2). Towards the end
of the spectral suite, the spectrum was similar, but the linewidth Fig. 4. S 2p spectrum from (a) frozen HIPETC; (b) multilayer CuIPETC on Cu metal;
(c) Cu metal native oxide conditioned 10 min in 104 M collector; (d) chalcocite
conditioned 10 min in 104 M collector with flood-gun on and specimen floating.
(a) (b)
was slightly broader (1.1 eV). The binding energy of the principal
doublet was close to that expected for a >C@S functional group
adjacent to an ether and amine group based on the values of
162.0 and 162.4 eV observed for thiourea (Lee and Rabalais,
1977; Srinivasan and Walton, 1977).
The C:O:N:S atomic ratio estimated from the C 1s, O 1s, N 1s and
S 2p intensities using theoretical photoionisation cross-sections in
the Avantage data processing software was 7.2:1.2:1.0:1.2, close to
the expected 6:1:1:1 when the influence of impurities and system-
atic errors arising from the theoretical cross-sections were taken
408 405 402 399 396 408 405 402 399 396
into account. The photoelectron spectra showed that the purity
of the commercial collector was acceptable for the purposes of this
Binding Energy (eV) Binding Energy (eV)
investigation. In particular, there was no evidence that DSP 009
was a mixture of isopropyl xanthate and ethyl amine as had been
(c) (d) raised as a possibility for Z-200 by Ackerman et al. (1984). The N 1s
binding energy for any ethyl amine present would be 399.1 eV
(Barber et al., 1973) rather than the 399.9 eV value observed, and
a significant concentration of a species with N 1s binding energy
0.8 eV lower than that for IPETC would give rise to a discernible
asymmetry to the photoelectron peak. The N 1s spectrum observed
was essentially symmetrical.

3.2. Residue of collector allowed to evaporate under UHV

In order to obtain data for any low vapour pressure IPETC

decomposition products or impurities, a droplet of the commercial
408 405 402 399 396 408 405 402 399 396
IPETC collector (DSP 009) was allowed to evaporate on an Al sub-
Binding Energy (eV) Binding Energy (eV) strate at ambient temperature under the vacuum of the photoelec-
Fig. 3. N 1s spectrum from (a) frozen HIPETC; (b) multilayer CuIPETC on Cu metal;
tron spectrometer introduction chamber. Spectra from the residue
(c) Cu metal native oxide conditioned 10 min in 104 M collector; (d) chalcocite were determined with the flood-gun on. The C:O:N:S atomic ratio
conditioned 10 min in 104 M collector with flood-gun on and specimen floating. was different for different evaporated droplets, but was within the
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132 125

range 47 ± 7:9 ± 2:1:5. Hence, the relative intensity of the N 1s (a) (b)
peak was markedly lower than for the frozen collector, indicating
at least one low vapour pressure residue that contained little or
no N. When adjusted for the shift caused by the flood-gun elec-
trons, the C 1s spectrum was broadly similar to that for the frozen
collector apart from the high binding energy region. Instead of a
component near 288.4 eV of intensity similar to that at
286.85 eV, there was a well-resolved component at 289.3 eV
accounting for 8% of the intensity in addition to a minor (2%)
unresolved component near 288 eV. The S 2p spectrum could be
fitted adequately with two components, one at 162.7 eV (13%)
and the other at 164.3 eV (87%). The N 1s spectrum consisted of
a single peak at 400.5 eV. The observation that there was no
908 912 916 920 924 928 908 912 916 920 924 928
noticeable S 2p3/2 component at 162.2 eV or N 1s component at
399.9 eV indicated that there was minimal HIPETC remaining in Kinetic Energy (eV) Kinetic Energy (eV)
the residue. The O 1s spectrum consisted primarily of two compo-
nents; one near 533.7 eV (40%) consistent with ether type O and (c) (d)
the other near 532.25 eV, a binding energy the same as that
observed for carbonyl O in an ester (López et al., 1991).
The minor residue species was broadly consistent with the
declared impurity 1,3-diethyl-2-thiourea, which has a melting
point of 77 °C, although the N 1s binding energy was 0.2 eV
higher than might have been expected. The C 1s, N 1s and S 2p3/2
binding energies for thiourea are 288.1, 400.1 and 162.4 eV
(Srinivasan and Walton, 1977), and the N 1s binding energy for
diethyl thiourea might be expected to be similar. The major species
was likely to have contained S and O but not N, and with compara-
ble concentrations of O in two different environments such as
those in an ester. From the S 2p binding energy near 164.3 eV it 908 912 916 920 924 928 908 912 916 920 924 928
is also likely that the species contained a disulfide group, and Kinetic Energy (eV) Kinetic Energy (eV)
hence the most probable major residue species would have been
isopropyl ‘carbonate disulfide’. On that basis, the most likely Fig. 5. Cu L3M4,5M4,5 spectrum from (a) Cu metal native oxide conditioned 10 min
decomposition of IPETC would have been initially to the monothio- in 104 M collector; (b) multilayer CuIPETC on Cu metal; (c) unconditioned abraded
chalcocite; (d) chalcocite conditioned 10 min in 104 M collector.
carbonate, reaction (4), followed by oxidation of the monothiocar-
bonate to the ‘carbonate disulfide’ (Murphy and Winter, 1973):

