The Interaction of Flotation Reagents With Metal Ions in Mineral Surfaces
The Interaction of Flotation Reagents With Metal Ions in Mineral Surfaces
The Interaction of Flotation Reagents With Metal Ions in Mineral Surfaces
Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng
A R T I C L E I N F O A B S T R A C T
Keywords: The selective interaction between reagents and mineral surfaces is the core basis of mineral flotation separation.
Mineral surface This paper creatively proposes a perspective from coordination chemistry to clarify the interaction mechanism of
Reagent reagents with mineral surfaces systematically and profoundly. The metal ion in mineral surface is far different
Coordination chemistry
from the free ion. The former is in a semi-constrained state, causing the properties of surface metal ions to be
π-backbonding
greatly affected by surface structures and properties of surrounding atoms. Based on coordination chemistry, the
π-backbonding model is advanced for the interaction between sulfhydryl collectors and sulphide minerals. It is of
interest that with more π electron pairs, the surface metal ion is more likely to interact with sulfhydryl collectors
containing unoccupied π orbitals; with greater polarizability, the metal ion is more prone to covalent interactions
with sulfhydryl collectors. In addition, the unoccupied orbitals play a crucial role in selectivity of depressants.
For example, the depressants NaCN and Ca(OH)+ containing unoccupied π orbitals can strongly depress pyrite
holding π electron pairs, but can hardly depress galena possessing no π electron pair. Furthermore, the crystal
field stabilization energy resulting from the interaction between reagents and surface metal ions can influence
the stability of reagent adsorption, and can adequately explain the order of flotation critical pH for sulphide
minerals. The coordination theory sheds new light on the interaction mechanism between flotation reagents and
mineral surfaces.
https://doi.org/10.1016/j.mineng.2021.107067
Received 22 February 2021; Received in revised form 2 July 2021; Accepted 4 July 2021
0892-6875/© 2021 Elsevier Ltd. All rights reserved.
J. Chen Minerals Engineering 171 (2021) 107067
the cationic collectors (anionic collectors) would be adsorbed. Never ions in the flotation system. The interaction between reagents and sur
theless, the negatively charged short-chain collector ions can adsorb on faces is essentially hetero-coordination, that is, the reagent molecule
a negatively charged surface by chemical interaction. For example, coordinates with the metal ion that has already been bound to sur
xanthate anion can still adsorb on sulphide mineral surface, charged rounding atoms. Therefore, the reactivity of metal ions is determined by
negatively, in strong alkaline pulp. the surface structure of minerals and the properties of coordinated
However, Cook and Nixon (1950) disagreed with the adsorption atoms. Pradip (2003) believed that there is “structural/stereochemical
mechanism, and ascribed the process of adsorption to the hydrolysis of compatibility” between molecular architectures of collector molecules
the collector to produce electrically neutral free-acid molecules, as and mineral surface structures.
shown in Eqn 1: Computational simulation based on density functional theory (DFT)
is a powerful tool to study microscopic surface structure and adsorption
MS| + HXaq ⇔ MS|HXaq (1)
mechanism (Chen et al., 2010, 2011, 2014; Gao et al., 2017; Li et al.,
Stelninger (1967) revealed the relationship between the pH limit of 2011; Liu et al., 2013; Reich and Becker, 2006; Sarvaramini et al., 2016).
sphalerite flotation and the pKa of various thiol collectors, suggesting Over the past few years, molecular modelling has gathered interest to
that the chemisorption of neutral molecules indeed played a role in the understand the key mechanisms that are the basis of flotation (Foucaud,
mineral-collector flotation system. However, the occurrence of adsorp et al., 2019). Atomistic simulations can be applied to describe the solid/
tion at high pH values indicated that the xanthate ion, instead of the liquid interface and the adsorption mechanisms (Foucaud et al., 2018,
xanthate acid, was the active substance in this system. 2021; Hounfodji et al., 2020; Souvi et al., 2017; Chen et al., 2020).
