Minerals Engineering 150 (2020) 106272

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

A review on the electrochemistry of galena flotation T

Yuehua Hu, Meirong Wu, Runqing Liu , Wei Sun
⁎

School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, PR China

ARTICLE INFO ABSTRACT

Keywords: Galena is the most important lead-containing mineral that has semiconductor properties which can cause
Galena flotation electrochemical reactions during flotation. This paper reviews studies of galena electrochemical flotation be-
Electrochemical potential havior. The electrochemical mechanisms on galena surfaces of oxidation, collector adsorption and depression are
Pulp chemistry described. Collectorless flotation requires a moderate oxidizing potential, and flotation cannot be achieved under
Mineral processing
reducing conditions. The hydrophobic entity of the galena surface for collectorless flotation may be elemental
sulfur, lead polysulfide or the deficiency of lead. Chemisorbed xanthate, lead dixanthate, or dixanthogen may be
responsible for xanthate-induced flotation. The flotation behavior can be optimized by adjusting and controlling
pulp potential, dissolved O2, and solution pH. The addition of depressants can be directly involved in redox
reactions between collectors and sulfide minerals, thereby depressing galena flotation. The grinding environ-
ment also greatly influences galena flotation. Various factors such as galvanic interactions, grinding media, gas
atmosphere, solution pH, and hydrogen peroxide (H2O2) formation can affect the extent of electrochemical
reactions. This review proposes that research on sulfide mineral flotation should focus on the combination of
theory and application of electrochemistry.

1. Introduction
Galena (PbS) is one of the most important base metal sulfide mi-
nerals and is a narrow band gap semiconductor. Galena often occurs
with other sulfide minerals, such as chalcopyrite or pyrite (Zárate et al.,
2012). Oxidation, reagent adsorption, and reactions between sulfide
minerals and aqueous solution play a key role in mineral processing
(Ralston, 1991). These reactions occurring during flotation are usually
electrochemical in nature and are dependent on the oxidation–reduc-
tion conditions and the semiconducting properties of galena
(Chernyshova, 2001a; Pillai and Bockris, 1984). In the electrochemical
process of sulfide minerals flotation, electrons can transfer across the
solid-liquid interface, the reagent and the mineral. Without under-
standing of the electrochemistry, the flotation process cannot be un-
derstood in essence (Grano et al., 1990; Woods, 2003).
The key factor affecting electrochemical processes is the redox po-
tential between minerals and solution interface (Buswell et al., 2002).
The redox potential controls the formation of surface hydrophilic spe-
cies (e.g., lead hydroxide or lead oxide) and surface hydrophobic spe-
cies (e.g., elemental sulfur), which are responsible for flotation and
depression of minerals (Buckley and Woods, 1991b; Chernyshova and
Andreev, 1997; Kartio et al., 1996b). The regulation of pulp potential
(Eh) can change the redox properties of the system, thereby improving
the flotation characteristics of the entire system (Becker et al., 2001).
Reduction or oxidation conditions are usually controlled by pH and
dissolved O2, that is, enabling the Eh value to be adjusted to obtain the
best flotation reaction (Chimonyo et al., 2017b).
This study provides a comprehensive review of the influence of
electrochemical conditions on galena surface chemistry and electro-
chemical processes in the flotation system. The electrochemical flota-
tion behavior of galena and its mechanism are systematically in-
troduced with consideration of oxidation of galena, adsorption of
collector on the mineral surface, action of depressants, and grinding
environment. The effects of pulp chemistry such as pulp potential, pH,
and O2 on the electrochemical behavior and flotation of galena are also
discussed. Understanding flotation electrochemistry is beneficial to
regulation and control of hydrophobic and hydrophilic electrochemical
reactions on the mineral surface, thereby determining the flotation and
depression of the value sulfide mineral and optimization the flotation
behavior.
2. Structure of galena
The crystal structure of galena is shown in Fig. 1. Galena belongs to
the octahedral sulfide mineral group, and its metal and sulfur ions are
located in the octahedral position. Divalent lead cations (Pb2+) and

⁎
Corresponding author.
E-mail address: liurunqing@126.com (R. Liu).

