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Mineral Processing and
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Electrochemical aspects in
some of the hydrometallurgical
processes
R. K. Paramguru
a
a
Regional Research Laboratory (Council of Scientific
and Industrial Research), Bhubaneswar, India
Version of record first published: 26 Oct 2010.
To cite this article: R. K. Paramguru (2002): Electrochemical aspects in some of the
hydrometallurgical processes, Mineral Processing and Extractive Metallurgy Review:
An International Journal, 23:2, 65-100
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ELECTROCHEMICAL ASPECTSINSOME OF THE
HYDROMETALLURGICAL PROCESSES
R.K. PARAMGURU
Regional Research Laboratory (Council of Scientific and
Industrial Research) Bhubaneswar, India
Hydrometallurgy deals with extraction of metal values from ore minerals
through aqueous processing by solubilizing the specific metal value into the
aqueous phase and subsequently taking it out of the solution. These steps may
be chemical or electrochemical in nature. The electrochemical phenomena
depends on the electrical properties of the solid material and the redox
characteristics of the solution. The present paper discusses electrochemical
aspects of some hydrometallurgical operations involving the following phe-
nomena: (i) corrosion coupling, (ii) galvanic coupling, (iii) dissolution via
cyclic action of a redox couple, (iv) displacement or cementation reaction, (v)
precipitation under reducing conditions, (vi) dissolution under high pressure,
and (vii) dissolution influenced by hole transfer.
Keywords: electrochemical aspects, hydrometallurgical operations, electron
transfer, hole transfer
Extractive metallurgy involves efficiently taking the valuable metal, present
as a compound, out of the ore body. Broadly, two types of operations
(i.e., pyro- and hydrometallurgy) are in practice. Although pyro-
metallurgical treatment is common, hydrometallurgical techniques are
generally preferable because of environmental and many other advantages.
The author wishes to thank Dr. V.N. Misra, Director, Regional Research Laboratory,
Bhubaneswar, for his keen interest in this paper and permission to publish this work.
Address correspondence to R. K. Paramguru, Regional Research Laboratory, Council
of Scientific and Industrial Research, Bhubaneswar, Orissa 751013, India.
E-mail: paramguru@rrlbhu.res.in
Mineral Processing and Extractive Metallurgy Review, 23: 65÷100, 2002
Copyright #2002 Taylor &Francis
0882-7508/02 $12.00+.00
DOI: 10.1080=08827500290110179
65
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Generally, hydrometallurgy operates in two distinct steps: (i) a
leaching step involving dissolution of the desired mineral(s) or a
processed mineral from the ore into solution, and (ii) the winning step for
the separation of metal values from the solution. Invariably, some other
operations, such as solid-liquid separation, solution purification, and
thickening, are also incorporated between these two steps.
Leaching is the process of selectively extracting a soluble con-
stituent from a solid into a solvent. In extractive metallurgy, this solid
can be a mineral or minerals present in an ore or concentrate, or a
metallurgical product, such as calcine, matte, scrap alloy, anodic slime,
etc. The solvent may range from simple water to strong acids, alkalis,
or aqueous salt solutions to provide a strong oxidizing or reducing
atmosphere during leaching or act as a complexing agent. The leaching
operation may be performed in situ, on a heap or dump, in a vat or
column via percolation or in a stirred tank reactor at ambient or
elevated temperatures. In case of operations at temperatures above the
boiling point of the solvent, a high-pressure reactor is used. At pres-
ent, use of bacteria to assist leaching is also in practice. Once the
metal value is solubilized, the leach liquor is filtered, purified, thick-
ened, and processed for winning the metal. The residue, if any, is
either rejected or processed further for recovering additional values.
The normal metal-winning operation involves any one or more of the
following processes: crystallization, adsorption, ionic precipitation, pre-
cipitation by either metals or gases, ion exchange, solvent extraction, or
electrolysis onto either solid cathode or mercury. Recent developments in
corrosion-resistant materials and the purification processes, like ion
exchange and solvent extraction, have made hydrometallurgy more ver-
satile and competitive. Table 1 lists some of the hydrometallurgical
processes, many of which are of commercial significance in different parts
of the world.
Most of the operations involved in the process routes listed in Table 1
are heterogenous in nature, involving at least solid and liquid phases.
Quite often the gaseous phase is also involved. The process steps may be
chemical or electrochemical in nature, which differs from each other both
from the thermodynamic as well as the kinetic considerations; however,
the present paper concentrates on the electrochemical aspects in hydro-
metallurgical operations. Many of such operations are electrochemical in
nature as indicated in the examples of Table 1, where the electrochemical
nature of some or all the process steps was already established. The
66 PARAMGURU
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Table 1. Hydrometallurgy used in the metal extraction processes
Serial
number
Metal
produced
Raw
material Operations
Whether
electrochemistry
involved in
some steps
1 Gold Native ore Leaching, precipitation Yes
2 Silver Native ore -do- Yes
3 Platinum Native ore,
anode slime
-do- and calcination —
4 Copper Native ore,
oxide ore,
sulphide ore
Leaching, SX-EW Yes
5 Nickel Native ore,
laterite
(oxide)
sulphide
Leaching, SX-EW, direct
electrowinning of metal
Yes
6 Aluminium Oxide ore Leaching-fused
salt electrolysis
Yes
7 Tin Oxide ore Pressure leaching,
amalgamation
Yes
8 Iron Low grade
oxide and
sulphide ore
Acid leaching (÷O
2
)
also bacterial leaching
Yes
9 Manganese Oxide Leaching (reductive)
precipitation=EW
Yes
10 Zinc Calcine
sulphide
Acid leaching-EW
Pressure leaching-EW
Yes
11 Titanium Complex
oxide
Acid leaching
(purification)