Taggart et al. (1934) did not accept the idea “adsorption” to describe However, DFT simulation for flotation system in which water, minerals
the formation of a film of collector on the mineral surface, and claimed and flotation reagents, namely, a huge number of atoms, are involved, is
that the action capacity of a reagent could be evaluated using the sol computation-intensive and time-consuming. Moreover, DFT simulation
ubility product constant of the compound formed by the reagent with cannot satisfactorily deal with the cases of ions and charged systems.
the metal ion contained in the mineral. Poling and Leja (1963) adopted The principle of coordination chemistry can very well describe both
infrared spectroscopy to demonstrate the nature of collector reaction on metal ions in complexes and in mineral crystals, so it is suitable for
the mineral surface. Mellgren (1966) used microthermometry to test the describing the interactions of reagents with metal ions in mineral sur
adsorption heat of ethyl xanthate on galena surface, suggesting that the face. The paper employs ligand field theory (LFT), which mainly deals
uptake of xanthate by oxidized galena was energetically equivalent to with metal ions containing d orbitals, for discussion. Therefore, minerals
the chemical reaction of forming lead ethyl xanthate from lead sulphate. containing d orbitals are investigated. In addition, coordination com
However, the solubility product constant obtained by adsorption was prises two major interactions: σ-bonding and π-backbonding. The latter
quite different from that obtained by solubility. Sutherland and Wark belongs to covalent interaction and plays a crucial role in mineral-
(1955) proved that the monolayer adsorption of collectors was not reagent interactions. Sulphide minerals with covalent properties are
directly related to the usual solubility product constant. thus studied. In order to explore the effect of spin state of d electrons on
Adsorption is merely a phenomenal description, and it cannot give an mineral-reagent interactions, hematite (high-spin iron) and pyrite (low-
explanation for the processes of attachment in which the polar groups of spin iron) are selected to investigate the interaction with xanthate. This
the collector bind with the mineral. Mechanisms of neither adsorption work is of great significance for further understanding the interaction
nor chemical reaction can explain why metal ions exhibit different mechanism of flotation reagents and sheds new light on the develop
reactivity to collectors on various mineral surfaces. For example, thio- ment of novel reagents based on mineral structures.
containing collectors respond strongly to sulphide minerals, but
weakly to oxide minerals. The properties of minerals have attracted 2. Samples and methods
people’s attention since 1953. Some scholars found that the flotation of
sulphide mineral was related to the pulp potential (Ewans and Ewers, 2.1. Mineral samples and flotation tests
1953; Salamy and Nixon, 1954). After that, the electrochemical prop
erties of sulphide mineral and its surfaces began to gain widespread In order to investigate the influence of spin states on the interaction
attention. Allison et al. (1972) proposed a theory that the electrostatic between minerals and reagents, two minerals with different spin states
potentials determined the oxidation product of the collector. Electro were selected for comparison, i.e., pyrite (low spin, non-magnetic) and
chemical investigations of thiol-containing collectors interacting with hematite (high spin, magnetic). Samples of pyrite were obtained from
sulphide minerals have demonstrated that the three anodic processes - the Dachang Mine in Guangxi Province, China, and hematite from
chemisorption, the reaction to form a metal collector compound, and the Anshan Mine in Liaoning Province, China. High purity samples were
formation of a dithiolate, play a significant role in creating hydrophobic hand-picked from the mine, and a chemical analysis revealed that the
surfaces (Woods, 1971). Although considering the effects of mineral purity of the hematite sample was 98.2% and pyrite 98.5%. Pyrite and
properties and surface oxidation, electrochemistry cannot explain the hematite samples were dry-ground in a porcelain ball mill and dry-
mechanism of non-ionic collectors such as Z-200 (O-isopropyl-N-ethyl screened to obtain – 150 + 74 µm particles.
thionocarbamate), nor can it give the microstructure of the interaction Impurity-doped ZnS samples were prepared by means of a copreci
between reagent molecules and mineral surfaces. pitation method (Vacassy et al., 2010). Certain amounts of sulfocarba
Ogwuegbu and Chileshe (2000) considered that the processes of mide and zinc chloride were mixed into an aqueous solution, and after 2
leaching, solvent extraction and flotation were major methods of min h of stirring, the dopant (copper chloride, cadmium chloride and ferrous
erals processing under aqueous conditions in which coordination chloride) was added to obtain the precursor. Next, the solution was
chemistry might play an important role; the success of flotation should heated in a boiling water bath at 95 ℃ for 2 h, and then NH3⋅H2O was
be ascribed to the ability of the chemical reagents to form stable com added to adjust the pH to 13–14. After pH adjustment, the solution was
plexes with metal ions in aqueous solution or on mineral surfaces. further heated to 100℃, stirred for 2 h, and then cooled to ambient
However, as we have known, the metal ions in mineral surfaces are temperature. The products were washed with distilled water and abso
completely different from free ions in solution. The former is in a semi- lute ethyl alcohol several times and then heated in a thermostatic drying
constrained state, coordinated with adjacent atoms in mineral surfaces, oven at 100 ℃.