2C3 H8 OCðOÞSH þ 0:5O2 ! C3 H8 OCðOÞSASðOÞCOC3 H8 þ H2 O
ð5Þ
The fact that a S 2p component near 164 eV was not observed
for any of the specimens conditioned in DSP 009 establishes that
any carbonate disulfide oxidation product present in the collector
would not have affected the findings of the investigation reported
here. However, it is likely that a minor concentration of isopropyl
monothiocarbonate was present as a decomposition product in
the collector, and therefore a low concentration of monothiocar-
bonate might have co-adsorbed with the IPETC, thereby adding
to the complexity of the O 1s (but not N 1s) spectrum, and making
minor contributions to the C 1s and S 2p spectra. In particular,
some intensity near 532.2 eV in the O 1s spectrum and near
289.3 eV in the C 1s spectrum could have arisen from minor co-
adsorbed monothiocarbonate, but C 1s intensity near 289 eV could
also have been from charge-shifted adsorbed HIPETC in poor elec-
trical contact with a conditioned surface.
3.3. Multilayer CuIPETC
Multilayer CuIPETC was prepared by treating a Cu metal sur-
face, freshly polished with alumina in air, with 0.01 M aqueous
DSP 009 for 10 min. It is pertinent to note that when the treated
surface was rinsed with water prior to characterisation it was
clearly hydrophobic. Multilayer coverage was evident from the
photoelectron and X-ray excited Auger electron spectra deter-
mined in suites 1 and 2. The Cu L3M4,5M4,5 spectrum (Fig. 5b) con-
firmed, from a barely discernible component at 918.3 eV, that
only a very low concentration of Cu metal remained within the
3 nm depth analysed by those Auger electrons, and the O 1s spec-
trum showed that the native oxide layer was also a minor compo-
nent within the depth analysed. The main Cu L3M4,5M4,5 peak was
at a kinetic energy of 915.0 ± 0.2 eV. The elemental composition of
the surface layer, estimated on the basis of theoretical photoionisa-
tion cross-sections, was consistent with a stoichiometry of CuIPETC
apart from a high O concentration that would have been aug-
mented by some hydroxylated native oxide within the depth ana-
lysed. Clearly, adsorption of the collector had not removed the
surface oxide, despite the high collector concentration.
The C 1s spectrum (Fig. 2b) was fitted with four components of
equal width, and when corrected for charge-shifting of the thick
layer of CuIPETC, the components were at 285.0 (assigned),
285.75 ± 0.15, 286.7 ± 0.1 and 287.35 ± 0.05 eV, with the uncer-
tainties depending on the constraints placed upon the relative
intensities of the three highest binding energy components. The
energy values were not very sensitive to the intensity of the high-
est binding energy component being constrained to the same as
only the next highest, the next two highest (shown in Fig. 2b), or
no other C 1s component. The most important difference between
the C 1s spectrum for HIPETC and multilayer CuIPETC is the posi-
tion of the highest binding energy component, with that of the for-
mer being 1 eV higher than for the latter.
The N 1s spectrum determined at the outset was essentially a
single, narrow (1.2 eV) peak at 398.7 eV (Fig. 3b), corresponding
to a single N electronic environment and confirming that the N
in CuIPETC was deprotonated. Less than 3% of the N 1s intensity
was in a component at 401.2 eV. The S 2p spectrum, too, indi-
cated a single S electronic environment; the spectrum could be fit-
ted with a principal doublet with relatively narrow component
126 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132

linewidth (<1.2 eV) at a 2p3/2 binding energy of 162.6 eV (Fig. 4b).
An attempt to fit a second doublet at 162.2 eV indicated that neg-
ligible HIPETC could have been adsorbed. Also, notwithstanding
the substantial multilayer coverage, the absence of a S 2p doublet
near 164 eV revealed that there was no (IPETC)2 adsorbed at the
solid/vacuum interface (and there had been no evidence for the
loss of a high vapour pressure adsorbate species during specimen
evacuation). The O 1s spectrum was dominated by a component
at 533.25 eV that could be assigned to adsorbed IPETC. A compo-
nent near 530 eV that would have arisen from oxide in the native
oxide layer accounted for only 6% of the O 1s intensity, but a com-
ponent at 531.6 eV can be attributed to hydroxyl groups at the sur-
face of the native oxide layer.
In the second spectral suite with the flood-gun on and specimen
earthed, all spectra were shifted to lower apparent binding energy
by different amounts, up to the 4 eV energy of the flood-gun elec-
trons, depending on the degree of electrical contact between the Cu
metal substrate and the CuIPETC layers. For example, the Cu 2p
spectrum (Fig. 6a) showed that about 20% of the Cu, within the
2 nm depth analysed by the 555 eV kinetic energy photoelec-
trons, gave rise to 2p intensity that was essentially unshifted,
and therefore would have been in Cu metal, Cu native oxide, or
Cu to which IPETC was chemisorbed. The remaining 80% was
shifted by 0.9–4.1 eV, and it is likely that the intensity shifted by
0.9 eV was from the CuIPETC adsorbed immediately on top of the
chemisorbed IPETC, while the intensity shifted by 4 eV was from
CuIPETC several layers remote from the chemisorbed collector. All
spectra could be fitted with five components of typical width
(a) (b)
shifted by 0, 0.9, 1.9, 3.0 and 4.1 eV, but because the shifted com-
ponents were not resolved, the fits would not have been unique.
3.4. Surfaces conditioned in IPETC solutions under conditions of
relevance to flotation
While it is the adsorption of IPETC, or any other sulfhydryl col-
lector, on sulfide minerals that is of principal industrial interest,
the adsorption on a surface of the relevant metal freshly prepared
in air can provide information that assists the interpretation of
spectra from sulfide minerals conditioned in that collector. In the
particular case of IPETC, it is its adsorption on a freshly-formed
native CuI oxide layer on Cu metal, or on cuprite (Cu2O), that would
be expected to be of use in helping to elucidate the mechanism of
interaction with CuI in the Cu sulfide minerals such as chalcocite
and chalcopyrite. It is clear from §3.3 that IPETC adsorbs readily
on air-exposed Cu metal. The adsorption of IPETC on pyrite is also
relevant given that pyrite is a common sulfide gangue mineral
from which the Cu sulfides should be separated. In general, low
concentrations of sulfhydryl collectors resulting in sub-monolayer
coverage are of greatest industrial relevance, but for research pur-
poses it is important to also include higher than normal concentra-
tions to investigate the effect of any multilayer collector
adsorption. Another reason multilayer coverage is of interest is in
the determination of whether any (IPETC)2 is formed and adsorbed.
It is possible that the vapour pressure of (IPETC)2 might be suffi-
ciently high at ambient temperature for any adsorbed at low col-
lector coverage to be lost from the solid/vacuum interface in the
spectrometer. However, for substantial multilayer coverage, some
of any adsorbed (IPETC)2 would be expected to desorb slowly
enough to be detected at the start of the analysis period.