12 Tungsten -do- Acid leaching=alkali
leaching=roast leaching

13 Uranium Oxide Acid leaching with oxide=
alkali carbonate leaching,
bacterial leaching.
Yes
14 Molybdenum Sulphide NAOCl leaching Yes
15 Lead Sulphide Leaching-EW Yes
‘ —’ implies ‘not yet established’.
HYDROMETALLURGICAL PROCESSES 67
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following sections of this paper present theoretical considerations
involved in these steps.
THEORETICAL CONSIDERATIONS
The electrochemical nature of a process is determined by the character of
the solid and the liquid associated with it, and involves a solid solution
interface, as is well understood in electrochemical literature. Some solid
ore bodies (e.g., native ores of gold, silver, platinum, and copper) are
good conductors. Most sulphides, which constitute primary sources for
many metals (e.g., chalcopyrite, chalcocite, and covellite for copper;
galena for lead; sphalerite for zinc), are semiconductors (Table 2)
(Habashi 1970; Koch 1975; Osseo-Asare 1992). Some oxides are also
semiconductors (e.g., nickel oxide, cassiterite [SnO
2
], hematite [Fe
2
O
3
],
magnetite [Fe
3
O
4
], and pyrolusite [MnO
2
]). They provide the necessary
solid surface for electrochemical interaction during leaching. The leach-
ant, which usually is either a reductant or an oxidant, acts as the elec-
trolyte. Table 3 provides the list of oxidants used in hydrometallurgical
operations (Peters 1992). In the winning step, the emerging product
usually is a metal, which generally is a good conductor. Thus, hydro-
metallurgy provides suitable conditions for the operation of electro-
chemical systems. Sometimes external electric current is supplied, as in
the case of direct electrowinning of metals (Serial 5, Table 1), electro-
winning or electrorefining of metals (Serials 4÷6, 9, 10, 15, Table 1), and
amalgamation (Serial 7, Table 1); however, this paper is confined to those
cases in Table 1 where electrochemical phenomena operate in situ with-
out any external electric current. These systems operate in a way similar
to metal corrosion systems familiar to any electrochemist. As will be
shown, many of these processes are examples of corrosion coupling,
galvanic coupling, etc., and follow the principles of metal corrosion.
Leaching as a Process Analogous to Corrosion
Leaching of conducting or semiconducting metals and minerals follows
electrochemical principles and can, therefore, be explained in terms of
electron transfer. The conducting solid surface in contact with an elec-
trolyte provides the solid=solution interface for electron transfer to take
place. In certain cases, presence of more than one such solid in contact
with the electrolyte may present a pathway for electron transfer through
68 PARAMGURU
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the solid-solid interface while the possibility of surface passivation or
catalytic activation in some cases is also not ruled out. All of these
processes are analogous to the well-established corrosion reaction for
metal systems. A corroding metal electrode dipped in an electrolyte
provides two half-cell reactions, namely, the anodic and cathodic, which
balance each other electronically so that there is no net charge transfer;
however, there is net mass transfer since the reactions, although different,
are not exactly the reverse of each other. Similarly, the leaching of
semiconducting minerals can be explained by applying the established
principles for metal corrosion involving charge transfer, though the
resistivity of the semiconductors is a critical factor. The resistivity values,
Table 2. List of Important Sulphide Minerals (Habayashi 1970; Koch 1975; Osseo-Asare
1992)
Metal Mineral Formula
Resistivity,
O m
Type of
semi-conductor
Energy
Gap, eV
Antimony Stibnite Sb
2
S
3
— — —
Arsenic Realgar As
4
S
4
— — —
Orpiment As
2
S
3
— — —
Arsenopyrite FeAsS 3-570 — —
Bismuth Bismuthinite Bi
2
S
3
— — —
Cadmium Greenockite=
Hewleyite
CdS — n 2.42
Cobalt Linnaeite Co
3
S
4
— — —
Copper Chalcocite Cu
2
S 10
72
÷10
75
p 1.10
Covellite CuS 0.3-83 ×10
76
Metallic, p —
Digenite Cu
9
S
5
— — —
Bornite Cu
5
FeS
4
1.6-6000 ×10
76
— —
Chalcopyrite CuFeS
2
150-9000 ×10
76
n 0.6*
Iron Pyrite FeS
2
1.2-600 ×10
73
p, n, & p-n junction 1.2
Pyrrhotite FeS 2-160 ×10
76
p Very low
Lead Galena PbS 6.8 ×10
76
n,p 0.37
Mercury Cinnabar HgS — n 2.00
Manganese Haverite MnS
2
10÷20 — —
Molybdenum Molybdenite MoS
2
— — —
Nickel Millerite NiS 2-4 ×10
77
— —
Pentlandite (Fe,Ni)S 1-11 ×10
76
— —
Silver Argentite Ag
2
S 1.5-2 ×10
73
n ~1
Tin Harzenbergite SnS 3 p 1.08
Zinc Sphalerite ZnS 2.7 ×10
73
÷1.2 ×10
4
n 3.67
*(Crundwell 1988).
HYDROMETALLURGICAL PROCESSES 69
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semiconducting type, and energy gap of some of the sulphide minerals are
given in Table 2. It can be seen that these values vary widely even for each
of the sulphides. This may be due to minor differences in their compo-
sition and the presence of hairline cracks. Koch (1975) pointed out that
some of the sulphides, like nickel, copper, iron, and lead, have resistivities
comparable to those of metals, and therefore can be used as massive
electrodes so that the rates of dissolution at current densities up to about
100 mA=cm
2
can be measured by the standard electrochemical tech-
niques. Cominco demonstrated the commercial applications of this
aspect by directly electrowinning nickel using massive nickel matte elec-
trodes (Habashi 1971). In this case, the oxidant is the direct current, and
the direct electrowinning process can be explained in terms of electron
transfer; however, in many of the leaching processes involving semi-
conducting minerals also, the reactions can be explained in terms of
electron transfer. In the case of zinc, cadmium, manganese, and bismuth
sulphides, their conductivity is good enough to use the techniques
developed in semiconductor electrochemistry. Recently, Osseo-Assare
(1992) discussed the importance of semiconductor electrochemistry in
mineral leaching highlighting the significance of hole transfer, and this
aspect will be briefly discussed at a later stage. The following section deals
with only the electron transfer phenomena.
Mixed Potential Concept
When a metal or mineral with sufficient conductivity is dipped in an
electrolyte, a steady-state (corrosion) potential is developed due to the
Table 3. Redox potentials of hydrometallurgical oxidants (Peters 1992) on the hydrogen
scale (V)
Oxidant Redox equation E
h
o
(pH=0) E
h
o
(pH=10)
Fe

Fe

÷e
7
=Fe

0.77 —
Fe(CN)
6
37
÷e
7
=Fe(CN)
6
47
— 0.46
O
2
(g) O
2
÷4H
÷
÷4e
7
=2H
2
O 1.23 0.64
HNO
3
NO
3
7
÷4H
÷
÷3e
7
=NO(g) ÷2H
2
O 0.957 (0.17)*
(HNO
2
) NO
2
7
÷2H
÷
÷e
7
=NO(g) ÷H
2
O 1.202 (0.02)*
(NO
÷
) NO
÷
÷e
7
=NO(g) 1.45 —
Cl
2
(g) Cl
2
(g) ÷2e
7
=2Cl
7
1.358 (1.36)*
(ClO
7
) ClO
7
÷2H
÷
÷2e =Cl
7
÷HO 1.63 1.126
*Calculated for standard conditions. These potentials are not realizable because of side
reactions.
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two partial half-cell reactions and is termed as the mixed potential, E
m
.
This system is called a corrosion cell, and the probable reactions may be
represented in a simple form as follows:
Anodic:
Me = Me

÷ 2e
÷
(1)
MeS = Me

÷ S ÷ 2 e
÷
; (2)
Cathodic (in acid):
O
2
÷ 4 H
÷
÷ 4 e
÷
= 2H
2
O; (3)
MeO
n
÷ 2nH
÷
÷ 2 e
÷
= Me

÷ nH
2
O; (4)
Anodic and cathodic (in presence of a redox couple R
n
=R
n÷1
):
R
(n÷1)÷
= R

÷ e
÷
; (5)
R

÷ e
÷
= R
(n÷1)÷
: (6)
A convenient way to deal with such a system is to plot the current-
potential curves for the respective half-cells involved in the leaching
reactions. Superposition of these two plots on one another gives the
mixed potential, E
m
, and the mixed current, i
m
. A conceptual diagram is
provided in Figure 1.
As seen in the figure, each polarization plot has three distinct seg-
ments: 1, 2, and 3 (A: anodic, C: cathodic). Segment 1 represents the
equilibrium (steady state) region where the particular electrode reaction is
mostly reversible and the potential obeys Nernst’s relation. Kinetics, in
this region, depend on conduction through the electrode and the elec-
trolyte. Stage 2 is known as the Tafel region, where the potential is
directly dependent on the logarithm of the current and the process is
under activation control. Stage 3 represents the limiting current region
where diffusion of either the reactant or the product species controls the
reaction. Partial and general kinetic expressions can be derived from the
position of the point of intersection with respect to the stage of each half
reaction. Earlier workers (Warren, Kim, and Heinen 1987; Rath,
HYDROMETALLURGICAL PROCESSES 71
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Paramguru, and Jena 1988) assumed Stage 2 for each half of the reaction
to derive the kinetic expressions, but Wadsworth (1984) derived separate
equations for all three situations. The present authors (Paramguru and
Ray 1996) derived equations with nine different combinations. Table 4
presents expressions for mixed potential, E
m
, and mixed current, i
m
, at
different situations for reactions (2) and (6), and Table 5 provides
expressions for reactions (4) (Me is Mn, n =2) and (5) (n =3).
The reliability of quantitative application of polarization data may
sometimes be questioned, especially when the purity and surface area of
the semiconducting electrodes are uncertain. Paramguru and Ray (1996)
have suggested a practical approach for studying the kinetics and
mechanism of the process using the polarization data. It involves the
approximate identification of the stages (1, 2, or 3) of each half plot at
the point of intersection, implying that only qualitative significance is
attached to the polarization data. Expressions are then derived theoreti-
cally for E
m
and i
m
as presented in the Tables 4 and 5. These expressions
are validated using the data from leaching studies. The methodology has
been successful in the study of reactions falling under situations 2÷8 of
Figure 1. Hypothetical polarization curves for anodic and cathodic reactions superimposed
on one another.
72 PARAMGURU
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Tables 4 and 5 (Paramguru and Ray 1996). These include reactions
under mixed control (Tafel-Tafel interaction) (Paramguru and Ray
1995), dissolution by diffusion-controlled half-cell reactions (Paramguru
and Ray 1995; Dutrizac 1985), leaching by activation-controlled half-cell
reactions (Warren et al. 1987; Paramguru 1995; Jin, Warren, and Heinen
1993), and significantly, the dissolution by cyclic action of a redox couple
(Paramguru and Kanungo 1995; Nayak, Parida, Rao, and Paramguru
1995). A similar analogy can also be extended to galvanic coupling,
cyclic action of a redox couple to dissolve two semiconducting minerals,
and other hydrometallurgical operations, such as cementation and
precipitation under reducing conditions, including high-pressure opera-
tions. Some of these aspects will now be discussed under the following
headings:
(i) Corrosion coupling
(ii) Galvanic coupling
(iii) Electrochemical aspects in high pressure operation.
In addition, semiconducting aspects will also be discussed briefly at
the end.
Table 4. Expressions for mixed potential, E
m
, and mixed current, i
m
, at different
situations for reactions (2) and (6)
Sl. no. Situation Expression for E
m
Expression for i
m
1 A1-Cl (2.3RT=F) log {(K
2
[Me