and their properties are thus dependent upon the properties and coor The micro-flotation tests were performed using an XFG-II flotation
dination numbers of surrounding bonding atoms (Chen and Zhu, 2021). machine (Wuhan Prospecting Machinery Factory) with a 40 mL cell
It is noteworthy that most of collector molecules and flotation medium volume under 1850 rpm impeller speed. In each micro-flotation test, 5.0
(water) are typical ligands that can also coordinate with surface metal g of mineral powder (–150 + 74 μm) and 40 mL deionized water were
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J. Chen Minerals Engineering 171 (2021) 107067
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J. Chen Minerals Engineering 171 (2021) 107067
Fig. 2. (A) The adsorption configuration of 5-coordinate Zn2+ on smithsonite surface and (B) Corey–Pauling–Koltun (CPK) molecular model of smithsonite surface.
orbital theory, only two orbitals with similar orbital symmetry can allow
effective bonding. The discussion on the orbital symmetry matching of simultaneously. Hence, Fig. 3 assumes the d electron arrangement of
reagent molecules with mineral surfaces will be introduced in another metal ions in a strong field. Meanwhile, the orbital of the collectors has
paper. unoccupied π orbitals and lone pairs (σ electron pairs) simultaneously.
The interaction of metal ion (Fe2+ in pyrite) in a strong octahedral field
3.2. Reagents coordinating with metal ions in mineral surface with reagents (xanthate, X− ), as shown in Fig. 3, will be discussed in the
following.
According to ligand field theory, when the metal ion in mineral In the octahedral field, the d orbitals are split into eg orbitals and t2g
surface is coordinated, the five d orbitals (dxy, dxz, dyz, dx2-y2, dz2) of the orbitals, which are σ orbitals and π orbitals, respectively. In the strong
metal ion will be split into two different sets. This will result in changes octahedral field, Fe2+ (d6) has three pairs of π electrons in t2g orbitals,
in orbital properties and d-electron distributions, further influencing the and its eg orbitals are unoccupied orbitals. The LUMO of xanthate is π
interaction of reagents with metal ions in mineral surface. In order to orbitals. According to the ligand field theory, the reagent molecule do
discuss the role of σ bonding and π-backbonding, the d orbital of the nates lone pairs to the unoccupied eg orbitals of the metal ion to form σ
metal ion requires to have unoccupied orbitals and π electron pairs bonding, denoted by E1; the π electron pairs in the t2g orbitals of the
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J. Chen Minerals Engineering 171 (2021) 107067
100
80
FeS2
60
40
20
Fe2O3
0
-5.0 -4.5 -4.0 -3.5 -3.0
5
J. Chen Minerals Engineering 171 (2021) 107067
Fig. 7. Adsorption configurations of xanthate on hematite surface (a) and pyrite surface (b).
Fig. 8. TOF-SIMS results before and after the interactions of KBX with hematite and pyrite.
can donate three π electron pairs to interact with the unoccupied π or understanding. Density functional theory is used to simulate the
bitals of xanthate, leading to relatively strong π-backbonding. Obvi adsorption of xanthate on the surfaces of hematite and pyrite, of which
ously, the Fe3+ in hematite cannot coordinate with xanthate, whereas results are displayed in Fig. 7. Fig. 7(a) shows the distance between the
Fe2+ in pyrite can. bonded sulphur atom of xanthate and the iron ion in hematite surface
The adsorption of xanthate on hematite (0 0 1) and pyrite (1 0 0) reaches 3.192 Å and 3.447 Å, far exceeding the sum of the radii of S2−
surfaces has been well interpreted in our published paper (Cui et al., and Fe3+ (2.44 Å). This indicates xanthate can only weakly interact with
2020). Some key points are recalled in this paper for better the iron ion in hematite surface. In Fig. 7(b), the distance between the
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J. Chen Minerals Engineering 171 (2021) 107067
sulphur atom of xanthate and the iron atom in pyrite surface is 2.225 Å It is found in practice that the floatability of marcasite is similar to and
and 2.220 Å, which is smaller than the sum of the radii of S2− and Fe2+ slightly better than that of pyrite. Pyrrhotite has the worst floatability.
(2.54 Å). Therefore, xanthate molecules can effectively bond with iron Generally, the floatability order of these minerals using xanthate as a
ions in pyrite surface. collector is as followed (Harada, 1964): marcasite > pyrite > pyrrhotite.
Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) was Although these iron(II) sulphides have similar molecular formulas, they
used to examine the surfaces of hematite and pyrite after the adsorption have different crystal structures, as shown in Fig. 9.
of KBX, and the results are shown in Fig. 8. The finding shows that KBX is Pyrite and marcasite, of which formulas are both FeS2, are of iden
hardly adsorbed on hematite surface, while it is strongly adsorbed on tical components with different structures. Pyrite is of an equiaxed
pyrite surface. The results of TOF-SIMS further confirmed the prediction crystal system with Fe-S bond length of 2.226 Å. Marcasite is of an
based on coordination theory: xanthate interacts weakly with hematite, orthorhombic crystal system, and two of the six Fe-S bonds are short and
whereas strongly with pyrite. four long, with lengths of 2.231 Å and 2.251 Å, respectively. The mo
According to the d-electron distribution of Fe3+ in hematite crystal, lecular formula of pyrrhotite is Fe1-xS, which belongs to the monoclinic
the following deduction can be made on the basis of ligand field model: system. And two of the six Fe-S bonds are long and four short, with
strong-field collectors containing sulfhydryl (-SH and C = S) fail to lengths of 2.515 Å and 2.241 Å, respectively. Regarding the properties of
interact with hematite, that is, sulphide ore collectors cannot be used for these iron-sulphur minerals, pyrite and marcasite are similar. However,
hematite flotation. This conclusion is consistent with the research results our DFT calculation results show that the magnetic moment of Fe2+ in
of Rao and Finch (2003), which show that hematite cannot be floated pyrite and marcasite is zero, but in pyrrhotite is not zero, indicating that
even with octyl xanthate as a collector. Moreover, Wang (2008) also the Fe2+ in pyrite and marcasite is in a low-spin state. Therefore, both
proposed: however high the concentration of the collectors, such as pyrite and marcasite are strong-field ligands. The Fe2+ in pyrrhotite is in
xanthate, dithiophosphate, ethyl thiocarbamate, and Z-200, they cannot a high-spin state, and thus pyrrhotite belongs to a weak-field ligand. In
collect hematite at any pH; on the contrary, those collectors can be used addition, the strength of the ligand can also be judged from their iron-
for pyrite flotation. sulphur bond lengths. The smaller Fe-S bond length indicates that the
π-backbonding and the ligand field are stronger; conversely, the larger
4.1.2. Crystal structure affecting the coordination ability of iron(II) Fe-S bond length suggests that the π-backbonding and the ligand field
Pyrite, marcasite and pyrrhotite are common iron-sulphur minerals. are weaker. Accordingly, pyrite and marcasite are strong-field ligands,
Fig. 10. Arrangements of d electrons of Fe2+ in the ligand fields of pyrite, marcasite and pyrrhotite.
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and pyrrhotite is a weak-field ligand. The arrangements of d electrons of σ-bonding and π-backbonding of pyrrhotite with xanthate are weaker
Fe2+ in the ligand fields of pyrite, marcasite and pyrrhotite are shown in than those of pyrite and marcasite, and pyrrhotite has the worst
Fig. 10. floatability.
As shown in Fig. 10, three pairs of π electrons occupy the t2g orbitals In addition, from the perspective of coordination theory, Fe2+ in
of Fe2+ in pyrite crystal, and so in marcasite crystal. The difference pyrrhotite is in a high-spin state, lacks π electron pairs and forms weak
between pyrite and marcasite is the t2g orbitals in pyrite are of the same π-backbonding with collectors, Thus, for collector design, we should
energy, while not in marcasite. According to π-backbonding model, both consider the ability to donate electron pairs (i.e., σ bonding), as well as
pyrite and marcasite can provide the same amount of π electron pairs, its capability to provide unoccupied π orbitals (i.e., π-backbonding), in
meaning the π-backdonation of them with xanthate is comparable, order to enhance the interaction of collectors with the 4 s and 4p orbitals
hence similar floatability of the two minerals. When we consider the of Fe2+ in pyrrhotite.
transition probability, two pairs of π electrons in marcasite have higher
energy level than the three π electron pairs in pyrite, and thus marcasite
can more easily interact with the unoccupied π orbitals in xanthate. 4.2. The amount of π electron pairs in metal cations and the strength of
Moreover, the Fe-S bond lengths of marcasite (2.231 Å and 2.251 Å) are π-backbonding
shorter than that of pyrite (2.269 Å), suggesting the ability of marcasite
to donate π electron pairs is slightly stronger than that of pyrite. 4.2.1. Floatability of copper sulphide minerals
Considering the above three factors, we can conclude that marcasite Common copper sulphide minerals include chalcopyrite, chalcocite,
interacts more actively with xanthate than pyrite does. bornite and covellite. Among them, chalcopyrite is the most important.