3.4.1. Cu metal
A copper metal surface, freshly polished in air with alumina,
was conditioned for 10 min in an aliquot of the same 104 M IPETC
solution as used for abraded chalcocite (Section 3.4.3). The rinsed
surface was clearly hydrophobic. The photoelectron spectra
(Figs. 2c and 4c) and Cu L3M4,5M4,5 Auger electron spectrum
(Fig. 5a) indicated that collector coverage was marginally higher
(4.1 at.% N) than for the similarly treated chalcocite (3.6 at.% N),
and that the N was predominantly deprotonated in IPETC chemi-
sorbed to Cu atoms with some molecular CuIPETC on top of the
965 955 945 935 925 965 955 945 935 925 chemisorbed collector. The spectra also showed that a substantial
Binding Energy (eV) Binding Energy (eV) native oxide layer remained.
Other Cu metal surfaces freshly polished in air were condi-
tioned for 10 min in 103 M IPETC solution. After being rinsed
(c) (d)
with water, the surfaces were clearly hydrophobic, and with
4.9 at.% N, collector coverage was greater than for the surface con-
ditioned for the same period in 104 M solution, but the native
oxide layer had a thickness similar to that for the specimen condi-
tioned in 104 M solution. The spectral behaviour under the influ-
ence of the flood-gun electrons showed that the adsorbed species
would have been mostly multilayer CuIPETC on top of chemisorbed
IPETC with only a minor concentration of HIPETC.

3.4.2. Cuprite (Cu2O)

Cuprite fracture surfaces conditioned for 10 min in 103 M
IPETC solution were too rough for their hydrophobicity to be
965 955 945 935 925 965 955 945 935 925
assessed by visual examination. The N and S concentrations (3.2–
Binding Energy (eV) Binding Energy (eV) 3.7 at.%) at these surfaces were comparable, as expected, but there
was evidence for preferential desorption of N relative to S with
Fig. 6. Cu 2p spectrum determined in (a) suite 2 or (b–d) suite 1 from (a) multilayer
CuIPETC; (b) chalcocite conditioned 10 min in 104 M collector; (c) covellite
increasing analysis time. The spectra indicated that most N was
conditioned 10 min in 103 M collector; (d) chalcopyrite conditioned 10 min in deprotonated in chemisorbed IPETC, with only minor HIPETC
103 M collector. adsorbed.
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132 127

3.4.3. Chalcocite (Cu2S) (a) (b)

Freshly abraded chalcocite surfaces conditioned for 10 min in
104 M IPETC solution appeared hydrophobic when rinsed with
water. The surface layer elemental composition included
3.6 at.% N. The spectra (Figs. 3d, 5c, d and 6b) revealed the pres-
ence of comparable concentrations of chemisorbed IPETC and
HIPETC. The absence of adsorbed molecular CuIPETC was con-
firmed by the similarity, within experimental variability, of the
Cu L3M4,5M4,5 spectra for the unconditioned and conditioned chal-
cocite surfaces (Fig. 5c and d), in conjunction with less surface sen-
sitive S 2p and N 1s components from chemisorbed collector. The
spectra also showed that for no greater than monolayer coverage,
the collector S interacted with a Cu atom in the mineral surface,
not a S atom as argued by Crozier (1991). 740 730 720 710 740 730 720 710
Freshly abraded chalcocite surfaces conditioned for 10 min in Binding Energy (eV) Binding Energy (eV)
103 M and 102 M IPETC solutions also appeared to be hydropho-
bic after being rinsed with water. For the 103 M solution, the sur-
(c) (d)
face N concentration was 6.4 at.%. The spectra indicated that there
was some HIPETC adsorbed as well as chemisorbed IPETC and
minor CuIPETC.

