Iron Precipitation During Leaching of Copper and Cobalt Ores - Geochemical Modelling

INDEPENDENT METALLURGIST
Iron precipitation
during leaching of
Copper and Cobalt ores
Geochemical modelling
Kafumbila Kasonta Joseph
2020
Joseph Kafumbila Page 0

Iron precipitation during leaching of copper and cobalt ores: Geochemical modelling
© Joseph Kafumbila
jokafumbila@hotmail.com
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https://www.researchgate.net/publication/338337129_Iron_precipitation_during_leaching_o
f_Copper_and_Cobalt_ores_Geochemical_modelling

Content
1. Introduction ....................................................................................................................................... 5
2. Pilot plant results ............................................................................................................................. 6
2.1. Pilot plant description.................................................................................................................... 6
2.2. Pilot plant results ............................................................................................................................. 8
3. Thermodynamic system .............................................................................................................. 13
3.1. Thermodynamic system ......................................................................................................... 13
3.2. Gibbs free energy ....................................................................................................................... 13
3.2.1. Definition .............................................................................................................................. 13
3.2.2. Equilibrium of a closed system .................................................................................... 13
3.2.3. Chemical potential energy ............................................................................................. 14
3.2.4. Electrochemical potential energy ............................................................................... 14
3.3. General equilibrium condition ............................................................................................. 15
3.4. Standard equilibrium constant ............................................................................................ 16
3.5. Activity of substances .............................................................................................................. 17
3.5.1. Activity of soluble substances ...................................................................................... 17
3.5.2. Activity of solid substances ........................................................................................... 18
3.6. Overall equilibrium diagram ................................................................................................. 21
3.6.1. Definition .............................................................................................................................. 21
3.6.2. Thermodynamic conditions .......................................................................................... 22
3.6.3. Construction step of E-pH diagram ............................................................................ 22
3.6.4. Boundary of two solid compounds............................................................................. 23
3.6.5. Concentrations of other soluble compounds.......................................................... 24
3.6.6. Boundary of aqueous solution and solid compounds ......................................... 24
4. Kinetic of chemical reactions .................................................................................................... 25
4.1. Definition ...................................................................................................................................... 25
4.2. Rate of chemical reaction ....................................................................................................... 25
4.3. Kinetic factors ............................................................................................................................. 26
4.3.1. Reactant concentrations ................................................................................................. 26
4.3.2. Temperature ....................................................................................................................... 26
4.4. Reaction mechanisms .............................................................................................................. 26
4.4.1. Definition .............................................................................................................................. 26
4.4.2. Kinetically determining step ......................................................................................... 26
4.4.3. Types of complex reactions ........................................................................................... 27

4.5. Solid-liquid surface reaction ................................................................................................. 27
4.6. Electrochemical reaction ........................................................................................................ 28
4.6.1. Electrochemical reaction ................................................................................................ 28
4.6.2. Electrochemical system .................................................................................................. 28
4.6.3. Kinetic .................................................................................................................................... 29
4.7. Metal electrochemical corrosion ......................................................................................... 30
5. Conversion of concentration unit of soluble compounds .............................................. 33
5.1. Specific gravity of a solution ................................................................................................. 33
5.2. Concentration of elements (mol/kg water) .................................................................... 34
6. Sulfate-Phosphate-Silicate-Sulfite-Ca-Mg-Al-Zn-Mn-Cu-Co-Fe-Water system ...... 36
6.1. Ionic strength of system.......................................................................................................... 36
6.2. Water .............................................................................................................................................. 36
6.3. Free sulfate................................................................................................................................... 37
6.4. Free phosphate ........................................................................................................................... 39
6.5. Silicate ............................................................................................................................................ 41
6.6. Sulfite - Ca ..................................................................................................................................... 42
6.7. Magnesium ................................................................................................................................... 46
6.8. Aluminum ..................................................................................................................................... 48
6.9. Zinc .................................................................................................................................................. 50
6.10. Manganese ............................................................................................................................... 52
6.11. Copper ....................................................................................................................................... 54
6.12. Cobalt ......................................................................................................................................... 57
6.13. Iron ............................................................................................................................................. 60
6.14. Summary................................................................................................................................... 64
7. Iron concentration in the copper circuit ............................................................................... 75
7.1. Goethite dissolution mechanism ......................................................................................... 75
7.2. Iron loss in the water balance bleed of copper circuit ................................................ 79
7.3. Iron saturation concentration in secondary leach solution ...................................... 79
7.3.1. Data ......................................................................................................................................... 79
7.3.2. Pure phases.......................................................................................................................... 82
7.3.3. Mixed phases ....................................................................................................................... 87
7.3.4. Observations ....................................................................................................................... 93
8. Loss of copper and cobalt in iron precipitates during leaching ................................... 94
9. Dissolution of cobalt (III)............................................................................................................ 96
9.1. Dissolution of cobalt (III) with SO2 .................................................................................... 96
9.2. Dissolution of cobalt (III) with ferrous ............................................................................. 96
9.3. Dissolution of cobalt (III) with ferrous and SO2 ........................................................... 96
9.3.1. Materials and experimental methods........................................................................ 96
9.3.2. Results and discussion .................................................................................................... 97
9.4. Mechanisms of cobalt (III) dissolution ............................................................................. 98
10. References ..................................................................................................................................... 103

1. Introduction
The main source of cobalt produced in the Democratic Republic of Congo is Copper-
Cobalt oxide ores having average grades of 2.5% for Copper and 0.7% for Cobalt. The main
minerals of Copper-Cobalt oxide ores are Malachite (CuCO3 . 2Cu2 (OH)2), Kolwezi
((Cu, Co)2 CO3 (OH)2 ) and Heterogenite (CoOOH) and the minor minerals are Pseudo-
Malachite, Chrysocolla, Cuprite and Chalcocite (S. Stuurman et al, 2014).
Direct whole ore leach technology has been adopted to increase the recoveries of both
Copper and Cobalt (K.G. Fisher, 2011) by removing the flotation step between mines and
hydrometallurgical plants. Cobalt (III) is about 50 to 80% of the total Cobalt in the oxide ores
(G. Miller, 2009). The dissolution of Cobalt (III) needs a reducing reagent to be leached. In
Direct whole ore leach technology used in Democratic Republic of Congo, the reducing
reagents are meta-bisulfite or SO2 gas. SO2 gas is injected in the leach trains in form of
liquefied SO2.
The disadvantage of using direct whole ore leach technology is gangue acid
consumption is high. There are two ways to reduce gangue acid consumption: the range of pH
during leaching must be between 1.5 and 2 and the size distribution of the feed of the leach
plant must have a d80 around 150 µm. In consequence the impeller of leach tank is designed
to have high pumping power. High pumping power of impeller compromises the dispersion of
SO2 gas in the open leach tanks. At redox potential of 350 mV (Ag/AgCl) the loss of SO2 gas in
leach tanks gas is low. In these conditions the leach residence time is around 8 hours to reach
0.1% of cobalt grade in the leach residue.
It has been observed that the maximum value of iron concentration in the leach
solution is between 1 - 2g/L in these conditions of leaching. At a certain value of Iron
concentration and pH below 1, S. Stuurman et al stated the possibility of precipitation of
CuFeO2 and CoFe2 O4 compounds. Therefore the goal of this publication is to study iron
precipitation during leaching of copper and cobalt oxide ores in open leach tanks. A
geochemical modelling is developed and applied to the results of the pilot plant carried out as
part of the design of Kingamiambo Musonoi Tailings plant (KMT) to obtain iron saturation
concentration in the leach circuit and types of iron precipitates.

2. Pilot plant results
2.1. Pilot plant description

As part of feasibility study, pilot plant has been operated during 2 months with
homogenous feed to recover Copper as full plate cathode from Copper-Cobalt ore. The flow
diagram of pilot plant is shown on Figure (2.1). Copper and Cobalt grades in the feed are
respectively 1.478 and 0.325%. Table (2.1) gives the mineralogical composition of pilot plant
feed.
The feed is leached in sulfuric acid and barren solution in the primary leach tanks.
Leaching dissolves the metals from the solids at pH 2 during 2 hours. SO2 gas is injected in the
primary leach tanks to reduce the redox potential at 350 mV (Ag/AgCl). The reduction of
redox potential prevents the iron precipitation. The purpose of the primary leach is to
produce a copper rich solution having a low concentration of free acid. The leach efficiencies
of copper and cobalt are respectively 75 and 70%. Slurry discharged from the primary leach is
thickened. Overflow solution is called the pregnant leach solution (PLS) and is fed to the
copper solvent extraction circuit. Underflow from the primary leach thickener proceeds to
the secondary leach.
Figure 2.1: Flow diagram of copper plant of pilot plant

Table 2.1: Mineralogical composition of pilot plant feed
Minerals Grade
%
Cu2(OH)2(CO3) 1.584
Cu3(PO4)2.Cu2(OH)4 0.146
2CuO.2SiO2.3H2O 0.199
CuO 0.503
CuS 0.005
Cu2S 0.005
CuFeS2 0.005
CoOOH 0.507
FeO(OH) 1.954
Ni(OH)2 0.001
CaCO3.MgCO3 0.900
MnO2 0.127
ZnS 0.007
SiO2 77.139
UO3 0.004
Mg2SiO4 5.381
Ca2SiO4 0.011
CaCl2 0.025
Al2SiO5 11.471
Cr2O3 0.026
CdO 0.001
The underflow from the primary leach thickener is leached in sulfuric acid and barren
solution in the secondary leach tanks at pH 1.5 during 6 hours. SO2 gas is injected in the
secondary leach tank to reduce the redox potential at 350 mV (Ag/AgCl ). The purposes of the
redox potential reduction and the increase of free acid concentration are to leach the
remaining cobalt. The leach efficiencies of copper and cobalt are respectively 20 and 18%.
Slurry discharged from the secondary leach is thickened. Overflow solution from this
thickener reports to the storage solution tank. Underflow from the thickener reports to the
filtration circuit.
The underflow from secondary leach thickener is pumped to the vacuum belt filter.
Vacuum is applied to the belt across two zones: The first zone, called the form zone or
dewatering zone, forms the slurry into a cake on the belt and removes the entrained leach
solution. In the second zone, called the washing zone, the filter cake on the belt is washed
using a number of wash bars to remove the remaining entrained leach solution. The leach
solution is recovered from the form zone of the belt filters as filtrate. The filtrate is pumped
back to the storage tank. The filter cake moves on the filter belt from the form zone to the
wash zone and the cake is washed with water that has been acidified to pH 3. Wash solution is
pumped to the secondary copper solvent extraction.

In the primary copper solvent extraction; Copper is thus recovered from the PLS into
an organic liquor, which contains an extractant within a diluent. The PLS aqueous solution is
stripped of copper and is now referred to as the copper raffinate. The copper raffinate stream
is returned to storage tank. The loaded organic stream (LO) from the extraction circuit is
stripped with spent copper electrolyte (SE) from the copper electrowinning (EW) section.
Stripping produces the advance electrolyte and stripped organic, the latter being recycled to
Cu SX.
Secondary Cu SX consists only of an extraction stage, designed to strip any residual

copper from the solution before it proceeds to iron precipitation. From the stripped organic, a
portion of the stripped organic stream is returned to the secondary SX.
Copper metal is electro-deposited from the advance electrolyte onto stainless steel
blanks, known as cathodes, over a 6-day cycle. Spent copper electrolyte is returned to the
copper SX circuit.
2.2. Pilot plant results

Pilot plant results are focus on cobalt dissolution in the secondary leach tanks. Figure
(2.2) gives cobalt grade in the leach residue (%) in the secondary leach versus redox potential
(mV) (Ag/AgCl).
Figure 2.2: Cobalt grade in the leach residue (%) in the secondary leach versus redox
potential (mV) (Ag/AgCl)
The pilot plant results show that the cobalt grade in the leach residue increases with
increasing the redox potential. In the range of redox potential of 340 – 360 mV, the cobalt

grade in the residue varies from 0.02 to 0.17%. These results show that there is another
parameter that increases the cobalt (III) dissolution rate.
In the range of redox potential (340 – 360 mV) (Ag/AgCl), Figure (2.3) gives the cobalt
grade in the leach residue (%) versus pH, Figure (2.4) gives the cobalt grade in the leach
residue versus the iron concentration in the leach solution and figure (2.5) gives the iron
concentration in the leach solution versus pH.
Figure 2.3: Cobalt grade in the leach residue (%) in the secondary leach versus pH (340 – 360
mV) (Ag/AgCl)
Figure 2.4: Cobalt grade in the leach residue (%) in the secondary leach versus iron
concentration in the leach solution (g/L) (340 – 360 mV) (Ag/AgCl)

Figure 2.5: Iron concentration (g/L) in the secondary leach versus pH (340 – 360 mV)
(Ag/AgCl)
The results show that:
 The cobalt grade in the leach residue increases with increasing pH.
 The cobalt grade in the leach residue increases with decreasing the iron
concentration in the leach solution.
 Iron concentration in the leach solution increases with decreasing pH.
In the range of redox potential (340 – 360 mV) (Ag/AgCl) and in the range of pH (1.4 –
1.6), Figure (2.6) gives the cobalt grade in the leach residue (%) versus the iron concentration
in the leach solution (g/L). The results show that the cobalt grade in the leach residue
increases with decreasing the iron concentration in the leach solution.
Figure 2.6: Cobalt grade in the leach residue (%) in the secondary leach versus iron
concentration in the leach solution (g/L) (340 – 360 mV) (Ag/AgCl) (pH 1.4-1.6)

Figures (2.7) gives the cobalt and copper grades in the secondary residue, iron
concentration in the secondary leach solution for each day and Figure (2.8) gives redox
potential and pH for each data on commissioning period of pilot plant.
Figure 2.7: Iron concentration in the secondary leach solution (g/L) and cobalt and copper
grades in the leach residue (%) versus date
Figure 2.8: Redox potential (mV) (Ag/AgCl) and pH versus date

Figures (2.7) and (2.8) show the effects of iron concentration, redox potential and pH
on the cobalt and copper grades in the leach residue. Increasing redox potential has bad effect
on the cobalt and copper grades in the leach residue and iron concentration in the leach
solution. Increasing pH has bad effect on the cobalt and copper grades in the leach residue and
iron concentration in the leach solution.

3. Thermodynamic system
3.1. Thermodynamic system
A thermodynamic system is a constituent or, group of constituents, which is isolated

from its surroundings. It means that there is no interchange of mass between the constituent
and its surroundings. This thermodynamic system is called a closed system. A closed system
can interchange energy with its surroundings. The internal energy of a closed system is the
sum of kinetic energy and potential energy. The isolated system cannot interchange energy
with its surroundings.
3.2. Gibbs free energy
3.2.1. Definition
In the closed system having chemical constituents, for transformations that occur at
constant temperature and pressure, the relative stability of the system is determined by its
Gibbs free energy giving by Equation (3.1). “H” is the enthalpy, “T” is the absolute
temperature and “S” is the entropy. The enthalpy is a quantity of the heat content of the
system and is given by Equation (3.2). “E” is the internal energy, “P” is the pressure and “V” is
the volume.
G=H-T*S (3.1)
H=E+PV (3.2)
The internal energy is the sum of microscopic kinetic energy (the thermic agitation of
particles) and potential energy (the intramolecular and intermolecular interactions). The
internal energy is not measurable; only the variation of internal energy can be determined. By
definition the elements in their stable forms at the specified temperature have their Gibbs free
energies set equal to zero.
3.2.2. Equilibrium of a closed system
A closed system is considered to be in equilibrium when it is in its most stable state

and has no desire to change with time. At a constant temperature and pressure, a closed
system with a fixed mass and composition is in a state of stable equilibrium if it has the lowest
possible value of the Gibbs free energy given by Equation (3.3).
dG = 0 (3.3)

From initial condition, the product phases with the lowest Gibbs free energies are the
most stable and represent the equilibrium state if all reactions went to completion. However
there are frequently other possible products which are metastable with respect the stable
phases, meaning that they have a higher Gibbs free energy. It violates no thermodynamic
principles that metastable phases are frequently observed, particularly in reactions near earth
surface temperatures. The metastable phases are predicted to eventually decay to the stable
phases, but eventually can be a very long time.
In aqueous precipitation system, the free internal energy of the system varies due to
the variation of quantity of substance and quantity of electronic charge. The variations of the
free internal due to the mixing of substances and the contact of substances are negligible. In
aqueous precipitation system, the variation of free interne energy is due, generally, to the
existence of chemical reaction in the system.
3.2.3. Chemical potential energy
If a small molar quantity of substance “dn” is added in the closed system due to an
existence of a chemical reaction at constant temperature and pressure; the molar quantity of
substance in the system increases by “dn” and the total free energy of the system increases
also by a small amount “dG”. “dG” is proportional to the molar quantity “dn” added. This
relation is given by Equation (3.4).
dG=μ*dn (3.4)
The proportionality constant (μ) is called the chemical potential. The chemical
potential depends on the temperature, pressure and the composition of the phase. Equation
(3.5) gives the relationship between chemical potential and composition.
μ=μ° + R*T*2.303*log(a) (3.5)
“μ° ” is standard chemical potential of a substance at constant temperature and

pressure for a pure substance, “R” is the gas constant (8.3143 J/mol*K), “T” is absolute
temperature and “a” is the activity.
The variation of free internal energy (dG) due to the variation of the molar quantity of
substance is called the chemical potential energy.
3.2.4. Electrochemical potential energy
If a small molar quantity of charge “dn” is added in the closed system at constant
temperature, pressure and electrochemical potential (E), the molar quantity of charge in the

system increases by “dn” and the total free energy of the system increases by a small quantity
“dG”. “dG” is proportional to the molar quantity of charge “dn” added. This relation is given by
Equation (3.6). “z” is the charge, “F” is faraday constant (96485 C/mol) and “E” is
electrochemical potential (V).
dG=Z*F*E*dn (3.6)
The charge of electron is “-e”. “e” is the elementary charge. The variation of free energy
due to the variation of electronic charge is given by equation (3.7).
dG=-F*E*dn (3.7)
The variation in internal energy (dG) due to the variation of the molar quantity of
electronic charge is called the electrochemical potential energy.
3.3. General equilibrium condition
In aqueous precipitation system, there is reversible chemical reaction given by the

chemical reaction (3.a). “υi ” is the stoichiometry coefficient of the substance “i” and “A”, “B”,
“C” and “D” are the chemical substances.
υa A + υb B + υe e− = υc C + υd D (3.a)
At constant temperature and pressure, the chemical potential energy is the sum of the
chemical potential energy of products minus the sum of the chemical potential energy of
reactants. Equation (3.8) gives the chemical potential energy of chemical reaction (a.1).
“dGcp ” is the chemical potential energy of the chemical reaction (a.1) and “μi ” is the chemical
potential of the substance “i”. At constant temperature and pressure, the electrochemical
potential energy is given by Equation (3.9). Where “dGep ” is the electrochemical potential
energy, “F” is faraday constant and “E” is the redox potential.
dGcp = υc *μC + υd *μD - υa *μA - υb *μB (3.8)
dGep = υe *F*E (3.9)
The equilibrium condition of the chemical reaction (3.a) is given by Equation (3.10).
dGcp + dGep = 0 (3.10)

3.4. Standard equilibrium constant
In aqueous solution, there is reversible chemical reaction between soluble compounds

given by the chemical reaction (3.b). “υi ” is the stoichiometry coefficient of the substance “i”
and “A”, “B”, “C” and “D” are the chemical substances. The equilibrium condition of the
chemical reaction (3.b) is given by Equation (3.11).
υa A + υb B +υe e− = υc C + υd D (3.b)
dGcp +dGep = υc *μC + υd *μD - υa *μA - υb *μB +υe *F*E =0 (3.11)
Combination of Equations (3.5) and (3.11) gives Equation (3.12).
υ υ
ac c x aDD
R*T*ln( υ υ ) = -(υC μ°C +υD μ°D − υA μ°A − υB μ°B ) - υe *F*E (3.12)
aAA x aBB
The standard equilibrium constant is given by Equation (3.13) at a given temperature

°
(T ).
υ υ
a cx a D
K °(T° ) = υcA DυB (3.13)
aA x aB
If υe is equal to zero, Equation (3.14) gives the value of the logarithm of the standard
equilibrium constant. ΔG° is given by Equation (3.15).
ΔG°
log(K °(T° ) ) = - 2.303𝑅𝑇 (3.14)
ΔG° =υC μ°C +υD μ°D − υA μ°A − υB μ°B (3.15)
If υe is not equal to zero, Equation (3.16) gives the relationship between the logarithm
of standard equilibrium constant and the redox potential. E ° (Standard redox potential) is
given by Equation (3.17).
2.303RT
*log(K °(T° ) ) = E ° - E (3.16)
υe ∗F
ΔG°
E°= - υ (3.17)
e ∗F
° ° °
If T ° is 298.15 K, and ΔH(T° ) ; ΔS(T° ) ; and the temperature dependence of ΔCp of the
(T° )
reaction are known, Equation (3.18) gives the value of standard equilibrium constant at
temperature (T) (I. Puigdomenech et al, 1999).“R” is the gas constant (8.3143 J/mol*K).