Pyrrhotite has completely different d electron configuration from The floatability order of these minerals using xanthate as a collector is as
pyrite and marcasite. The d electrons of pyrrhotite are in a high-spin followed (Wark and Cox, 1934b):
state, and merely one π electron pair is distributed in the lowest Chalcocite > Covellite > Bornite > Chalcopyrite
orbital of t2g, i.e., dyz. As a result, pyrrhotite has the weakest ability to The chemical formulas of these copper minerals are: Cu2S (chalco
provide π electron pairs and to form π-backbonding with xanthate. In cite), CuS (covellite), Cu5FeS4 (bornite), CuFeS2 (chalcopyrite). It is
addition, there are two unoccupied orbitals in the eg orbitals of pyrite generally believed that the more Cu in mineral surface, the stronger the
and marcasite, which can interact with the lone pair of xanthate to form interaction of xanthate with Cu2+. Actually, the component of copper
inner-orbital coordination. However, the eg orbitals of pyrrhotite has minerals is far more complicated than their chemical formulas. For
two single electrons and no unoccupied orbital, resulting in the inca example, bornite and covellite have both Cu2+ and Cu+; chalcopyrite
pability of pyrrhotite to form inner-orbital coordination with xanthate possesses two configurations(Buckley and Woods, 1984): Cu+Fe3+S2
but the ability to form outer-orbital coordination. Therefore, both the and Cu2+Fe2+S2; Bornite also presents two structures (Goh et al., 2006):
Cu+4Cu2+Fe2+S4 and Cu+5Fe3+S4. How do these possibly existing ions
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Fig. 13. Distributions of d electrons in a high-spin state of Cu2+, Cu+, Fe3+ and Fe2+ in the tetrahedral field.
like Cu+, Cu2+, Fe2+, and Fe3+ interact with xanthate? And what are the
Table 2
differences between the interactions? The following will discuss the
The number of π electron pairs donated by the metal cations of copper sulphide
questions according to disparity in ligand fields of minerals.
minerals.
The crystal and coordination structures of different copper sulphide
Mineral Formula Amount of π electron pairs Average
minerals are presented in Fig. 11. It is found that the structures of
chalcopyrite and bornite crystals are relatively simple, in which Cu and Cu+ Cu2+ Fe2+ Fe3+
Fe are 4-coordinate atoms. The copper atoms in chalcocite are mostly 3- Chalcocite Cu2S 5 5.0
coordinate with few of a 2-coordinate structure, meaning Cu mainly has Covellite Cu2+S2⋅Cu+2S 5 4 4.67
one valence state in chalcocite crystal. Covellite has both 3-coordinate Bornite Cu+4Cu2+Fe2+S4 5 4 1 4.16
Cu+5Fe3+S4 5 0 4.16
and 4-coordinate Cu, suggesting two valence states of copper exist in
Chalcopyrite Cu2+Fe2+S2 4 1 2.5
covellite crystal. In general, Cu2+ is blue and Cu+ is greyish purple. It Cu+Fe3+S2 5 0 2.5
can be inferred from the colour that the content of Cu2+ in covellite is
greater than in chalcocite, while Cu+ is dominant in the latter. The
chemical formulas of the two also reflect the relationship between surfaces, and correspondingly the ligand fields become tetrahedral.
colour and valence: Cu+ 2S
2−
(chalcocite), Cu2+S2− (covellite). Fig. 13 illustrates the high-spin distribution of d electrons of Cu2+,
The stable cleavage surfaces of four copper sulphide minerals are Cu+, Fe3+ and Fe2+ in the tetrahedral field, where the e is pure π orbitals
shown in Fig. 12. It is observed that the stable cleavage surfaces of and the t2 is both σ and π orbitals. Cu2+ has four π electron pairs while
chalcocite, chalcopyrite, and bornite are all of a 3-coordinate structure. Cu+ possesses five in the tetrahedral field. Although Cu+ is of a d10
Although there are 3- and 4-coordinate structures in covellite crystal, the configuration, the d10 → d9s1 energy barrier is relatively low, with
cleavage surface of covellite (0001) presents solely 3-coordinate struc strong d orbital activity of Cu+. This can also be confirmed by the
ture. As a result, after collector molecules interact with these minerals, smaller solubility product constant of Cu+ ethyl xanthate (Ksp =
the originally 3-coordinate Cu atoms turn to 4-coordinate ones in the 10− 19.28) (Kakovsky, 1957). In the weak tetrahedral field, Fe3+ has no π
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100 Table 3
Solubility product constants of compound formed by ethyl-xanthate with
different metal ions (Glembotskii, 1981).