]
÷K
4
[R

])=(K
1
÷K
3
[R
(n71)÷
])}
K7[R

]={(K
1
÷K
3
[R
(n71)÷
])
(K
2
[Me

]÷K
4
[R
n÷1
])}
1=2
2 A2-C1 (2.3RT=F) log {K
4
[R

])=
(K
1
÷K
3
[R
(n71)÷
])}
FK
1
{K
4
[R

]=
(K
1
÷K
3
[R
(n71)÷
])}
1=2
3 A3-Cl ~Ec =E
c
o
÷(2.3RT=
Z
c
F) log {[R

]=[R
(n71)÷
]}
FK
5
[Me

]
4 A1-C2 (2.3RT=F) log {(K
2
[Me

]
÷ K
4
[R

])=K
1
}
FK
4
[R

](K
1
)
1=2
=
(K
2
[Me

]÷K
4
[R
n÷1
])}
1=2
5 A2-C2 (2.3RT=F) log {K
4
[R

]=K
1
} FK
1
{K
4
[R

]=K
1
}
1=2
6 A3-C2 (2 ×2.3RT=F) log {K
4
[R

])=
K
5
[Me

]}
FK
5
[Me

]
7 Al-C3 ~E
a
=E
a
o
÷(2.3RT=Z
a
F)
log [Me

]}
FK
6
[R*]
8 A2-C3 (2 ×2.3RT=F) log {K
6
[R*]=K
1
} FK
6
[R*]
9 A3-C3 — —
K
1
K
7
are constants, and *may be n
÷
or (n71)
÷
.
HYDROMETALLURGICAL PROCESSES 73
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CORROSIONCOUPLING
In hydrometallurgy there are several examples of corrosion coupling.
Fathi Habashi (1970) has chosen the 18th century process of gold
leaching in cyanide bath to demonstrate the corrosion coupling. Li et al.
(1992) have cited three classic examples, such as copper=iron cementa-
tion, silver dissolution in cyanide, and leaching of chalcocite in ferric
chloride solution involving corrosion coupling. The present author has
chosen the dissolution of base metal sulphides in ferric chloride, cyclic
action of a redox couple to dissolve two minerals, cementation of copper
by zinc, and electroless deposition of copper as examples for a detailed
discussion on this aspect.
Dissolution of Base Metal Sulphides in Ferric Chloride
Galena, sphalerite, and chalcopyrite are a few base metal sulphide
minerals that have commercial significance. The CYMET Process
Table 5. Expressions for mixed potential, E
m
and mixed current, i
m
, at different
situations for reactions (4) and (5)
Sl.
no. Situation Expression for E
m
Expression for i
m
1 A
/
1-C
/
l (2.3RT=F) log{(C
2
[Fe

]
÷C
4
[H
÷
])=(C
1
[Fe

]
÷C
3
[Me

])}
C
7
[H
÷
][Fe

]={(C
1
[Fe

]{(C
1
[Fe

]
÷C
3
[Me

])
1=2
(C
2
[Fe

]÷C
4
[H
÷
])}
1=2
2 A
/
2-C
/
1 (2.3RT=F)log{C
4
[H
÷
])=
(C
1
[Fe

]÷C
3
[Me

])}
FC
1
{C
4
[H
÷
]=(C
1
[Fe

]
÷C
3
[Me

])}
1=2
3 A
/
3-C
/
l ~Ec =E
c
o
÷(2.3RT=Z
c
F)
log{[H
÷
]
2
=[Me

]}
FC
5
[Fe*]
4 A
/
1-C
/
2 (2.3RT=F)log{(C
2
[Fe

]
÷C
4
[H
÷
])=C
1
[Fe

]
FC
4
[H
÷
]{(C
1
[Fe

])=(C
2
[Fe

]
÷C
4
[H
÷
])}
1=2
5 A
/
2-C
/
2 (2.3RT=F)log {C
4
[H
÷
]=
K
1
[Fe

]}
F{C
1
C
4
[Fe

][H
÷
]}
1=2
6 A
/
3-C
/
2 (2 ×2.3RT=F) log{C
4
[H
÷
])=
C
5
[Fe*]}
FC
5
[Fe*]
7 A
/
l-C
/
3 ~E
a
=E
a
o
÷(2.3RT=Z
a
F)
{[Fe

]=[Fe

]}
FC
6
[Me

]
8 A
/
2-C
/
3 (2 ×2.3RT=F) log{C
6
[Me

]=
C
1
[Fe

]
FC
6
[Me

]
9 A
/
3-C
/
3 — —
C
1
÷C
7
are constants corresponding to reactions (4)÷(5), identical to K
1
÷K
7
in Table 4;
*may be n
÷
or (n71)
÷
.
74 PARAMGURU
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m
b
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r

2
0
1
2

(McNamara, Ahrens, and Franek 1980), the CLEAR-Duval Process
(Atwood and Livinston 1980), the ZINCEX Process (Nogueira,
Regife, and Vigas 1982), the ELKEM Process (Barbery, Fletcher, and
Sirois 1980), the MINEMET Recherches Process (Demarthe, Gandon,
and Georgeaux 1976), and the USBM Process (Wong, Haver, and
Sandberg 1980) are a few processes that attempt to solubilize the
metal values using a redox system like Fe

=Fe

or Cu

=Cu
÷
or
both, and remain the classic examples of use of corrosion coupling
principles. Many investigations have been carried out on the elec-
trochemical character of these leaching systems (Wadsworth 1984;
Dutrizac 1985; Warren et al. 1987; Rath et al. 1988; Jin et al. 1993;
Paramguru and Ray 1995; Paramguru 1995; Paramguru and Kanungo
1995; Nayak et al. 1995; Paramguru and Ray 1996). Figure 2 pre-
sents a conceptual diagram of such corrosion coupling, and Figures 3
and 4 present polarization plots for galena (Paramguru and Ray
1995) and sphalerite (Paramguru 1995) leaching in ferric chloride.
Leaching of galena in ferric chloride has been studied in detail, and
Kobayashi, Dutrizac, and Toguri (1990) have published an extensive
review on this subject. The leaching mechanism in dilute ferric
chloride solutions is different from that in more concentrated media.
The former conforms to linear kinetics, the latter to diffusion
kinetics. The polarization data (Paramguru and Ray 1995) presented
in Figure 3 provides explanation for this difference. Plots (b) show
cathodic polarization plots for a range of ferric ion concentrations
while plot (a) presents the anodic one for the galena electrode. In
relatively dilute solutions, E
m
lies on the Tafel regions of both the
anodic and cathodic half reactions, conforming to linear kinetics as
described by case 5 of Table 4. Replacing R

with Fe

, the fol-
lowing equations for E
m
and I
m
are obtained:
E
m
= (2:3 RT=F) log ¦K
4
[Fe