ΔH° ° 1 1 1 T 1 T ΔC°p
Log(K °(T) ) log(K °(T° ) )
(T )
= - 2.303R (T - T° ) - 2.303RT ∫T° ΔCp° dT + 2.303R ∫T° dT (3.18)
T
3.5. Activity of substances
3.5.1. Activity of soluble substances
Ions in solution interact with each other as well as with water molecules. At low
concentrations and low background salt concentrations these interactions can possibly be
ignored, but at higher concentrations ions behave chemically like they are less concentrated
than they really are. Standard equilibrium constants calculated from the standard free energy
of reaction are expressed in terms of this effective concentration which is formally called the
activity.
Activity of soluble compound “A” in water is given by Equation (3.19). “γA ” is activity
coefficient and 𝑚𝐴 is the concentration (mol/kg water) of soluble compound.
aA = γA * mA (3.19)
The calculations of individual ion activity coefficient have been approximated by

Equation (3.20) in concentrated as well as dilute electrolyte solutions involved in geochemical
processes at high temperatures and pressures (H.C. Helgeson et al, 1981) and suitable for
overall equilibrium diagram calculations. “γi ” is the activity coefficient of soluble compound
“i”, “Zi ” is the electrical charge of compound “i” and “I” is the ionic strength (mol/kg of water).
Equation (3.21) gives value of ionic strength. “mi ” is the concentration of soluble compound
(mol/kg of water). “A”, “B” and “b” are temperature-dependent parameters. Table (2) gives
values of parameters “A”, “B” and “b” at 298.15 K (B. Beverskog et al, 1998 and I.
Piugdomenech et al, 2000). “ä” is a distance of closest approach, which may be taken to be
equal to that of NaCl (3.72 10−10m).
Z2 A√I
Log(γi )= - (1+Bä√I)
i
– log(1+0.018015*I)+b*I (3.20)
1
I=2 x ∑i Zi2 ∗ mi (3.21)
Table 2: values of A, B and b parameter at 298.15K
A B x 10−10 b
0.509 0.328 0.064
For neutral aqueous species it is usually approximated that the activity coefficients are
unity at all values of ionic strength and temperature. The approximate applicability is up to
value of ionic strength around 5 (mol/kg of water) (H.C. Helgeson et al, 1981).
If IZi I is absolute value of charge of soluble substance “i”, IZi I is called “t” (IZi I = t = 0,
1, 2, …). “γt ” is the activity coefficient of soluble substance having an absolute value of charge
“t”. The value of “γ0 ” is one. The value of “γt ” ( t= from 1, 2, 3, …) is given by Equation (3.22)
from Equation (3.20).
0.509∗t2 ∗√I
Log(γt )= - (1+1.22∗√I) – log(1+0.018015*I)+0.064*I (3.22)
The activity of water (solvent) (𝑎𝑤 ) is given by Equation (3.23). “ϕ” is the osmotic
coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑖 ” is the concentration
(mol/kg water) of soluble compounds (Charles E. Harvie et al, 1984)
W
ln (aw ) = - 1000 *ϕ *∑i mi (3.23)
The calculations of osmotic coefficient have been approximated by Equation (3.24)

(H.C. Helgeson, 1969). The value of “u” is given by Equation (3.25). Table (3) gives values of
parameters “a”, “b”, “c” and “d” at 298.15 K. “A” comes from Debrye-Huckel equation for
activity coefficient and is function of temperature. The value of “A” is 0.5092 at 298.15K. “I” is
the ionic strength (mol/kg of water).
2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) - u] + + + (3.24)
a3 ∗I 2 3 4
u=1+a*√I (3.25)
Table 4: values of a, b, c and d parameter at 298.15K
a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4
3.5.2. Activity of solid substances
3.5.2.1. Pure solid phase
When a solid phase contains a single substance (salt, sulfide or hydrate), the activity of
solid phase is unity. Equation (3.26) coming from Equation (3.5) gives the chemical potential
of the solid phase.
μS = μ°S (3.26)

When there is coexistence of at least two solid substances in equilibrium with the same
soluble compounds, there are two assumptions used for the calculation of Eh - pH diagram
(W.T. Thompson, 2000):
- When solid substances are precipitated, each solid substance is considered as

pure solid phase and the activity of this pure solid phase is unity and equilibrium
condition must be respected.
- When solid phase is alloy containing at least two elements, the activity of element
in the alloy is its molar fraction.
In the geochemical modelling, solid substances are considered as pure solid phase. The
equilibrium between aqueous phase and the solid substance (Aα Bβ . nH2 O) consisting of α
cations A, β anions B, and n water molecules is described by the chemical reaction (3.c).
Aα Bβ . nH2 O = αA + βB + nH2 O (3.c)
At equilibrium, the chemical potential of the solid substance is equal to the sum of the
chemical potentials of the solid substance’s constituent parts. The condition for equilibrium
therefore is given by Equation (3.27). The solubility product (K ps ) is given by Equation (3.28).
“𝑎𝑖 ” is the activity of ion “i”.
μ°𝑠 = αμA + βμB + nμw (3.27)
K ps = aA α xaB β xaw n (3.28)
The degree of saturation or the solubility index (SI) of a solid substance is defined as
the activity product of a solid substance divided by its solubility product (Equation 3.29). The
solubility index of a solid substance is unity at saturation. In a supersaturation solution it is
greater than one and in unsaturated solutions it is less than one (Vuyiswa Dube, 2015).
aA α xaB β xaw n
SI = (3.29)
Kps
3.5.2.2. Mixed solid phases
a. Substitution
Example: Radium sulfate and barium sulfate can precipitate together in aqueous
solution to form a solid-solution (Ra, Ba)SO4. The aqueous solubility product 𝐾𝑆 of Radium
sulfate for the reaction (3.d) is given by Equation (3.30) (V.L. Vinograd et al, 2018). a(Ra+2 ) is
activity of Ra+2 in aqueous solution, a(SO−2
4 )
is activity of SO−2
4 in aqueous solution and a (RaSO4 )
is activity of RaSO4 in the solid-solution,. “X” is the molar fraction of each solid in the mixture
and “γ” is the activity coefficient. For a constant value of a(SO−2
4 )
, the value of a(Ra+2 ) calculated
with Equation (3.30) is lower than the value calculated with Equation (3.28).
Ra+2 + SO−2
4 = RaSO4 (3.d)
a(Ra+2 ) ∗a(SO−2 ) a(Ra+2 ) ∗a(SO−2 )

Ks= 4
= 4
(3.30)
a(RaSO4 ) γ∗X
Sulfates formed by divalent cations have the simplified formula MSO4 . nH2 O, “M”
represents divalent Fe, Co, Ni, Mg, Cu or Zn and “n” ranges from 1 to 7 (Example: FeSO4 . 7H2 O,
CuSO4 . 5H2 O, etc). Sulfates formed by trivalent cations are characterized by the general
formula A2 (SO4 )3 . nH2 O, “A” represents Al or Fe and “n” ranges from 6 to 17 (Example:
Fe2 (SO4 )3 . 9H2 O, Al2 (SO4 )3 . 17H2 O, etc). There are also some sulfates with mixed divalent-
trivalent metal ions in their composition, the general formula is MA2 (SO4 )2 . nH2 O, “M”
represents divalent cation Mg, Fe, Mn, Co or Zn and “A” represents trivalent cation Al, Fe or Cr
(Example: halotrichite group). There is also a group of OH-bearing minerals known as the
copiapite group with the formula MA2 (SO4 )6 (OH)2 . 20H2 O. The less soluble sulfate minerals
are divided into two groups; the poorly crystalline oxy-hydroxysulfates of Fe and Al (Example:
schwertmannite, gibbsite, etc), and the well-crystalline minerals, represented by the alunite
super group, in which the jarosite sub-group is included. The jarosite general formula is
MFe3 (TO4 )2 (OH)6. “M”=Na, K, Ag, Ti, NH4 , H3 O and 1⁄2Pb and “TO4 ”= SO4 , PO4 and AsO4 (J.
Murray et al, 2014).
The substitution of the cations in the minerals changes the solubility of the mineral
(Example: Substitution of Fe by Al in Fe2 (SO4 )3 . 9H2 O (logk=26.2707) (S.W. Squyres et al,
2005) produces Fe1.47 Al0.53 (SO4 )3 . 9.65H2 O (logk=-7.28)(B.P.C. Grover et al, 2016.))
If A and B are two solids of the same group (Example: K-jarosite and Na-jarosite).
Solids A and B are precipitated in the same time from solution. Solids A and B form a solid-
solution (Example: (K,Na)-jarosite). The chemical potential of initial solid in the solid-solution
is given by Equation (3.31). “X” is the molar fraction of each solid in the mixture and “γ” is the
activity coefficient.
μ𝑠 =μ°𝑠 +2.303RTlog(γ*X) (3.31)
b. Transition zone
Each solid solution that precipitates from aqueous solution has a stability zone.
Between two stability zones, there is a transition zone where both solid precipitate. Example
of transition zone: Cobalt sulfide is one of more complicated metal sulfide systems, with a
number of phases and differing chemical compositions, including Co4 S3, Co9 S8 , CoS, Co1−x S,
Co3 S4 , Co2 S3 and CoS2 . The precipitation of cobalt sulfide at 25°C in thiourea gives mixed
phases of Co3 S4 , CoS1.097 and CoS2 with the dominance of Co3 S4 phase (O.O. Balayeva et al,
2016). This is a mixed precipitation in the transition zone.

If solid is considered as pure phase, the precipitation of each solid phase in the mixed
precipitation must respect the precipitation condition (Equation 3.29). The proportion of
phases in the mixed precipitate is known if the initial quantities of reactants are known (P.S.O.
Beltrao et al, 2010).
The stability zone of anilite (Cu1.75 S) is between the stability zones of covellite (CuS)
and chalcocite (Cu2 S). Anilite is in the transition zone of covellite and chalcocite. Anilite can be
considered as mixing of covellite and chalcocite and the chemical reaction (3.e) gives the
reaction of formation of anilite. Chemical potential of reactants before mixing is calculated
using Equation (3.32). The standard free Gibbs energies of covellite (CuS) and chalcocite
(Cu2 S) are respectively-48.65 and -84.11 kJ/mol (I. Piugdomenech et al, 2000). The standard
free Gibbs energy of reactants (μreactants ) calculated using Equation (3.32) is -75.245 kJ/mol.
0.25 CuS + 0.75Cu2 S = Cu1.75 S (3.e)
μ°reactants = 0.25*μ°CuS + 0.75*μ°Cu2 S (3.32)
The free Gibbs energy after mixing is calculated using Equation (3.33). In the case of
ideal mixing, the values of activity coefficients are equals to one. The free Gibbs energy of
anilite calculated considering that anilite is an ideal mixing of covelite and chalcocite is -
76.64KJ/mol. The standard free energy of formation of anilite is -76.4KJ/mol (I.
Piugdomenech et al, 2000). The two free Gibbs energies are close.
μmixing =μ°reactants +2.303*R*T*(0.25*log(0.25*γCuS )+0.75*log(0.75*γCu2 S ) (3.33)
The generalization of this assumption is that: in the transition zone of two solids, there
is a formation of solid-solution that is an ideal mixing of the two solids. The chemical potential
of initial solid in the solid-solution is given by Equation (3.34). “X” is the molar fraction of
each solid in the mixture.
μ𝑠 =μ°𝑠 +2.303RTlog(X) (3.34)
3.6. Overall equilibrium diagram
3.6.1. Definition
The overall equilibrium diagram of a chemical element is a 2D graph representing the

stability areas of the solid compounds as a function of redox potential (placed on the
ordinate) and pH (placed on the abscissa). In the overall equilibrium diagram, the solid, in its
stability area, is in equilibrium with all soluble compounds simultaneously. This overall

equilibrium diagram is used for the hydrometallurgy application especially when complex
ligand is used in the process (Rutio-Luo, 1978).
There are two kinds of 2D representation of the overall equilibrium diagram. The first
2D representation gives the boundary of the existence areas of aqueous solution and solid
compounds as a function of Eh and pH at a known value of total concentration of soluble
compounds. The second 2D representation gives the fraction of concentrations of soluble
compounds on total concentration as a function of pH at fixed value of Eh or as a function of Eh
at fixed value of pH.
3.6.2. Thermodynamic conditions
The thermodynamic conditions of an overall equilibrium diagram are the following:
 The solid compound is pure. The activity of solid is equal to 1. The chemical potential
of a solid compound is given by Equation (3.26).
 The concentration of soluble compounds is the saturation concentration coming from
the precipitation reaction.
 At each point on Eh -pH diagram, one solid compound is in equilibrium with all soluble
compounds.
 The soluble compounds are in equilibrium each other.
 The partial pressure of hydrogen and oxygen gases is equal to 1Bar. The partial
pressure of other gases must be known.
3.6.3. Construction step of E-pH diagram
The conventional procedure of the construction of an overall equilibrium Eh -pH

diagram is the following:
 To identify all chemical compounds (solid, soluble and gas), that this element can
form with water or another soluble compound.
 To choice one soluble compound as the reference.
 To establish the precipitation reactions between each solid compound with the
reference.
 To establish Equation giving the saturation concentration of the reference for each
solid compound.
 To establish the boundary of two solid compounds. At the boundary of two solid
compounds; the saturation concentrations of the reference of two solid compounds
are equal.
 To establish the chemical reactions between the reference with the other soluble
compounds.

 To establish Equations giving the concentration of other soluble compounds as
function of the concentration of the reference, Eh - and pH.
 To establish the Equation giving the sum of the concentrations of all soluble
compounds as a function of the concentration of the reference, Eh - and pH.
 For a known value of the sum of the concentration of all soluble compounds and the
value of the saturation concentration of the reference is known for each solid
compound, the resulting Equation is the boundary of the existence areas of aqueous
solution and the solid compound.
 At a giving value of the concentration of the reference and at known values of Eh - and
pH; the ratios of the concentrations of soluble compounds on the sum of the
concentrations of soluble compounds can be calculated.
3.6.4. Boundary of two solid compounds
The system contains two solid compounds “A” and “B”. The two solids are in
equilibrium with all the soluble compounds. “C” is a soluble compound that does not contain
the element whose Eh --pH diagram is established. Equation of the boundary of the two solids
“A” and “B” is obtained as follows:
 “D” is a soluble compound and it is the reference.

 To establish the precipitation reactions between the reference “D” and the two solid
compounds “A” and “B” (the chemical reactions (3.f) and (3.g) give the precipitation
reactions of the two solids “A” and “B”).
υ1D *D + υ1H+ *H + + υ1e *e− + υ1C *C= υ𝐴 *A (3.f)
υ2D *D + υ2H+ *H + + υ2e *e− + υ2C *C= υB *B (3.g)
 To establish Equations giving the saturation concentrations of the reference from the
equilibrium conditions of the precipitation reactions (3.f) and (3.g). Equations (3.35)
and (3.36) gives the concentrations of soluble compound “D” established from the
equilibrium conditions of the chemical reactions (3.f) and (3.g). “mD ” is concentration
(mol/kg water) of soluble compound D.
υ1e ∗F (υA ∗μ°A − υ1D ∗μ°D − υ1c ∗μC ) υ1H+ ∗

Log(mD *γ𝐷 )= υ *E + + *pH (3.35)
1D ∗R∗T∗2.303 h υ1D ∗R∗T∗2.303 υ1D
υ2e ∗F (υA ∗μ°A − υ2D ∗μ°D − υ2C ∗μC ) υ2H+ ∗

Log(mD *γD )= υ *E + + *pH (3.36)
2D ∗R∗T∗2.303 h υ2D ∗R∗T∗2.303 υ2D
 The boundary Equation of the two solids is obtained when the concentrations of
soluble compound “D” obtained from Equations (3.35) and (3.36) are equal.

3.6.5. Concentrations of other soluble compounds
The general equilibrium chemical reaction of a soluble compound with the reference is
given by the chemical reaction (3.h). “G” is the soluble compound and “D” is the reference. “C”
is a soluble compound that does not contain the element whose Eh -pH diagram is established.
υG *G + υH+ *H + + υe *e− + υC *C= υD *D (3.h)
Equation (3.37) gives the concentration of soluble compound “G” as a function of the
concentration of the reference, Eh and pH. The concentration of soluble compound “C” is
known.
υe ∗F υ1H+ ∗ υ ∗ (υD ∗μ°D − υG ∗μ°𝐺 − υc ∗μC )

Log(mG *γG )= υ *E + *pH+ υD *Log(mD *γD ) + (3.37)
𝐺 ∗R∗T∗2.303 h υ𝐺 𝐺 υG ∗R∗T∗2.303
3.6.6. Boundary of aqueous solution and solid compounds
The system contains soluble compounds “D”, “G” and “H” and solid compound “A”. The
soluble compound “D” is the reference. Equation (as Equation (3.35)) giving the saturation
concentration of soluble compound “D” is established. Equations (as Equation (3.37)) giving
the concentration of other soluble compounds as function of the concentration of the
reference, Eh and pH are established.
The total concentration of soluble compounds (“D”, “G” and “H”) is equal to “mtS ” that
is the known value. Equation (3.35) gives the total concentration of soluble compounds.
mD +mG +mH = mtS (3.38)
In the stability area of a giving solid compound; at known value of Eh or at known value
of pH, the value of pH or the value of Eh can be calculated.