3.4.4. Covellite (CuS)

Surfaces prepared initially by cleavage parallel or perpendicular
to the basal {0 0 1} plane, and subsequently abraded, might be
expected to have retained some preferential orientation rather
than have become completely random. The S(2)AS(2) distance in
covellite is 0.207–0.209 nm, significantly shorter than the
0.214 nm in pyrite, so the covellite SAS bonds are expected to be
stronger than the CuAS bonds and hence be less likely to cleave
(Rosso and Hochella, 1999). On that basis, a basal plane fracture
surface would be expected to be dominated by broken CuAS bonds
parallel to the c-axis rather than broken disulfide bonds, and hence
significant reconstruction of the two different opposing fracture
surfaces would be anticipated. However, Ohmasa et al. (1977)
argued that the highly perfect cleavage characteristic of covellite
could be ascribed to the short (0.219 nm) trigonal Cu(1)AS(1)
bonds being stronger than the more typical tetrahedral 0.234 nm
Cu(2)AS(1) and 0.231 nm Cu(2)AS(2) bonds. They also noted that
the S(2)AS(2) distance was longer than for VS4 (0.203–0.204 nm),
but they did not speculate on the more likely bond broken during
cleavage of covellite.
Freshly abraded covellite surfaces, that initially had been either
parallel or perpendicular to the {0 0 1} cleavage plane, conditioned
for 10 min in 103 M IPETC solution and subsequently rinsed with
water, appeared to be slightly hydrophobic. For the conditioned
abraded edges, the N concentration was 1.9 at.%, and the spectra
(including Fig. 6c) showed that, surprisingly, the predominant
adsorbed species was HIPETC rather than IPETC chemisorbed to
Cu atoms.
The spectra from conditioned abraded surfaces predominantly
parallel to the basal plane indicated very low (1.3 at.%) initial
concentrations of N, predominantly in adsorbed HIPETC as well
as minor chemisorbed IPETC.
3.4.5. Chalcopyrite (CuFeS2)
A chalcopyrite fresh fracture surface conditioned for 10 min in
103 M IPETC solution, then rinsed with water, was too rough for
a visual assessment of its hydrophobicity. Collector adsorption
was quite low (1.6 at.% N), and the spectra (including Figs. 6d,
7a and 8a) indicated that about 70% of the collector was adsorbed
as HIPETC. The HIPETC was in good electrical contact with the
surface, perhaps because it was adsorbed directly on the FeAO or
CuFe 1xS2 rather than on top of chemisorbed IPETC.
Freshly abraded chalcopyrite surfaces were conditioned for
10 min in 103 M IPETC solution, and when subsequently rinsed
with water, the surfaces appeared to be slightly hydrophobic. Note,
740 730 720 710 740 730 720 710
Binding Energy (eV) Binding Energy (eV)
Fig. 7. Fe 2p spectrum from (a) chalcopyrite or (b–d) pyrite (b) abraded or (a, c and
d) fracture surface conditioned for 10 min in (a–c) 103 M collector; (d) 102 M
collector.
however, that even unconditioned abraded chalcopyrite surfaces
are usually hydrophobic to some extent because of the sulfur-rich
CuFe1xS2 regions formed during air exposure (Zachwieja et al.,
1989). The N concentration at the conditioned surfaces was
2.2 at.%, higher than for fresh fracture surfaces treated for the
same period in collector solutions of similar concentration. The
spectra showed that there was no molecular CuIPETC adsorbed,
but there was clear evidence for monolayer and multilayer HIPETC,
the predominant adsorbed collector species. Similar species were
adsorbed on freshly abraded chalcopyrite surfaces conditioned
for 1 min in 103 M IPETC solution or 10 min in 102 M solution.
In each case, the conditioned surface was hydrophobic.
A chalcopyrite fracture surface, exposed to air for 60 min prior
to conditioning for 10 min in another aliquot of the same 103 M
IPETC solution that had been used for conditioning a fresh fracture
surface for 10 min, was too rough to assess its hydrophobicity. Col-
lector coverage was low (1.7 at.% N), comparable with that
observed for a chalcopyrite fresh fracture surface that had been
conditioned for the same period in another aliquot of the same
dilution. The spectra showed that more than 80% of the collector
was strongly adsorbed as HIPETC, with minor IPETC chemisorbed
to Cu atoms.
Another chalcopyrite fracture surface exposed to air for 7 d was
conditioned for 10 min in 102 M IPETC solution. The surface was
too rough to assess its hydrophobicity. The spectra indicated that
collector coverage was very low (1.2 at.% N), and were consistent
with collector that was strongly adsorbed primarily as HIPETC.
3.4.6. Cubanite (CuFe2S3)
The reactivity of freshly exposed cubanite surfaces has been
found to be comparable with that for chalcopyrite, and the Cu, Fe
128 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132

and S core electron binding energies are similar to those for chal- (a) (b)
copyrite (Goh et al., 2010). While the (Cu + Fe):S ratio is 1:1 in both
minerals, the Cu concentration in cubanite is lower, and hence the
CuAOHsurf concentration for air-exposed surfaces might also be
expected to be lower for cubanite because of the comparable rates
of FeAO formation.
Cubanite surfaces that had been abraded in air, conditioned for
10 min in 103 M IPETC solution and subsequently rinsed with
water were moderately hydrophobic. This hydrophobicity was
despite a significant concentration of FeAO species within the
depth analysed, but no SAO species were retained at the rinsed
surface. The surface N concentration was 1.8 at.%, and 80% of
the adsorbed collector was present as HIPETC in good electrical 171 168 165 162 159 156 171 168 165 162 159 156
contact with the mineral substrate. There was no evidence for Binding Energy (eV) Binding Energy (eV)
any adsorbed molecular CuIPETC.
(c) (d)
3.4.7. Bornite (Cu5FeS4)
Freshly abraded bornite surfaces were conditioned for 10 min in
103 M IPETC solution, and after being rinsed with water, were
clearly hydrophobic. The obvious hydrophobicity was surprising
given the low N concentration (1.2 at.%) and hence low collector
coverage. More than 80% of that coverage had been adsorbed as
HIPETC, and the spectra also revealed the presence of FeOOH
patches rather than a uniform layer of FeAO species across the sur-
face. No molecular CuIPETC was detected.
Abraded bornite surfaces exposed to air for 1 h prior to condi-
tioning for 10 min in 103 M collector solution were clearly hydro-
phobic. The surface N concentration was 1.8 at.%, and the spectra 171 168 165 162 159 156 171 168 165 162 159 156
were consistent with the adsorption of predominantly HIPETC,
Binding Energy (eV) Binding Energy (eV)
with less than 5% as chemisorbed IPETC.
A bornite fracture surface exposed to air for 25 h was condi- Fig. 8. S 2p spectrum from (a) chalcopyrite or (b–d) pyrite (b) abraded or (a, c and
tioned for 10 min in 103 M collector solution. The fracture surface d) fracture surface conditioned for 10 min in (a–c) 103 M collector; (d) 102 M
was rough, but fine particles broken off by the agitation during collector.