[=K
1
¦; (7)
i
m
= FK
1
¦K
4
[Fe

[=K
1
¦
1=2
: (8)
These equations have been verified through polarization measure-
ments (Paramguru and Ray 1995) for lower ferric ion concentrations.
The leaching rate has also been found to follow equation (8) (Rath et al.
1988).
HYDROMETALLURGICAL PROCESSES 75
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2
:
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8

0
4

D
e
c
e
m
b
e
r

2
0
1
2

At higher ferric ion concentrations, the cathodic plots (Fig. 3)
intersect the anodic curve on its limiting current region, signifying dif-
fusion kinetics. Situation 6 of Table 4 should describe E
m
and i
m
, which
indicates a slope of (4.6 RT=F) or 0.118 V at 298 K when E
m
is plotted
Figure 2. Conceptual diagram for a mineral sulphide solution corrosion coupling.
Figure 3. Concurrent polarization curves at a ramp rate of 1 mA=s. (a) anodic galena in
(1 M NaCl ÷ 0.1 N HCl); (b) cathodic platinum in different fenic ion concentrations in
(1 M NaCl ÷ 0.1 N HCl ÷ 0.001 M Fe

); (1) 1.2, (2) 0.4, (3) 0.12, (4) 0.04, (5) 0.012,
(6) 0.004, (7) 0.0012, and (8) 0.00012 M Fe

.
76 PARAMGURU
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2

against log [Fe

], and i
m
should be independent of [Fe

] but should
depend on [Pb

]. This dependence of E
m
and i
m
on [Fe

] has been
verified from polarization measurements (Paramguru and Ray 1995).
Leaching studies reported by Dutrizac (1985) also support these
observations (i.e., the rate follows parabolic kinetics and depends on
[Pb

] and [Cl
7
], but independent of [Fe

] and [Fe

]). These results
stand as illustrative examples of a leaching reaction following corrosion
coupling principles.
Leaching of ZnS in FeCl
3
is another attempt of this kind. Earlier
studies (Warren et al. 1987, Rath et al. 1988) indicated that the dis-
solution reaction was controlled by electrochemical surface reaction.
The leaching rate was proportional to [Fe

]
1=2
and [Cl
7
] at lower
concentrations, but the rate became insensitive to the concentration of
these ions at higher concentrations. Addition of large amounts of Fe

ion rather retarded the reaction. Warren et al. proposed an electro-
chemical model incorporating a charge transfer process for each ion
and an adsorption step for Fe

and Cl
7
ions to explain these results.
Polarization measurements reported recently (Jin et al. 1993, Param-
Figure 4. Concurrent polarization curves at a ramp rate of 1 mA=s. (a) anodic sphalerite in
(1 M NaCl ÷ 0.1 N HCl); (b) cathodic platinum in different fenic ion concentrations in (1 M
NaCl ÷ 0.1 N HCl ÷ 0.001 M Fe

); (1) 1.2, (2) 0.4, (3) 0.12, (4) 0.04, (5) 0.012, (6) 0.004, (7)
0.0012, and (8) 0.00012 M Fe

.
HYDROMETALLURGICAL PROCESSES 77
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:
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0
4

D
e
c
e
m
b
e
r

2
0
1
2

guru 1995) indicate that situation 2 of Table 4 is followed in this case,
and the expressions for E
m
and i
m
are given under (Fe

in place of
R
(n71)÷
):
E
m
= (2:3 RT=F) log ¦K
4
[Fe

[=(K
1
÷ K
3
[Fe

[¦; (9)
i
m
= FK
1
¦K
4
[Fe

[=(K
1
÷ K
3
[Fe

[)¦
1=2
: (10)
These expressions are well supported by the experimental results. If
[Fe

] is much less than K
1
, then i
m
is directly dependent on [Fe

]
1=2
;
when [Fe

] is much larger, then it affects i
m
. As concentration of [Fe

]
decreases, the process deviates from situation 2 to 5 of Table 4 and the
[Fe

] term vanishes from equations (9) and (10).
Cyclic Action of a Redox Couple
Earlier studies (Nayak et al. 1995; Paramguru and Kanungo 1995;
Paramguru and Ray 1996) revealed that reduction leaching of MnO
2
in
the presence of FeS
2
in acidic solution is accomplished by the simulta-
neous action of the two corrosion couples, FeS
2
=Fe

and MnO
2
=Fe

.
The slower of the two controls the overall rate, and the other is main-
tained at that rate by adjustment of [Fe

] or [Fe

], whichever is
involved in that couple.
Recent studies (Paramguru and Kanungo 1998a; Paramguru and
Kanungo 1998b; Paramguru, Mishra, and Kanungo 1998) provide more
insight into this mechanism. The dissolution mechanism may not always
fall under the nine situations described in Tables 4 and 5. The mixed
potential E
m
, depending at times on the solution conditions, may lie on
linear-Tafel transition region of one of the polarization plots or below the
self-corrosion point on the current axis. In both cases the kinetic equa-
tions given in Tables 4 and 5 do not hold good. For dissolution of
manganese nodule in the presence of FeS
2
in dilute HCl medium
(Paramguru and Kanungo 1998b), the following situations have been
observed:
(i) In presence of sufficient acid, dissolution of FeS
2
=Fe

couple runs at
a slower rate. The following two kinetic equations give close fit to the
experimental leaching data:
78 PARAMGURU
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(a) E
m
on anodic linear-Tafel transition and cathodic Tafel:
[Fe

[=(Rate)
2
= K
8
([Fe

[[H
÷
[[SO
4

[=[Fe

[) ÷ K
9
: (11)
(b) E
m
on anodic Tafel and cathodic linear-Tafel transition region:
[Fe

[=(Rate)
2
= K
10
[Fe

[ ÷ K
11
: (12)
When [Fe

]=[Fe

] is greater than 50, the first situation may exist
(Paramguru and Kanungo 1995, Paramguru and Kanungo 1998b),
otherwise, the second one is valid.
(ii) In presence of insufficient acid, the following two kinetic equations
hold good:
(Rate) = K
12
([Fe

[[H
÷
[[SO
4

[); (13)
(Rate) = K
13
([H
÷
[[Fe

[)
1=2
: (14)
These equations refer to self-corrosion of FeS
2
and Tafel-Tafel interac-
tion of MnO
2
=Fe

couple, respectively. Owing to the low acid con-
centrations, the MnO
2
=Fe

rate came down to a level of rate-controlling
stage. Depletion of Fe

through precipitation as hydroxide or basic
sulphate due to low acid may push the i
m
of FeS
2
=Fe

couple to a value
lower than the self-corrosion current of this couple. There is a possibility
that both couples operate at the same rate. Figure 5 provides the proof
for these findings (i.e., b
a
( =i
m
of FeS
2
=Fe