4. Kinetic of chemical reactions
4.1. Definition
A chemical reaction is the modification of assembly of atoms constituting the molecules

of reactants to lead to new molecules, the products. The complete description of such a
transformation requires three components, two of which depend only on the initial and final
states (the quantitative aspect and thermodynamic aspect) while the third requires
knowledge of the reaction mechanism, this is dynamic aspect or kinetic.
Chemical Kinetic: study of reaction rates, factors influencing it, and the sequence of
molecular events, called the reaction mechanism, according to which reactions take
place.
4.2. Rate of chemical reaction
Chemical rate (R): variation of quantity per unit of time (Equation (4.1)). The rate of
chemical reaction is defined either relative to the disappearance of reagent, or relative
to the appearance of product. The reaction rate is always positive.
−[reactant] d[product]
R= = (4.1)
dt dt
Progress of the reaction (ξ): Equation (4.2) gives the progress of chemical reaction.
“ni (t)” is the quantity of species “i” at time (t), “ni (t = 0)” is the quantity of species “i”
at time (t=0) and “υi ” is stoichiometric value of species “i”.
ni (t)−ni (t=0)
ξ= (4.2)
υi
Volume rate: Equation (4.3) gives the volume rate of chemical reaction. “C” is the
concentration expressed mol/L and “υi ” is stoichiometric value of species “i”.
1 dC
R= * (4.3)
υi dt

4.3. Kinetic factors
4.3.1. Reactant concentrations
Equation (4.4) gives the volume rate of chemical reaction (4.a). “k” is rate constant of
chemical reaction, “α” and “β” are partial order of chemical reaction and the sum (α+ β) is the
global order of chemical reaction.
υA A+υB B = products (4.a)
β
R=k *CAα *CB (4.4)
4.3.2. Temperature
Arrhenius’ Law: rate constant is given by Equation (4.5). “A” is frequency factor, “R” is
perfect gas constant, “T” is temperature and “Ea ” is activation energy. The activation energy is
the energy barrier to be crossed for the chemical reaction to take place.
Ea
K=Ae−(RT) (4.5)
4.4. Reaction mechanisms
4.4.1. Definition
The mechanism of chemical reaction is the sequence of steps, at the molecular level,
leading from reactants to products. Some reactions only require a collision (elementary
reaction). Others require several and produce intermediates compounds formed during one
step and consumed in a subsequent step (complex reaction).
4.4.2. Kinetically determining step
The rate of formation of a species produced by a series of successive elementary

reactions is determined by the slowest step. This step, called kinetically determining step of
the global reaction, imposes its rate on the following steps.

4.4.3. Types of complex reactions
Parallel reaction: two reactions having the same reactants but forming different
products.
Reversible reaction: when in the same place and same time reactants give products and
products give reactants.
Successive reactions: when the products of the first reaction are reactants of second
reaction.
Chain reaction: chain reaction is a reaction in which a free species catalyze a series of
faster steps which perform the global reaction.
4.5. Solid-liquid surface reaction
Solid-liquid surface reaction is divided in three steps:
 First step - adsorption of reagent from liquid on the active surface.

 Second step - chemical reaction.
 Third step - desorption of chemical reaction products.
Adsorption is facilitated if the reagent can form a complex with free charge on the
active surface. Desorption is facilitated if the chemical reaction products can form a complex
with a substance in the solution (H. Grénman et al, 2011).
At the beginning, the studies done on leaching step consisted to vary a number of
parameters (leach residence time, temperature, size distribution, concentration of reagent
and power of agitation). The kinetic model has been introduced: first-for determination of the
rate controlling step that help to make a decision on the leach technology and second - for
prediction of recovery and reagent consumption using available mineralogical data.
The shrinking core models are the earliest models developed to describe leaching
process in the hydrometallurgy and are remained popular (Hlanhla. Othusitse et al, 2015).
Now there are twelve kinetic models that find application in the leaching process. The
mathematical models of these kinetics modes are given in Table (4.13) (H. Grénman et al,
2011).
If model No. 5 in Table (4.1) is assumed, (1-(1 − α)(1/⁄3) ) (“α” represents the
dissolved fraction of metal) is plotted as a function of time for the experimental data and if the
plot gives a linear correlation, the assumption is considered to be correct.

Table 4.1: Solid-liquid reaction kinetic models
N° γ Type of model
1 -ln(1-α) Frist – order kinetics
2 (1 − α)(−1⁄2) - 1 Three –halves-order kinetics
3 (1 − α)(−1) Second – order kinetics
One-half-order kinetics; two-dimensional advance of
4 1-(1 − α)(1⁄2)
the reaction interface
Two-thirds-order kinetics; three-dimensional advance
5 1-(1 − α)(1/3)
of the reaction interface
6 1-(1 − α)(2/3) One-third-order kinetics; film diffusion
7 [1 − (1 − α)(1⁄3) ](2) Jander; three dimensional
Crank-Ginstling-Brounshtein, mass transfer across a
8 1-(2⁄3)α-(1 − α)(2⁄3)
nonporous product layer
Zhuravlev – Lesoklin – Tempelman, diffusion,
9 [(1 − α)(−1⁄3) − 1](2)
concentration of penetration species varies with α
10 [1 − (1 − α)(1⁄2) ](2) Jander, cylindrical diffusion
11 (1 − α)(−1⁄3) - 1 Dickinson, Heal, transfer across the contacting area
Shrinking core, Product layer (different form of Crank-
12 1-3(1 − α)(2⁄3) + 2(1-α)
Ginstling-Brounshtein
4.6. Electrochemical reaction
4.6.1. Electrochemical reaction
An electrical conductor is a body within which charged particles are liable to move
under the effect of an electric field. The conductor is said to be electronic when the particles
are electrons and ionic when the particles are ions. Ions and electrons can sometimes move
simultaneously in the same conductor called mixed conductor.
An electrochemical reaction is a heterogeneous charge transfer reaction which takes

place on the contact surface of two conductors whose mode of conduction is identical or
different.
4.6.2. Electrochemical system
An electrochemical system is a physical system formed by the association of electronic

conductors and ionic or mixed conductors.

4.6.3. Kinetic
The chemical reaction of oxidation of ferric ion or the inverse reaction of oxidation of
ferrous ion is given by the chemical reaction (4.b) on the surface of an electrode immersed in
an aqueous solution. This chemical reaction is considered as simply redox reaction because
the reactional mechanism has one step of electronic transfer on the surface of electrode and
solution.
Fe+3 +e− =Fe+2 (4.b)
The chemical reaction (4.c) gives the general electrochemical reaction. “R” is a
reducing species, “O” is an oxidant species and “n” is number of electrons exchanged in the
reaction.
O+ne− =R (4.c)
The global rate “R g ” of electrochemical reaction is the difference between the rate of
reduction reaction “R r ” and oxidation reaction “R o ” (Equation (4.6)). The oxidation and
reduction reactions are the first order reaction. “k r ” and “k o ” are respectively rate constant of
reduction and oxidation reactions. “Cr ” and “Co ” are respectively the concentrations of
oxidizing and reducing species.
R g =R r - R o = k r *Cr - k o *Co (4.6)
The rate constants “k r ” and “k o ” are given by Equations (4.7) and (4.8). “Ar ” and “Ao ”
are respectively frequency factor of electronic transfer rate of reduction and oxidation
reactions, “αr ” and “αo ” are symmetric factors characterized by Equation (4.9), F is faraday
constant, R is perfect gas constant and T is temperature.
F∗E
k o =Ao *exp(αo *n*R∗T) (4.7)
F∗E
k r =Ar *exp(-αr *n*R∗T) (4.8)
αr + αo =1 (4.9)
The current density passing through the electrode is given by Equation (4.10) when
the electronic transfer step is kinetically determining step.
Ig =-n*F*R g =n*F*(k o *Co -k r *Cr ) (4.10)
At equilibrium, the value of global current density (Ig ) is equal to zero. This means that
the rates of oxidation and reduction reaction are equals. The rates of oxidation and reduction
reactions are proportional to the exchange current density (I0 ). The exchange current density
eq eq
is given by Equation (4.11). “Co ”, “Cr ”, and “Eeq ” are respectively concentrations of oxidant
and reducing species and electrode potential at equilibrium.
eq F∗Eeq eq F∗Eeq
I0 =n*F*Ao *Co * exp(αo *n* )= n*F*Ar *Cr * exp(-αr *n* ) (4.11)
R∗T R∗T
Equation (4.12) gives the global current density expressed as function of exchange
current density. “η” is the over-potential.
F∗η F∗η
Ig =I0 *(exp(αo *n*R∗T)- exp(-αr *n*R∗T)) (4.12)
At high value of over-potential (η>0), Equation (4.13) gives the value of the global
current density called anodic current density (Ia ).
F∗η
Ia =I0 *exp(αo *n* R∗Ta ) (4.13)
At low value of over-potential (η<0), Equation (4.14) gives the value of the global
current density called cathodic current density (Ic ).
F∗η
Ic =-I0 *exp(-αr *n* R∗Tc ) (4.14)
Equations (4.15) and (4.16) give the Tafel Equations for anodic and cathodic
electrodes. “a” and “b” are constants.
ηa =a+b*log(Ia ) (4.15)
ηc =a-b*log(Ic ) (4.16)
4.7. Metal electrochemical corrosion
Take for example, the case of an active divalent metal, M corroding in an acid
electrolyte. The chemical reactions (4.d) and (4.e) give respectively the anodic reaction and
the cathodic reaction.
M=M +2+2e− (4.d)
2H + +2e− =H2 (4.e)
The metal corrodes with the evolution of hydrogen. There are two half-reactions as
shown above and each half reaction has its own electrode potential and exchange current
density.

At time t=0 when metal is immersed into the solution, there is an adsorption of
hydrogen ion on the active surface of the metal. On the active surface of metal there is a place
where electron is in excess, hydrogen ions take these electrons and form hydrogen gas. At this
moment there is an electronic deficit in the metal structure. There is another place on the
active surface of the metal, the metal is oxidized in metal ion and releases electrons to fill the
electronic deficit in the metal structure. It appears an electronic movement in the metal from
the place where the metal is oxidized called anodic electrode to the place where hydrogen ion
is reduced called cathodic electrode. At this moment there is a polarization of the
electrochemical system.
The cathodic potential decreases from potential E(H+ −H2 ) when the global current is
corr
zero to the potential E(H + −H ) where the global current is corrosion current (Icorr ). Equation
2
(4.17) gives the value of E(H+−H2 ) . “a(H+) ” is the activity of hydrogen ion on contact surface and
corr
“P(H2 ) ” is the partial pressure of hydrogen gas. The difference between E(H + −H ) and E(H+ −H )
2 2
is called cathodic over-potential (𝜂𝑐 ). Equation (4.18) gives cathodic Tafel Equation.
2.303∗R∗T a +
°
E(H+ −H2 )=E(H + −H ) + *log(P(H ) ) (4.17)
2 F (H2 )
corr
ηc =E(H + −H ) -E(H+ −H ) = a c -bc *log(Icorr )
2 2
(4.18)
The anodic potential increases from potential E(M+2 −M) when the global current is zero
corr
to the potential E(M +2 −M) where the global current is corrosion current (Icorr ). Equation (4.19)
gives the value of E(M+2 −M) . “a(M+2 ) ” is the activity of metal ion on contact surface and “a(M) ” is
corr
the activity of metal M in the metal structure. The difference between E(M+2 −M) and E(M +2 −M)
is called anodic over-potential (𝜂𝑎 ). Equation (4.20) gives anodic Tafel Equation.
2.303∗R∗T a(M+2 )
°
E(M+2 −M) =E(M +2 −M) + *log( ) (4.19)
2∗F aM
corr
ηa =E(M +2 −M) -E(M+2 −M) =a a +ba *log(Icorr ) (4.20)
corr corr
The difference between E(H + −H ) and E(M+2 −M) is the over-potential due to the
2
electrical conductivity of the metal (Equation 4.21). “R” is the electrical resistance of the
metal. The difference between E(H+−H2 ) and E(M+2 −M) gives the global over-potential
(Equation 4.22). Figure (4.1) gives the polarization curves of the corrosion of metal in the
acid.
corr corr
E(H + −H ) -E(M+2 −M) =R*Icorr
2
(4.21)
E(H+ −H2 ) - E(M+2 −M) =ηa + R*Icorr - ηc (4.22)

Figure 4.1: Polarization of anodic and cathodic reactions to reach corrosion potential

5. Conversion of concentration unit of soluble compounds
Unit of concentration of elements in the solution of pilot plant is expressed in “g/L”.
This unit is converted to “mol/kg water” to facilitate the use of Equation (3.21). The
procedure of conversion is explained below.
5.1. Specific gravity of a solution

The solution is characterized by a mass (Ms ) expressed in (kg) and a volume (Vs )
expressed in (m3). The specific gravity (SGs ) expressed in (kg/m3) is the ratio of the mass
onto the volume of solution. Equation (5.1) links the mass, the volume and the specific gravity
of solution.
SGs =
Ms (
Vs (5.1)
A solution is homogeneous mixture of solvent and solutes. In this publication, the

solvent is water and solutes are the elements dissolved in water as sulphate. It assumes that
phosphorous is in solution as phosphoric acid. In the range of pH 1.2-2, the solubility of acid
mono-silicic is very low. For the acid silicic is removed from conversion procedure.
At this level, it is defined two other parameters; the mass of element of index “k” (Mk )
expressed in (kg) in the solution and the concentration of element of index “k” (Ck ) expressed
in (kg/m3) in the solution. Equation (5.2) links the mass of element of index “k”, the
concentration of element of index “k” and the volume of solution.
(
Mk = Vs x Ck
(5.2)
It has been observed for a liquid containing copper sulphate and sulphuric acid that
(H.D. Holler et al, 1913):
 The specific gravity of solution containing copper sulphate or sulphuric acid is

approximately a linear function of concentration expressed in (%).
 The specific gravity of solutions of equal concentration expressed in (%) of
copper sulphate and of sulphuric acid is nearly identical.
 The specific gravity of solution containing appreciable amounts of copper
sulphate and sulphuric acid is dependent principally upon the total
concentration (%) and is almost independent of their proportion.
These observations have been extended to the elements appearing in the Copper
metallurgy and the simplest method that allows having the approximated value of specific
gravity of solution from the chemical composition is given. The method consists of finding a

total concentration (Cts ) expressed in (kg/m3) of elements as salt in the solution. In this case,
the salt is in form of sulphate except the phosphoric acid. After, the total concentration must
be applied in the equation (5.3) which gives the relation between the solution specific gravity
and the total concentration of elements. The equation (5.3) comes from data which give the
specific gravity of solution as a function of concentration of element as salt in binary system
(David R. Lide, 2005).
SGs = -6.139 x 10−4 x [Cts ]2 + 0.9742 x Cts + 1000 (kg/m3) (5.3)
Therefore, it is defined a constant αk of element of index “k”. The constant αk is the

value to multiply to the concentration of element index “k” to have the concentration as
sulfate salt “Cks ”. The values of constant 𝛼𝑘 are given in Table (5.1). The value of concentration
“Cks ” of element of index “k” is given by Equation (5.4).
Table 5.1: Value of constant αk
Element Index (k) αk

H2SO4 1 1.000
Cu 2 2.511
Co 3 2.629
Fe 4 2.719
Zn 5 2.468
Mn 6 2.747
Mg 7 4.949
Al 8 6.337
Ca 9 3.395
H3PO4 10 1.000
Cks = αk x Ck (5.4)
Thus, the value of total concentration “Cts ” of elements in the solution is calculated
using Equation (4.5).
Cts = ∑k1 Cks = ∑k1 αk x Ck (5.5)
5.2. Concentration of elements (mol/kg water)

The specific gravity of solution is calculated by using Equation (5.3). The mass of water
(Mw ) is given by Equation (5.6) for one Liter (SGs (g/L) and Cts (g/L)).
(SGs − Cst )
Mw = (kg) (5.6)
1000

Equation (4.7) gives the concentration (mol/kg water) of elements. “𝑚𝑘 ” is
concentration (mol/kg water) of element “k” and “𝑀𝑘𝑚 ” molar mass of element “k”. Table (A)
in appendix gives concentration (mol/kg water) of element from pilot plant results.
Ck
mk =Mm xM (5.7)
k w
The concentration of sulfuric acid (g/L) is given by Equation (5.8).
CAc = 98x10−pH (5.8)

6. Sulfate-Phosphate-Silicate-Sulfite-Ca-Mg-Al-Zn-Mn-Cu-Co-
Fe-Water system
The secondary leach solution (Table A) contains sulfate anions coming from sulfuric
acid, phosphate anions coming from leaching of Pseudo-Malachite, silicate coming from
leaching of soluble silicate and carbonate coming from leaching of carbonates. In the range of
pH (1.2-2), the concentration of free carbonate anions is very low. The secondary leach
solution contains also sulfite anions coming from reducing reagent (SO2 ) and carbonate
anions coming from leaching of carbonate minerals. The purpose of the thermodynamic study
is to find the abundant iron compound in the secondary leach solution. For that Sulfate –
Phosphate – Silicate – Sulfite – Calcium – Magnesium – Aluminum – Zinc – Manganese –
Copper – Cobalt – Iron – Water system is established at 25°C.
6.1. Ionic strength of system
The ionic strength of the system is given by Equation (6.1). Ie is the contribution of
soluble compounds of elements in the value of ionic strength. The designation of contribution
of elements in the ionic strength Equation is the following: Iw for water, I𝑆𝑎 for free sulfate, Ip
for free phosphate, ISc for free silicate, ISi for free sulfite, ICa for calcium compounds, IMg for
magnesium compounds, IAl for aluminum compounds, IZn for zinc compounds, IMn for
manganese compounds, ICu for coper compounds, ICo for cobalt compounds, and IFe for iron
compounds.
1
I = 2x∑ Ie (6.1)
6.2. Water
The chemical reaction (6.a) gives the water ionization reaction. The reference soluble
substance of water species is “H + ”ion. Logarithm of the equilibrium constant of the chemical
reaction (6.a) is equal to -13.998 at 25°C (MINTEQA2-V.4, 1999). The designation of
concentration (mol/kg water) of water species is the following:
Concentration of H + is mH1 ,
Concentration of OH − is mH2 ,
H2 O = H + + OH − (6.a)
The concentration mH2 is calculated using Equation (6.1) coming from the mass action
of the chemical reaction (6.a).

aw
mH2 =10(−13.998) * m 2
(6.1)
H1 ∗(γ1 )
The concentration mH1 is given by Equation (6.2). The value of pH is a variable.
10−pH
mH1 = (6.2)
γ1
The activity “aw ” is calculated from Equations from (6.3) to (6.5). “I” is ionic strength
and the value of ionic strength is given by Equation (6.1).
ln (aw1 ) = - 1.802*10−2 *ϕ*N (6.3)
0.3815 1
ϕ=1- [u -2ln(u) - u] + 1.118*10−2*I+6.253*10−3*(I)2 -4.022*10−4*(I)3 (6.4)
I
u=1+1.454√I (6.5)
The value of “N” is given by Equation (6.6). “ Ne ” is the contribution of soluble

compounds of elements in the value of “N”. The designation of contribution of elements in the
“N” Equation is the following: Nw for water, N𝑆𝑎 for free sulfate, Np for free phosphate, NSc for
free silicate, NSi for free sulfite, NCa for calcium compounds, NMg for magnesium compounds,
NAl for aluminum compounds, NZn for zinc compounds, NMn for manganese compounds, NCu
for coper compounds, NCo for cobalt compounds, and NFe for iron compounds.
N=∑ Ne (6.6)
The values of IW and NW are given by Equations (6.7) and (6.8).
Iw =mH1 +mH2 (6.7)
Nw =mH1 +mH2 (6.8)
6.3. Free sulfate
The free soluble compounds are the following: H2 SO4 , HSO4 − and SO4 −2 . The sulfate
compounds are stable species that can be oxidized in persulfates only by electrolyze. It is not
unusual to find substantial concentrations of sulfate compounds in reducing environments
where sulfides should be the stable sulfur compounds (I. Piugdomenech et al, 2000).
The soluble compound SO4 −2 is taken as reference. The chemical reactions (6.b) and
(6.c) give the equilibrium reactions between reference and the other soluble compounds.
Table (6.1) gives the equilibrium constants of the chemical reactions (6.b) and (6.c).