conditioning accumulated at the liquid/air interface and hence

were deduced to be hydrophobic. Almost all of the Fe within the
depth analysed by the Fe 2p photoelectrons was present as FeAO
species. The N concentration was 2.0 at.%. The spectra indicated
about 70% of the adsorbed collector was present as HIPETC in good
electrical contact with the mineral surface; the other 30% was pres-
ent as chemisorbed IPETC and molecular CuIPETC with some of the
multilayer CuIPETC in poor electrical contact with the surface.
3.4.8. Pyrite (FeS2)
Freshly abraded surfaces of pyrite conditioned for 10 min in
102 M or 103 M IPETC solution were not obviously hydrophobic.
After conditioning in 103 M solution, the surface N concentration
was 1.5 at.%, with the collector adsorbed largely as monolayer
HIPETC. The concentration of FeAO species at the rinsed surface
was relatively low (Fig. 7b), and there were no SAO species evident
(Fig. 8b).
Fresh fracture surfaces of pyrite conditioned for 10 min in 103
or 102 M IPETC solution were too rough to reliably assess their
hydrophobicity. Fracture surfaces of this relatively pure Navajún
pyrite exposed only to air for 10 min became oxidised to a negligi-
ble extent, but surfaces conditioned in the collector solution
became substantially oxidised, and at least some of the oxidation
products were retained at the surface after rinsing with water.
For the fracture surface conditioned in 103 M IPETC solution, the
N surface concentration (0.7 at.%) revealed that collector coverage
was considerably lower than for similarly conditioned abraded sur-
faces. The predominant adsorbed collector species was HIPETC. The
concentrations of FeAO and SAO species were both appreciable
(Figs. 7c and 8c), however, the retention of such a high concentra-
tion of SAO species was unusual, and it is possible that they had
been present as an inclusion at the fresh fracture surface prior to
conditioning. Note that the SAO species would not have been
formed after the surface had been conditioned, as negligible SAO
species were retained at other surfaces conditioned in IPETC
solution.
For the fracture surface conditioned in 102 M IPETC solution,
collector coverage was found to be low, but not negligible at
1.8 at.% N, with 85% present as HIPETC. The collector coverage
on a Cu metal surface polished in air and treated with another ali-
quot of the same IPETC solution under exactly the same conditions
had been substantial (6.6 at.% N). In contrast to the fracture surface
conditioned in 103 M solution, this surface layer contained a
greater concentration of FeAO species (with Fe 2p3/2 peak maxi-
mum at 711.0 eV) but negligible SAO species (Figs. 7d and 8d). Oxi-
dation of the pyrite surface while in the collector solution would
probably not have occurred if the fracture surface had been ‘pro-
tected’ by an appreciable coverage of collector.
4. Discussion
4.1. Identity of collector species adsorbed
The predominant collector species adsorbed on each (air-
exposed) surface investigated, as deduced from the electron spec-
tra, are summarised in Table 2. The N concentration resulting from
conditioning for 10 min in 103 M collector solution is also tabu-
lated as an indicator of the relative degree of coverage of each sur-
face by all adsorbed collector species, but note that the different
mineral compositions and extents of surface oxidation should be
taken into account in any direct comparison of coverage based
on the N concentration. The predominant collector species varied
from chemisorbed IPETC and multilayer CuIPETC for Cu metal
native CuI oxide and cuprite, through comparable concentrations
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132
Table 2
Summary of species adsorbed on substrate surface (freshly abraded, 10 min conditioning in 103 M collector, unless otherwise specified) from IPETC solution. In all cases where
HIPETC was the main adsorbed species, it was mostly not adsorbed on top of chemisorbed IPETC.
Substrate Main adsorbed collector species
Cu native oxide Chemisorbed IPETC and CuIPETC
Cuprite (fracture) Chemisorbed IPETC
Chalcocite Comparable CuIPETC on chemisorbed IPETC and HIPETC
Covellite HIPETC
Chalcopyrite HIPETC
Chalcopyrite (fracture) HIPETC
Chalcopyrite (fracture; 7 d air-exposure; 102 M) HIPETC
Cubanite HIPETC
Bornite HIPETC
Bornite (1 h air-exposure) HIPETC
Bornite (fracture; 25 h air) HIPETC (with minor CuIPETC on chemisorbed IPETC)
Pyrite HIPETC
Pyrite (fracture) HIPETC
of HIPETC and CuIPETC on chemisorbed IPETC for chalcocite, to
HIPETC for covellite, the CuAFe sulfides and pyrite. This progres-
sion in predominant adsorbed collector species from chemisorbed
IPETC and CuIPETC to HIPETC correlates with a decrease in the sur-
face availability of CuAOHsurf to facilitate reaction (6):
CuAOHsurf þ HIPETC ! CuAIPETCads þ H2 O
where CuAIPETCads represents the collector chemisorbed to surface
Cu atoms. In air, hydroxyl groups chemisorbed to Cu atoms at the
surface of a Cu sulfide mineral such as chalcocite could result from
the reaction of the mineral surface with oxygen:
Cu2 S þ 0:25xO2 ! Cu2x S þ 0:5xCu2 Osurf
followed by the reaction of the Cu2O at the solid/air interface with
water vapour:
Cu2 Osurf þ H2 O ! 2CuAOHsurf
While such a dependence of adsorbed collector species on the
availability of CuAOHsurf might be obvious in the case of pure pyr-
ite that had not been Cu-activated, it is not at all self-evident for a
mineral such as covellite. Also, it might not have been expected
that the species adsorbed on chalcocite would be different from
those adsorbed on freshly exposed surfaces of the Cu-rich mineral
bornite. Furthermore, there appeared to be a second-order differ-
ence in the HIPETC physically adsorbed as a multilayer species
on top of chemisorbed IPETC (such as on chalcocite), and HIPETC
adsorbed in good electrical contact with the surface (and hence
most probably adsorbed strongly) as a monolayer species (such