) is less than b
c
(=i
m
of
MnO
2
=Fe

) at higher acid level, and a
c
is smaller than a
a
(a
c
and a
a
refer
to insufficient acid).
Similar studies have also been made on the MnO
2
-FeS
2
system in
H
2
SO
4
(Nayk, Mishra, and Paramguru 1999).
Dissolution of ZnS in presence of MnO
2
has also been explained
recently on these lines (Rao and Paramguru 1996). Pande, Gupta, and
Altekar (1982) reported an attractive method of acid processing of
sphalerite concentrates in the presence of manganese dioxide with the
dissolution reaction:
ZnS ÷ MnO
2
÷ 2H
2
SO
4
= ZnSO
4
÷ MnSO
4
÷ S
0
÷ 2H
2
O: (15)
HYDROMETALLURGICAL PROCESSES 79
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Neither ZnS nor MnO
2
dissolves as such in dilute H
2
SO
4
; however,
they dissolve when placed together in the acid by the action of two
corrosion couples, namely, ZnS=Fe

and MnO
2
=Fe

. Equations (2)
and (6) constitute the first couple by replacing Me, R, and n, respectively,
with Zn, Fe, and 3. MnO
2
=Fe

couple is represented by the reactions (4)
replacing Me with Mn and n with 2, and (5) replacing R with Fe and
n with 3.
These two couples run simultaneously to cause the dissolution of
both ZnS and MnO
2
(Rao and Paramguru 1996, Rao and Paramguru
1998). The couples balance each other through adjustment of Fe

and
Fe

concentrations. The couples may operate as per the situation 5 of
Figure 5. Concurrent polarization curves for anodic FeS
2
and cathodic MnO
2
at a ramp
rate of 1 mA=s at different HCl concentrations. (a) 0.08 M, (b) 0.25 M, and (c) 1.0 M. Also
present for platinum electrode in electrolyte: Fe

: 0.05 M, Fe

: 0.001 M.
80 PARAMGURU
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Tables 4 and 5, and both play a role in the rate-controlling process.
Equation (16), indicating a constant ratio between [Fe

] and ([Fe

]
[H
÷
]), describes the dissolution process:
([Fe

[=[Fe

[[H
÷
[) = K
14
: (16)
Cementation of Cu
2+
on Zinc
Zinc dust cementation for impurity (Cu

, Co

, and Cd

) removal
from the zinc electrolyte is one classic example of the cementation reac-
tion. It has been established in Power and Ritchie (1976) that for
cementation of Cu

, the mixed potential lies on the Tafel region of the
anodic (Zn) and the diffusion segment of the cathodic Cu

plot.
Therefore, the reaction is diffusion controlled with limited dependence on
temperature. The rate follows a first-order process with respect to [Cu

].
The initial rate is followed by a second stage with an enhanced rate. Zinc
dissolution via hydrogen reduction also takes place simultaneously.
Recently, studies by Mishra and Paramguru (2000), dealing indepen-
dently with the anodic (Zn=Zn

) and cathodic (Cu

=Cu) half-cell
reactions in a dual cell have indicated that the protonation reaction is
catalyzed by the deposited copper on the zinc surface. Expressions for E
m
and i
m
were derived for the following reactions:
Zn(S) = Zn

÷ 2e
÷
; (17a)
Cu

÷ 2e
÷
= Cu(S); (17c)
Zn(S) ÷ Cu

= Zn

÷ Cu(S); (17)
E
m
= ¦(2:303 × 2RT)=F¦ log(K
15
[Cu

[); (18)
i
m
= K
16
[Cu

[; (19)
Zn(S) = Zn

÷ 2e
÷
; (17a)
HYDROMETALLURGICAL PROCESSES 81
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b
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r

2
0
1
2

2[H
÷
÷ e
÷
= 1=2 H
2
[; (20c)
Zn ÷ 2H
÷
= Zn

÷ H
2
; (20)
E
m
= ¦(2:303 RT)=F¦ log(K
17
[H
÷
[); (21)
i
m
= K
18
[H
÷
[
1=2
: (22)
In case of reaction (20), E
m
was found to lie on the Tafel regions of
both the anodic and cathodic half polarization plots. The practical
cementation data was found to be the result of these two reactions (17
and 20), i.e., the experimental slope (of E
m
versus log [H
÷
]) of 0.105 V per
decade is in between 0.059 (eqn. 21) and 0.118 V per decade (eqn. 18).
Electroless Copper Deposition
Electroless metal deposition onto a substrate is a good example of pre-
cipitation under reducing conditions. This system can be well understood
using polarization studies, as the solid involved is a good conductor and
does not pose measurement problems. Recently, electroless deposition of
copper onto a copper substrate was explained through polarization stu-
dies (Mishra and Paramguru 1996, 1997a, 1997b, 1999). The following
reactions were mentioned:
Anodic: 2HCHO ÷ 4OH
÷
= 2HCOO
÷
÷ H
2
÷ 2H
2
O ÷ 2e
÷
; (23a)
Cathodic: Cu(L)
2
÷ 2e
÷
= Cu
0
÷ 2L
÷
; (23c)
Overall: Cu(L)
2
÷ 2HCHO ÷ 4OH
÷
= Cu
0
÷ 2HCOO
÷
÷ H
2
÷ 2H
2
O ÷ 2L
÷
: (23)
Here L represents the complexing agent.
Kinetic experessions can be derived on the basis of the position of E
m
on the individual polarization plots, and these can be validated with
reference to actual deposition rate. Table 6 gives four such cases for
which E
m
and i
m
have been derived and experimentally verified (Mishra
and Paramguru 1996, 1997a, 1997b, 1999). Deposition rates reported by
82 PARAMGURU
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Ohno (1991) under different conditions were also found to support this
view (Fig. 6). Many other precipitation processes used in hydro-
metallurgy are of this nature.
GALVANICCOUPLING
As galvanic interaction is known to take place during leaching operations
involving metals and semiconductors, leaching of sulphide minerals
always involves some galvanic coupling since these minerals are semi-
conductors and contain other sulphide minerals as impurities. Replacing
Me in reaction (2) with any two metals provides the two reactions of the
galvanic couple, and the one with higher potential acts as the cathode. On
galvanic contact, dissolution of the cathodic mineral gets retarded, while
that of the anodic one is enhanced. Wadsworth (1984) has brought out the
importance of the concept of mixed potential to describe the trend of
galvanic interactions. Using the Butler-Volmer equation, he has expressed
the rate of anodic dissolution of the active electrode as a function of
various parameters. Yelloji Rao and Natarajan (1986) measured the
combination potentials and galvanic currents for different sulphide
mineral couples and established the order of galvanic activity. Nowak,
Krause, and Pomianowski (1984) used a small-scale amplitude cyclic
voltametry to study the galvanic behavior of minerals and developed
equations in terms of the rest and mixed potentials along with Tafel slopes
to describe galvanic interaction. Holmes and Crundwell (1995) used a
voltage balance over the galvanic couple as basis for a mathematical
Table 6. Different mechanisms of electroless copper deposition based on position of E
m
on specific regions of polarization plots of anodic and cathodic half reactions
Polarization regions
in which E
m
lies
Solution condition
Mechanism [HCHO] [Cu

]
(1) Cathodic linear and
anodic limiting current
Anodic diffusion control Very low —
(2) Cathodic Tafel and
anodic limiting current
Anodic diffusion Low Moderate
(3) Cathodic and anodic
Tafel
Activation control Low to moderate Modrate to
high
(4) Cathodic-limiting current
and anodic Tafel
Cathodic diffusion
control
High Low to
moderate
HYDROMETALLURGICAL PROCESSES 83
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2
:
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0
4

D
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m
b
e
r

2
0
1
2

description of the magnitude of the galvanic interaction. The present
author used compact mineral electrodes in a dual cell to generate polari-
zation plots for the partial anodic and cathodic parts of the galvanic
couple, which not only measured galvanic interaction quantitatively, but
also provided the mechanism of interaction (Rao, Paramguru, Das, and
Ray 1992; Paramguru 1992). One interesting finding (Nayak, Parida, Rao,
Sahoo, and Paramguru 1994; Rath and Paramguru 1994; Paramguru and
Nayak 1996) has been the galvanic interaction between sulphide minerals
with MnO
2
. Here both the minerals corrode, MnO
2
as cathode and MeS
as anode, and the potential difference between the electrodes is much
larger than that of the sulphide-sulphide galvanic couples and results in
larger galvanic currents. The couple may be better understood following
an approach similar to that of corrosion coupling. The two partial
polarization plots can be obtained independently to get E
m
and i
m
(in this
case, E
g
, galvanic potential, and i
g
, galvanic current) on superimposition.
Equations (4) (replacing Me with Mn and n with 2) and (2) provide the
cathodic and anodic reactions, respectively. Figure 7 presents the Evans
diagram for MeS-MnO
2
galvanic couples and shows the interaction in the
Tafel region of both the anodic and cathodic plots for FeS
2
-MnO
2
and
Figure 6. Plots of log i
plating
versus log [Cu