SO−2 + −
4 + H =HSO4 (6.b)
SO−2 +
4 +2H =H2 SO4 (6.c)
Table 6.1: Log(K) of sulfate-water system at 25°C
Chemical reactions logK Reference

6.b 1.99 MINTEQA2-V.4, 1999
6.c 0.08 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble substances of sulfate is the

following:
Concentration of SO−2
4 is mSa1 ,
Concentration of HSO−4 is mSa2 ,
Concentration of H2 SO4 is mSa3 .
The concentrations of sulfate soluble substances are calculated as function of

concentration of reference soluble substance (H + and SO−2
4 ) using Equations (6.9) and (6.10)
coming from the mass actions of the chemical reactions from (6.b) to (6.c).
mSa2 =10(1.99) *mH1 *msa1 *γ2 (6.9)
mSa3 =10(0.08) *(mH1 )2*msa1 *γ2 *(γ1 )2 (6.10)
The concentration mS1 is fixed by a constraint on the neutrality of the solution

(Equation 6.11). “ChP” is the sum of all positive charge (Equation 6.12). “ChN” is the sum of all
negative charge (Equation 6.13). “ ChPe ” and “ ChNe ” is respectively the contribution of
soluble compounds of elements in the value of “ChP” and “ChN”.
ChP
=1 (6.11)
ChN
ChP=∑ ChPe (6.12)
ChN=∑ ChNe (6.13)
The values of ChPw and ChPSa are given by Equation (6.14) and (6.15). The values of
ChNw and ChNSa are given by Equation (6.16) and (6.17).
ChPw =mH1 (6.14)
ChPSa =0 (6.15)
ChNw =mH2 (6.16)

ChNSa =2*mSa1 + mSa1 (6.17)
The values of ISa and NSa are given by Equations (6.18) and (6.19).
ISa =4*mSa1 +mSa2 (6.18)
NSa =mSa1 +mSa2 +mSa3 (6.19)
6.4. Free phosphate
In the range of cobalt leach redox potential, phosphorous is in oxidation state +V that
is the stable state in nature (I. Piugdomenech et al, 2000). Free phosphate soluble compounds
−2 −3
are the following: H3 PO4 , H2 PO− − −2 −3
4 , HPO4 ; PO4 , H4 P2 O7 , H3 P2 O7 , H2 P2 O7 and HP2 O7 . The
soluble compound PO4 −3 is taken as reference. The chemical reactions from (6.d) to (6.j) give
the equilibrium reactions between reference and the other soluble compounds. Table (6.2)
gives the equilibrium constants of the chemical reactions from (6.d) to (6.j).
PO−3 + −2
4 + H =HPO4 (6.d)
PO−3 + −
4 +2H =H2 PO4 (6.e)
PO−3 +
4 +3H =H3 PO4 (6.f)
2PO−3 + −3
4 + 3H = HP2 O7 + H2 O (6.g)
2PO−3 + −2
4 + 4H =H2 P2 O7 + H2 O (6.h)
2PO−3 + −
4 + 5H = H3 P2 O7 + H2 O (6.i)
2PO−3 +
4 + 6H = H4 P2 O7 + H2 O (6.j)
Table 6.2: Log(K) of phosphate -water system at 25°C

6.d 12.375 MINTEQA2-V.4, 1999
6.e 19.573 MINTEQA2-V.4, 1999
6.f 21.721 MINTEQA2-V.4, 1999
6.g 30.714 Akira Kitamura; 2014
6.h 37.654 Akira Kitamura; 2014
6.i 39.614 Akira Kitamura; 2014
6.j 40.614 Akira Kitamura; 2014

The designation of concentration (mol/kg water) of free phosphate soluble substances
is the following:
Concentration of PO−3
4 is mp1 ,
Concentration of HPO4 −2 is mp2 ,

Concentration of H2 PO−
4 is mp3 ,
Concentration of H3 PO4 is mp4 ,
Concentration of HP2 O−3
7 is mp5 ,
Concentration of H2 P2 O−2
7 is mp6 ,
Concentration of H3 P2 O−
7 is mp7 ,
Concentration of H4 P2 O7 is mp8 .
The concentrations of free phosphate soluble substances are calculated as function of

concentration of reference soluble substance (H + and PO−3
4 ) using Equations from (6.20) to
(6.26) coming from the mass actions of the chemical reactions from (6.d) to (6.j).
γ1 ∗γ3
mp2 =10(12.375) *mH1 *mp1 * (6.20)
γ2
mp3 =10(19.573) *(mH1 )2*mp1 *γ1 * γ3 (6.21)
mp4 =10(21.721) *(mH1 )3*mp1 *(γ1 )3*γ3 (6.22)
γ3 ∗(γ1 )3
mp5 =10(30.714) *(mH1 )3*(mp1 )2 * (6.23)
aw
(γ3 )2 ∗(γ1 )4
mp6 =10(37.364) *(mH1 )4*(mp1 )2 * (6.24)
γ2 ∗aw
(γ3 )2 ∗(γ1 )4
mp7 =10(39.614) *(mH1 )5*(mp1 )2 * (6.25)
aw
(γ3 )2 ∗(γ1 )6
mp8 =10(40.614) *(mH1 )6*(mp1 )2 * (6.26)
aw
The values of ChPP and ChNp are given by Equation (6.27) and (6.28). The values
of Ip and Np are given by Equations (6.29) and (6.30).
ChPp =0 (6.27)
ChNp =3*mp1 +2*mp2 + mp3 +3*mp5 +2*mp6 + mp7 (6.28)
Ip =9*mp1 +4*mp2 +mp3 +9*mp5 +4*mp6 +mp7 (6.29)

Np =mp1 +mp2 +mp3 +mp4 +mp5 +mp6 +mp7 +mp8 (6.30)
The concentration mp1 is fixed by total concentration of phosphorous in solution that is

equal to phosphorous concentration PT from Table (A) (Equation 6.31). “ Pe ” is the
contribution of phosphate soluble compounds of elements in the value of “PT”. The
contribution of free phosphate (Pp ) is given by Equation (6.32)
PT=∑ Pe (6.31)
Pp =mp1 +mp2 +mp3 +mp4 +2*mp5 +2*mp6 +2*mp7 +2*mp8 (6.32)
6.5. Silicate
In the range of cobalt leach pH, soluble silicates react with water and give SiO2 -gel and
monomeric silica (H4 SiO4 ). Monomeric silica de-protonates twice in the range of pH 0-14 as
solution pH increases (Ehron D. Baca, 2017). The solubility of SiO2 -gel is low.
Silicate soluble compounds are the following: H4 SiO4 , H3 SiO− −2

4 and H2 SiO4 . The
soluble compound H4 SiO4 is taken as reference. The chemical reactions (6.k) and (6.l) give
the equilibrium reactions between reference and the other soluble compounds. Table (6.3)
gives the equilibrium constants of the chemical reactions (6.k) and (6.l).
H4 SiO4 =H3 SiO−

4 +H
+
(6.k)
H4 SiO4 = H2 SiO−2
4 + 2H
+
(6.l)
Table 6.3: Log(K) of silicate -water system at 25°C

6.k -9.84 MINTEQA2-V.4, 1999
6.l -23.04 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of silicate soluble substances is the

following:
Concentration of H4 SiO4 is mSc1 ,

Concentration of H3 SiO−
4 is mSc2 ,
Concentration of H2 SiO−2
4 is mSc3 ,
The concentrations of silicate soluble substances are calculated as function of

concentration of reference soluble substance (H + and H4 SiO4 ) using Equations (6.33) and
(6.34) coming from the mass actions of the chemical reactions from (6.k) to (6.l).

mSc1
mSc2 =10(−9.84) *m 2
(6.33)
H1 ∗(γ1 )
mSc1
mSc3 =10(−23.04) *(m 2 2
(6.34)
H1 ∗(γ1 ) ∗γ2
)
The concentration mSc1 is fixed by Equation (6.35) that is the mass action of the
chemical reaction (6.m). Logarithm of equilibrium constant of chemical reaction (6.m) is
equal to -2.71 at 25°C (Ehron D. Baca, 2017).
SiO2 +2H2 O =H4 SiO4 (6.m)
mSc1 =10−2.71*(aw )2 (6.35)
The values of ChPSc and ChNSc are given by Equation (6.36) and (6.37). The
values of ISc and NSc are given by Equations (6.38) and (6.39).
ChPSc =0 (6.36)
ChNSc = mSc2 +2*mSc3 (6.37)
ISc =mSc2 +4*mSc3 (6.38)
NSc =mSc1 +mSc2 +mSc3 (6.39)
6.6. Sulfite - Ca
The SO2 is a gas. The SO2 gas dissolves in water by following the Henry’ law (Equation
6.40). 𝑚SO2 is the concentration (mol/kg water) of soluble SO2 and PSO2 is the partial pressure
of SO2 gas (bars) (R.N. Goldberg et al, 1985). Soluble SO2 reacts with water and gives the
following soluble compounds: H2 SO3 , HSO3 − , SO3 −2 and S2 O5−2.
mSO2 = 1.23 * PSO2 (6.40)
In the sulfuric acid media, the redox conversions between the different sulfur species
are very slow, especially at low temperatures; therefore sulfite soluble compounds can exist
in the sulfate media with very small interaction with sulfate compounds (I. Piugdomenech et
al, 2000). Sulfite soluble compounds are oxidized in sulfate soluble compounds or S2 O−26 in
presence of oxidizing agents.
The soluble compound SO3 −2 is taken as reference. The chemical reactions from (6.n)
to (6.p) give the equilibrium reactions between reference and the other soluble compounds.
Table (6.4) gives the equilibrium constants of the chemical reactions from (6.n) to (6.p).

SO−2
3 + H + =HSO−
3 (6.n)
SO−2
3 + 2H + =H2 SO3 (6.o)
−2
2SO−2 +
3 + 2H =S2 O5 +H2 O (6.p)
Table 6.4: Log(K) of sulfite -water system at 25°C

6.n 6.34 Gabor Lente, 2001
6.o 8.1 Gabor Lente, 2001
6.p 11.185 R.N. Goldberg et al, 1985
The calcium soluble substances are the following: Ca+2 , Ca(OH)+ , CaSO4 , CaPO− 4,
+ −2 + +2
CaHPO4 , CaH2 PO4 , CaP2 O7 , CaH3 SiO4 , CaH2 SiO4 and CaSO3 . The soluble compound Ca is
taken as reference. The chemical reactions from (6.q) to (6.y) give the equilibrium reactions
between reference and the other soluble compounds. Table (6.5) gives the equilibrium
constants of the chemical reactions from (6.q) to (6.y).
Ca+2 + H2 O = Ca(OH)+ + H + (6.q)
Ca+2 + SO−2
4 = CaSO4 (6.r)
Ca+2 + PO−3 −
4 = CaPO4 (6.s)
Ca+2 + H + + PO−3
4 =CaHPO4 (6.t)
Ca+2 + 2H + + PO−3 +
4 =CaH2 PO4 (6.u)
Ca+2 + 2H + + 2PO−3 −2
4 =CaP2 O4 + H2 O (6.v)
Ca+2 + H4 SiO4 = CaH3 SiO+

4 +H
+
(6.w)
Ca+2 + H4 SiO4 =CaH2 SiO4 + 2H + (6.x)
Ca+2 + SO−2
4 = CaSO3 (6.y)
The designation of concentration of soluble substances of calcium and sulfite soluble

compounds is the following:
Concentration of SO3 −2 is mSi1 ,

Concentration of HSO3 − is mSi2 ,
Concentration of H2 SO3 is mSi3 ,

Table 6.5: Log(K) of Calcium soluble compounds system at 25°C

6.q -12.697 MINTEQA2-V.4, 1999
6.r 2.36 MINTEQA2-V.4, 1999
6.s 6.46 MINTEQA2-V.4, 1999
6.t 15.035 MINTEQA2-V.4, 1999
6.u 20.923 MINTEQA2-V.4, 1999
6.v 28.136 Thermoddem
6.w -8.69 W. Hummel et al, 2002
6.x -18.44 W. Hummel et al, 2002
6.y 2.62 D. Rai et al, 2002
Concentration of S2 O−2
5 is mSi4 ,
+2
Concentration of Ca is mCa1 ,
Concentration of Ca(OH)+ is mCa2 ,
Concentration of CaSO4 is mCa3 ,
Concentration of CaPO− 4 is mCa4 ,
Concentration of CaHPO4 is mCa5 ,
Concentration of CaH2 PO+ 4 is mCa6 ,
−2
Concentration of CaP2 O4 is mCa7 ,
Concentration of CaH3 SiO+ 4 is mCa8 ,
Concentration of CaH2 SiO4 is mCa9 ,
Concentration of CaSO3 is mCa10 .
The concentrations of sulfite and calcium soluble substances are calculated as function
of concentration of reference soluble substance (Ca+2 , H + , SO4 −2 , PO4 −3, SO3 −2 and H4 SiO4 )
using Equations from (6.41) to (6.52) coming from the mass actions of the chemical reactions
from (6.n) to (6.p) and from (6.q) to (6.y).
mSi2 =10(7.17) *mH1 *mSi1 *γ2 (6.41)
mSi3 =10(9.03) *(mH1 )2 *mSi1 *γ2 *(γ1 )2 (6.42)
(mSi1 )2 ∗γ2 ∗(mH1 )2 ∗(γ1 )2

mSi4 =10(12.85) * (6.43)
(aw )2
mCa1 ∗γ2 ∗aw

mCa2 =10(−12.697) * (6.44)
mH1 ∗(γ1 )2
mCa3 =10(2.36) *mCa1 *mSa1 *(γ2 )2 (6.45)
mCa1 ∗γ2 ∗mp1 ∗γ3

mCa4 =10(6.46) * (6.46)
γ1

mCa5 =10(15.035) *mCa1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.47)
mCa6 =10(20.923) *mCa1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.48)
mCa1 ∗γ2 ∗(mH1 )2 ∗(γ1 )2 ∗(mp1 )2 ∗(γ3 )2

mCa7 =10(28.136) * (6.49)
aw ∗γ2
mCa1 ∗γ2 ∗mSc1

mCa8 =10(−8.69) * (6.50)
mH1 ∗(γ1 )2
m ∗γ ∗m
mCa9 =10(−18.44) * (mCa1 )22∗(γ Sc1 (6.51)
H1 )2 1
mCa10 =10(2.62) *mCa1 *mSi1 *(γ2 )2 (6.52)
The concentration mCa1 is fixed by Equation (6.53) that is the mass action of the
chemical reaction (6.z). pKs of gypsum is between 4.503 (David R. Lide, 2005) and 4.61
(MINTEQA2-V.4, 1999) at 25°C. pKs of gypsum in this work is taken at 4.58 (W. Hummel et al,
2002).
10−4.58
mCa1 =m 2 2
(6.53)
Sa1 ∗(γ2 ) ∗(aw )
Ca+2 + SO−2
4 + 2H2 O = CaSO4 .2H2 O (6.z)
The concentration mSi1 is fixed by total concentration of Calcium in solution that is

equal to Calcium concentration CaT from Table (A) (Equation 6.54).
CaT =mCa1 +mCa2 +mCa3 +mCa4 +mCa5 +mCa6 +mCa7 +mCa8 +mCa9 + mCa10 (6.54)
The values of ChPSi and ChNSi are given by Equation (6.55) and (6.56). The values of
ChPCa and ChNCa are given by Equation (6.57) and (6.58). The values of ISi and NSi are given
by Equations (6.59) and (6.60). The values of ICa and NCa are given by Equations (6.61) and
(6.62). The value of PCa is given by Equation (6.63).
ChPSi =0 (6.55)
ChNSi =2*mSi1 +mSi2 +2*mSi4 (6.56)
ChPCa =2*mCa1 +mCa2 +mCa6 +mCa8 (6.57)
ChNCa =mCa4 +2*mCa7 (6.58)
ISi =4*mSi1 +mSi2 +4*mSi4 (6.59)
NSi =mSi1 +mSi2 +mSi3 +mSi4 (6.60)

ICa =4*mCa1 +mCa2 +mCa4 +mCa6 +4*mCa7 +mCa8 (6.61)
NCa = mCa1 +mCa2 +mCa3 +mCa4 +mCa5 +mCa6 +mCa7 +mCa8 +mCa9 +mCa10 (6.62)
PCa= mCa4 +mCa5 +mCa6 +2*mCa7 (6.63)
6.7. Magnesium
The magnesium soluble substances are the following: Mg +2 , Mg(OH)+ , MgSO4 , MgPO− 4,
+ + +2
MgHPO4 , MgH2 PO4 and MgH3 SiO4 . The soluble compound Mg is taken as reference. The
chemical reactions from (6.aa) to (6.af) give the equilibrium reactions between reference and
the other soluble compounds. Table (6.6) gives the equilibrium constants of the chemical
reactions from (6.aa) to (6.af).
Mg +2 + H2 O = Mg(OH)+ + H + (6.aa)
Mg +2 + SO−2
4 = MgSO4 (6.ab)
Mg +2 + PO−3 −
4 = MgPO4 (6.ac)
Mg +2 + H + + PO−3
4 =MgHPO4 (6.ad)
Mg +2 + 2H + + PO−3 +
4 =MgH2 PO4 (6.ae)
Mg +2 + H4 SiO4 = MgH3 SiO+

4 +H
+
(6.af)
Table 6.6: Log(K) of Magnesium soluble compounds system at 25°C

6.aa -11.397 MINTEQA2-V.4, 1999
6.ab 2.26 MINTEQA2-V.4, 1999
6.ac 4.654 MINTEQA2-V.4, 1999
6.ad 15.175 MINTEQA2-V.4, 1999
6.ae 21.2561 MINTEQA2-V.4, 1999
6.af -8.34 W. Hummel et al, 2002
The designation of concentration of soluble substances of magnesium soluble

Concentration of Mg +2 is mMg1 ,
Concentration of Mg(OH)+ is mMg2 ,
Concentration of MgSO4 is mMg3 ,
Concentration of MgPO− 4 is mMg4 ,