as on pyrite). For none of the surfaces investigated was there any
evidence for the adsorption of (IPETC)2, however, it is possible that
when the coverage was low, this species might have been adsorbed
at the solid/solution interface but, because of an insufficiently low
vapour pressure, lost from the solid/vacuum interface at ambient
temperature.
The predominant collector species (HIPETC) adsorbed on exten-
sively air-exposed chalcopyrite or moderately air-exposed bornite
was similar to that on fresh chalcopyrite or bornite surfaces. This is
somewhat surprising, as it might have been expected that there
would have been a difference similar to that exhibited by CuAFe
sulfide surfaces towards hydroxamate collector adsorption, which
was influenced by increased air exposure leading to FeAO patches
and more exposed Fe-deficient Cu sulfide regions between the
oxide patches (Buckley et al., 2014). The only sign of that behaviour
was displayed by the bornite fracture surface exposed to air for
25 h. At that surface, essentially all the Fe would have been present
in patches of FeAO species, thereby exposing Fe-depleted Cu sul-
fide regions that probably would have presented CuAOHsurf for
interaction with HIPETC during the conditioning. Even so, CuIPETC
129
at.% N Coverage (0.001 M collector solution)
4.9 Multilayer
3.7 Monolayer
6.4 Multilayer
1.9 Monolayer
2.2 Multilayer
1.7 Monolayer
1.2 Monolayer
1.8 Monolayer
1.2 Monolayer
1.8 Monolayer
2.0 Multilayer
1.5 Monolayer
0.7 Monolayer
adsorbed on chemisorbed IPETC remained a minority adsorbed col-
lector species. The adsorption of predominantly HIPETC on chalco-
pyrite was in partial agreement with the conclusions of Fairthorne
et al. (1997); they estimated that approximately two layers of
IPETC were adsorbed on chalcopyrite at pH 5.
ð6Þ
4.2. IPETC collector adsorption mechanisms
In order to unequivocally corroborate the chemisorption of
IPETC to Cu atoms in a mineral surface, rather than collector bond-
ing to surface S atoms, or interaction by a dissolution–precipitation
ð7Þ mechanism, it would be necessary to limit coverage to monolayer
at most, but to have sufficient coverage for both the N 1s and S 2p
spectra from the adsorbed collector to be well-resolved, and to
confirm equal surface concentrations of N and S from the adsorbed
collector. Equal concentrations of N and S would be necessary to
ð8Þ
eliminate the possibility of collector decomposition. The N and C
1s spectra would need to establish that a substantial proportion
of the collector had been deprotonated (and hence not adsorbed
as HIPETC). For the S 2p component from IPETC to be resolved from
the S 2p spectrum from a sulfide mineral substrate, the latter
would need to have no components with 2p3/2 binding energy
above about 161.8 eV. Under those sub-monolayer conditions,
the absence of a Cu L3M4,5M4,5 Auger component near 915 eV
would confirm the absence of adsorbed CuIPETC, and hence pre-
clude a dissolution–precipitation mechanism. Those criteria were
best satisfied by a chalcocite substrate conditioned in collector
solution more dilute than 103 M.
When chalcocite was conditioned for 10 min in 104 M IPETC
solution, the C 1s, N 1s and S 2p spectra confirmed the adsorption
of both protonated (HIPETC) and deprotonated (IPETC) collector,
without the formation of S-S bonds, and with concentrations of N
and S that were equal within experimental error. However, the
Cu L3M4,5M4,5 Auger spectrum showed that no CuIPETC had been
formed, therefore the deprotonated collector would have been
IPETC chemisorbed to Cu atoms in the chalcocite surface. The Cu
L3M4,5M4,5 Auger electrons (915 eV kinetic energy) are more sur-
face sensitive than the S 2p photoelectrons (1325 eV kinetic
energy), therefore the absence of a component at 915 eV kinetic
energy cannot be due to insufficient sensitivity. These observations
for chalcocite constitute definitive evidence for the chemisorption
of IPETC rather than the adsorption of sub-monolayer CuIPETC, and
hence definitive evidence for the inapplicability of a dissolution–
precipitation mechanism for this system. Similar behaviour was
observed for at least some of the other Cu sulfide minerals, how-
ever the evidence was not as definitive, as although chemisorption
of IPETC was revealed by the N 1s spectrum, and the absence of
CuIPETC confirmed by the Cu L3M4,5M4,5 Auger spectrum, the
130 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132
adsorption of IPETC could not be unequivocally corroborated by
the S 2p spectrum because of the complexity of the component
from the mineral substrate. Broadly similar behaviour was
observed for cuprite and native CuI oxide on Cu metal, too, but con-
ditioning of the latter for 10 min in 104 M solution resulted in suf-
ficient coverage for minor multilayer CuIPETC to be adsorbed on
top of the major chemisorbed IPETC.
Controversially, Crozier (1991) had argued that sulfhydryl col-
lector–sulfide mineral bonding was a S-to-S bond rather than a
S-to-metal bond, and that such SAS bonds could not be distin-
guished spectroscopically from that in dithiolates. While the latter
statement might be true, when dithiolates are not present, the
absence of SAS bonds (as observed in the present investigation)
provides confirmation that collector chemisorption is via bond for-
mation between the S in the collector and a metal atom in the min-
eral surface.
The C 1s, N 1s and S 2p spectra from CuI native oxide on Cu
metal or cuprite conditioned in dilute IPETC solution revealed the
adsorption of predominantly deprotonated IPETC, without the
wholesale removal of the native oxide layer. This observation
was in agreement with previous reports. For cuprite, the Cu
L3M4,5M4,5 Auger spectrum revealed the presence of either IPETC
chemisorbed to Cu at the surface of the oxide lattice or molecular
CuIPETC, or both, as those two species could not be differentiated
on the basis of the Auger spectrum alone. The fate of O atoms at