https://doi.org/10.1016/j.mineng.2020.106272
Received 26 June 2019; Received in revised form 16 November 2019; Accepted 11 February 2020
0892-6875/ © 2020 Elsevier Ltd. All rights reserved.
Y. Hu, et al.
Fig. 1. Crystal structure of galena (Noda et al., 1987). (a) Side view and (b)
top view of galena crystal.
sulfur anions (S2−) form compact packed cubic unit cells, similar to
mineral halides. Cleavage is in the [0 1 0], [1 0 0], and [0 0 1] direc-
tions. The cleaved galena surface is hydrophilic (Hu et al., 2010). The
formation of galena crystal is based on the following reaction (Chen
et al., 2014):
S2− + Pb2+ → PbS
Eq. (1) indicates that galena is formed under the reductive atmo-
sphere, so it possesses reductive property. This property of galena ac-
counts for its low electrode rest potentials and electron exclusion
characteristics (Chen et al., 2014).
The natural flotability of some minerals depends on crystal struc-
ture; some minerals have layer structures that make them float easily
without creating special conditions or using any collector for col-
lectorless flotation (Janusz and Jan, 1990). In the presence of O2, water
molecules form hydrogen bonds to the mineral surface, and sulfide ores
undergo oxidation to form sulfur-oxy species and loose their natural
flotability (Fuerstenau and Sabacky, 1981). Zhao et al. (2014) used
density functional theory (DFT) method to study the adsorption of
water on the galena surface and its natural flotability. All calculation
models were established in a vacuum environment to eliminate the
influences of O2 and other factors. Water molecules prefer to interact
with water rather than the mineral surfaces, implying the galena sur-
face is hydrophobic.
3. Semi-conducting properties
Almost all metal sulfide minerals have semiconducting properties.
When a group of atoms are brought together to form a solid, the in-
dividual electron levels of the individual atoms overlap to form con-
duction, forbidden, and valence bands. The lower band completely
filled with electrons is called valence band. The electrons in a valence
band can be forced up into a conduction band by applying large amount
of energy. The bottom of the conduction band and the top of the va-
lence band are separated by band gap or forbidden energy gap (Hu
et al., 2010). Sulfide minerals can be classified into conductors, semi-
conductors, and insulators in accordance with the band gap width (Eg).
When Eg = 0, the mineral is a conductor; when 0 < Eg < 2, the
mineral is a semiconductor; when Eg > 2, the mineral is an insulator
(Vijh, 1973).
Galena is a semiconductor with a narrow band gap (Eg = 0.41 eV)
which plays an important role in the adsorption of O2 and the elec-
trochemical processes undergone by galena during flotation (Oertel
et al., 1999). The semiconductor type of galena can be classified into p-
type and n-type semiconductors on the basis of conductivity types. P-
type semiconductors have dominant hole concentration for conduction,
and n-type semiconductors have dominant electron concentration for
conduction, thereby weakening or enhancing electrochemical adsorp-
tion on the mineral surface (Chen et al., 2015a). The presence of im-
purities in the galena lattice can change the structure of energy band,
Minerals Engineering 150 (2020) 106272
control the semiconductor type of minerals, and affect the reduction or
oxidation reactions (Ellmer and Höpfner, 2006; Lan et al., 2016; Oertel
et al., 1999).
Zn, Cd, Mn, Cu, Bi, Sb, Tl, Ag, As, and In impurities greatly influence
the band structure of galena. The presence of Mn and Zn impurities
increase the band gap of galena, whereas Tl, Sb As, and Bi impurities
work oppositely. In, Cd, Cu, and Ag impurities have a minimal effect on
the band gap of galena. In general, the increased band gap may reduce
the electrical conductivity of galena and may be detrimental to elec-
trochemical reactions (Chen et al., 2015b). Adsorbed O2 may also
convert galena surface from an n-type to a p-type, which has an en-
ergetic state on the surface that is more conducive for oxidation of
xanthate ion (Richardson and O'Dell, 1985).
4. Effect of semi-conducting properties on flotation
The difference in the interaction between sulfide minerals and col-
lector under certain conditions is caused by the different semiconductor
properties of the mineral surface. The p-type semiconductor is more
beneficial to xanthate adsorption than the n-type semiconductor
(Richardson and O'Dell, 1985). Xanthate can spontaneously adsorb on
(1) fresh galena with strong p-type properties, but the surface of galena
with strong n-type properties must be oxidised to enable the chemi-
sorption of xanthate (Plaksin and Shafeev, 1963). In addition, oxidation
rate varies with the stoichiometry of lead sulfide. Specifically, the
slowest rate occurs under sulfur deficiency (i.e., n-type) and a faster
rate occurs in sulfur-rich lead sulfide (i.e., p-type) (Eadington, 1966).
The flotation results conducted by Glembotskii (1981) confirm that the
flotation recovery of p-type galena is higher than that of n-type galena.
5. Oxidation of galena
Oxidation plays a key role in mineral processing. Collectorless flo-
tation, collector-induced flotation, and mineral oxidation have a close
relationship. Understanding surface oxidation is of great significance
for optimization of the flotation behavior. Oxidation products may form
on the mineral surface, thereby changing the surface characteristics of
minerals and their surface hydrophilicity and hydrophobicity
(Hampton et al., 2011). The rates, mechanisms, and products of oxi-
dation are dependent on several factors, such as pulp potential
(Goktepe, 2002), temperature (Buckley and Woods, 1984; Shapter
et al., 2000), solution pH (Kim et al., 1995). O2 is an important factor
that controls the extent to which sulfide mineral is oxidised to sulfur-
oxy species. The reduction of O2 as a cathodic process is critical for the
electrochemical reaction on the surface of sulfide minerals. Moderate
oxidation contributes to galena collectorless flotation, and when galena
is strongly oxidised, the surface is covered by hydrophilic oxidation
products, which depress flotation (Hayes and Ralston, 1988).
The removal of excess oxidized species on the surface of galena can
improve the flotation. Ethylene diamine tetraacetic acid (EDTA) solu-
tion has good solubility for typical galena oxidation products, such as
lead hydroxide, lead carbonate, lead hydroxide, and lead sulfate, but no
obvious dissolution of galena or lead occurs on the sulfur-rich surface
(Greet and Smart, 2002). In the case of moderate EDTA concentration
and pH range, EDTA removes the hydrophilic metal hydroxide layer on
the galena surface, thus exposing the sulfur-rich surface to water. Ex-
cess EDTA destroys the sulfur-rich surface layer. At low pH, EDTA
cannot remove hydrophilic metal hydroxide (Xianghuai and Forssberg,
1990).
5.1. Surface oxidation products of galena
Many electrochemical studies have been conducted on galena oxi-
dation to understand its mechanism and influence on flotation.
Scanning tunneling microscopy (STM) (Kim et al., 1995; Kim et al.,
1996a), Fourier-transform infrared spectroscopy (FTIR) (Chernyshova,
2
Y. Hu, et al.
2003; Chernyshova and Andreev, 1997), Raman spectroscopy (Buckley
and Woods, 1994a; Shapter et al., 2000), atomic force microscopy
(AFM) (Hampton et al., 2011), X-ray photoelectron spectroscopy (XPS)
(Buckley et al., 1994; Buckley and Woods, 1994a; Chernyshova and
Andreev, 1997; Kartio et al., 1998; Nowak and Laajalehto, 2000;
Nowak et al., 2000), and various electrochemical techniques have been
applied to determine the surface oxidation products of galena (Gardner
and Woods, 1979). Galena oxidation generally results in the production
of sulfate as the end oxidation product and the release of lead ions into
the solution, as well as Pb hydroxy-carbonate precipitate, lead oxide,
elemental sulfur, and intermediates, such as thiosulfate (Chernyshova,
2003; Fornasiero et al., 1994; Hsieh and Huang, 1989; Kartio et al.,
1996a; Kartio et al., 1997; Manocha and Park, 1977; Nowak and
Laajalehto, 2000; Nowak et al., 2000). These reactions are electro-
chemical in nature. Therefore, controlling the oxidation process in the
flotation pulp can improve the selective flotation. The oxidation of
galena in neutral or alkaline solution is more complex than in acid
media. For galena, the following reactions may generate elemental
sulfur (Hu et al., 2010):
in acidic media
PbS → Pb2+ + S0 + 2e− (2)
in weak alkaline media
PbS + 2H2O → Pb(OH)2 + S0 + 2H+ + 2e− (3)
in alkaline media
PbS + 2H2O → HPbO2− + S0 + 3H+ + 2e− (4)
The reactions not producing hydrophobic species are:
2PbS + 3H2O → 2Pb2+ + S2O32− + 6H+ + 8e− (5)
2− + −
2PbS + 7H2O → 2Pb(OH)2 + S2O3 + 10H + 8e (6)
2PbS + 7H2O → 2HPbO2− + S2O32− + 12H+ + 8e− (7)
The initial oxidation product is elemental sulfur at all pH ranges,
Pb2+ is formed in acidic solution, HPbO22− and Pb(OH)2 are formed in
alkaline media (Chernyshova, 2003; Gardner and Woods, 1979). Sulfur-
oxy species, such as thiosulfate (S2O32−), can be formed in the solution.
These species are thermodynamically unstable, and will decompose
with time or with changing environments. Sulfate is the most stable
sulfur-oxy species under acid and weak alkaline conditions; the ex-
istence of metastable species suggests that several steps are required to
generate sulfate from sulfide (Kim, 1998). The properties of the oxi-
dation products generally determine the subsequent flotation behavior.
The oxidation of sulfide can occur through several possible pathways;
the following reaction pathway represents the possible intermediate
species (Kim et al., 1996a):
S2− → S22− → Sn2 −
→ S0 → sulfur-oxy species → SO42− (8)
Although extensive studies have been carried out on the oxidation
of galena, an agreement has not been achieved with regard to the de-
tails of the oxidation process, especially the surface composition of the
oxidised galena. Fornasiero et al. (1994) determined the proportions of
various lead and sulfur species on the galena surface and in solution for
various pretreatment conditions of the mineral in which most of the
galena surface was not oxidised, and lead oxide and lead hydroxide
were the major oxidation products. In that study, no elemental sulfur,
polysulfide or metal-deficient sulfur were generated, whereas lead
sulfate was formed but in small quantities. Kartio et al. (1998) found
that the main oxidation product of galena is elemental sulfur when
anodized at a potential of 0.3 V at pH 4.6. Hampton et al. (2011) in-
vestigated the electrochemical behavior of galena at pH 4.5 and found
that the presence of elemental sulfur, polysulfide, or metal-deficient
sulfide could not be detected.
In addition, a consensus has not been made on the oxygen source for
3
Minerals Engineering 150 (2020) 106272
sulfate during oxidation. Hsieh and Huang (1989) indicated that the
oxygen in the sulfate was completely derived from molecular oxygen,
which was inconsistent with the findings of Fornasiero et al. (1994).
Heidel and Tichomirowa (2011) performed isotope analysis on the
sulfate produced and found that the oxygen in the sulfate was mainly
derived from water molecules, with a small amount was derived from
molecular oxygen, indicating that the adsorption of water molecules
plays a very important role in the oxidation of galena. Chen et al.
(2017) carried out DFT computation simulation to study the adsorption
of O2 and H2O on the galena (1 0 0) surface and found that the galena
surface was oxidised by the continuous reaction of the adsorbed O2 and
water molecules. The study also revealed that water molecules were
involved in the surface oxidation of galena, and the oxygen in the
sulfate was derived from water.
5.2. Collectorless flotation
The collectorless flotation of sulfide minerals can only occur in
moderately oxidizing environments, which can be controlled by the
pulp potential, but cannot be achieved under reducing conditions
(Ralston, 1991). Elemental sulfur (S0) (Hampton et al., 2011), lead
polysulfide (PbSn, n > 1, unbranched sulfur chains connected to the
metal sulfide lattice by covalent or ionic bonds) (Aghazadeh et al.,
2015) and lead-deficient sulfide (Pb1-XS, X < 1, lead ions are removed
from the crystal lattice) (Buckley, 1996; Mineralurgii, 2002) are oxi-
dation products that result in hydrophobicity on the surface of sulfides,
which help to increase the rate of collectorless flotation. The col-
lectorless flotation recovery of galena is determined by the relative
amounts of substances containing hydrophobic species (e.g., elemental
sulfur) and hydrophilic species (e.g., lead hydroxide Pb(OH)2 produced
during oxidation), depending on the solution pH and pulp potential.
Suitable pH and Eh values are necessary for collectorless flotation. Gu
et al. (2002) studied the electrochemical oxidation of galena at pH
above 12.5 and a potential smaller than 0.17 V and found that the
oxidation products of galena were elemental sulfur and HPbO−.
Moreover, elemental sulfur exceeded the oxidised lead species, which is
beneficial to collectorless flotation of galena.
5.2.1. Effect of pH on the collectorless flotation of galena
Collectorless flotation is related to solution pH, becoming is more
favorable with decreasing pH (Lutterll and Yoon, 1984). Galena is ea-
sily depressed under alkaline conditions due to the formation of metal
hydroxides, such as lead hydroxide Pb(OH)2, which provides hydro-
philicity to the mineral surface (Cheng and Iwasaki, 1992). Kang and
Chen (2011) studied the effect of pH on the collectorless flotation of
galena and found that the recovery of galena was low in strongly acidic
solution (pH 2) and strongly alkaline solution (pH 11) but was high at
other pH values (over 75%). Kocabag et al. (1990) found that galena
has maximum recovery at pH of approximately 5.5. The flotation of
galena in acidic solution occurs due to the formation of elemental sulfur
on the surface and increased hydrophobicity. Moreover, increase in
flotability at low pH is due to the stability of elemental sulfur and its
greater hydrophobicity than polysulfide (Lutterll and Yoon, 1984). Sun
et al. (1994) suggested that the balance relationship between the hy-
drophobicity and hydrophilicity of collectorless flotation can be de-
scribed as [S0]/[OH–]. At a certain pH value, the greater the [S0], the
greater the hydrophobicity, and the better the flotability. At high pH
values, large [S0] is required, whereas small [S0] is required for flota-
tion at low pH.
5.2.2. Effect of pulp potential on the collectorless flotation of galena
Pulp potential is an important electrochemical parameter that is
related to the flotation efficacy. It can determine the type of species
formed on the surface of the sulfide ore and can be used to predict the
optimal flotation conditions (Chander, 2003). The flotation recovery
and pulp potential in various flotation systems have been found to have
Y. Hu, et al.
a clear relationship (Hintikka and Leppinen, 1995). Chernyshova et al.
(1997a) found that in moderately alkaline solution (pH 9.2), the main
product of anodic oxidation at + 0.4 V (SHE) in the presence of O2 is
lead hydroxide. Hayes and Ralston (Hayes and Ralston, 1988) in-
vestigated the collectorless flotation of galena and obtained maximum
recovery of 35% at pH 9.2 and Eh of 500–550 mV (SHE). Kartio et al.
(1996a) studied galena oxidation at pH 4.6 with synchrotron X-ray
photoelectron spectroscopy (SR-XPS) and found that metallic lead
formed at low potential, and galena started to oxidize at high potential,
forming new species, such as metal polysulfides and lead-deficient
sulfides. At + 250 mV (SHE), the formation of metal polysulfide in-
creased sharply. They also considered that metal deficiency may be the
precursor for the formation of metal polysulfides. When the potential
increases, polysulfides can be further oxidised to elemental sulfur. The
initial oxidation reaction involves the removal of lead atoms from the
sulfide lattice to form a metal-deficient surface layer, which affects the
collectorless flotation of galena. The reaction producing lead deficiency
is represented by Eq. (8) (Buckley, 1996).
PbS + 1/2xO2 + xH2O → Pb1−xS + xPb(OH)2
Fig. 2 shows the Eh–pH diagram for the PbS–H2O system. The figure
visually describes the thermodynamic stability range of different spe-
cies of lead and sulfur species and the relationship of the formation of
various components as a function of pH and potential. If the pulp po-
tential is appropriate, elemental sulfur is present throughout the pH
range. When the pH is fixed, the formation of elemental sulfur has a
corresponding potential range, beyond which it is difficult to oxidise
galena, or elemental sulfur is further oxidised to hydrophilic species.
6. Collector adsorption on galena surface
The adsorption of collectors on galena essentially involves an elec-
trochemical reaction, which is affected by the electrochemical condi-
tions during flotation (Ho and Conway, 1978; Page and Hazell, 1989;
Ranta et al., 1981). Knowledge about the mineral surface composition
after adsorption of the collector is critical to understanding the me-
chanism of action of the collector (Laajalehto et al., 1993). Xanthate
(dithiocarbonate, ROCSS−) is a widely used collector in the flotation of
sulfide minerals. The chemical structure of xanthate is shown in Fig. 3,