Concentration of MgHPO4 is mMg5 ,
Concentration of MgH2 PO+4 is mMg6 ,
Concentration of MgH3 SiO+4 is mMg7 ,
The concentrations of magnesium soluble substances are calculated as function of

concentration of reference soluble substance (Mg +2 , H + , SO4 −2 , PO4 −3 , and H4 SiO4 ) using
Equations from (6.64) to (6.69) coming from the mass actions of the chemical reactions from
(6.aa) to (6.af).
mMg1 ∗γ2 ∗aw

mMg2 =10(−11.397) * (6.64)
mH1 ∗(γ1 )2
mMg3 =10(2.26) *mMg1 *mSa1 *(γ2 )2 (6.65)
mMg1 ∗γ2 ∗mp1 ∗γ3

mMg4 =10(4.654) * (6.66)
γ1
mMg5 =10(15.175) *mMg1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.67)
mMg6 =10(21.2561) *mMg1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.68)
mMg1 ∗γ2 ∗mSc1

mMg7 =10(−8.34) * (6.69)
mH1 ∗(γ1 )2
The concentration mMg1 is fixed by total concentration of magnesium in solution that is

equal to magnesium concentration Mg T from Table (A) (Equation 6.70).
Mg T =mMg1 +mMg2 +mMg3 +mMg4 +mMg5 +mMg6 +mMg7 (6.70)
The values of ChPMg and ChNMg are given by Equation (6.71) and (6.72). The values of
IMg and NMg are given by Equations (6.73) and (6.74). The value of PMg is given by Equation
(6.75).
ChPMg =2*mMg1 +mMg2 +mMg6 +mMg7 (6.71)
ChNMg =mMg4 (6.72)
IMg =4*mMg1 +mMg2 +mMg4 +mMg6 +mMg7 (6.73)
NMg =mMg1 +mMg2 +mMg3 +mMg4 +mMg5 +mMg6 +mMg7 (6.74)
PMg = mMg4 +mMg5 +mMg6 (6.75)

6.8. Aluminum
Aluminum soluble substances are the following: Al+3 , Al(OH)+2, Al(OH)+ 2 , Al(OH)3 ,
− + − +2 + +2
Al(OH)4 , AlSO4 , Al(SO4 )2 , AlH2 PO4 , AlHPO4 , and AlH3 SiO4 . The soluble compound Al+3 is
taken as reference. The chemical reactions from (6.ag) to (6.ao) give the equilibrium reactions
constants of the chemical reactions from (6.ag) to (6.ao).
Al+3 + H2 O = Al(OH)+2 + H + (6.ag)
Al+3 + 2H2 O= Al(OH)+

2 + 2H
+
(6.ah)
Al+3 + 3H2 O= Al(OH)3 + 3H + (6.ai)
Al+3 + 4H2 O= Al(OH)−

4 + 4H
+
(6.aj)
Al+3 + SO−2 +
4 = AlSO4 (6.ak)
Al+3 +2SO−2 −
4 = Al(SO4 )2 (6.al)
Al+3 + 2H + + PO−3 +2
4 =AlH2 PO4 (6.am)
Al+3 + H + + PO−3 +
4 =AlHPO4 (6.an)
Al+3 + H4 SiO4 = AlH3 SiO+2

4 +H
+
(6.ao)
Table 6.7: Log(K) of Aluminum soluble compounds system at 25°C

6.ag -4.997 MINTEQA2-V.4, 1999
6.ah -10.094 MINTEQA2-V.4, 1999
6.ai -16.971 MINTEQA2-V.4, 1999
6.aj -22.807 MINTEQA2-V.4, 1999
6.ak 3.89 MINTEQA2-V.4, 1999
6.al 4.92 MINTEQA2-V.4, 1999
6.am 22.673 Thermoddem
6.an 19.763 Thermoddem
6.ao -2.44 W. Hummel et al, 2002
The designation of concentration of soluble substances of aluminum soluble

Concentration of Al+3 is mAl1 ,

Concentration of Al(OH)+2 is mAl2 ,
Concentration of Al(OH)+2 is mAl3 ,

Concentration of Al(OH)3 is mAl4 ,
Concentration of Al(OH)− 4 is mAl5 ,
+
Concentration of AlSO4 is mAl6 ,
Concentration of Al(SO4 )−2 is mAl7 ,
+2
Concentration of AlH2 PO4 is mAl8 ,
Concentration of AlHPO+ 4 is mAl9 ,
Concentration of AlH3 SiO+2
4 is mAl10 .
The concentrations of aluminum soluble substances are calculated as function of

concentration of reference soluble substance (Al+3, H + , SO4 −2 , PO4 −3, SO3 −2 and H4 SiO4 ) using
Equations from (6.76) to (6.84) coming from the mass actions of the chemical reactions from
(4.ag) to (4.ao).
mAl1 ∗γ3 ∗aw

mAl2 =10(−4.997)* (6.76)
mH1 ∗γ1 ∗γ2
m ∗γ3 ∗(aw )2
mAl3 =10(−10.094)* (m
Al1
2 3
(6.77)
H1 ) ∗(γ1 )
m ∗γ3 ∗(aw )3
mAl4 =10(−16.971)* (m
Al1
3 3
(6.78)
H1 ) ∗(γ1 )
m ∗γ3 ∗(aw )4
mAl5 =10(−22.807)* (m
Al1
4 5
(6.79)
H1 ) ∗(γ1 )
mAl1 ∗γ3 ∗mSa1 ∗γ2

mAl6 =10(3.89)* (6.80)
γ1
mAl1 ∗γ3 ∗(mSa1 )2 ∗(γ2 )2

mAl7 =10(4.92)* (6.81)
γ1
mAl1 ∗γ3 ∗(mH1 )2 ∗mP1 ∗γ3

mAl8 =10(22.673)* (6.82)
γ2
mAl9 =10(19.763)*mAl1 *γ3 *mH1 *mP1 *γ3 (6.83)
mAl1 ∗γ3 ∗mSc1

mAl8 =10(−2.44)* (6.84)
mH1 ∗γ1 ∗γ2
The concentration mAl1 is fixed by total concentration of aluminum in solution that is

equal to aluminum concentration AlT from Table (A) (Equation 6.85).
AlT =mAl1 +mAl2 +mAl3 +mAl4 +mAl5 +mAl6 +mAl7 +mAl8 +mAl9 +mAl10 (6.85)
The values of ChPAl and ChNAl are given by Equation (6.86) and (6.87). The values of
IAl and NAl are given by Equations (6.88) and (6.89). The value of PAl is given by Equation
(6.90).

ChPAl =3*mAl1 +2*mAl2 +mAl3 +mAl6 +2*mAl8 +mAl9 +2*mAl10 (6.86)
ChNAl =mAl5 +mAl7 (6.87)
IAl =9*mAl1 +4*mAl2 +mAl3 +mAl5 +mAl6 +mAl7 +4*mAl8 +mAl9 +4*mAl10 (6.88)
NAl = mAl1 +mAl2 +mAl3 +mAl4 +mAl5 +mAl6 +mAl7 +mAl8 +mAl9 +mAl10 (6.89)
PAl=mAl8 +mAl9 (6.90)
6.9. Zinc
Zinc soluble substances are the following: Zn+2, Zn(OH)+, Zn(OH)2, Zn(OH)− 3,
−2 + − +2
Zn(OH)4 , ZnSO4 , ZnH2 PO4 , ZnHPO4, and ZnPO4 . The soluble compound Zn is taken as
reference. The chemical reactions from (6.ap) to (6.aw) give the equilibrium reactions
constants of the chemical reactions from (6.ap) to (6.aw).
Zn+2 + H2 O = Zn(OH)+ + H + (6.ap)
Zn+2 + 2H2 O= Zn(OH)2 + 2H + (6.aq)
Zn+2 + 3H2 O= Zn(OH)−

3 + 3H
+
(6.ar)
Zn+2 + 4H2 O= Zn(OH)−2

4 + 4H
+
(6.as)
Zn+2 + SO−2
4 = ZnSO4 (6.at)
Zn+2 +2H + + PO−3 +

4 =ZnH2 PO4 (6.au)
Zn+2 +H + + PO−3
4 =ZnHPO4 (6.av)
Zn+2 + PO4−3 =ZnPO−

4 (6.aw)
The designation of concentration of soluble substances of zinc soluble compounds is

the following:
Concentration of Zn+2 is mZn1,

Concentration of Zn(OH)+ is mZn2,
Concentration of Zn(OH)2 is mZn3,
Concentration of Zn(OH)−3 is mZn4 ,

Table 6.8: Log(K) of Zinc soluble compounds system at 25°C

6.ap -8.92 MINTEQA2-V.4, 1999
6.aq -17.8 MINTEQA2-V.4, 1999
6.ar -28.1 MINTEQA2-V.4, 1999
6.as -40.5 MINTEQA2-V.4, 1999
6.at 2.34 MINTEQA2-V.4, 1999
6.au 21.163 Thermoddem
6.av 15.663 Thermoddem
6.aw 8.063 Thermoddem
Concentration of Zn(OH)−24 is mZn5 ,

Concentration of ZnSO4 is mZn6,
Concentration of ZnH2 PO+4 is mZn7 ,
Concentration of ZnHPO4 is mZn8,
Concentration of ZnPO−4 is mZn9 .
The concentrations of zinc soluble substances are calculated as function of

concentration of reference soluble substance (Zn+2, Al+3, H + , SO4 −2 , PO4 −3 , SO3 −2 and H4 SiO4 )
using Equations from (6.91) to (6.99) coming from the mass actions of the chemical reactions
from (6.ap) to (6.aw).
mZn1 ∗γ2 ∗aw

mZn2=10(−8.92)* (6.91)
mH1 ∗(γ1 )2
mZn1 ∗γ2 ∗(aw )2

mZn3=10(−17.8)* (6.92)
(mH1 )2 ∗(γ1 )2
mZn1 ∗γ2 ∗(aw )3

mZn4=10(−28.1)* (6.93)
(mH1 )3 ∗(γ1 )4
m ∗(a )4
mZn5=10(−40.5)*(mZn1)4 ∗(γw )4 (6.94)
H1 1
mZn6=10(2.34)*mZn1*mSa1 *(γ2 )2 (6.95)
mZn7=10(21.163)*mZn1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.97)
mZn8=10(15.663)*mZn1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.98)
mZn1 ∗γ2 ∗mP1 ∗γ3

mZn9=10(8.063)* (6.99)
γ1
The concentration mZn1 is fixed by total concentration of zinc in solution that is equal
to zinc concentration ZnT from Table (A) (Equation 6.100).

ZnT1 =mZn1+mZn2+mZn3+mZn4+mZn5+mZn6+mZn7+mZn8+mZn9 (6.100)
The values of ChPZn and ChNZn are given by Equation (6.101) and (6.102). The values
of IZn and NZn are given by Equations (6.103) and (6.104). The value of PAl is given by
Equation (5.105).
ChPZn =2*mZn1+mZn2 +mZn7 (6.101)
ChNZn =mZn4+2*mZn5 +mZn9 (6.102)
IZn =4*mZn1+mZn2+mZn4+4*mZn5+mZn7+mZn9 (6.103)
NZn =mZn1+mZn2+mZn3+mZn4+mZn5+mZn6+mZn7+mZn8+mZn9 (6.104)
PZn=mZn7+mZn8+mZn9 (6.105)
6.10. Manganese
Manganese soluble substances are the following: Mn+2, Mn(OH)+, Mn(OH)− 3,

−2 + − +3 +2
Mn(OH)4 , MnSO4, MnH2 PO4 , MnHPO4, MnPO4 and Mn . The soluble compound Mn is
taken as reference. The chemical reactions from (6.ax) to (6.be) give the equilibrium reactions
constants or standard redox potentials of the chemical reactions from (6.ay) to (6.be).
Mn+2 + H2 O= Mn(OH)+ + H + (6.ax)
Mn+2 + 3H2 O= Mn(OH)−

3 + 3H
+
(6.ay)
Mn+2 + 4H2 O= Mn(OH)−2

4 + 4H
+
(6.az)
Mn+2 + SO−2
4 = MnSO4 (6.ba)
Mn+2 +2H + + PO−3 +

4 =MnH2 PO4 (6.bb)
Mn+2 +H + + PO4−3 =MnHPO4 (6.bc)
Mn+2 + PO−3 −
4 =MnPO4 (6.bd)
Mn+3 + 𝑒 − = Mn+2 (6.be)

Table 6.9: Log(K) and 𝐸ℎ of Mn soluble compounds system at 25°C

6.ax -10.597 MINTEQA2-V.4, 1999
6.ay -34.8 MINTEQA2-V.4, 1999
6.az -48.288 MINTEQA2-V.4, 1999
6.ba 2.25 MINTEQA2-V.4, 1999
6.bb 20.913 Thermoddem
6.bc 15.943 Thermoddem
6.bd 7.233 Thermoddem
6.be ° David R. Lide, 2005
𝐸ℎ =1.542V
The designation of concentration of soluble substances of manganese soluble

Concentration of Mn+2 is mMn1 ,

Concentration of Mn(OH)+ is mMn2 ,
Concentration of Mn(OH)− 3 is mMn3 ,
Concentration of Mn(OH)−24 is mMn4 ,
Concentration of MnSO4 is mMn5 ,
Concentration of MnH2 PO+4 is mMn6 ,
Concentration of MnHPO4 is mMn7 ,
Concentration of MnPO−4 is mMn8 ,
+3
Concentration of Mn is mMn9 ,
The concentrations of manganese soluble substances are calculated as function of

concentration of reference soluble substance (Mn+2, Zn+2, Al+3 , H + , SO4 −2 , PO4 −3 , SO3 −2 and
H4 SiO4 ) using Equations from (6.106) to (6.113) coming from the mass actions of the
chemical reactions from (6.ay) to (6.be).
mMn1 ∗γ2 ∗aw

mMn2 =10(−10.597) * (6.106)
mH1 ∗(γ1 )2
mMn1 ∗γ2 ∗(aw )3

mMn3 =10(−34.8) * (6.107)
(mH1 )3 ∗(γ1 )4
m ∗(a )4
mMn4 =10(−48.288) *(mMn1)4 ∗(γw )4 (6.108)
H1 1
mMn5 =10(2.25) *mMn1 *mSa1 *(γ2 )2 (6.109)
mMn6 =10(21.163) *mMn1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.110)
mMn7 =10(15.663) *mMn1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.111)
mMn1 ∗γ2 ∗mP1 ∗γ3

mMn8 =10(8.063) * (6.112)
γ1

(Eh −1.542)
Log(mMn9 *γ3 )= +log(mMn1 *γ2 ) (6.113)
0.059
The concentration mMn1 is fixed by total concentration of manganese in solution that is

equal to manganese concentration MnT from Table (A) (Equation 6.114).
MnT =mMn1 +mMn2 +mMn3 +mMn4 +mMn5 +mMn6 +mMn7 +mMn8 +mMn9 (6.114)
The values of ChPMn and ChNMn are given by Equation (6.115) and (6.116). The values
of IMn and NMn are given by Equations (6.117) and (6.118). The value of PMn is given by
Equation (6.119).
ChPMn =2*mMn1 +mMn2 +mMn6 +3*mMn9 (6.115)
ChNMn =mMn3 +2*mMn4 +mMn8 (6.116)
IMn =4*mMn1 +mMn2 +mMn3 +4*mMn4 +mMn6 +mMn8 +9*mMn9 (6.117)
NMn =mMn1 +mMn2 +mMn3 +mMn4 +mMn5 +mMn6 +mMn7 +mMn8 +mMn9 (6.118)
PMn = mMn6 +mMn7 +mMn8 (6.119)
6.11. Copper
Copper soluble substances are the following: Cu+2 , Cu(OH)+ , Cu(OH)2, Cu(OH)− 3,
−2 +3 + − +
Cu(OH)4 , Cu2 (OH) , CuSO4 , CuH2 PO4 , CuHPO4 , CuPO4 , and Cu . The soluble compound
Cu+2 is taken as reference. The chemical reactions from (6.bf) to (6.bo) give the equilibrium
reactions between reference and the other soluble compounds. Table (6.10) gives the
equilibrium constants or standard redox potentials of the chemical reactions from (6.bf) to
(6.bo).
Cu+2 + H2 O= Cu(OH)+ + H + (6.bf)
Cu+2 + 2H2 O= Cu(OH)2 + 2H + (6.bg)
Cu+2 + 3H2 O= Cu(OH)−

3 + 3H
+
(6.bh)
Cu+2 + 4H2 O= Cu(OH)−2

4 + 4H
+
(6.bi)
2Cu+2 + H2 O= Cu2 (OH)+3 + H + (6.bj)
Cu+2 + SO−2
4 = CuSO4 (6.bk)

Cu+2 +2H + + PO−3 +
4 =CuH2 PO4 (6.bl)
Cu+2 +H + + PO−3
4 =CuHPO4 (6.bm)
Cu+2 + PO−3 −
4 =CuPO4 (6.bn)
Cu+2 + 𝑒 − = Cu+ (6.bo)

6.bf -7.497 MINTEQA2-V.4, 1999
6.bg -16.194 MINTEQA2-V.4, 1999
6.bh -26.879 MINTEQA2-V.4, 1999
6.bi -39.98 MINTEQA2-V.4, 1999
6.bj -6.28 MINTEQA2-V.4, 1999
6.bk 2.36 MINTEQA2-V.4, 1999
6.bl 21.333 Thermoddem
6.bm 16.413 Thermoddem
6.bn 9.893 Thermoddem
6.bo 𝐸ℎ =0.16V David R. Lide, 2005
The designation of concentration of soluble substances of copper soluble compounds is

the following:
Concentration of Cu+2 is mCu1 ,

Concentration of Cu(OH)+ is mCu2 ,
Concentration of Cu(OH)2 is mCu3 ,
Concentration of Cu(OH)− 3 is mCu4 ,
Concentration of Cu(OH)−2 4 is mCu5 ,
Concentration of Cu2 (OH)+3 is mCu6 ,
Concentration of CuSO4 is mCu7 ,
Concentration of CuH2 PO+ 4 is mCu8 ,
Concentration of CuHPO4 is mCu9 ,
Concentration of CuPO− 4 is mCu10 ,
+
Concentration of Cu is mCu11 ,
The concentrations of copper soluble substances are calculated as function of

concentration of reference soluble substance (Cu+2 , Mn+2, Zn+2, Al+3, H + , SO4 −2 , PO4 −3,
SO3 −2 and H4 SiO4 ) using Equations from (6.120) to (6.129) coming from the mass actions of
the chemical reactions from (6.bf) to (6.bo).
mCu1 ∗γ2 ∗aw

mCu2 =10(−7.497) * (6.120)
mH1 ∗(γ1 )2

mCu1 ∗γ2 ∗(aw )2
mCu3 =10(−16.194) * (6.121)
(mH1 )2 ∗(γ1 )2
mCu1 ∗γ2 ∗(aw )3

mCu4 =10(−26.897) * (6.122)
(mH1 )3 ∗(γ1 )4
m ∗(a )4
mCu5 =10(−39.98) *(mCu1)4 ∗(γw )4 (6.123)
H1 1
(mCu1 )2 ∗(γ2 )2 ∗aw

mCu6 =10(−6.28) * (6.124)
mH1 ∗γ1 ∗γ3
mCu7 =10(2.36) *mCu1 *mSa1 *(γ2 )2 (6.125)
mCu8 =10(20.913) *mCu1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.126)
mCu9 =10(15.943) *mCu1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.127)
mCu1 ∗γ2 ∗mP1 ∗γ3

mCu10 =10(7.233) * (6.128)
γ1
(0.16−Eh )
Log(mCu11 *γ1 )= +log(mCu1 *γ2 ) (6.129)
0.059
The concentration mCu1 is fixed by total concentration of copper in solution that is

equal to copper concentration CuT from Table (A) (Equation 6.130).
CuT =mCu1 +mCu2 +mCu3 +mCu4 +mCu5 +2*mCu6 +mCu7 +mCu8 +mCu9 +mCu10 +mCu11
(6.130)
The values of ChPCu and ChNCu are given by Equation (6.131) and (6.132). The values
of ICu and NCu are given by Equations (6.133) and (6.134). The value of PCu is given by
Equation (6.135).
ChPCu =2*mCu1 +mCu2 +3*mCu6 +mCu8 + mCu11 (6.131)
ChNCu =mCu4 +2*mCu5 +mCu10 (6.132)
ICu =4*mCu1 +mCu2 +mCu4 +4*mCu5 +9*mCu6 +mCu8 +mCu10 +mCu11 (6.133)
NCu =mCu1 +mCu2 +mCu3 +mCu4 +mCu5 +mCu6 +mCu7 +mCu8 +mCu9 +mCu10 +mCu11
(6.134)
PCu= mCu8 +mCu9 + mCu10 (6.135)