the surface of Cu metal, CuI oxide or air-exposed Cu sulfide miner-
als during conditioning raises the question as to whether the col-
lector chemisorbs directly to a Cu in the oxidised metal or
cuprite (and possibly Cu sulfide mineral) surface, as in reaction
(6), or whether it forms a SAOACu bond. The S 2p spectrum, with
a 2p3/2 binding energy of 162.6 ± 0.1 eV, shows unequivocally that
the SACu bond is direct. The 2p3/2 binding energy for a SAS bond
(in [DTP]2, for example) is no lower than 164.0 eV, and the corre-
sponding binding energy for a SAO bond would be at least as high.
A corollary of direct SACu bond formation with predominant
native CuI oxide retention is collector adsorption in patches, with
adsorption of multilayer CuIPETC without the completion of a uni-
form monolayer of chemisorbed IPETC.
The increase in the S 2p3/2 binding energy from 162.2 eV in
HIPETC to 162.6 eV in multilayer CuIPETC and the chemisorbed
collector indicated a reduction in the electron density at S atoms
in IPETC, consistent with the formation of a CuAS bond. Accord-
ingly, the XPS data supported the conclusion reached in almost
all previous studies of thionocarbamate adsorption that the princi-
pal interaction between the surface and the collector is through its
S. However, the question remains as to whether there is also a sig-
nificant interaction of either N or O with Cu atoms.
For bulk HIPETC, the 1s binding energy for the C bonded to N, S
and O is 288.4 eV, and the O 1s binding energy is 533.4 eV. For mul-
tilayer CuIPETC, in which the N is deprotonated, the 1s binding
energy for C bonded to N, S and O is 1 eV lower (287.4 eV), indicat-
ing that the electron density on that C atom is higher. A higher
electron density on the C would mean that the electron density
on the O would be unlikely to be lower, and could be slightly
higher, than in HIPETC, so that the O 1s binding energy would be
expected to be no greater or slightly lower than 533.4 eV unless
there was significant interaction between the O and a metal atom
to offset any increase in the electron density that might have
derived from the increase on the C atom. The observation of a mar-
ginally lower O 1s binding energy in CuIPETC than in HIPETC sug-
gests no more than minor interaction between the O and Cu. Ab
initio calculations of the charge on the S atom in HIPETC were
reported by Liu et al. (2008), but corresponding charges for the
other atoms in HIPETC and for IPETC were not. Solozhenkin
et al. (2013) calculated atomic charges for HIPETC, but their value
for S (-0.465) was significantly more negative than the values
(0.306 to 0.352) calculated by Liu et al. (2008) and did not
appear to be comparable.
The N 1s binding energy in multilayer CuIPETC, 398.7 eV, is
quite low and characteristic of N that has not only been deproto-
nated but also is not interacting with a metal atom. If there had
been significant interaction between deprotonated N and Cu, a N
1s binding energy near 399.4 eV would have been expected. There-
fore there is no evidence for significant interaction between either
the O or N and the Cu to which the S is bonded or to a Cu in a neigh-
bouring molecule in the multilayer.
The O and N 1s binding energies observed for chemisorbed
IPETC were within the ranges 533.1–533.5 eV and 398.3–
398.8 eV. Each energy spread probably reflected the uncertainty
in fitting a minor unresolved component of the O 1s or N 1s spec-
trum rather than interaction with the particular mineral, neverthe-
less, the N 1s component was usually near 398.3 eV for
chalcopyrite, 398.5 eV for chalcocite and covellite, 398.6 eV for
cuprite, and 398.8 eV for bornite and pyrite. Within experimental
uncertainty, however, the O and N 1s binding energies were similar
for IPETC chemisorption as for multilayer CuIPETC, indicating that
there was no significant interaction between the O or N and a Cu
atom in that sub-monolayer species either. This finding for pH
6 is broadly in agreement with the conclusions of Woods and
Hope (1999) and Leppinen et al. (1988).
It would be expected that when HIPETC adsorbed on top of
chemisorbed IPETC, an alkyl group of the HIPETC would interact
physically with an alkyl group of the chemisorbed IPETC. That rel-
atively weak interaction would be consistent with the observed
poor or moderate electrical contact between the HIPETC and the
substrate. On the other hand, when minimal IPETC was chemi-
sorbed, and HIPETC adsorbed directly on to a mineral surface, elec-
trical contact between the HIPETC and the mineral surface
appeared to be good. It is possible that even though the HIPETC
remained protonated, interaction with the mineral surface was
via the S atom. Such an interaction would be weaker than the CuAS
bond in chemisorbed IPETC, but significantly stronger than the
alkyl–alkyl interaction for HIPETC physically adsorbed on top of
chemisorbed IPETC.
In their molecular modelling of the in vacuo interaction of IPETC
collector with pyrite (represented by an isolated FeS2 or cyclic
FeS2AFeS2), Solozhenkin et al. (2013) found that in monodentate
bonding of the collector N with the pyrite Fe, charge was trans-
ferred from the mineral to the collector S. By contrast, in bidentate
bonding of the collector N and S with the Fe, charge was trans-
ferred from the collector to the mineral. The situation for bidentate
bonding of the collector S and O with the Fe, or for interaction of
HIPETC with pyrite, was not reported, nevertheless their calcula-
tions suggested that IPETC should interact with the Fe in pyrite.
In principle, the direction of any charge transfer should be evident
from the collector S 2p3/2 binding energy, but in practice such
information would not be available for pyrite because the mineral
S 2p3/2 binding energy is almost the same as that of any adsorbed
IPETC. The direction of any charge transfer should also be evident
in the 1s binding energy of the C bonded to the collector S. For pyr-