where R represents the nonpolar group, an alkyl chain, e.g., ethyl-C2H5
and iso-butyl-C4H9 (O'Dea et al., 2001). The polar group of xanthate
collector can firmly adsorb on the surface of the sulfide ore, whereas the
nonpolar hydrophobic groups are oriented outwardly on the mineral
surface, resulting in hydrophobicization of the surface of the sulfide
mineral and easy adhesion to bubbles (Polikg and Leja, 1963). The
mechanism of xanthate-induced flotation is usually explained on the
basis of the mixed potential mode, in which an anodic reaction of
electron transfer from collector to mineral is combined with a cathodic
reduction of O2 (Woods, 2003).
Pb(OH)2+S2O32-
HPbO2-+S2O32-
Pb+S2O32-
Pb2++S
Pb(OH)2+S
PbS
HPbO2-+S
Fig. 2. Eh–pH diagram for the PbS–H2O system in aqueous solution for dis-
solved species at 10%4 M (Hu et al., 2010).
Minerals Engineering 150 (2020) 106272
S
R O C S Na or K
Nonpolar group Polar group
Cation
Anion
Fig. 3. Chemical structure of xanthate (Greenler, 1962).
The generally accepted the hydrophobic entity of the galena surface
for xanthate-induced flotation is lead dixanthate. Lead dixanthate may
be formed via the following reactions (Guy and Trahar, 1984; Leppinen
and Rastas, 1986; Wang and Yen, 1990; Woods, 1972):
PbS + 2X− + 4H2O → PbX2 + SO42− + 8H+ + 8e−(10-a)
2PbS + 4X− + 3H2O → 2PbX2 + S2O32− + 6H+ + 8e−(10-b)
(9) PbS + 2X− → PbX2 + S + 2e−(10-c)
where X− represents the xanthate ion.
Although lead dixanthate is the primary hydrophobic product
formed on the galena surface (Laajalehto et al., 1993; Nowak, 1993),
dixanthogen and chemisorbed xanthate (Buckley and Woods, 1994b)
are also found. They are also considered hydrophobic and may be re-
sponsible for xanthate-induced flotation (Gardner and Woods, 1977).
The electrochemical process of the oxidation of xanthate to dix-
anthogen and the charge transfer in the chemisorption of xanthate ions
are considered to be an anodic process (Woods, 1971).
Formation of chemisorbed xanthate is shown as follows:
X− → Xads + e− (11)
Chemisorption provides the most efficient use of the collector, be-
cause a monolayer layer is formed before the formation of multilayers
of bulk lead dixanthate (Woods, 2003). The solubility of chemisorbed
xanthate is smaller than that of bulk lead dixanthate (Buckley and
Woods, 1994b).
Formation of dixanthogen is shown as follows:
2X− → X2 + 2e− (12)
Electrochemical reactions between xanthate and galena includes the
anodic process of electron transfer from the collector to the mineral in
Eq. (10), (11), and (12) and the cathodic reduction of O2 in Eq. (13)
(Gardner and Woods, 1973).
O2 + H2O + 2e− → 2OH– (13)
Electrochemical methods and surface sensitive techniques, such as
FTIR (Leppinen et al., 1989), STM (Kim et al., 1996b), and XPS
(Laajalehto et al., 1993) have been widely used to study various anodic
reactions on sulfide surfaces. These reactions are strongly dependent on
O2, pulp potential, solution pH, and other parameters. The presence of
water molecules has a significant influence on the covalent bonding,
electron distribution, and reactivity of the surface atoms, which will
improve the adsorption of xanthate on the galena surface (Long et al.,
2016).
Greenler (1962) has shown that galena samples with a high degree
of oxidation adsorb more xanthate than those with low oxidation.
Xanthate chemisorption occurs at a potential lower than the reversible
potential of lead dixanthate or dixanthogen formation (Grano et al.,
1997c). Therefore, the initial reaction between galena and xanthate
involves the chemisorption of xanthate via a mixed potential me-
chanism, and the collector bonds to the lead atoms in the galena lattice
(Buckley and Woods, 1994b). When the potential is held in the region
of −0.15 to +0.1 V (SHE), xanthate will chemisorb onto galena. At
high anodic potential, both lead dixanthate and dixanthogen are
4
Y. Hu, et al.
formed (Woods, 1972). In the presence of xanthate, an anodic peak is
observed (Gardner and Woods, 1977; Richardson and O'Dell, 1985;
Woods, 1971) on the voltammograms of galena, which corresponds to
the potential of flotation beginning of galena. This peak occurs at po-
tential lower than the reversible value for the formation of dixanthogen
or lead dixanthate and is considered as the chemisorption reaction. A
necessary condition for the formation of dixanthogen is that the mixed
potential generated by the O2 reduction and surface oxidation of xan-
thate must exceed the equilibrium potential of dixanthogen/xanthate
coupling (Allison et al., 1972). Woods (1971) demonstrated that the
rest potentials of galena in ethyl xanthate solutions that were greater
than the equilibrium potential of dixanthogen formation, thus con-
firming that dixanthogen can be formed.
Chemisorbed xanthate is a precursor of lead dixanthate and dix-
anthogen, which are formed via the following reactions (Chernyshova,
2002):
PbS + 2Xads → PbX2 + S0 (14)
0
PbS + 4Xads → PbX2 + X2 + S (15)
In addition to lead dixanthate, dixanthogen and chemisorbed xan-
thate, metastable monothiocarbonates (MTC) have also been found on
the galena surface, which are important derivatives of xanthate
(Chernyshova, 2002; Grano et al., 1997c; Harris and Finkelstein, 1975).
The formation of MTC represents a mechanism in which the adsorbed
xanthate ion can be removed from the mineral surface (Harris and
Finkelstein, 1975). The reaction is provided as follows (Finkelstein,
1972):
Pb(OH)2 + ROCSS −
→ PbS + H2O + ROCSO −
(16)
MTC is an anodic decomposition product of dixanthogen, which
may be formed via the following reaction (Chernyshova, 2002):
(ROCS2)2 + Pb(OH)2 + 3OH– + 8h+ → (ROCSO)2 + PbS2O3 + 5H+
(17)
where h+ stands for hole. The oxidation chemistry of galena is
related to the rate of formation of metastable MTC during adsorption
(Grano et al., 1997c).
The adsorption of xanthate and adsorbed oxidation products on the
galena surface has been extensively studied, but the structure of the
adsorption layer remains controversial. The widely accepted structure
is that the monolayer of chemisorbed xanthate is formed first on the
galena surface without changing the position of the atom in the PbS
lattice. Under certain conditions, the top of the chemisorbed xanthate
layer can form multilayers of bulk lead dixanthate (Cases and De
Donato, 1991; Kartio et al., 1999; Plescia, 1993; Smart et al., 2003a).
Poling and Leja (1963) used infrared multiple reflectance spectroscopy
to study xanthate adsorption on galena and found that the lead-to-
xanthate ratio of the species adsorption layer was 1:1, while that of
multi-layer adsorption was 1:2. Rastas and Sten (1990) investigated the
chemisorption of xanthate on the surface of lead sulfide via thermo-
dynamic calculations and found that the thermodynamic stability of the
surface layer is different from that of bulk lead dixanthate. Kartio et al.
(1999) used SR-XPS and found that the first molecular layer of ethyl
xanthate on the surface of PbS comprised chemisorbed xanthate radi-
cals rather than lead ethyl xanthate, consistent with previous findings
(Buckley and Woods, 1991a; Laajalehto et al., 1993; Polikg and Leja,
1963; Shchukarev et al., 1994). Electrochemical flotation results and
cyclic voltammograms (Gardner and Woods, 1973; Woods, 1971) in-
dicate that dixanthogen in multilayers is the key species for the hy-
drophobicity of the galena. The adsorption of xanthate on the galena
surface consists of the following steps (Cases and Donato, 1991; De
Donato et al., 1990; Woods, 1972):
1- Xanthate ion adsorbs on the galena surface and forms a monolayer
of chemisorbed xanthate
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Minerals Engineering 150 (2020) 106272
2- Adsorbed Xanthate ion oxidation takes place and dixanthogen oc-
curs.
3- A multilayer of lead dixanthate is formed on top of the chemisorbed
xanthate layer with the increase of xanthate concentration.
In addition to xanthate, other collectors are used for the flotation of
sulfide minerals. Leppinen and Mielczarski (1986) studied the adsorp-
tion of potassium diphenyldithiophosphate, potassium ethyl xanthate,
and sodium diethyldithiophosphate. The main type of adsorption pro-
duct formed by collectors on lead sulfide is similar to the corresponding
lead salt, such as lead dixanthate. Gu et al. (2002) indicated that die-
thyldithiocarbamate (DDTC- abbreviated as D) is a suitable collector for
the flotation of galena in strong alkaline solution (pH > 12.5). Hy-
drophobic PbD2 was found on the galena surface at the potential range
of 0–0.2 V (SHE). DDTC can also depress the overoxidation of galena
surface.
6.1. Effect of collector concentration on collector adsorption