6.12. Cobalt
Cobalt soluble substances are the following: Co+2 , Co(OH)+ , Co(OH)2 , Co(OH)−
3,
−2 +3 +4 − −2 − +3
Co(OH)4 , Co2 (OH) , Co4 (OH)4 , CoOOH , CoSO4 , CoHPO4 , CoP2 O7 , HCoP2 O7 , Co and
Co(OH)+2. The soluble compounds Co+2 and Co+3 are taken as reference. The chemical
reactions from (6.bp) to (6.cb) give the equilibrium reactions between reference and the
other soluble compounds. Table (6.11) gives the equilibrium constants or standard redox
potentials of the chemical reactions from (6.bp) to (6.cb).
Co+2 + H2 O= Co(OH)+ + H + (6.bp)
Co+2 + 2H2 O= Co(OH)2 + 2H + (6.bq)
Co+2 + 3H2 O= Co(OH)−

3 + 3H
+
(6.br)
Co+2 + 4H2 O= Co(OH)−2

4 + 4H
+
(6.bs)
2Co+2 + H2 O= Co2 (OH)+3 + H + (6.bt)
4Co+2 + 4H2 O= Co4 (OH)+4

4 + 4H
+
(6.bu)
Co+2 + 2H2 O= CoOOH − + 3H + (6.bv)
Co+2 + SO−2
4 = CoSO4 (6.bw)
Co+2 +H + + PO−3
4 = CoHPO4 (6.bx)
Co+2 +2H + + 2PO−3 −2

4 =CoP2 O7 + H2 O (6.by)
Co+2 +3H + + 2PO−3 −

4 =HCoP2 O7 + H2 O (6.bz)
Co+3 + 𝑒 − = Co+2 (6.ca)
Co+3 + H2 O= Co(OH)+2 + H + (6.cb)
The designation of concentration of soluble substances of cobalt soluble compounds is

the following:
Concentration of Co+2 is mCo1,

Concentration of Co(OH)+ is mCo2 ,
Concentration of Co(OH)2 is mCo3 ,
Concentration of Co(OH)−3 is mCo4 ,


6.bp -9.697 MINTEQA2-V.4, 1999
4.bq -18.794 MINTEQA2-V.4, 1999
6.br -31.491 MINTEQA2-V.4, 1999
6.bs -46.288 MINTEQA2-V.4, 1999
6.bt -10.548 MINTEQA2-V.4, 1999
6.bu -30.488 MINTEQA2-V.4, 1999
6.bv -32.0915 MINTEQA2-V.4, 1999
6.bw 2.3 MINTEQA2-V.4, 1999
6.bx 15.4128 MINTEQA2-V.4, 1999
6.by 29.985 Akira Kitamura; 2014
6.bz 35.815 Akira Kitamura; 2014
6.ca 𝐸ℎ° =1.953V David R. Lide, 2005
6.cb -1.291 MINTEQA2-V.4, 1999
Concentration of Co(OH)−2
4 is mCo5 ,
Concentration of Co2 (OH)+3 is mCo6 ,
Concentration of Co4 (OH)+4
4 is mCo7 ,
−
Concentration of CoOOH is mCo8 ,
Concentration of CoSO4 is mCo9,
Concentration of CoHPO4 is mCo10 ,
Concentration of CoP2 O−2
7 is mCo11 ,
Concentration of HCoP2 O−
7 is mCo12 ,
+3
Concentration of Co is mCo13,
Concentration of Co(OH)+2 is mCo14 ,
The concentrations of cobalt soluble substances are calculated as function of

concentration of reference soluble substance (Co+2, Co+3 , Cu+2 , Mn+2, Zn+2, Al+3 , H + , SO4 −2 ,
PO4 −3 , SO3 −2and H4 SiO4 ) using Equations from (6.136) to (6.148) coming from the mass
actions of the chemical reactions from (6.bf) to (6.cb).
mCo1 ∗γ2 ∗aw

mCo2=10(−9.697)* (6.136)
mH1 ∗(γ1 )2
mCo1 ∗γ2 ∗(aw )2

mCo3=10(−18.794)* (6.137)
(mH1 )2 ∗(γ1 )2
mCo1 ∗γ2 ∗(aw )3

mCo4=10(−31.491)* (6.138)
(mH1 )3 ∗(γ1 )4
m ∗(a )4
mCo5=10(−46.288)*(mCo1)4 ∗(γw )4 (6.139)
H1 1
(mCo1 )2 ∗(γ2 )2 ∗aw

mCo6=10(−10.548)* (6.140)
mH1 ∗γ1 ∗γ3

(mCo1 )4 ∗(γ2 )4 ∗(aw )4
mCo7=10(−30.488)* (6.141)
(mH1 )4 ∗(γ1 )4 ∗γ4
mCo1 ∗γ2 ∗(aw )2

mCo8=10(−32.0915)* (6.142)
(mH1 )3 ∗(γ1 )4
mCo9=10(2.30) *mCo1*mSa1 *(γ2 )2 (6.143)
mCo10=10(15.4128)*mCo1*γ2 *mH1 *γ1 *mP1 *γ3 (6.144)
mCo1 ∗γ2 ∗(mH1 )2 ∗(γ1 )2 ∗(mP1 )2 ∗(γ3 )2

mCo11=10(29.985)* (6.145)
aw10 ∗γ2
mCo1 ∗γ2 ∗(mH1 )3 ∗(γ1 )3 ∗(mP1 )2 ∗(γ3 )2

mCo12=10(35.315)* (6.146)
aw10 ∗γ1
(Eh −1.953)
Log(mCo13*γ3 )= +log(mCo1*γ2 ) (6.147)
0.059
mCo13 ∗γ3 ∗aw

mCo14=10(−1.291)* (6.148)
mH1 ∗γ1 ∗γ2
The concentration mCo1 is fixed by total concentration of cobalt in solution that is equal
to Cobalt concentration CoT from Table (A) (Equation 6.149).
CoT =mCo1+mCo2+mCo3+mCo4+mCo5+2*mCo6 +4*mCo7+mCo8+mCo9+mCo10+

mCo11+mCo12+mCo13+mCo14 (6.149)
The values of ChPCo and ChNCo are given by Equation (6.150) and (6.151). The
values of ICo and NCo are given by Equations (6.152) and (6.153). The value of PCu is
given by Equation (6.154).
ChPCo =2*mCo1+mCo2 +3*mCo6+4*mCo7+3*mCo13 +4*mCo14 (6.150)
ChNCo =mCo4+2*mCo5 +mCo8+2*mCo11+mCo12 (6.151)
ICo =4*mCo1+mCo2+mCo4+4*mCo5+9*mCo6+16*mCo7+mCo8+4*mCo11+mCo12+9*
mCo5+4*mCo14 (6.152)
NCo =mCo1+mCo2+mCo3+mCo4+mCo5+mCo6+mCo7+mCo8+mCo9+mCo10 +mCo11+

mCo12+mCo13+mCo14 (6.153)
PCo= mCo10+2*mCo11 +2*mCo12 (6.154)

6.13. Iron
Iron soluble substances are the following: Fe+2 , Fe(OH)+, Fe(OH)2, Fe(OH)− +
3 , FeHSO4 ,
+ +4
FeSO4 , FePO− + +3 +2 −
4 , FeH2 PO4 , FeHPO4 , Fe , Fe(OH) , Fe(OH)2 , Fe(OH)3 , Fe(OH)4 , Fe2 (OH)2 ,
Fe3 (OH)+5 +2 + − +2 + +2
4 , FeHSO4 , FeH(SO4 )2 , Fe2 (SO4 )2 , FeSO4 , Fe(SO4 )2 , FeH2 PO4 , FeHPO4 , FeH3 SiO4 ,
and FeSO+ 3 . The soluble compounds Fe
+2
and Fe+3 are taken as reference. The chemical
reactions from (6.cc) to (6.cz) give the equilibrium reactions between reference and the other
soluble compounds. Table (6.12) gives the equilibrium constants or standard redox potentials
of the chemical reactions from (6.cc) to (6.cz).

4.cc -9.397 MINTEQA2-V.4, 1999
4.cd -20.494 MINTEQA2-V.4, 1999
4.ce -28.991 MINTEQA2-V.4, 1999
4.cf 1.09 Thermoddem
4.cg 2.39 MINTEQA2-V.4, 1999
4.ch 7.943 Thermoddem
4.ci 22.273 MINTEQA2-V.4, 1999
4.cj 15.975 MINTEQA2-V.4, 1999
4.ck 𝐸ℎ° =0.769V David R. Lide, 2005
4.cl -2.187 MINTEQA2-V.4, 1999
4.cm -4.594 MINTEQA2-V.4, 1999
4.cn -12.56 MINTEQA2-V.4, 1999
4.co -21.588 MINTEQA2-V.4, 1999
4.cp -2.854 MINTEQA2-V.4, 1999
4.cq -6.888 MINTEQA2-V.4, 1999
4.cr 2.48 Thermoddem
4.cs 7.49 Thermoddem
4.ct 8.02 Thermoddem
4.cu 4.05 MINTEQA2-V.4, 1999
4.cv 5.38 MINTEQA2-V.4, 1999
4.cw 23.2515 MINTEQA2-V.4, 1999
4.cx 22.292 MINTEQA2-V.4, 1999
4.cy -0.11 W. Hummel et al, 2002
4.cz 6.47 Gabor Lente, 2001
Fe+2 + H2 O= Fe(OH)+ + H + (6.cc)
Fe+2 + 2H2 O= Fe(OH)2 + 2H + (6.cd)
Fe+2 + 3H2 O= Fe(OH)−

3 + 3H
+
(6.ce)
Fe+2 + H + + SO−2 +
4 =FeHSO4 (6.cf)

Fe+2 + SO−2
4 = FeSO4 (6.cg)
Fe+2 +PO−3 −
4 =FePO4 (6.ch)
Fe+2 +2H + + PO−3 +

4 =FeH2 PO4 (6.ci)
Fe+2 +H + + PO4−3 =FeHPO4 (6.cj)
Fe+3 + 𝑒 − = Fe+2 (6.ck)
Fe+3 + H2 O= Fe(OH)+2 + H + (6.cl)
Fe+3 + 2H2 O= Fe(OH)+

2 + 2H
+
(6.cm)
Fe+3 + 3H2 O= Fe(OH)3 + 3H + (6.cn)
Fe+3 + 4H2 O= Fe(OH)−

4 + 4H
+
(6.co)
2Fe+3 + 2H2 O= Fe2 (OH)+4

2 + 2H
+
(6.cp)
3Fe+3 + 4H2 O= Fe3 (OH)+5

4 + 4H
+
(6.cq)
Fe+3 + H + + SO−2 +2
4 =FeHSO4 (6.cr)
Fe+3 + H + +2SO−2
4 =FeH(SO4 )2 (6.cs)
2Fe+3 + 3SO−2
4 =Fe2 (SO4 )2 (6.ct)
Fe+3 + SO−2 +
4 = FeSO4 (6.cu)
Fe+3 + 2SO−2 −
4 =Fe(SO4 )2 (6.cv)
Fe+3 +2H + + PO−3 +2

4 =FeH2 PO4 (6.cw)
Fe+3 +H + + PO4−3 =FeHPO+

4 (6.cx)
Fe+3 +H4 SiO4 =FeH3 SiO+2

4 +H
+
(6.cy)
+
Fe+3 + SO−2
3 = FeSO3 (6.cz)
The designation of concentration of soluble substances of iron soluble compounds is

the following:
Concentration of Fe+2 is mFe1 ,

Concentration of Fe(OH)+ is mFe2 ,
Concentration of Fe(OH)2 is mFe3 ,
Concentration of Fe(OH)− 3 is mFe4 ,
+
Concentration of FeHSO4 is mFe5 ,
Concentration of FeSO4 is mFe6 ,
Concentration of FePO− 4 is mFe7 ,
Concentration of FeH2 PO+ 4 is mFe8 ,
Concentration of FeHPO4 is mFe9 ,
Concentration of Fe+3 is mFe10 ,
Concentration of Fe(OH)+2 is mFe11 ,
Concentration of Fe(OH)+ 2 is mFe12 ,
Concentration of Fe(OH)3 is mFe13 ,
Concentration of Fe(OH)− 4 is mFe14 ,
Concentration of Fe2 (OH)+4 2 is mFe15 ,
Concentration of Fe3 (OH)+5 4 is mFe16 ,
+2
Concentration of FeHSO4 is mFe17 ,
Concentration of FeH(SO4 )2 is mFe18 ,
Concentration of Fe2 (SO4 )2 is mFe19 ,
Concentration of FeSO+ 4 is mFe20 ,
Concentration of Fe(SO4 )− 2 is mFe21 ,
+2
Concentration of FeH2 PO4 is mFe22 ,
Concentration of FeHPO+ 4 is mFe23 ,
Concentration of FeH3 SiO+24 is mFe24 ,
+
Concentration of FeSO3 is mFe25 ,
The concentrations of iron soluble substances are calculated as function of

concentration of reference soluble substances (Fe+2, Fe+3, Co+2 , Cu+2, Mn+2, Zn+2, Al+3, H + ,
SO4 −2 , PO4 −3, SO3 −2 and H4 SiO4 ) using Equations from (6.155) to (4.180) coming from the
mass actions of the chemical reactions from (4.cc) to (4.cz).
m ∗γ ∗aw
mFe2 =10(−9.397)* mFe1 ∗(γ2 2 (6.155)
H1 1)
m ∗γ2 ∗(aw )2
mFe3 =10(−20.494)* (m
Fe1
2 2
(6.156)
H1 ) ∗(γ1 )
m ∗γ2 ∗(aw )3
mFe4 =10(−28.991)* (m
Fe1
3 4
(6.157)
H1 ) ∗(γ1 )
mFe5 =10(1.09)*mFe1 *mH1 *mSa1 *(γ2 )2 (6.158)
mFe6 =10(2.39)*mFe1 *mSa1 *(γ2 )2 (6.159)
mFe1 ∗γ2 ∗mP1 ∗γ3

mFe7 =10(7.943)* (6.160)
γ1

mFe8 =10(22.273)*mFe1 *γ2 *(mH1 )2*γ1 *mP1 *γ3 (6.161)
mFe9 =10(15.975) *mFe1 *γ2 *mH1 *γ1 *mP1 *γ3 (6.162)
(Eh −0.771)
Log(mFe10 *γ3 )= +log(mFe1 *γ2 ) (6.163)
0.059
mFe10 ∗γ3 ∗aw

mFe11 =10(−2.187)* (6.164)
mH1 ∗γ1 ∗γ2
mFe10 ∗γ3 ∗(aw )2

mFe12 =10(−4.594)* (6.165)
(mH1 )2 ∗(γ1 )3
mFe10 ∗γ3 ∗(aw )3

mFe13 =10(−12.56)* (6.166)
(mH1 )3 ∗(γ1 )3
mFe10 ∗γ3 ∗(aw )4

mFe14 =10(−21.588)* (6.167)
(mH1 )4 ∗(γ1 )5
(mFe10 )2 ∗(γ3 )2 ∗(aw )2

mFe15 =10(−2.854)* (6.168)
(mH1 )2 ∗(γ1 )2 ∗γ4
(mFe10 )3 ∗(γ3 )3 ∗(aw )4

mFe16 =10(−6.888)* (6.169)
(mH1 )4 ∗(γ1 )4 ∗γ5
mFe17 =10(2.48)*mFe10 *γ3 *mH1 *γ1 *mSa1 (6.170)
mFe18 =10(7.49)*mFe10 *γ3 *mH1 *γ1 *(mSa1 )2*(γ2 )2 (6.171)
mFe19 =10(8.02) *(mFe10 )2 *(γ3 )2 *(mSa1 )3*(γ2 )3 (6.172)
mFe10 ∗γ3 ∗mSa1 ∗γ2

mFe20 =10(4.05)* (6.173)
γ1
mFe10 ∗γ3 ∗(mSa1 )2 ∗(γ2 )2

mFe21 =10(5.38)* (6.174)
γ1
mFe10 ∗(γ3 )2 ∗(mH1 )2 ∗(γ1 )2 ∗mP1

mFe22 =10(23.2515)* (6.175)
γ2
mFe23 =10(−0.11)*mFe10 *(γ3 )2*mH1 *mP1 (6.176)
mFe10 ∗γ3 ∗mSc1

mFe24 =10(−0.11)* (6.177)
mH1 ∗γ1 ∗γ2
mFe10 ∗γ3 ∗mSi1 ∗γ2

mFe25 =10(8.718)* (6.178)
γ1

The concentration mFe1 is fixed by total concentration of iron in solution that is equal
to iron concentration FeT from Table (A) (Equation 6.179).
FeT =mFe1 +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +mFe10 +mFe11 +
mFe12 +mFe13 +mFe14 +2*mFe15 +3*mFe16 +mFe18 +mFe19 +mFe20 +mFe21 +
mFe22 +mFe23 ++mFe24 +mFe25 (6.179)
The values of ChPFe and ChNFe are given by Equation (6.180) and (6.181). The values
of IFe and NFe are given by Equations (6.182) and (6.183). The value of PFe is given by
Equation (6.184).
ChPFe =2*mFe1 +mFe2 +mFe5 +mFe8 +3*mFe10 +2*mFe11 +mFe12 +4*mFe15 +

5*mFe16 +2*mFe17 +mFe20 +2*mFe22 +mFe23 +2*mFe24 +mFe25 (6.180)
ChNFe =mFe4 +mFe7 +mFe14 +mFe21 (6.181)
IFe =4*mFe1 +mFe2 +mFe4 +mFe5 +mFe7 +mFe8 +9*mFe10 +4*mFe11 +mFe12 +mFe14
+16*mFe15 +25*mFe16 +4*mFe17 +mFe20 +mFe21 +4*mFe22 +mFe23 +4*mFe24
+mFe25 (6.182)
NFe =mFe1 +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +mFe10 +mFe11 +
mFe12 +mFe13 +mFe14 +mFe15 +mFe16 +mFe18 +mFe19 +mFe20 +mFe21 +mFe22 +
mFe23 +mFe24 +mFe25 (6.183)
PFe=mFe7 +mFe8 +mFe9 +mFe22 +mFe23 (6.184)
6.14. Summary
Figure (6.1) gives the ionic strength for each date. The values of ionic strength are
below the upper value about 5mol/kg water for the applicability of this geochemical
modelling.
Figures (6.2), (6.3) and (6.4) give respectively the Total concentration of free sulfate
compounds versus pH and Eh and the molar fractions free sulfate compounds versus pH. The
total concentration of free sulfate decreases with increasing pH and seems to be independent
to Eh . the anion SO−2
4 is the predominant sulfate species in range of pilot plant pH.