Zn(Cu)S
80 Ion Mn2+ Fe2+ Zn2+ Cu+ Cu2+ Cd2+
Zn(Cd)S
− 9.9 − 7.1 − 8.2 − 19.28 − 24.1 13.59
ksp 10 10 10 10 10 10−
60
%
is poor, with the recovery of only 14%; the doping of iron and manga
40
nese ions has a relatively small effect on the recovery, while that of
Zn(Fe)S
copper and cadmium ions greatly increases the recovery. From another
20 perspective, the interaction of xanthate with sulphide minerals is an
Zn(Mn)S electrochemical process, and the electrochemical adsorption of xanthate
Zns and the reduction of oxygen are conjugated reactions. The sphalerite is
0 an insulator, of which width of forbidden band reaches 3.6 eV. Thus,
0 1 2 3 4 5 oxygen cannot be adsorbed on sphalerite surface, thereby depressing the
impurity content % electrochemical adsorption of xanthate. In fact, iron and manganese
impurities can greatly enhance the conductivity of sphalerite, and even
Fig. 14. Relationship between the recoveries and doping concentrations of make sphalerite transform from an insulator into a conductor. However,
impurity ions (KBX: 6.0 × 10− 4mol/L). iron and manganese do not improve the interaction of sphalerite with
xanthate, and the floatability of sphalerite with manganese and iron
electron pair, and Fe2+ has merely one. impurities is still poor. The electrochemical theory of flotation can
Table 2 lists the amount of π electron pairs that metal cations can hardly explain the influence of impurities on the floatability of
provide. Chalcocite mainly contains Cu+, with too small content of Cu2+ sphalerite.
to be noticed, thereby providing 5 pairs of π electrons. Covellite is blue Table 3 lists the solubility product constants of metal xanthates
due to the overwhelming presence of Cu2+. It is generally believed that (sodium butyl xanthate). The Ksp of copper xanthate and cadmium
one-third of copper in covellite has a + 2 valence state, and two-thirds of xanthate is the smallest, consistent with the fact that sphalerite con
copper possess a + 1 valence state. The quantity ratio of 3-coordinate taining copper and cadmium impurities has better floatability. However,
copper to 4-coordinate copper in chalcocite crystal is 1:2. Moreover, the Ksp of manganese xanthate, iron xanthate, and zinc xanthate does not
the probability of 3- and 4-coordinate copper atoms appearing on the correspond to their floatability. The Ksp of iron xanthate is larger than
(0001) cleavage surface of chalcocite is also 1:2. Therefore, the ratio of that of manganese xanthate and zinc xanthate and Fe2+ interacts most
Cu2+ and Cu+ in the chemical formula can be used to calculate the π weakly with xanthate, but sphalerite containing iron impurity has
electron pairs chalcocite provides, and the calculation result is 4.67. The higher floatability than other impurity-bearing sphalerite. This indicates
valence states of copper and iron in bornite and chalcopyrite have been that the interaction of metal ions with xanthate alone cannot explain the
controversial. In practice, different valence states and structures may flotation behaviour; the influence of the coordination structure of min
exist. As a result, when calculating the amount of π electron pairs, the erals on the properties of metal ions should also be considered.
contribution of different valence states should be considered. According Sphalerite is of a tetrahedral structure. The tetrahedral field is
to the chemical formulas, the calculated result of π electron pairs is 4.16 commonly a weak field due to its relatively small splitting energy.
pairs for bornite and 2.5 for chalcopyrite. Therefore, the d electrons of metal cations are distributed in a high-spin
According to previous discussion, xanthate possesses unoccupied π state in the tetrahedral field. Fig. 15 shows the d orbital splitting of
orbitals; with more π electron pairs, copper sulphide is more likely to Mn2+(3d5), Fe2+(3d6), Cu2+(3d9), and Zn2+(3d10) and their electron
form π-backbonding with xanthate, thereby improving floatability of arrangements.