Differences were found in the adsorption mechanism of xanthate at
high and low concentrations (Chernyshova, 2002). When xanthate is
adsorbed, the concentration decreases, and the pulp potential increases
(Leppinen and Mielczarski, 1986). The adsorption of xanthate on galena
occurs at potentials below the reversible potential, Er, which has the
following relationship with xanthate concentration (Woods, 1971):
Er = 0.124 0.059logC (18)
where C is the molar concentration of ethyl xanthate.
Low concentrations of xanthate cause the formation of the adsorbed
species of PbX. At high concentrations, infrared spectra indicated that
precipitated lead dixanthate was formed on the surface of PbS
(Fredriksson and Holmgren, 2008). IR measurement analysis and ad-
sorption enthalpies also confirmed this (Arnaud et al., 1989).
Fredriksson and Holmgren (2008) used Attenuated total reflectance-
Fourier transform infrared spectrometry (ATR-FTIR) and determined
the only surface reaction product is heptyl xanthate at low concentra-
tions (≤0.1 mM); lead dixanthate precipitated on the PbS surface at
high concentrations. O’Dea et al. (2001) indicated the balance between
PbX2 precipitation and monolayer adsorption depends on Eh and the
concentration of X and Pb in the solution. At low Eh and xanthate
concentrations, surface oxidation is reduced, and the overall con-
centration of adsorbed xanthates is higher than at high Eh. Moreover,
increasing potassium ethyl xanthate (KEX) addition and Eh is beneficial
to the generation of X2 (Pritzker and Yoon, 1984).
6.2. Effect of pH on collector adsorption
Xanthates are used for sulfide ore flotation, but are not stable under
certain pH conditions in aqueous solution. Potassium ethylxanthate is
unstable at pH < 7 and undergoes total decomposition at pH < 4
(Maillot et al., 1984). Redox potential plays a crucial role in sulfide
minerals flotation, which affects the reaction of mineral surfaces and
thus affects the flotation behavior of minerals (Chimonyo et al., 2017a).
The potential generally decreases with increasing pH, and low pH is
beneficial to the chemisorption of ethyl xanthate under anaerobic
conditions (Rastas and Sten, 1990). Galena is easily depressed under
alkaline conditions, with the formation of metal hydroxides, such as
lead hydroxide Pb(OH)2, resulting in hydrophilicity of the mineral
surface. From an electrochemical point of view, when alkalinity in-
creases, pulp potential shifts towards more cathodic, and the shift in
potential prevents the oxidation of xanthate ions to dixanthogen (Cheng
and Iwasaki, 1992).
Goktepe (2002) found that galena flotation is feasible below pH 7
with the recovery of galena decreasing sharply above this pH. Hence, in
alkaline solution, galena is difficult to float due to the decomposition of
xanthate and the formation of hydrophilic metal hydroxides. Moreover,
Y. Hu, et al.
the potential is not linearly related to pH; the potential changed from
35 mV to − 25 mV (SHE) from pH 2 to 11, and dropped to − 125 mV
(SHE) at pH 12. Elizondo-Álvarez et al. (2018) observed that as the pH
increased from 5.5 to 9.5, galena recovery continued to decrease, which
may be explained by increasing hydroxyl concentration possibly com-
peting for adsorption sites with collector molecules and ultimately
leading to the formation of metal hydroxides.
6.3. Effect of O2 on collector adsorption
The O2 demand during the flotation of sulfide minerals with xan-
thate confirms the electrochemical mechanism in which the anodic
reaction involving xanthate is combined with the cathodic reduction of
O2. The simultaneous presence of xanthate and O2 is necessary for the
rapid attachment of bubbles to the particles during flotation (Ahmed,
1978).
The flotation behavior of minerals depends on the concentration of
O2 in the solution. The standard O2 concentration of water in equili-
brium with air is 8 mg /L at standard temperature and pressure (Sheni
et al., 2018). The flotability increases with increasing O2 content
(Finkelstein, 2007) and affects the pulp potential (Ekmekçi et al.,
2005), resulting in the increase in oxidation rate of xanthate on the
galena surface (Gaudin and Finkelstein, 1965; Plaksin, 1959; Smart
et al., 2003b). In the absence of O2, significant xanthate coverage can
only be obtained when the concentration of xanthate is high in alkaline
and neutral solution (Buckley and Woods, 1994b). Moreover, in the
absence of O2, the nonpolar hydrophobic group of the xanthate may be
attached to the surface of sulfide minerals by the van der Waals forces,
whereas the polar group is exposed to the solution to maintain the
hydrophilicity of the surface. This adsorption reduces the electrode
potential and inhibits the reduction of O2 (Ahmed, 1978). The calcu-
lation results by Chen et al. (2014) suggests that dixanthogen cannot be
formed on the galena surface in the absence of O2 because of the re-
ductive properties of galena.
7. Depressants
7.1. Inorganic depressants
Depressants can be simply classified into two types, inorganic and
organic depressants (Feng et al., 2019). Different mechanisms have
been proposed to explain the nature of the influence of depressants on
galena, including competition between collectors and depressants at the
surface adsorption sites, the creation of thermodynamic conditions
unfavorable to the formation of metal collector salts, and the formation
of hydrophilic coatings on the surface. In another mechanism, de-
pressants may be directly involved in the redox reaction between col-
lectors and sulfide minerals (Chander, 1985).
Galena can be depressed by oxidizing (dichromate and chromite)
and reducing agents (sulfide ions). Chromate or dichromate is fre-
quently used as a depressant in the flotation of complex sulfide ores
containing galena. Dichromate is a more effective galena depressant
than chromate. The relationship between dichromate and chromate can
be expressed (Okada and Majima, 2013):
2CrO42− + 2H+ → 2HCrO4− → Cr2O72− + H2O (19)
Generally, in the presence of dichromate, the depression of galena
flotation can be explained in two ways. First, when galena is treated
with dichromate, lead chromate with high hydrophilicity is formed on
the surface. Secondly, xanthate can be desorbed from the galena surface
(Okada and Majima, 2013; Ralston, 1994). Kocabağ and Güler (2007)
indicated the following reactions may occur on galena to form lead
chromate and chromium oxide:
3PbS + l1CrO42−+16H+ → 3PbCrO4 + 4Cr2O3 + 3SO42− + 8H2O
(20)
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Minerals Engineering 150 (2020) 106272
3PbS + 5HCr2O42−+5H+ → 3PbCrO4 + Cr2O3 + 3S0 + 5H2O (21)
These two reactions consume H+, increase the pH of the pulp, and
produce hydrophilic Cr2O3 and PbCrO4, the deposition of which on the
surface of the galena inhibits flotation. At alkaline conditions, the fol-
lowing reactions occur (Kocabağ and Güler, 2007):
PbS + CrO42− + 4H2O → PbCrO4 + SO42− + 8H+ + 8e- (22)
2PbS + Cr2O72− + 9H2O → 2PbCrO4 + 2SO42− + 18H+ + 16e-
(23)
The depression of galena by sulfite is complex, and various me-
chanisms have been proposed. Grano et al. (1997a) investigated the
effect of sulfite on the flotation of galena induced by ethyl xanthate and
found that sulfite decomposes xanthate ions in solution and forms
perxanthate (ROCSSO−), as shown in Eq. (24). The sulfite consumes
dissolved O2, resulting in a decrease in pulp potential. This condition
reduces the amount of dixanthogen or lead dixanthate formed due to
the low content of O2 available (Grano et al., 1997b). When galena is
treated with sulfite, lead dixanthate on the galena surface is decom-
posed, and lead sulfite with high hydrophilicity is formed on the surface
(Eq. (25)) (Chander, 1985).
ROCSS−+HSO3−+ SO32− + O2 → ROCSSO− + ROH + 2S2O32− +
CO2 (24)
PbX2 + SO32− → PbSO3 + 2X− (25)
The galena flotation ceases above a certain sodium sulfide con-
centration, because sodium sulfide reduces the solution redox potential,
thereby inhibiting the chemisorption of xanthate on the mineral surface
(Herrera-Urbina et al., 1999). Electrode potential measurement studies
also show that galena has a strong reduction potential in sulfide solu-
tion. Under these conditions, lead dixanthate is unstable compared with
lead sulfide (Sato, 1960). Qin et al. (2013) found that the adsorption
density of butyl xanthate (BX) on the galena surface was reduced as the
concentration of BX increased compared with the absence of Na2S. The
mechanism by which Na2S removes the collector can be explained:
(1) HS− is the main hydrolyzed component of Na2S in the pH range of
8.5–10, and competes with butyl xanthate ion (BX−) to inhibit the
further adsorption of xanthate.
(2) HS− can desorb lead butyl xanthate (Pb(BX)2) from galena surfaces:
Pb (BX)2 + HS− → PbS + H+ + 2BX− (26)
2+ −
Pb (BX)2 → Pb + 2BX (27)
2+ 2−
PbS → Pb +S (28)
− 2− +
HS →S +H (29)
7.2. Organic depressants
Inorganic depressants are toxic and hazardous to the environment
(Qin et al., 2012). Some natural organic compounds or their derivatives
have been used as galena depressants to replace dichromate, such as
sodium humate (HA) with ammonium persulfate ((NH4)2S2O8) (Liu
et al., 2016), carboxymethyl cellulose (Xiang, 2015) or in combination
with sodium silicate (Na2SiO3) and sodium sulfite (Na2SO3) (López-
Valdivieso et al., 2017), and dextrin (Bolin and Laskowski, 1991; Rath
and Subramanian, 1999).
Polysaccharide is a high-molecular-weight polycondensation
polymer having a monosaccharide as a monomer. Polysaccharides have
many different types in nature, but only a few of them are used in the
mineral industry. Polysaccharides including starch, dextrin, guar gum,
cellulose, and their derivatives are mainly used as flotation depressants.
Polysaccharides contain large amounts of hydroxyl groups, which allow
Y. Hu, et al.
their use as flotation depressants (Qi et al., 2000). The most widely
proposed adsorption mechanisms between polysaccharides and mi-
nerals are hydrogen bonding, hydrophobic interaction, chemical com-
plexation, and electrostatic interactions (Xiang, 2015). Natural poly-
saccharide may be adsorbed on the mineral surface by bonding to the
metal hydroxyl groups. The nature of the interaction between the sur-
face metal hydroxyl groups with a lower acidity and the natural poly-
saccharides may be the result of acid/base interaction (Qi et al., 2000).
Dextrin is a water-soluble polysaccharide, which is obtained by
partial thermal degradation of starch under acidic conditions
(Bulatovic, 1999; Radley, 1976). The treatment leads to the breakage
and reversal of the starch molecular chain. The only structural differ-
ence between dextrin and starch is that dextrin is a smaller molecule
with a highly branched structure, whereas starch is a macromolecule
composed of linear and branched components (Qi et al., 2000). Dextrin
is used to selectively depress galena during chalcopyrite flotation with
xanthate by using NaOH to adjust the pH value of the pulp; the ad-
sorption of dextrin on galena strongly depends on the pH and reaches
the maximum at pH 10.5–11 (Li and Zhang, 2000). The adsorption of
dextrin was the largest around the pH at which the mineral surface is
highly hydroxylated. The study found that the interaction mechanism
between dextrin and surface metal hydroxyl groups occurs through
chemical complexation (Raju et al., 1997).
Carboxymethyl cellulose (CMC) is a typical organic polymer, which
is an anionic polysaccharide obtained from the reaction of mono-
chloroacetic acid or its sodium salts with alkali cellulose (Arinaitwe and
Pawlik, 2014). The COO– groups of CMC and PbOH+ are adsorbed on
PbS via an acid/base bond. PbOH+ is formed by the dissolution of Pb2+
ions from the surface of PbS. The carboxyl group COOH of CMC ionizes
to form an anionic group COO– as shown below (López-Valdivieso
et al., 2017):
–CH2-COOH → CH2-COO– + H+ (30)
Li et al. (2018) found CMC has no significant effect on depressing
galena, and KMnO4 can enhance the depression of CMC on galena.
Element sulfur is oxidised to form thiosulfate when KMnO4 and CMC
are added to the flotation system, and the element sulfur content is
reduced remarkably. CMC can be easily adsorbed on the galena surface.
As the amount of adsorption of CMC increased, the adsorption of the
collector decreased.
HA is a sodium salt of humic acid and can be extracted from leo-
nardite, an organic compound with a relatively high molecular mass
(Chen et al., 2011a). Liu et al. (2016) proposed the mechanism of ga-
lena depression of ammonium persulfate and HA by adsorption mea-
surements and infrared spectroscopy. The results indicated that ap-
propriate galena surface oxidation and pulp oxidation environment are
the prerequisites for HA adsorption on galena. Adsorbing HA on fresh
galena surfaces is difficult. HA was chemically adsorbed onto lead
sulfate, and the chemical equation is:
nPbSO4 + 2HAn− → Pbn(HA)2 + nSO42− (31)
The electrochemical behavior of the galena electrode was in-
vestigated in the presence of NaHA. The cyclic voltammogram in-
dicated that no redox reaction occurred between NaHA and galena.
However, the current density of the oxidation and reduction peaks
decreased compared with that in the absence of NaHA. Therefore,
NaHA can be absorbed on the galena surface and form cover layer that
enables passivation of the electrode surface (Wang et al., 2017).
Some new organic depressants have been synthesized for galena.
Piao et al. (2013, 2014) studied two new depressants O,O-bis(2,3-di-
hydroxypropyl) dithiophosphate and sodium 2,3-dihydroxypropyl di-
thiocarbonate, which have good selective depression for galena. Syn-
thetic polymers, such as polyacrylamide, are widely used in mineral
processing. Zhang et al. (2017) designed and synthesized a macro-
molecular depressant polymaleamide-propyl dithiocarbamate based on
7
Minerals Engineering 150 (2020) 106272
DFT calculations, which has a stronger depressant ability and better
selectivity for galena than chalcopyrite. Wang et al. (2012) synthesized
a xanthation-modified polyacrylamide (PAM-X) based on the prepara-
tion of potassium ethyl xanthate, which was formed by the hydro-
lyzation of PAM after treatment with carbon disulfide under alkaline
environment. PAM-X showed strong depression and a good selectivity
for galena through chemical bonds of the –C = S group and the –COO–
group with the galena surfaces.
8. Effect of grinding environment on galena flotation
8.1. Effect of galvanic interactions
Grinding conditions have a great influence on the flotation of sulfide
minerals (Allahkarami et al., 2014). During grinding between sulfide
minerals and between the grinding media and the sulfide minerals,
electrons may be transferred from one another in a process called gal-
vanic interaction. Galvanic interactions due to different electrochemical
reactions can be predicted by the mineral rest potential (Rao and Finch,
2013). Each metal sulfide mineral has a different electrochemical re-
activity as determined by its rest potential, which can be expressed by
the following redox equilibrium (Bruckard et al., 2011):
MS = M2+ + S0 + 2e− (32)
E= E0 + RT /2F lnaM 2 + (33)
0
where E is the standard half-cell reduction potential, E is the rest
potential, R is the universal gas constant (8.31 J K−1 mol−1), F is the
Faraday constant (9.65 × 104 C mol−1), T is the absolute temperature
(Kelvin), and a is the chemical activity for the relevant species. The
electrochemical activity determines which minerals or materials act as
anodes or cathodes in the electrical interactions between minerals and
grinding media.
The results of this interaction not only increase the corrosive wear of
the grinding media but will also change the surface properties of the
minerals and the pulp chemistry, which affects the subsequent flotation
properties of the sulfide minerals through unselective surface coatings
by oxidation products. In the interaction among the sulfide minerals, a
mineral with the higher rest potential acts as the cathode, while a mi-
neral with the lower rest potential acts as the anode (Gonçalves et al.,
2003). For instance, pyrite, which generally has the highest rest po-
tential, acts as a cathode, and the oxidation is inhibited, while galena
has the lowest rest potential, which acts as anode and is oxidised upon
contact and when galvanic interaction occurs (Rao and Finch, 2013). In
the galvanic interaction between galena and grinding media, the
grinding media, which has a low potential, acts as anode, is oxidised
and releases ferrous ions. Galena acts as the cathode resulting in the
reduction of O2 and the formation of hydroxyl ions (Peng et al., 2002).
The hydroxyl ions formed on the cathodic mineral may be attract to the
iron ions, resulting in the precipitation of iron hydroxide on the mineral
surface rendering the mineral hydrophilic (Peng et al., 2003a, b).
Electrochemical reactions will occur during galvanic interactions
between galena and grinding media, causing changes in pulp chemical
variables, such as dissolved O2, pulp potential, pH. The main result of
galvanic interactions is the iron oxidation species generated from the
grinding media. The main reactions occurring in the mill are (Peng and
Grano, 2010):
Anodic oxidation:
Fe → Fe2+ + 2e− E0 = 0.447 V (34)
2+ 3+ − 0
Fe → Fe +e E = 0.771 V (35)
Cathodic reduction:
O2 + 2H2O + 4e− → 4OH− E0 = 0.401 V (36)
Hydrolysis:
Y. Hu, et al. Minerals Engineering 150 (2020) 106272