] and log [HCHO] for results obtained from
Ref. (Ohno 1991). Hetched areas indicate regions of different mechanisms.
84 PARAMGURU
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CuFeS
2
-MnO
2
. For PbS-MnO
2
, the interaction is on the anodic limiting
current region. The ZnS-MnO
2
couple is in between these two. Situation 5
of Table 4 should apply for the FeS
2
-MnO
2
couple replacing equation (6)
with equation (4) and equation (2) with the following:
FeS
2
÷ 8H
2
O = Fe

÷ 2SO
4

÷ 16H
÷
÷ 14e
÷
: (24)
The relationships for E
g
and i
g
are as given below:
E
g
= 2:3 RT/F log ¦K
19
[H
÷
[¦; (25)
Figure 7. Concurrent anodic polarization curves of (1) PbS, (2) ZnS, (3) CuFeS
2
, and (4)
FeS
2
against (5) cathodic plot of MnO
2
in 0.1 M HCl at room temperature. Ramp rate: 1
mA=s. 1M NaCl incorporated in the bath for PbS electrode.
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i
g
= K
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[H[
1=2
: (26)
These equations have been verified experimentally (Paramguru and
Nayak 1996). The same equations with different constants are valid for
E
g
and i
g
of the other galvanic couple MnO
2
-CuFeS
2
, where the inter-
action takes place in the Tafel regions of both the plots. This has been
observed in case of this couple also (Madhuchhanda, Devi, Rao, Rath,
and Paramguru 2000). When the interaction takes place in the limiting
current region of the anodic curve, as in the case of the MnO
2
-PbS
couple, the expression for i
g
would not contain the [H
÷
] term because the
anodic reaction of PbS, which is expected to be rate controlling, does
not contain H
÷
term and hence no diffusion of H
÷
. Thus, i
g
, instead of
depending on H
÷
, may depend on Pb

ion concentration. Since the
anodic plot of zinc appears to be somewhere in between the Tafel and
limiting current regions at the point of intersection, the dependence of i
g
on [H
÷
] should be in between. In fact, the experimental dependence of i
g
on [H
÷
] for PbS-MnO
2
and ZnS-MnO
2
couples have been found to be
zero and around 0.2, respectively (Madhuchhanda et al. 2000).
It is interesting that pyrite-chalcopyrite-sphalerite and galena are
in this order in their declining noble character. Hence, their potential
difference in the galvanic cells with MnO
2
increases in this order and also
the observed i
g
values. Thus, the polarization plots in the case of
the MnO
2
-PbS couple, with the highest potential difference, traverse
the longest path in the current axis and the plot for galena (with lower
corrosion current density) is already in the limiting current region by the
time it intersects the MnO
2
plot. E
g
being the farthest from E
PbS
(in
comparison to E
MnO
2
), the process is under anodic control; however,
the case is different for the MnO
2
-FeS
2
couple with lower potential
difference. The intersection takes place in the Tafel-Tafel regions and
the process is controlled by the cathodic reaction. CuFeS
2
-MnO
2
and ZnS-MnO
2
couples appear in between these two extremes
(Madhuchhanda et al. 2000).
ELECTROCHEMICAL ASPECTSINHIGH-PRESSURE OPERATIONS
High-pressure operations are a part of hydrometallurgical practices in
some cases and involve high-temperature and high-pressure aqueous
solutions. Thus, many of the electrochemical aspects, such as corrosion
coupling and galvanic coupling, are also involved in these operations.
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Though the same principles are extended to understand the phenomena,
with the advent of facilities to monitor electrochemical parameters of
aqueous solutions under high temperature and pressure electrochemical
aspects are now being studied in detail for high-pressure systems. The
present study considers the following cases for discussion:
(i) Aqueous oxidation of sulphide minerals with oxygen pressure: (a)
Ammoniacal pressure oxidative leaching; (b) acid pressure oxidative
leaching.
(ii) Pressure leaching of reduced ilmenite.
(iii) Pressure reduction of aqueous metals by hydrogen.
Aqueous Oxidation of Sulphide Minerals with Oxygen
Under Pressure
Gaseous oxygen can also act as an oxidant to solubilize sulphide
minerals. Reaction (3) describes the cathodic half of the reaction in acidic
conditions, and the following equation holds in alkaline medium:
O
2
÷ 2H
2
O ÷ 4e
÷
= 4OH
÷
: (27)
Unfortunately, the oxidation reaction of sulphide minerals with
oxygen or air proceeds too slowly to be of commercial significance;
however, with the advent of pressure technology, the aqueous oxidation
of sulphide minerals could be affected at a rate suitable for commercial
application. Pressure operation improves the kinetics of aqueous reaction
dramatically by the following means:
(i) Raising the reaction temperature above the boiling point of the sol-
vent or leachant
(ii) Increasing the partial pressure of the gaseous oxidant
Thus, pressure leaching has already been commercially practiced for
treating sulphide minerals in ammoniacal (Rosenzweig 1969; Kerfoot
1989; Veltman and Weir 1981) as well as acidic medium (Parker and
Romanchuk 1979; Parker 1981). Recently, Deng (1995) has published an
excellent review describing the development and application of pressure
oxidation technology, including the chemistry involved. Some aspects of
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the process may now be discussed with emphasis on electrochemical
operations.
Ammoniacal Pressure Oxidative Leaching. Sherrit Gorden was the first
commercial operator to employ the ammoniacal pressure leaching proc-
ess for extracting nickel directly from sulphide ores (Deng 1995). The
large commercial scale operation at Fort Saskatchewan, Alberta, has
successfully treated nickel-copper-cobalt sulphide minerals. The chem-
istry of this process has been described by Forward and Mackiw (1955).
Anacondas’ Arbitor Process (Kuhn, Arbiter, and Kling 1974) avoided
high partial pressure of oxygen by intense mixing of the slurry. Recently,
the Regional Research Laboratory, Bhubaneswar, India, reported
another approach to treat complex copper-zinc-lead sulphide mineral in
ammoniacal medium under oxygen pressure (Rao et al. 1984). A number
of studies have also been made to understand the kinetics (Beckstead and
Miller 1977; Das, Anand, and Rao 1984; Warren and Wadsworth 1984;
Anand, Rao, and Das 1985a, 1985b; Rao et al. 1992). Interesting studies
conducted on chalcopyrite indicate that the dissolution process is iden-
tical to that of the corrosion of metals. Beckstead and Miller have shown
that the ammonia oxidation leaching of chalcopyrite is controlled by a
catalytic electrochemical surface reaction. The anodic and cathodic half-
cell reactions are as follows:
Anodic:
CuFeS
2
÷ 19OH
÷
= Cu

÷ 1=2 Fe
2
O
3
÷ 2SO
4

÷ 19=2 H
2
O ÷ 17e
÷
;
(28)
Cathodic:
O
2
÷ 2H
2
O ÷ Cu

÷ 4e
÷
= 4OH
÷
÷ Cu

: (29)
Equation (27) also runs along with equation (29) as the cathodic
reaction.
The authors have analyzed this system like a corrosion couple and
used the Butler-Volmer equation to derive the kinetic expression. Sub-
sequently, Warren and Wadsworth (1984) investigated the anodic oxi-
dation of CuFeS
2
in ammoniacal solutions using potentiodynamic
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polarization and constant potential techniques to give further support to
this theory. They observed the formation of a copper-deficient sulphide
layer during the initial dissolution at low overpotentials according to the
following reaction:
(1=x)CuFeS
2
÷ 4NH
3
= (1=x)Cu
1÷x
FeS
2
÷ Cu(NH
3
)
4