minerals. As found in Table 2, the amount order of the π electron pairs of In the tetrahedral field, the e is π orbitals, and the t2 is π and also σ
copper sulphide minerals is as followed: orbitals. As seen in Fig. 15, the amount of π electron pairs of Mn2+ in the
Chalcocite > Covellite > Bornite > Chalcopyrite tetrahedral field is 0, resulting in its incapability to form π-backbonding
Accordingly, the π-backbonding of xanthate with chalcocite is the with xanthate, hence the worst floatability of Mn-doped sphalerite; Fe2+
strongest, followed by covellite and bornite, and chalcopyrite the has a pair of π electrons and can form weak π-backbonding with
weakest. This is consistent with the floatability order of copper sulphide xanthate, and thus the sphalerite containing iron impurity has better
using xanthate as a collector. floatability than that containing manganese; Cu2+ has four pairs of π
electrons and strong ability to form π-backbonding with xanthate, hence
4.2.2. Floatability of sphalerite containing impurities the best floatability. In addition, although Zn2+ has five pairs of π
It has been found in industry that sphalerite from different deposits electrons, the floatability of natural sphalerite is relatively poor. This is
or separate sections of the same deposit has diverse colours because of because Zn2+ is of a d10 configuration with fully occupied orbitals, it is
distinct impurities, ranging from light green, tan, and dark brown to inert, it is strongly localized, and it provides π electrons poorly.
steel grey. The floatability of sphalerite of different colours varies Cd2+ is also of a d10 configuration, and similarly its d orbitals are
greatly. Pure sphalerite is almost colourless since the 3d orbitals of the inactive. However, sphalerite containing cadmium impurity shows
zinc ion are fully occupied and no electronic transition occurs. When better floatability according to the results in Fig. 14. This is because the
sphalerite crystals contain impurity ions, especially transition metal ions polarizability of Cd2+ (1.09 Å3) is greater than that of Zn2+ (0.288 Å3),
whose 3d orbitals are not fully occupied, such as iron, manganese, which enhances the covalent interaction between the cations and li
copper, and the like, sphalerite will show diverse colours. Impurity ions gands. According to the ligand field theory, xanthate with unoccupied π
greatly influence the flotation of sphalerite. Generally, impurities such orbitals belongs to soft base and interacts readily with soft acid of high
as manganese and iron will reduce the floatability of sphalerite, while polarizability. Therefore, the greater the polarizability of a metal cation,
those such as copper and cadmium will improve. We used the water bath the more easily it changes the electron cloud shape, and the stronger
method to synthesize sphalerite with different doping contents of covalent interaction between the metal ion and xanthate. It can be
manganese, iron, copper and cadmium ions, and the corresponding re predicted that the metal cations of large polarizability such as Hg2+
coveries are shown in Fig. 14. (1.24 Å3), Au+ (1.88 Å3), Pb2+ (2.00 Å3), Bi3+ (1.74 Å3), Tl+ (3.13 Å3),
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J. Chen Minerals Engineering 171 (2021) 107067
Fig. 15. The d-electron configurations of Mn2+, Fe2+, Cu2+, Zn2+ in the tetrahedral field.
Ce3+ (1.03 Å3), Bi3+ (1.74 Å3), and Pt2+ (1.43 Å3) activates sphalerite in an octahedral field. It can provide three π electron pairs, thereby
effectively. Sutherland and Wark (1955) studied the activation effect of easily interacting with the unoccupied π orbitals of Ca(OH)+ to form
the metal ions in sphalerite, and the result is in line with the prediction π-backbonding, which enhances the interaction between Ca(OH)+ and
based on the polarizability. In particular, the activation of thallium ions pyrite. On the contrary, OH– cannot provide unoccupied π orbitals to
is in perfect agreement with the prediction. The solubility product form π-backbonding with Fe2+ on pyrite surface; the interaction be
constant of thallium xanthate is 2.9 × 10− 8, close to that of zinc xanthate tween OH– and pyrite surface is merely σ-bonding, which is weak.
(4.9 × 10− 8) (Glembotskii, 1981). Polarizability can well explain the (2) Lime depresses pyrite, arsenopyrite, pentlandite, chalcopyrite
activation effect of thallium ions, whereas solubility product constant and sphalerite strongly whereas it depresses galena weakly. The valence
cannot. shell configuration of Pb2+ in galena is 6s26p0 without d orbitals, and the
s and p orbitals are σ orbitals in an octahedral field. Thus, galena cannot
provide π electron pairs or form π-backbonding with Ca(OH)+. In
4.3. Unoccupied π orbitals and selectivity of depressants
contrast, pyrite, arsenopyrite, pentlandite, chalcopyrite and sphalerite
have d orbitals and π electron pairs in the t2g (octahedral) or e (tetra
The density functional theory was used to calculate the molecular
hedral) orbitals. The electron pairs can interact with the unoccupied
orbitals of common depressants, and the results are shown in Fig. 16.