Figure 6.1: Ionic strength versus Date at 25°C
Figure 6.2: Total concentration (mol/kg water) of sulfate versus pH at 25°C

Figure 6.3: Total concentration (mol/kg water) of free sulfate versus 𝐸ℎ (V) at 25°C
Figure 6.4: Molar fractions (%) of free sulfate compounds versus pH at 25°C
Figures (6.5), (6.6) and (6.7) give respectively the Total concentration of free sulfite
compounds versus pH and Eh and the molar fractions free sulfite compounds versus pH.

Figure 6.5: Total concentration (mol/kg water) of sulfite versus pH at 25°C
Figure 6.6: Total concentration (mol/kg water) of free sulfite versus 𝐸ℎ (V) at 25°C

Figure 6.7: Molar fractions (%) of free sulfite compounds versus pH at 25°C
The total concentration of free sulfite decreases with increasing pH and Eh . The anions
HSO−
3 and SO−2
3 are respectively predominant species at pH below and above 1.6.
Figures (6.8) and (6.9) give the molar fractions of total sulfur in form of sulfate and
sulfite.
Figure 6.8: Molar fractions (%) of total sulfur in form of sulfate and sulfite versus pH at 25°C

Figure 6.9: Molar fractions (%) of total sulfur in form of sulfate and sulfite versus Eh at 25°C
The total sulfur in form of sulfite is the predominant species. The total sulfur in form of
sulfite decreases with increasing pH and Eh . The total sulfur in form of sulfate increases with
increasing pH and Eh .
Figure (6.10) gives the molar fractions of free phosphorous compounds versus pH at
25°C. The predominant species is H2 PO−4 in the range of pilot plant pH.
Figure (6.11) gives molar fractions of calcium compounds versus Eh at 25°C. The
contribution of calcium sulfite and phosphate aqueous complexes is very small. Figure (6.12)
gives the calcium concentration (mol/kg) versus SO−2 4 concentration (mol/kg). Calcium
−2
concentration decreases with increasing SO4 concentration.
Figures (6.13) and (6.14) give molar fractions of ferrous compounds versus pH and Eh .
The predominant species is Fe+2 in the range of pH and Eh of pilot plant.
Figures (6.15) and (6.16) give molar fractions of ferric compounds versus pH and Eh .
The predominant species are FeH(SO4 )2 and FeSO+ 4 respectively below and above pH 1.6 in
the range of pH. The predominant species is FeH(SO4 )2 in all range of Eh of pilot plant.
Figures (6.17) and (6.18) give molar fractions of total ferric and total ferrous
compounds versus respectively pH and Eh at 25°C.

Figure 6.10: Molar fractions (%) of free phosphorous compounds versus pH at 25°C
Figure 6.11: Molar fractions (%) of calcium compounds versus Eh at 25°C

Figure (6.12): Calcium concentration (mol/kg) versus SO−2
4 concentration (mol/kg)
Figure 6.13: Molar fractions (%) of ferrous compounds versus pH at 25°C

Figure 6.14: Molar fractions (%) of ferrous compounds versus Eh at 25°C
Figure 6.15: Molar fractions (%) of ferric compounds versus pH at 25°C

Figure 6.16: Molar fractions (%) of ferric compounds versus Eh at 25°C
Figure 6.17: Molar fractions (%) of total ferric and total ferrous compounds versus pH at 25°C

Figure 6.18: Molar fractions (%) of total ferric and total ferrous compounds versus Eh at 25°C

7. Iron concentration in the copper circuit
The iron equilibrium concentration in the coper circuit depends on: the iron
dissolution rate from the ore and the iron loss in the water balance bleed of copper circuit.
Equation (7.1) gives the value of the iron equilibrium concentration in the copper circuit.
“Cec ” is iron equilibrium concentration (g⁄L), “DR Fe ” is the iron dissolution rate (Kg⁄h) and
“VWBB ” is the flowrate of water balance bleed (m3 ⁄h)
DRFe
Cec = V (7.1)
WBB
The iron equilibrium concentration coming from Equation (7.1) must be less than the
iron saturation concentration (Csc ). The iron saturation concentration is the iron
concentration from which iron starts to precipitate.
7.1. Goethite dissolution mechanism
The iron abundant mineral in the feed is Goethite (FeOOH). In the secondary leach
tanks, iron dissolution rate depends on (J. Torrent at al, 1987 and Konstantin Klyukin et al,
2018): ferric reduction in goethite, solution pH, crystallite size and morphology, crystallinity,
structural defects and substitution of iron by aluminum.
There are two major mechanisms of iron dissolution:
 Acidic dissolution - iron dissolves as ferric ion species:
 The protonation of surface oxygen atoms at acidic pH produces water.

The rate of protonation increases with increasing the acidity of solution
and temperature. The global reaction of protonation is controlled by
the chemical reaction (Ikram Boukerche et al, 2010). The protonation
breaks the Fe-O bond.
 Fe(OH)+2 compound remains on the surface attached to the goethite

structure. The facility of Fe(OH)+2 compound to form strong complexes
with anions (sulfate, sulfite, phosphate and silicate) presented in
solution promoting detachment of ferric compounds into solution
(Ikram Boukerche et al, 2010).
 The chemical reactions (7.a) and (7.b) give the global reactions of
acidic dissolution of goethite. The complexation of Fe+3 into FeH(SO4 )2
and FeSO+ 4 increases the rate of acidic dissolution of goethite.

FeOOH+4H + +2SO−2
4 =FeH(SO4 )2 +2H2 O (at pH<1.6) (7.a)
FeOOH+3H + +SO−2 +
4 =FeSO4 +2H2 O (at pH>1.6) (7.b)
 The conversion of ferric sulfite complex with H2 SO3 produces

dithionate and the conversion of free ferric or other ferric complexes
produces sulfate. The rate of reduction of ferric sulfite complex with
H2 SO3 decreases with increasing the concentration of ferrous in the
solution (P. Warneck, 2018). The rate of the conversion of ferric to
ferrous increases with increasing concentration of copper in the
solution (P. Warneck, 2018). The presence of copper decreases the
formation of dithionate. The rate of reduction of free ferric with
cuprous is 10times greater than the rate of reduction free ferric with
H2 SO3 (P. Warneck, 2018). The reduction of cupric with H2 SO3
produces cuprous.
 The chemical reactions (7.c), (7.d) and (7.e) give the conversion of
ferric to ferrous and the conversion of cupric to cuprous.
FeH(SO4 )2+Cu+ =Fe+2+Cu+2+H + +2SO−2

4 (7.c)
FeSO+ + +2 +2 + −2
4 +Cu =Fe +Cu +H +SO4 (7.d)
2Cu+2 +H2 SO3 +H2 O=2Cu+ +4H + +SO−2

4 (7.e)
 Reductive dissolution – iron dissolves as ferrous ion species: the reduction

dissolution mechanism proposed in the publication is the following.
 Magnetite and/or hematite rich rocks can be moderate to good

electrical conductors. The electrical behavior of magnetite and hematite
is related to factors such as quantity, grainsize and texture and their
electrical response can be considerably enhanced by relatively small
amounts of sulfides, such as chalcopyrite (Lisa Vella et al, 2012).
 Goethite is a good electron acceptor (Aoron Regberg et al, 2011).
 The anodic electrode is located at one face and cathodic electrode is

located at different face; there is a potential gradient between the two
electrodes (Konstantin Klyukin et al, 2018).
 The electron transport between the two electrodes takes place inside of
goethite.

 On the cathodic electrode, there are two simultaneous reactions: the
first reaction is the reduction of ferric ion in the goethite structure and
this process breaks the Fe-O bond. The second reaction is the
protonation of oxygen surface atoms and process breaks the second Fe-
O bond and ferrous ion is released into solution. The global cathodic
electrochemical reaction is given by the reaction (7.f). The cathodic
potential is given by Equation (7.2). “a(FeOOH) ” is the activity of FeOOH
in the goethite and “a(Fe+2 −L) ” is the activity of ferrous ion into solution.
FeOOH + 3H + + e− =Fe+2 + 2H2 O (7.f)
° 2.303∗R∗T a(FeOOH)
E(FeOOH−Fe+2 )=E(FeOOH−Fe+2 ) + *log(a ) (7.2)
F (Fe+2 −L)
 On the anodic electrodes, the first step is the migration of reactants to

the goethite surface and adsorption of the reactants on the goethite
surface. The adsorptions of HSO− 3 and Fe+2 are facilitated by
neutralization process of free electric charge on the goethite surface.
The second step is the reactions of oxidations of sulfite to sulfate
compounds and ferrous to ferric compounds on the surface of goethite
(chemical reactions (7.g), (7.h), and (7.i)) and the electrons are
transferred into the goethite structure. Anodic potentials are given by
Equations (7.3), (7.4) and (7.5).
H2 SO3 +H2 O=SO−2 +

4 +4H +2e
−
(at pH<1.7) (7.g)
HSO− −2 +
3 +H2 O=SO4 +3H +2e
−
(at pH>1.7) (7.h)
Fe+2 =Fe+3 + e− (7.i)
2.303∗R∗T a(SO−2 −L) ∗(a(H+ −L) )4

°
E(SO−2
4 −H2 SO3 )
=E(SO −2 −H SO ) + *log( 4
) (7.3)
4 2 3 2∗F a(H2 SO3 −L)
2.303∗R∗T a(SO−2 −L) ∗(a(H+ −L) )3

°
E(SO−2 − =E
4 −HSO3 ) (SO−2 −HSO− ) + *log( 4
) (7.4)
4 3 2∗F a(HSO− −L)
3
2.303∗R∗T a(Fe+3 −L)

°
E(Fe+3 −Fe+2 )=E(Fe+3 −Fe+2 ) + *log( ) (7.5)
F a(Fe+2 −L)
 The cathodic potential moves to cathodic corrosion potential and the

difference between the two potentials is the cathodic over-potential
(ηc ). Equation (7.6) gives the relationship between cathodic over-
potential and corrosion current density.

corr
ηc =E(FeOOH−Fe+2 ) -E(FeOOH−Fe+2 ) = a c -bc *log(Icorr ) (7.6)
 The anodic potentials move to anodic corrosion potentials and the

difference between the two potentials are the anodic over-potentials
(ηa ). When the anodic reactions are controlled by the electron transfer,
Equations (7.7), (7.8) and (7.9) give the relationship between over-
 The corrosion current density for each anodic reaction must be less the
limit current density. The limit current density is the corrosion current
density when the anodic reaction is controlled by the migration of
reactants to the electrode surface.
 Complexation of Fe+3into FeSO+ 4 or/and FeH(SO4 )2 decreases the

potential of anodic electrode of electrochemical reactions (7.i).
(SO−2
4 −H2 SO3 ) corr (SO−2
4 −H2 SO3 ) (SO−2
4 −H2 SO3 ) (SO−2 −H2 SO3 )
η𝑎 =E(SO−2 −H SO ) -E(SO−2 −H SO ) =a a
2 3 4 2 3
+ba *log(Icorr4 ) (7.7)
4
− − −
(SO−2
4 −HSO3 ) corr (SO−2
4 −HSO3 ) (SO−2
4 −HSO3 ) (SO−2 −HSO−
3)
η𝑎 =E(SO −2 −HSO− ) -E(SO−2 −HSO− ) =a a
4 3
+ba *log(Icorr4 ) (7.8)
4 3
(Fe+3 −Fe+2 ) corr (Fe+3 −Fe+2 ) (Fe+3 −Fe+2 ) (Fe+3 −Fe+2 )

η𝑎 =E(Fe +3 −Fe+2 ) -E(Fe+3 −Fe+2 ) =a a +ba *log(Icorr ) (7.9)
 The difference between the cathodic corrosion potential and the anodic
corrosion potential gives over-potential due to the electrical resistivity
of goethite (Equations (7.10), (7.11) and (7.12)). The electrical
resistivity of goethite depends on the temperature, the thickness
between anode and cathode, the purity of goethite and crystallinity of
goethite structure (the electrical conductivity of amorphous structure
is high).
(SO4 −2 −H SO )
corr corr
E(FeOOH−Fe+2 ) -E(SO−2 −H SO ) =R (goethite) *Icorr
4 2 3
2 3
(7.10)
(SO4 −2 −HSO− )
corr corr
E(FeOOH−Fe+2 ) -E(SO−2 −HSO− ) =R (goethite) *Icorr
4 3
3
(7.11)
(Fe +3 −Fe+2 )
corr corr
E(FeOOH−Fe+2 ) -E(Fe+3 −Fe+2 ) =R (goethite) *Icorr (7.12)
 There are two cases: - the anodic corrosion current densities of sulfite
compounds are restricted by the limit current densities. The diffusion
of sulfite compounds in the pores of goethite is controlling step (R.C.
Hubli et al, 1997). - the anodic corrosion current densities of ferrous

compounds are restricted by value of the electrical conductivity of
goethite. The difference between E(FeOOH−Fe+2 ) and E(Fe+3 −Fe+2 ) called
global over-potential is very low and the value of over-potential due to
the electrical conductivity starts to be close to the global over-potential.
The two cases explain the low goethite reductive dissolution rate.
 Figure (7.1) gives the graphic representation of the reduction

dissolution of goethite with soluble SO2 .
Figure (7.1): Tafel curves of reductive dissolution of goethite with soluble SO2
7.2. Iron loss in the water balance bleed of copper circuit
The water balance bleed of copper circuit is located in the filter cake between the
dewatering zone and the cake wash zone. The flowrate of the water balance bleed depends on
the solid residue flowrate and the moisture of the cake.
7.3. Iron saturation concentration in secondary leach solution
7.3.1. Data
Table (7.1) gives the solid compounds of iron that can precipitate at pH above one and
standard free Gibbs energy of formation of each solid compound at 25°C. The solubility of

FeSO4 . 7H2 O is very high it is why it is not on the list. The free Gibbs energy of formation of
FePO4 and ZnFe2 O4 are calculated by using logk of the chemical reactions (7.j) and (7.ah) and
standard free Gibbs energy from Table (7.2).
FePO4 =Fe+3 + PO−3

4 (7.j)
ZnFe2 O4 +8H + =Zn+2 +2Fe+3+4H2 O (7.k)
Table (7.1): Free Gibbs energy of formation of iron solid compounds at 25°C
Formula ΔG logk Reference

(KJ/mol)
Fe5 (SO4 )6 O(OH). 20H2 O -9899 Bruce S. Hemingway et al
(H3 O)Fe3 (SO4 )2 (OH)6 -3232.3 Giles M. Marion, 2008
Fe8 O8 (OH)6 SO4 . 8H2 O -6040.188 Thermoddem
Fe(OH)3 -708.294 Thermoddem
FePO4 -1154.7 -23.0 I. Takacs et al, 2006
ZnFe4 (PO4 )3 (OH)5 -4799.048 Thermoddem
MgFe2 O4 -1326.602 Thermoddem
MnFe2 O4 -1121.825 Thermoddem
ZnFe2 O4 -1048.75 9.85 Thomas J. Schroder, 2008
CuFe2 O4 -863.24 U.S. Department of Energy, 2004
CoFe2 O4 -980.455 U.S. Department of Energy, 2004
CaFe2 O4 -1412.731 U.S. Department of Energy, 2004
CuFeO2 -388.21 APV: Stoffbewertung, 2009
+2 Bruce S. Hemingway et al
Fe Fe4 (SO4 )6 (OH)2 . 20H2 O -9971
Fe+2 Fe2 O2 (OH)4 -1447.92 Thermoddem
(Fe+2 )6 Fe2 (OH)16 SO3 . 4H2 O -5465 Thermoddem
(Fe+2 )4 Fe2 (OH)12 SO4 . 2H2 O -4244.67 Thermoddem
Fe+2 Fe2 (SO4 )4 . 14H2 O -6486 Bruce S. Hemingway et al
Fe+2 Fe2 O4 -1015.46 John A. Dean, 1979.
Fe+2 Al2 (SO4 )4 . 22H2 O -9306.07 Thermoddem
Fe+2 Al2 O4 -1879.669 U.S. Department of Energy, 2004
(Fe+2 )2 SiO4 -1379.05 John A. Dean, 1979.
Fe+2 (OH)2 -486.975 U.S. Department of Energy, 2004
Fe+2, Co+2 , Cu+2 , Mn+2, Zn+2, Al+3 , H + , SO4 −2 , PO4 −3 , SO3 −2 and H4 SiO4 are taken as
reference soluble compounds. The chemical reactions from (5.c) to (5.y) give the precipitation
reactions of iron solid substances.
Fe5 (SO4 )6 O(OH). 20H2 O + 3H + + 5e− =5Fe+2 + 6SO4−2 + 22H2 O (7.l)
(H3 O)Fe3 (SO4 )2 (OH)6 + 5H + +3e− =3Fe+2 + 2SO−2

4 + 7H2 O (7.m)
Fe8 O8 (OH)6 SO4 . 8H2 O + 22H + + 8e− =8Fe+2 +SO−2

4 + 22H2 O (7.n)

Table (7.2): Standard free Gibbs energy of reference soluble compounds at 25°C
Soluble compounds ΔG (KJ/mol) Reference

H2O -237.129 NBS, Wagman et al, 1982
SO−2
4 -744.53 NBS, Wagman et al, 1982
PO−3
4 -1018.70 NBS, Wagman et al, 1982
−2
SO3 -486.6 NBS, Wagman et al, 1982
H4 SiO4 -1316.60 NBS, Wagman et al, 1982
Fe+2 -78.9 NBS, Wagman et al, 1982
Fe+3 -4.7 NBS, Wagman et al, 1982
Ca+2 -553.58 NBS, Wagman et al, 1982
Mg +2 -454.80 NBS, Wagman et al, 1982
Al+3 -485.00 NBS, Wagman et al, 1982
Zn+2 -147.06 NBS, Wagman et al, 1982
Mn+2 -228.1 NBS, Wagman et al, 1982
Co+2 -54.4 NBS, Wagman et al, 1982
Cu+2 65.49 NBS, Wagman et al, 1982
Cu+ 49.98 NBS, Wagman et al, 1982
Fe(OH)3 + 3H + + e− =Fe+2 + 3H2 O (7.o)
FePO4 +e− =Fe+2 + PO4−3 (7.p)
ZnFe4 (PO4 )3 (OH)5 +5H + + 4e− =4Fe+2 +Zn+2 + 3PO−3

4 + 5H2 O (7.q)
MnFe2 O4 + 8H + + 2e− =Mn+2+2Fe+2 + 4H2 O (7.r)
ZnFe2 O4 + 8H + + 2e− =Zn+2+2Fe+2 + 4H2 O (7.s)
CuFe2 O4 + 8H + + 2e− =Cu+2+2Fe+2 + 4H2 O (7.t)
CoFe2 O4 + 8H + + 2e− =Co+2+2Fe+2 + 4H2 O (7.u)
CaFe2 O4 + 8H + + 2e− =Ca+2 +2Fe+2 + 4H2 O (7.v)
CuFeO2 + 4H + =Cu+2 +Fe+2 + 2H2 O (7.w)
MgFe2 O4 + 8H + + 2e− =Mg +2 +2Fe+2 + 4H2 O (7.x)
Fe+2 Fe4 (SO4 )6 (OH)2 . 20H2 O + 2H + + 4e− =5Fe+2 + 6SO4−2 + 22H2 O (7.y)
Fe+2 Fe2 O2 (OH)4+ 8H + + 2e− =3Fe+2 + 6H2 O (7.z)
(Fe+2 )6 Fe2 (OH)16 SO3 . 4H2 O+ 16H + + 2e− =8Fe+2 + SO−2