÷ 2e
÷
: (30)
The catalytic effect of copper ion is on the cathodic half reaction. The
reaction model proposed by them was typical of the corrosion of some
metals. This reaction is a charge transfer reaction of first order with
respect to the [OH
7
] and is in agreement with that proposed by Beckstead
and Miller (1977).
Acid Pressure Oxidative Leaching. Acid pressure oxidative leaching is
generally used more extensively in commercial operations of (i) extraction
of nickel, cobalt, and copper from matte or sulphide minerals; (ii) direct
leaching of zinc sulphides; and (iii) pretreatment of refractory gold ores.
For Ni
3
S
2
dissolution, the following reaction scheme has been reported
(Hofirek and Kerfoot 1992).
3Ni
3
S
2
÷ 4H
÷
÷ O
2
= Ni
7
S
6
÷ 2Ni

÷ 2H
2
O; (31)
Ni
7
S
6
÷ 2H
÷
÷ 0:5O
2
= 6NiS ÷ Ni

÷ H
2
O: (32)
During this process, a substantial quantity of ferrous iron is also
released into the solution. It is therefore assumed that the dissolved iron
acts as an electron carrier and enhances the leaching rate as per the
following equations:
Ni
3
S
2
÷ 2Fe

= 2Fe

÷ 2NiS ÷ Ni

; (33)
2Fe

÷ 2H
÷
÷ 0:5O
2
= H
2
O ÷ 2Fe

: (34)
Thus, in the corrosion coupling type of reactions (2) and (3), pressure
operation provides a higher partial pressure of oxygen, which enhances
not only the dissolution reactions (31) and (32), but also the Fe

to Fe

oxidation reaction (34). As a result, reaction (33) is also enhanced.
HYDROMETALLURGICAL PROCESSES 89
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Direct acid pressure leaching of ZnS is another recent development
(Deng 1995). At elevated temperature and oxygen pressure, sphalerite
dissolves according to the following reactions:
ZnS ÷ 2O
2
= ZnSO
4
; (35)
2ZnS ÷ O
2
÷ 2H
2
SO
4
= 2ZnSO
4
÷ 2S
0
÷ 2H
2
O: (36)
Both reactions proceed very slowly with chemically pure zinc sul-
phide (Bjorliy 1954), but the presence of dissolved iron can accelerate the
reaction significantly with the following leaching mechanism:
Fe
2
(SO
4
)
3
÷ ZnS = 2FeSO
4
÷ ZnSO
4
÷ S
0
; (37)
4FeSO
4
÷ O
2
÷ 2H
2
SO
4
= 2Fe
2
(SO
4
)
3
÷ 2H
2
O: (38)
This is similar to the nickel sulphide dissolution (33) and (34) by the
action of Fe

=Fe

couple. Further, hole conduction might play a
prominent role in this dissolution process. This will be discussed in the
next section.
The pre-treatment of refractory gold ores mostly aims at oxidation of
pyritic sulphur to sulphate or elemental sulphur and release of ferrous ion
which oxidizes to ferric for hydrolysis to take place. The gold part is left
in the residue for cyanidation. The pyrite dissolution mechanism is
identical to that of the other sulphides discussed above.
Pressure Leaching of Reduced Ilmenite
One of the processes to treat ilmenite is to reduce it in a rotary kiln to
produce reduced ilmenite followed by the removal of metallic iron by
leaching in aerated ammonium chloride solution (Behr, Canning,
Goodheart, and Uusna 1965). The second step in this process is essen-
tially a redox reaction represented by equation (3) as the cathodic and the
following reaction as the anodic half:
Fe = Fe

÷ 2e
÷
: (39)
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Ammonium chloride aids this corrosion process by preventing the
precipitation of Fe

as hydroxide within the pores of the rutile grain
through the following equilibrium:
NH
4
÷
÷ OH
÷
= NH
3
÷ H
2
O: (40)
Recent studies such as Jayasekera, Marinovich, Avraamides, and
Bailey (1995), have considered electrochemical measurements to gain
understanding of the process. Evans diagrams based on the individual
anodic (eqn 39) and cathodic (eqn 3) half processes were constructed for
0.2 M NH
4
Cl solution in (a) saturated air at 80
·
C and (b) with 300 kPa
p
o2
at 150
·
C. The intersection occurred in the limiting current region of
the cathodic curve, implying that the reaction rate is controlled by the
diffusion of O
2
to the iron surface. It was observed that the reaction
rate at 300 kPa p
o2
and 150
·
C was about 50 times faster than with air
under atmospheric pressure at 80
·
C. At a constant temperature, the
corrosion rate, i
corr
, increased with increasing oxygen partial pressure,
and at a constant oxygen partial pressure, it increased with increasing
temperature. Preliminary pressure leaching trials indicated that the rate
of reaction increased significantly at elevated temperature and pressure.
Pressure Reduction of Aqueous Metals by Hydrogen
Reduction of aqueous metal ions with hydrogen at elevated temperature
and pressure is described by the following reaction:
Me

÷ H
2
= Me ÷ 2H
÷
: (41)
This electrochemical reaction proceeds with the following half-cell reac-
tions:
Anodic: H
2
= 2H
÷
÷ 2e
÷
; (41a)
Cathodic: Me

÷ 2e
÷
= Me: (41c)
Recently, Nagai and Sato (1978) conducted electrochemical investi-
gations on nickel in sulphate-acetate aqueous solutions treated with
hydrogen under pressures ranging from 0.5 to 2.0 Mp
a
. Individual anodic
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polarization curves for Ni

reduction were plotted along with those for
anodic oxidation of hydrogen. The intersection point provided the
reduction rate (exchange current of reaction). Wajszezuk and Charewicz
(1994a) carried out similar studies for the reduction of aqueous cobalt
and observed that the kinetic dependencies on [Co

], p
H2
, and tem-
perature obtained from the polarization measurements were identical to
those found from kinetic measurements (Wajszezuk and Charewicz
1994b). They also observed that the exchange current (reduction rate)
increased with [Co

] at a constant p
H2
and temperature and increased
with temperature at a constant [Co