orbitals of Ca(OH)+ to form π-backbonding and thus improve the
OH– is a hard base and has no unoccupied π orbitals; it can provide two
depressing ability of Ca(OH)+.
pairs of σ electrons, and only the σ-bonding occurs in adsorption. Ca
(3) NaOH is not as effective as lime in depressing pentlandite. The
(OH)+ has an unoccupied π orbital at the secondary level, making it a
d electron arrangement of Ni2+ in pentlandite is (t2g)6(eg)2. There are
softer base than OH–; it provides two lone pairs, and both σ-bonding and
two electrons in the eg orbital; without unoccupied orbitals, Ni2+ can
π-backbonding exist in adsorption. HS− has no unoccupied π orbitals for
merely form outer-orbital coordination with OH–, instead of inner-
LUMO; it provides two lone pairs; the σ-bonding is dominant in
orbital coordination. The two electrons in the eg orbital repel OH–
adsorption. The LUMO of CN– is π orbitals, suggesting it is a typical soft
strongly, weakening the adsorption of OH–. Three π electron pairs in the
base; there is one lone pair in the anti-bonding orbital, and the π-back
t2g orbital of Ni2+ enable it to form π-backbonding with Ca(OH)+ easily,
bonding plays a dominant role in adsorption. The LUMO of SO2− 3 is π
and thus lime is more effective in depressing pentlandite than NaOH is.
orbitals, while the LUMO of S2O2− 2−
3 is σ orbitals, and thus SO3 can accept
π electron pairs from metal ions to form π-backbonding, but S2O2− 3
4.3.2. NaCN
cannot.
Galena crystal is of a 6-coordinate structure and its ligand field is
octahedral. The s and p orbitals are σ orbitals, and the t2g orbitals (of
4.3.1. Ca(OH)+ and OH–
d orbitals) are π orbitals. However, the outer-shell configuration of Pb2+
Due to the difference between the unoccupied π orbitals of Ca(OH)+
in galena is 6s26p0 and its 5d orbitals are completely blocked. As a result,
and OH–, the following conclusions can be obtained according to the
galena cannot donate π electrons to form π-backbonding with cyanide,
coordination theory:
and thus NaCN does not virtually depress galena. In addition, bismu
(1) Lime depresses pyrite more efficiently than NaOH. The Fe2+ of
thinite (Bi3+: 5d106s2) and antimonite (Sb3+: 4d105s2) resemble galena.
pyrite is in a low-spin state, and its d electron arrangement is (t2g)6(eg)0
11
J. Chen Minerals Engineering 171 (2021) 107067
Table 4
The spin values before and after adsorption of reagents on pyrite surface.
BX− DTP DTC H2O O2 OH– CaOH+ CN–
12
J. Chen Minerals Engineering 171 (2021) 107067
Fig. 17. Changes of the coordination number and ligand field in pyrite surface before and after adsorption of OH–.
Table 7
Effect of adsorption of OH– on ligand field structures and CFSE.
Mineral Ligand field Ion CFSE ΔE
2+
Chalcopyrite Surface Trigonal planar Cu − 5.48 Dq 3.70Dq
Adsorption Tetrahedral Cu2+ − 1.78 Dq
Surface Trigonal planar Fe2+(HS) − 3.87 Dq 1.20Dq
Adsorption Tetrahedral Fe2+(HS) − 2.67 Dq
Cu-activated sphalerite Surface Trigonal planar Cu2+ − 5.48 Dq 3.70Dq
Adsorption Tetrahedral Cu2+ − 1.78 Dq
Pyrite Surface Tetragonal pyramidal Fe2+(LS) − 20 Dq − 4.0Dq
Adsorption Octahedral Fe2+(LS) − 24 Dq
Arsenopyrite Surface Tetragonal pyramidal Fe2+(LS) − 20 Dq − 4.0Dq
Adsorption Octahedral Fe2+(LS) − 24 Dq
Pyrrhotite Surface Tetragonal pyramidal Fe2+(HS) − 4.57 Dq -(η-0.57Dq)
Adsorption Monoclinic octahedral Fe2+(HS) − 4.0Dq-η
Note: HS denotes the high spin state and LS denotes the low spin state.
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J. Chen Minerals Engineering 171 (2021) 107067
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