Fe(OH)2 mineral surfaces, thereby preventing the flotability of these minerals

Fe3+ Fe(OH)3 (Fuerstenau et al., 2007). In addition, galvanic interactions may cause
Fe2+ severe media wear due to corrosion. Controlling galvanic interactions is
important for reduction of these adverse effects. Reducing galvanic
e OH
interactions can be achieved by adjusting pulp chemistry (e.g., solution
Galena pH) and adding corrosion inhibitors (e.g., sodium nitrite, sodium
Grinding media
chromate) (Leja, 2012; Ayyala et al., 2015).
O2 + H2O

8.2. Effect of grinding media type

Anode Cathode
Fig. 4. Galvanic interaction between galena and grinding media.
Fe2+ + 2H2O → Fe(OH)2 + 2H+
Fe 3+
+ 3H2O → Fe(OH)3 + 3H +
These iron hydroxides are hydrophilic and may completely or par-
tially cover the sulfide mineral surface, decreasing the interaction be-
tween collectors and minerals and thus reducing flotability (Smart,
1991). Fig. 4 shows a schematic of the galvanic interaction between
galena and grinding media.
Galvanic interactions will reduce the concentration of dissolved O2
due to the reaction of dissolved O2 with active sulfides and the corro-
sion of grinding media (Kelebek and Yoruk, 2002). The decrease in
dissolved O2 also hinders the adsorption of xanthate on the sulfide
Numerous studies have been done on the influence of grinding
media on mineral flotation. Iron oxidation species produced by the
galvanic interaction between grinding media and sulfide minerals have
(37) a depression effect on mineral flotation (Peng et al., 2003a, b). When
(38) the difference between the rest potential of the grinding medium and
the sulfide mineral is large, the galvanic interaction is more obvious in
the grinding system, and causes the potentials of the two materials to
change from their rest potential to mixed potential (Adam et al., 1984;
Martin et al., 1991; Zhang et al., 2018). A less electrochemically active
steel media, such as high-chromium media or stainless steel, have a
relatively small difference between the rest potential of galena and the
grinding media, and produce a reduced concentration of iron oxidation
species as compared to mild steel media during grinding, resulting in
greater recoveries of sulfide minerals.
Pulp potential is a very valuable parameter for controlling and

Table 1
Relationship between electrochemical conditions and processes of galena flotation.
Electrochemical process Effect Factors Explanation

Oxidation Collectorless flotation Pulp potential Collectorless flotation of galena occurs only under moderately oxidizing environments, and hydrophobic
sulfur-rich species are formed on galena surface.
Strong oxidation or reduction environments are not conducive to collectorless flotation.

pH Collectorless flotation is pH-dependent and becomes more favorable with decreasing pH.
At low pH, elemental sulfur has high stability and hydrophobicity, which increases flotability.
In strong alkaline solutions, hydrophobic sulfur species are hydrolysed to hydrophilic species precipitated on
the surface.
In strong acid solution, a strong oxidizing environment is produced, and hydrophobic sulfur on the surface are
oxidised to a hydrophilic species.
O2 Dissolved O2 controls the degree of oxidation of sulfide mineral to sulfur-oxy species.
Collector adsorption Collector concentration As the concentration of xanthate is reduced the potential increases.
When the concentration of xanthate is low adsorbed PbX species are formed.
When the concentration of xanthate is high adsorbed PbX2 species are formed.
Increasing the potential and KEX concentration is beneficial to X2 generation.
pH Potential generally decreases with increasing pH.
Galena is easily depressed under alkaline conditions, under which the formation of hydrophobic lead oxide/
hydroxide species occurs, also preventing the oxidation of xanthate ions to produce hydrophobic species.
O2 The presence of O2 improves the xanthate adsorption.
The increase in dissolved O2 concentration leads to the increase in pulp potential, resulting in an increase in
oxidation rate of xanthate.
Depressants Depressant dosage In the presence of dichromate, xanthate desorbs decomposes and PbCrO4(s) covers the galena surface and
pH prevents xanthate adsorption at moderate pH and pulp potential.
In the presence of sulfite, the solution redox potential may be reduced, decomposition of xanthate and
formation of perxanthate may occur along with surface complexation of lead sulfite.
In the addition of sodium sulfide results in reducing potentials and the chemisorption of xanthate is inhibited,
and Pb(EX)2 is decomposed.
Organic depressants are adsorbed on the mineral surface by bonding with surface metal hydroxyl species.
Appropriate galena surface oxidation and pulp oxidation environment are the prerequisites for depressant
adsorption.
Grinding Galvanic interaction Galvanic interaction causes pulp chemical changes, such as O2 consumption, and pulp potential decreases,
resulting in the corrosion of grinding media and the production of hydrophilic iron hydroxides.
Grinding media A less electrochemically active steel media, such as high-chromium media, weakens galvanic interaction,
increases pulp potential, and produces less iron oxidation species and a high recovery of galena.
Gas atmosphere In contrast to O2 purging during grinding, N2 purging can weaken galvanic interaction and decrease iron
oxidation, thus increasing the galena recovery.
An increase in dissolved O2 during grinding enhances galvanic interaction and increases the pulp potential and
increases the formation of iron hydroxide species.
H2O2 production H2O2 formation increases with decreasing pH and increasing Eh of the pulp.
Greater amount of H2O2 is formed in O2 atmosphere due to the increasing of pulp potential.
In a galena–pyrite mixture, increasing the content of pyrite with higher rest potential, causes the
concentration of H2O2 to increase.