ite, that C 1s binding energy was 288.3 eV, consistent with
adsorbed HIPETC rather than IPETC chemisorbed to the pyrite Fe.
4.3. Correlation of adsorbed collector species with observed floatability
and implications for flotation
Apart from pyrite, conditioned surfaces that were smooth
enough to assess by visual inspection appeared to be hydrophobic.
For not extensively oxidised abraded surfaces, the order of decreas-
ing coverage was chalcocite > native CuI oxide > cuprite > chalco-
pyrite > covellite ffi cubanite > bornite ffi pyrite. For the sulfide
minerals, that order was broadly in agreement with the
 A.N. Buckley et al. / Minerals Engineering 69 (2014) 120–132
microflotation data of Ackerman et al. (1999), and the (pH 8)
adsorption data of Finkelstein and Goold (1972). It should be noted
that for the mineral surfaces investigated in both forms, the cover-
age on fracture surfaces was significantly different from that on
abraded surfaces. Coverage on an extensively oxidised surface
was usually significantly different from that on a freshly exposed
surface.
The question of whether the coverage, and predominant
adsorbed collector species, on pyrite is consistent with its lack of
obvious hydrophobicity and the low recovery observed for that
mineral relative to the Cu sulfides is a vexed one. Under the pH
conditions used, adsorption on pyrite was low, but perhaps not
as low as might have been expected relative to adsorption on born-
ite, especially as Navajún pyrite is not a particularly reactive pyrite.
The lack of obvious hydrophobicity for pyrite was surprising given
the hydrophobicity observed for bornite surfaces bearing compara-
ble coverages of HIPETC. Even the form in which the collector was
adsorbed, strongly adsorbed HIPETC, was similar for pyrite and the
CuAFe sulfides. Flotation tests have shown that at pH 6, IPETC col-
lector affords good separation of chalcopyrite from pyrite, but the
origin of that differentiation might be more than merely one of col-
lector coverage. It is surmised that reasons for the difference in flo-
atability might include the rate of collector adsorption as well as
the eventual coverage or the particular species adsorbed.
Leppinen et al. (1988) had suggested that the differentiation might
have been the inability of IPETC to remove oxidation products from
the surface of pyrite, and while oxidation products are certainly
not removed from pyrite surfaces, the photoelectron spectra have
shown that IPETC doesn’t remove oxidation products from the Cu
sulfides or Cu metal either. It is true that the nature of the surface
oxidation products formed on pyrite and the CuAFe sulfides is dif-
ferent, but it would be the nature of the alteration products
retained at the surface under flotation conditions that would be
of relevance. For pyrite, freshly-formed SAO species would nor-
mally be expected to enter the aqueous phase, whereas some
freshly-formed FeAO species could be retained at the surface. For
the CuAFe sulfides, some freshly-formed FeAO species would enter
the aqueous phase and some would be retained, but SAO species
are not formed initially, and patches of metastable Fe-deficient sul-
fide would be more prevalent at the mineral/solution interface
than for pyrite. As noted in Section 3.4.5, there is strong evidence
for the S-rich (Fe-deficient) sulfide surface layer to be hydrophobic,
so the macroscopic mineral surface hydrophobicity is probably
determined by both the adsorbed collector and the hydrophobicity
or hydrophilicity of the mineral surface regions not bearing
adsorbed collector. Therefore while removal of oxidation products
by the collector does not appear to be a factor in determining the
effective hydrophobicity of conditioned sulfide minerals, the alter-
ation products retained at the surface do appear to be important.
5. Conclusions
Under the conditions investigated, the predominant thionocar-
bamate collector species adsorbed on Cu sulfide ore minerals were
found to vary from chemisorbed IPETC (and molecular CuIPETC for
sufficiently high concentrations) on cuprite, through comparable
concentrations of HIPETC and chemisorbed IPETC on chalcocite,
to HIPETC adsorbed on covellite, the CuAFe sulfides and pyrite.
This progression from chemisorbed IPETC to HIPETC correlated
with a decrease in CuAOHsurf availability for exchange of surface
OH with IPETC. No evidence was observed for the adsorption
of (IPETC)2.
When monolayer IPETC was adsorbed, it was chemisorbed to
the Cu atoms in the mineral surface rather than to surface S atoms.
Monolayer IPETC adsorption was not in the form of molecular CuI-
PETC, and did not lead to the concomitant wholesale removal of
131
the oxide layer from the air-exposed mineral surface. HIPETC could
be adsorbed as a multilayer species on top of chemisorbed IPETC,
or when chemisorbed IPETC coverage was low, as a monolayer spe-
cies in good contact with the surface. Surfaces bearing such
adsorbed monolayer HIPETC were hydrophobic.
The decrease in coverage of chemisorbed IPETC on the different
Cu sulfide ore minerals was broadly in agreement with their previ-
ously observed decreasing floatability. However, the lack of obvi-
ous hydrophobicity and the poor floatability of pyrite appeared
to be anomalous, in that the coverage of HIPETC on pyrite was
not markedly different from that on the CuAFe sulfides such as
bornite. It was surmised that this anomaly might be attributable
to the different oxidation and alteration products retained at the
surface of conditioned pyrite.
Acknowledgements
The authors are grateful to Dr. Bill Gong (UNSW Analytical Cen-
tre) for assistance in obtaining the XPS data, and to Prof. Bill Skin-
ner (Ian Wark Research Institute, University of South Australia) for
providing the cuprite and cubanite specimens.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.mineng.20
14.08.002.
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