] and p
H2
.
MINERAL DISSOLUTIONINFLUENCEDBYHOLE TRANSFER
Hitherto, electrochemical aspects mostly based on electron transfer
principles have been covered; however, another important facet of
semiconductors is that they are characterized by a limited concentration
of charge carriers. Thus, there are interfacial reactions through hole
transfer. This aspect has been analyzed by Vaughan (1984); Crundwell
(1988); and (Osseo-Asare) 1992. Some salient features are briefly dis-
cussed here.
Semiconductors are marked by the presence of energy gaps between
the valence and conduction bands. When this gap is low, it is possible for
thermal agitation to promote an electron from the valence band to the
conduction band, thereby producing an electron hole in the valence band
(Osseo-Asare 1992). Such materials are known as intrinsic semi-
conductors. When a material acquires conduction band electrons and
valence band holes by receiving impurity atoms, it is called an extrinsic
semiconductor. It may be termed as n-type or p-type, depending on
whether the donor atom possesses extra or less electron in comparison to
those of the material. The importance of the semiconductor solid-state
properties in the electrochemistry of semiconductors is well known. In the
case of a metal, the application of the mixed potential theory to leaching
kinetics assumes that the potential across the solid side of the interface
(known as the space-charge region) remains constant so that the applied
potential difference appears across the Helmholtz layer. The dissolution
reaction is predicted to have a charge transfer coefficient of 0.5 and a
Tafel slope of 0.118 V=log(mA) for an ideal single-electron reaction;
however, in the case of a semiconductor-solution interface charge con-
centrations can be found in the space-charge region, the Helmholtz plane,
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and the Gouy layer. The net effect in the case of an ideal semiconductor is
that the current-voltage curve for a single-electron reaction results in a
charge-transfer coefficient of 1 and a Tafel slope of 0.059 V=log(mA).
Crundwell (1988) observed that sulphide electrodes do not display
classical semiconductor-solution behavior, owing to the formation of
surface states that aid the transfer of charge. The presence of surface
states, especially those due to zero valent sulphur, may give rise to beha-
vior which is intermediate between that of a metal and a semiconductor.
The bonding structure, nonstoichiometry present in the sulphides also
affect the dissolution process. These aspects are discussed below.
Holes and Sulphide Dissolution
In general, the position of the Fermi level with respect to the band
structure of semiconductor in the solid side and the energy level of the
redox couple in the solution side determine whether electron or hole
transfer would result. It has also been observed that, for a given polar-
ization, the higher the energy gap, the higher is the hole pathway relative
to the electron pathway. In semiconductors with a band gap greater than
1 eV, anodic dissolution occurs almost entirely as a result of hole injection
into the valence band (Gerischer and Mindt 1968). The oxidative
decomposition of a sulphide semiconductor can occur in the following
steps (Crundwell 1988).
(MeS)s ÷ X = (MeX)
÷
÷ vSs ÷ e
÷
; (42a)
(MeS)s ÷ X ÷ h
÷
= (MeX)
÷
÷ vSs; (42b)
vSs ÷ Y = (SY)
÷
÷ e
÷
; (42c)
vSs ÷ Y ÷ h
÷
= (SY)
÷
; (42d)
vSs ÷ vSs = (S-S)s; (42e)
S
n
÷ vSs = S
n÷1
: (42f)
Here, X, Y represents ionic species in the solution.
Dissolution of ZnS in ferric ion-containing solution and in acid
under pressure have been discussed in previous sections. In the case of the
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former, a half-order dependence of the rate on the concentration of
[Fe

] has been explained in terms of electron transfer as happens in
metal-like conduction. In the case of the latter, it has been indicated that
presence of lattice Fe in ZnS structure enhances dissolution. Crundwell
(1988) has explained these facts in terms of hole transfer process. Zinc
sulphide is a semiconductor, with a band gap of 3.6 eV and a high
resistivity; however, presence of 12.4 atomic % Fe showed a band gap of
only 0.49 eV with little change in the resistivity, as the substitution of iron
in sphalerite provides d-band energy levels within the band gap. Another
consequence of the iron impurity is that the Fermi level is pinned at the
energy level of the d-orbital. Hence, all the applied potential appears
across the Helmhoz layer. From fundamental principles based on hole
transfer, Crundwell derived an equation which indicated a first-order
dependence of rate on the occupied states in the d-orbital band (i.e., the
concentration of Fe impurity in the [Zn, Fe] S), and half order in the
concentration of oxidant. A stronger oxidant and ultraviolet irradiation
should enhance the dissolution rate. The latter has been proved by Exner,
Gerlach, and Pawlek (1969).
The dissolution of ZnS in the presence of Fe

ion has been
explained in terms of surface states created by the Fe

ion. It has been
proposed that, simultaneous with the Fe

reaction, a nonoxidative
reaction occurs, causing partial disruption of surface chemical bonds at
the ZnS surface, resulting in surface states with energy levels in the for-
bidden gap. These surface states are believed to be -SH
d-
groups formed
by the protonation of the ZnS surface (Tributsch and Bennett 1981;
Osseo-Asare 1992).
The nonstoichiometry of galena influences the semiconduction type.
Galena is a good conductor displaying n- and p-type semiconduction,
depending on whether sulphur is deficient or in excess. The band gap is
about 0.37 eV. A Tafel slope consistent with the semiconductor model is
observed, though this is influenced by the equilibrium with lead ions in
solution, and the applied potential is distributed across both the space-
charge layer and the Helmholtz layer (Crundwell 1988); however, when
the electrode potential is more in the anodic direction, the potential
difference appears across the Helmholtz layer and metal-like Tafel
behavior occurs (Richardson and O’Dell 1984).
The kinetics of chalcopyrite dissolution is complicated by the for-
mation of a surface film. The influence of redox couples is in accordance
with the semiconductor model, and a dissolution mechanism involving
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both electrons and holes is proposed (Crundwell 1988). In the case of
pyrite and molybdenite, however, the valence band is narrow and of
nonbonding character because of crystal-field splitting. Therefore, elec-
tron transfer with this band (hole injection) has no effect on the bonding
of the solid. Thus, these two minerals do not get oxidized easily.
Holes and Oxide Dissolution
Dissolution of oxides may be oxidative and reductive, as well as non-
oxidative. Irrespective of the type of reaction path, reaction rates are
influenced due to stoichiometry and thermal history of the solid, storage
environment, and nature and concentration of solid-state impurities
(Osseo-Asare 1992). Oxide dissolution may be best illustrated through an
example. Studies have been undertaken to understand the acidic dis-
solution of NiO (Nii 1970; Jones, Segall, Smarth, and Turner 1977, 1978;
Lussiez, Osseo-Asare, and Simkovich 1981; Furrer and Stumm 1986;
Stumm, Suzberger, and Sinniger 1990), which expectedly follows the
following nonoxidative reaction:
NiO ÷ 2H
÷
= Ni

÷ H
2
O: (43)
It has been observed that this reaction is affected by oxygen pressure
(Nii 1970), dopant type (Lussiez et al. 1981), annealing temperature
(Jones et al. 1977), and Co

(Jones et al. 1978). The first three factors,
in some way, influence the concentration of the holes. Nickel oxide is a
p-type semiconductor, where the defects are holes and cation vacancies.
The nonstoichiometry is a function of oxygen pressure; the higher the
oxygen pressure, the higher the amount of oxygen in the crystal lattice,
and therefore the higher the concentration of holes and cation vacancies
(Nii). Doping with lower valence cation, Li
÷
, increases the concentra-
tion of holes, whereas the higher valence cation, Cr

, has the opposite
effect (Lussiez et al.). Heat treatment like annealing is known to affect
the hole concentration (Jones et al. 1977). Stumm et al. (1986, 1990)
analyzed the adsorption phenomena in this dissolution process and
proposed the ligand-promoted dissolution mechanism. In light of this
mechanism, the effect of Co

on NiO can be explained in terms of hole
injection (Osseo-Asare 1992; Jones et al. 1978; Furrer and Stumm 1986;
Stumm et al. 1990).
HYDROMETALLURGICAL PROCESSES 95
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t

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2
:
1
8

0
4

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e
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e
m
b
e
r

2
0
1
2

Thus it can be said that hole transfer plays an important role in
semiconducting mineral dissolution, which is gaining importance.
CONCLUSION
Many hydrometallurgical processes are electrochemical in nature. There
is an increasing recognition of application of electrochemical approaches
to study and understand them. As of today, the interfacial electro-
chemistry of mineral dissolution is treated in terms of electron transfer.
The hole transfer phenomenon, which is an inherent part of semi-
conductor mineral leaching, is now gaining its deserving importance.
More understanding of these aspects may pave the way for further
improvements in hydrometallurgical operations.
LIST OF SYMBOLSUSED
e
7
: The electron
h : The electron hole
i : The current
i
g
: The galvanic current
i
m
: The mixed current
n : No. of oxygen atoms
E : Electrode potential
E
a
: Rest potential of the anode
E
c
: Rest potential of the cathode
E
a
o
: Standard equilibrium potential of the anodic reaction
E
c
o
: Standard equilibrium potential of the cathodic reaction
E
g
: Galvanic potential
E
m
: The mixed potential
E
MnO
2
: The rest potential of MnO
2
electrode
E
PbS
: The rest potential of PbS electrode
F : Faraday’s number
L : The complexing agent
Me : The metal
R : Universal gas constant
T : Absolute temperature
X,Y : The ionic species
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