8
Y. Hu, et al.
monitoring flotation processes, and is dependent on the type of grinding
media used and changes as the pulp flows to the flotation cells
(Chander, 2003). Allahkarami et al. (2014) found that in the case of less
active grinding media (ceramic media), the recovery of galena flotation
was greater than for in more active grinding media (mild steel media).
According to XPS analysis, the concentration of iron hydroxide on ga-
lena surfaces was very high for mild steel. These results were in good
agreement with the EDTA extraction (Peng et al., 2003b). Peng et al.
(2002, 2012) demonstrated that at pH 9.0, the oxidised species under
all different grinding conditions should be iron (III) hydroxide. More-
over, as the chromium content increased in the grinding media, the Eh
in the mill correspondingly increased, leading to a series of changes in
the pulp chemistry. High-chromium media has a relatively high cor-
rosion resistance and hardness (Sailors, 1989). The application of high
chromium grinding medium in the grinding process reduces the con-
sumption of the media and the contamination of iron hydroxide on the
galena surface.
8.3. Effect of gas atmosphere in grinding system
O2 plays a key role in galvanic interaction during grinding. The
presence of O2 increases galvanic interaction, because O2 can form
hydroxyl ions on acceptance of electron, thereby promoting the oxi-
dation of the grinding media and increasing the concentration of iron
hydroxide on the mineral surface (Natarajan and Iwasaki, 1984). In
most sulfide systems, these electrochemical reactions consume O2, re-
sulting in a reduction in pulp potential (Bruckard et al., 2011).
Peng et al. (2002) studied the effects of NaOH addition on the flo-
tation recovery of galena during grinding under different atmospheres
including O2, air, and N2. The results showed that N2 purge reduced the
iron oxidation compared with the air purge, the requirement for NaOH
reduced, and the recovery of galena was high. In contrast to N2 purging
during grinding, O2 purging increases the galvanic interaction and pulp
potential, resulting in the increase in the iron hydroxide concentration
on sulfide minerals surface and hindering the adsorption of xanthate
(Rabieh et al., 2016). Therefore, the flotability of sulfide minerals is
substantially depressed (Forssberg et al., 1988; Yuan et al., 1996).
8.4. Effect of the formation of hydrogen peroxide (H2O2) in the grinding
system
In addition to iron oxidation species, H2O2 is found in the grinding
system. It is formed during wet grinding and when freshly dry ground
galena is mixed with water immediately after dry grinding (Nooshabadi
and Rao, 2014a, b). Dissolved O2 can form superoxide anions (O2%)−
(Ahlberg and Broo, 1996; Elisabet and Broo, 1996), which reacts with
H+ to form H2O2 (Eqs. (39)–(42)) (Nooshabadi and Rao, 2014a, b;
Nooshabadi et al., 2013).
O2 + e− → (O2%)− (39)
% − + and pyrite is conducted in lime-modified alkaline pulp with
2(O2 ) + 2H → H2O2 + O2 (40)
PbS + H2O2 → Pb 2+ 0 −
+ S + 2e + 2 OH%
(41)
2 OH → H2O2
%
(42)
In the absence of O2, H2O2 is formed by combining two hydroxyl
radicals via the reaction of galena with water (Eqs. (43)–(44))
(Nooshabadi and Rao, 2014a, b; Nooshabadi et al., 2013).
PbS + H2O → %OH + H%+Pb2++ S0 + 2e% (43)
2 OH → H2O2
%
(44)
H2O2 is an oxidizing agent that is stronger than O2, which can
oxidize galena and depress its flotation (Nooshabadi and Rao, 2014b).
H2O2 could accelerate anodic oxidation and increase the corrosion rate
of galena, thereby promoting the formation of lead oxide, thiosulfate
9
Minerals Engineering 150 (2020) 106272
and sulfate (Wang et al., 2017). Nooshabadi and Rao (2014a) in-
vestigated multiple factors affecting the formation of H2O2 and found
that the amount of H2O2 increased with increased grinding time and
galena loading due to the increase of surface area and its interaction
with water. In addition, the concentration of H2O2 produced increased
with decreasing pH and increasing Eh. Moreover, H2O2 produced in a
N2 atmosphere was smaller than that in an air environment, because N2
purging reduces the pulp potential. In addition, the effect of pyrite
percentage on the formation of H2O2 in the galena–pyrite mixture was
illustrated. The concentration of H2O2 increases with increasing pyrite
percentage. The formation of large amounts of H2O2 when pyrite was
mixed with a second sulfide mineral may indicate that the electro-
chemical activity of galena is related to the proportion of pyrite. The
formation of H2O2 increases with increasing content of minerals with
high rest potential in the mixed components; at a high rest potential,
more H2O2 is formed (Javadi, 2015).
Galena ground with mild steel media in O2 atmosphere has a smaller
recovery than galena ground with stainless steel media in N2 atmo-
sphere, which is attributed to the greater amount of H2O2 produced in
mild steel media and O2 atmosphere. In presence of xanthate collectors,
the strong depressing action of H2O2 on galena could be attributed to
the oxidation of xanthates to perxanthates (Jones and Woodcock, 1978)
and its strong oxidizing action on lead dixanthate, which causes oxi-
dation and decomposition (Wang, 1992). These reactions are:
Formation of perxanthate
X% + H2O2 → XO% + H2O (45)
where XO is perxanthate.
%
Decomposition of lead dixanthate
Pb(EX)2 + H2O2 → Pb(OH)2 + (EX)2 (46)
9. Electrochemical potential controlling flotation
The flotation behavior of sulfide minerals can be optimized by ad-
justing and controlling pulp potential. Two types of control methods
have been developed to adjust the pulp potential: addition of oxidizing
or reducing agents and an outside polarized electrode. Both methods
have several disadvantages, such as difficulty in stabilizing potential
and low efficiency of polarized potential (Qing et al., 2008). A tech-
nique for accurate potential control in grinding-flotation systems based
on the intrinsic electrochemical behavior of sulfide minerals has been
developed. Using the original potential to improve the separation of
sulfide minerals is named “original potential control flotation” (OPCF).
Industrial test of OPCF technology has been successfully applied to
the Nanjing lead–zinc mine (Hu et al., 2010). In common flow sheet,
ZnSO4 and Na2SO3 as the depressants of ZnS and FeS2 are used under
neutral pH conditions, and the flotation separation of galena from
sphalerite and pyrite is poor. The OPCF separation of galena, sphalerite,
pH = 12.4–12.5, and pulp potential is kept less than 170 mV (SHE).
Sodium diethyldithiocarbamate (DDTC) is used as a collector in galena
flotation. Compared with common flowsheet, the grade and recovery of
lead concentration increase from 52.1% to 60.0% and from 85.9% to
88.9%, respectively. The grade and recovery of zinc concentration in-
crease from 52.6% to 53.0% and from 87.0% to 91.9%, respectively.
The OPCF technology is also successfully applied to Fankou lead–-
zinc mine in Guangdong Province, China (Hu et al., 2010). Here, pH is
modified to 12 by lime, and pulp potential is kept less than 170 mV
(SHE). The mixture of xanthate and DDTC is used as a collector in ga-
lena flotation. CuSO4 is used as a collector in sphalerite flotation. The
results show that OPCF technology greatly improves the efficiency of
flotation separation of lead–zinc in Fankou mine. The grade and re-
covery of lead concentration increase from 58.02% to 61.44% and from
82.4% to 87.66%, respectively. The grade and recovery of zinc
Y. Hu, et al.
concentration increase from 53.03% to 56.34% and 92.27% to 94.62%,
respectively. The reagent consumption in OPCF is diminished relative
to the old flowsheet.
10. Summary
Galena is a narrow band gap semiconductor. The flotation of galena
occurs via an electrochemical mechanism in which the anodic processes
are the mineral and collector oxidation, and the cathodic processes are
O2 and mineral reduction. Various electrochemical processes related to
galena in the flotation system and their influencing factors have been
discussed in this review. The electrochemical behavior of galena in
flotation process has been widely studied. The flotation and separation
of sulfide minerals can be realized by controlling the electrochemical
conditions of the flotation system. Table 1 summarizes the relationship
between the galena flotation process and electrochemical conditions.
These electrochemical processes are influenced by multiple factors,
such as solution pH, dissolved O2 content, pulp potential, concentration
and type of oxidizing or reducing agent, each of which has an important
influence on the overall flotation performance of the system. Galvanic
interaction between conductive grinding media also has an important
influence on flotation processes. Grinding time, grinding atmosphere,
grinding media, and the formation of H2O2 are all important factors
associated with the galvanic interaction and pulp potential. The change
in pulp properties caused by change in grinding environment leads to
differences in the flotation behavior of sulfide minerals. The flotation
and separation of sulfide minerals can be improved by adjusting the
grinding environment in many ways.
Sulfide ore flotation system have special complexity. For example,
the surface properties of sulfide ores easily change with time and en-
vironment. Moreover, modern mineral resources tend to be poor, fine,
and miscellaneous, and protection of the environment is gaining in-
creasing attention. The search for non-toxic and effective separation
processes for sulfide minerals is urgent. Therefore, production practice
introduces increased requirements for the theoretical study of flotation
electrochemistry. Thus, sulfide mineral flotation research should focus
on the combination of the theory and application of electrochemistry.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The research was supported by the National 111 Project (No.
B14034), the Fundamental Research Funds for the Central Universities
of Central South University (2019zzts699) and Collaborative
Innovation Center for Clean and Efficient utilization of Strategic Metal
Mineral Resources.
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