3 + 20H2 O (7.aa)

(Fe+2 )4 Fe2 (OH)12 SO4 . 2H2 O + 12H + + 2e− =6Fe+2 + SO−2
4 + 14H2 O (7.ab)
Fe+2 Fe2 (SO4 )4 . 14H2 O + 2e− =3Fe+2 + 4SO−2

4 + 14H2 O (7.ac)
Fe+2 Fe2 O4+ 8H + + 2e− =3Fe+2 + 4H2 O (7.ad)
Fe+2 Al2 (SO4 )4 . 22H2 O =Fe+2 + 2Al+3 + 4SO−2

4 + 22H2 O (7.ae)
Fe+2 Al2 O4 + 8H + =Fe+2+2Al+3 + 4H2 O (7.af)
(Fe+2 )2 SiO4 + 4H + =2Fe+2 + H4 SiO4 (7.ag)
Fe+2 (OH)2 + 2H + =Fe+2 + 2H2 O (7.ah)
7.3.2. Pure phases
The designation of iron saturation concentration of each solid compound is the

following:
The iron saturation of Fe5 (SO4 )6 O(OH). 20H2 O is mSFe1 ,

The iron saturation of (H3 O)Fe3 (SO4 )2 (OH)6 is mSFe2 ,
The iron saturation of Fe8 O8 (OH)6 SO4 . 8H2 O is mSFe3 ,
The iron saturation of Fe(OH)3 is mSFe4 ,
The iron saturation of FePO4 is mSFe5 ,
The iron saturation of ZnFe4 (PO4 )3 (OH)5 is mSFe6 ,
The iron saturation of MgFe2 O4 is mSFe7 ,
The iron saturation of MnFe2 O4 is mSFe8 ,
The iron saturation of ZnFe2 O4 is mSFe9 ,
The iron saturation of CuFe2 O4 is mSFe10 ,
The iron saturation of CoFe2 O4 is mSFe11 ,
The iron saturation of CaFe2 O4 is mSFe12 ,
The iron saturation of CuFeO2 is mSFe13 ,
The iron saturation of Fe+2 Fe4 (SO4 )6 (OH)2 . 20H2 O is mSFe14 ,
The iron saturation of Fe+2 Fe2 O2 (OH)4 is mSFe15 ,
The iron saturation of (Fe+2 )6 Fe2 (OH)16 SO3 . 4H2 O is mSFe16 ,
The iron saturation of (Fe+2 )4 Fe2 (OH)12 SO4 . 2H2 O is mSFe17 ,
The iron saturation of Fe+2 Fe2 (SO4 )4 . 14H2 O is mSFe18 ,
The iron saturation of Fe+2 Fe2 O4 is mSFe19 ,
The iron saturation of Fe+2 Al2 (SO4 )4 . 22H2 O is mSFe20 ,
The iron saturation of Fe+2 Al2 O4 is mSFe21 ,
The iron saturation of (Fe+2 )2 SiO4 is mSFe22 ,
The iron saturation of Fe+2 (OH)2 is mSFe23 ,
The designation of standard chemical potential at 25°C of each solid is the following:
The standard chemical potential of Fe5 (SO4 )6 O(OH). 20H2 O is μO Fe1 ,

O
The standard chemical potential of (H3 O)Fe3 (SO4 )2 (OH)6 is μFe2 ,
The standard chemical potential of Fe8 O8 (OH)6 SO4 . 8H2 O is μO Fe3 ,
O
The standard chemical potential of Fe(OH)3 is μFe4 ,
The standard chemical potential of FePO4 is μO Fe5 ,
The standard chemical potential of ZnFe4 (PO4 )3 (OH)5 is μO Fe6 ,
O
The standard chemical potential of MgFe2 O4 is μFe7 ,
The standard chemical potential of MnFe2 O4 is μO Fe8 ,
O
The standard chemical potential of ZnFe2 O4 is μFe9 ,
The standard chemical potential of CuFe2 O4 is μOFe10 ,
O
The standard chemical potential of CoFe2 O4 is μFe11 ,
The standard chemical potential of CaFe2 O4 is μO Fe12 ,
The standard chemical potential of CuFeO2 is μO Fe13 ,
The standard chemical potential of Fe Fe4 (SO4 )6 (OH)2 . 20H2 O is μO
+2
Fe14 ,
+2 O
The standard chemical potential of Fe Fe2 O2 (OH)4 is μFe15 ,
The standard chemical potential of (Fe+2 )6 Fe2 (OH)16 SO3 . 4H2 O is μO Fe16 ,
The standard chemical potential of (Fe )4 Fe2 (OH)12 SO4 . 2H2 O is μO
+2
Fe17 ,
+2 O
The standard chemical potential of Fe Fe2 (SO4 )4 . 14H2 O is μFe18 ,
The standard chemical potential of Fe+2 Fe2 O4 is μO Fe19 ,
The standard chemical potential of Fe Al2 (SO4 )4 . 22H2 O is μO
+2
Fe20 ,
+2 O
The standard chemical potential of Fe Al2 O4 is μFe21 ,
The standard chemical potential of (Fe+2 )2 SiO4 is μO Fe22 ,
+2 O
The standard chemical potential of Fe (OH)2 is μFe23 ,
The geochemical modelling developed in chapter (6) for Sulfate-Phosphate-Silicate-

Sulfite-Ca-Mg-Al-Zn-Mn-Cu-Co-Fe-Water system remains the same. Only the Fe+2 saturation
concentration (mSFeM ) is minimum value of Fe+2saturation concentration of iron solid
compounds. The Fe+2 saturation concentrations are given by Equations from (7.13) to (7.35)
that are coming from equilibrium conditions of chemical reactions from (7.j) to (7.ah).
2.303*5*R*T*log(mSFe1 *γ2 )= μO
Fe1 +3μ(H+ ) -5*F*E-6μ(SO−2
4 )
-22μ(H2 O) -5μO
(Fe+2 ) (7.13)
2.303*3*R*T*log(mSFe2 *γ2 )= μO
Fe2 +5μ(H+ ) -3*F*E-2μ(SO−2 4 )
-7μ(H2 O) -3μO(Fe+2 ) (7.14)
2.303*8*R*T*log(mSFe3 *γ2 )= μO
Fe3 +22μ(H+ ) -8*F*E-μ(SO−2 4 )
-22μ(H2 O) -8μO (Fe+2 ) (7.15)
O
2.303*R*T*log(mSFe4 *γ2 )= μO
Fe4 +3μ(H+ ) -F*E-3μ(H2 O) -μ(Fe+2 ) (7.16)
Fe5 -F*E-μ(PO−3
4 )
-μO
(Fe+2 ) (7.17)
2.303*4*R*T*log(mSFe6 *γ2 )= μO
Fe6 +5μ(H+ ) -4*F*E-3μ(PO−3 4 )
-μ(Zn+2 ) -5μ(H2 O) -4μO(Fe+2 ) (7.18)

O
2.303*2*R*T*log(mSFe7 *γ2 )= μO
Fe7 +8μ(H+ ) -2*F*E-μ(Mg+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.19)
O
2.303*2*R*T*log(mSFe8 *γ2 )= μO
Fe8 +8μ(H+ ) -2*F*E-μ(Mn+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.20)
O
2.303*2*R*T*log(mSFe9 *γ2 )= μO
Fe9 +8μ(H+ ) -2*F*E-μ(Zn+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.21)
O
2.303*2*R*T*log(mSFe10 *γ2 )= μO
Fe10 +8μ(H+ ) -2*F*E-μ(Cu+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.22)
O
2.303*2*R*T*log(mSFe11 *γ2 )= μO
Fe11 +8μ(H+ ) -2*F*E-μ(Co+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.23)
O
2.303*2*R*T*log(mSFe12 *γ2 )= μO
Fe12 +8μ(H+ ) -2*F*E-μ(Ca+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.24)
O
2.303*2*R*T*log(mSFe13 *γ2 )= μO
Fe13 +4μ(H+ ) -μ(Cu+2 ) -2μ(H2 O) -μ(Fe+2 ) (7.25)
2.303*5*R*T*log(mSFe14 *γ2 )= μO
Fe14 +2μ(H+ ) -4*F*E-6μ(SO−2 4 )
-22μ(H2 O) -5μO(Fe+2 ) (7.26)
O
2.303*3*R*T*log(mSFe15 *γ2 )= μO
Fe15 +8μ(H+ ) -2*F*E-6μ(H2 O) -3μ(Fe+2 ) (7.27)
2.303*8*R*T*log(mSFe16 *γ2 )= μO
Fe16 +16μ(H+ ) -2*F*E-μ(SO−2 3 )
-20μ(H2 O) -8μO(Fe+2 ) (7.28)
S O
2.303*6*R*T*log(mFe17 *γ2 )= μFe17 +12μ(H+) -2*F*E-μ(SO−2 4 )
-14μ(H2 O) -6μO(Fe+2 ) (7.29)
O
2.303*3*R*T*log(mSFe18 *γ2 )= μO
Fe18 -2*F*E-4μ(SO−2 4 )
-14μ(H2 O) -3μ(Fe+2 ) (7.30)
O
2.303*3*R*T*log(mSFe19 *γ2 )= μO
Fe19 +8μ(H+ ) -2*F*E-4μ(H2 O) -2μ(Fe+2 ) (7.31)
Fe21 +2μ(Al+3 ) -4μ(SO−2
4 )
-22μ(H2 O) -μO(Fe+2 ) (7.32)
O
Fe22 +2μ(Al+3 ) -4μ(H2 O) -μ(Fe+2 ) (7.33)
O
2.303*2*R*T*log(mSFe22 *γ2 )= μO
Fe23 +4μ(H+ ) -μ(H4 SiO4 ) -2μ(Fe+2 ) (7.34)
O
Fe24 +2μ(H+ ) -2μ(H2 O) -μ(Fe+2 ) (7.35)
The chemical potentials of Co+2 , Cu+2, Mn+2, Zn+2, Al+3, H + , SO4 −2 , PO4 −3, SO3 −2 and
H4 SiO4 are given respectively by Equation from (7.36) to (7.45).
μ(Co+2 ) =μO
(Co+2 ) +2.303*R*T*log(mCo1 *γ2 ) (7.36)
μ(Cu+2 )=μO
(Cu+2 ) +2.303*R*T*log(mCu1 *γ2 ) (7.37)
μ(Mn+2 ) =μO
(Mn+2 ) +2.303*R*T*log(mMn1 *γ2 ) (7.38)
μ(Zn+2 ) =μO(Zn+2 ) +2.303*R*T*log(mZn1 *γ2 ) (7.39)
μ(Al+3 ) =μO
(Al+3 ) +2.303*R*T*log(mAl1 *γ3 ) (7.40)
μ(H+ ) =2.303*R*T*log(mH1 *γ1 ) (7.41)
μ(SO−2
4 )
=μO
(SO−2 +2.303*R*T*log(mSa1 *γ2 ) (7.42)
4 )
μ(PO−3
4 )
=μO
(PO−3 +2.303*R*T*log(mP1 *γ3 ) (7.43)
4 )
μ(SO3 −2 ) =μO
(SO −2
)
+2.303*R*T*log(mSi1 *γ2 ) (7.44)
3
μ(H4 SiO4 )=μO

(H4 SiO4 ) +2.303*R*T*log(mSc1 ) (7.45)
The total saturation concentration of iron (FeST ) is given by equation (7.46). Figure
(7.2) shows the total iron concentration in the secondary leach solution from pilot plant and
from modelling.

FeST =mSFeM +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +mFe10 +mFe11 +
mFe12 +mFe13 +mFe14 +2*mFe15 +3*mFe16 +mFe18 +mFe19 +mFe20 +mFe21 +
mFe22 +mFe23 ++mFe24 +mFe25 +mFe26 (7.46)
The types of iron solid compounds that precipitate are the following:
Fe5 (SO4 )6 O(OH). 20H2 O (Ferricopiapite) on July-20 where the redox potential (Eh) is 0.668V
, Fe8 O8 (OH)6 SO4 . 8H2 O (Schwertmannite) on July-9 and July-15 where pH are respectively
1.96 and 2.04 and Fe+2 Fe4 (SO4 )6 (OH)2 . 20H2 O (Copiapite) on the remaining dates.
Figure 7.2: Total iron concentration in the secondary leach solution from pilot and modelling
versus date
Figure (7.3) shows the total iron concentration in the secondary leach solution from
pilot plant and from modelling versus pH where the range of Eh 0.57V - 0.58V (industrial Eh
range). Figure (7.4) shows the total iron concentration in the secondary leach solution from
pilot plant and modelling versus Eh where the range of pH 1.35 -1.65.

versus pH (Eh 0.57-0.58V)
versus Eh(v) (pH 1.35-1.65)

7.3.3. Mixed phases
Iron solid compounds are the mixed precipitates localized in the transition zone. The
designation of iron saturation concentration of each solid compound remains the same. The
designation of standard chemical potential at 25°C of each solid remains the same. The
designation of molar fraction of solid compounds is the following:
The standard chemical potential of Fe5 (SO4 )6 O(OH). 20H2 O is X1 ,

The standard chemical potential of (H3 O)Fe3 (SO4 )2 (OH)6 is X2 ,
The standard chemical potential of Fe8 O8 (OH)6 SO4 . 8H2 O is X3 ,
The standard chemical potential of Fe(OH)3 is X 4 ,
The standard chemical potential of FePO4 is X5 ,
The standard chemical potential of ZnFe4 (PO4 )3 (OH)5 is X6 ,
The standard chemical potential of MgFe2 O4 is X7 ,
The standard chemical potential of MnFe2 O4 is X8 ,
The standard chemical potential of ZnFe2 O4 is X 9 ,
The standard chemical potential of CuFe2 O4 is X10 ,
The standard chemical potential of CoFe2 O4 is X11 ,
The standard chemical potential of CaFe2 O4 is X12 ,
The standard chemical potential of CuFeO2 is X13 ,
The standard chemical potential of Fe+2 Fe4 (SO4 )6 (OH)2 . 20H2 O is X14 ,
The standard chemical potential of Fe+2 Fe2 O2 (OH)4 is X15 ,
The standard chemical potential of (Fe+2 )6 Fe2 (OH)16 SO3 . 4H2 O is X16 ,
The standard chemical potential of (Fe+2 )4 Fe2 (OH)12 SO4 . 2H2 O is X17 ,
The standard chemical potential of Fe+2 Fe2 (SO4 )4 . 14H2 O is X18 ,
The standard chemical potential of Fe+2 Fe2 O4 is X19 ,
The standard chemical potential of Fe+2 Al2 (SO4 )4 . 22H2 O is X20 ,
The standard chemical potential of Fe+2 Al2 O4 is X21 ,
The standard chemical potential of (Fe+2 )2 SiO4 is X22 ,
The standard chemical potential of Fe+2 (OH)2 is X23 ,
The chemical potentials of solid compounds are given by general Equation (7.47).
Equation (7.48) gives the constraint on the molar fractions.
μFen =μO
Fen + 8.314*298.15*2.303log(X n ) (7.47)
1=∑23
1 Xn (7.48)
The geochemical modelling developed in chapter (6) for Sulfate-Phosphate-Silicate-

Sulfite-Ca-Mg-Al-Zn-Mn-Cu-Co-Fe-Water system remains the same. Only the Fe+2 saturation
concentration (mSFe ) is changed. The Fe+2 saturation concentrations are given by Equations
from (7.49) to (7.72) that are coming from equilibrium conditions of chemical reactions from
(7.j) to (7.ah).
2.303*5*R*T*log(mSFe1 *γ2 )=μFe1 +3μ(H+) -5*F*E-6μ(SO−2
4 )
-22μ(H2 O) -5μO
(Fe+2 ) (7.49)
2.303*3*R*T*log(mSFe2 *γ2 )= μFe2 +5μ(H+) -3*F*E-2μ(SO−2
4 )
-7μ(H2 O) -3μO
(Fe+2 ) (7.50)
2.303*8*R*T*log(mSFe3 *γ2 )= μFe3 +22μ(H+ ) -8*F*E-μ(SO−2
4 )
-22μ(H2 O) -8μO
(Fe+2 ) (7.51)
2.303*R*T*log(mSFe4 *γ2 )= μFe4 +3μ(H+) -F*E-3μ(H2 O) -μO
(Fe+2 ) (7.52)
2.303*R*T*log(mSFe5 *γ2 )= μFe5 -F*E-μ(PO−3
4 )
-μO
(Fe+2 ) (7.53)
2.303*4*R*T*log(mSFe6 *γ2 )= μFe6 +5μ(H+) -4*F*E-3μ(PO−3 4 )
-μ(Zn+2 ) -5μ(H2 O) -4μO(Fe+2 ) (7.54)
2.303*2*R*T*log(mSFe7 *γ2 )= μFe7 +8μ(H+) -2*F*E-μ(Mg+2 ) -4μ(H2 O) -2μO (Fe+2 ) (7.55)
2.303*2*R*T*log(mSFe8 *γ2 )= μFe8 +8μ(H+) -2*F*E-μ(Mn+2 ) -4μ(H2 O) -2μO (Fe+2 ) (7.56)
2.303*2*R*T*log(mSFe9 *γ2 )= μFe9 +8μ(H+) -2*F*E-μ(Zn+2 ) -4μ(H2 O) -2μO (Fe+2 ) (7.57)
2.303*2*R*T*log(mSFe10 *γ2 )= μFe10 +8μ(H+) -2*F*E-μ(Cu+2 ) -4μ(H2 O) -2μO (Fe+2 ) (7.58)
S O
2.303*2*R*T*log(mFe11 *γ2 )= μFe11 +8μ(H+) -2*F*E-μ(Co+2 ) -4μ(H2 O) -2μ(Fe+2 ) (7.59)
2.303*2*R*T*log(mSFe12 *γ2 )= μFe12 +8μ(H+) -2*F*E-μ(Ca+2 ) -4μ(H2 O) -2μO (Fe+2 ) (7.60)
2.303*2*R*T*log(mSFe13 *γ2 )= μFe13 +4μ(H+) -μ(Cu+2 ) -2μ(H2 O) -μO (Fe+2 ) (7.61)
2.303*5*R*T*log(mSFe14 *γ2 )= μFe14 +2μ(H+) -4*F*E-6μ(SO−2 4 )
-22μ(H2 O) -5μO (Fe+2 ) (7.62)
2.303*3*R*T*log(mSFe15 *γ2 )= μFe15 +8μ(H+) -2*F*E-6μ(H2 O) -3μO (Fe+2 ) (7.63)
S
-20μ(H2 O) -8μO (Fe+2 ) (7.64)
S
-14μ(H2 O) -6μO (Fe+2 ) (7.65)
O
2.303*3*R*T*log(mSFe18 *γ2 )= μFe18 -2*F*E-4μ(SO−2 4 )
-14μ(H2 O) -3μ(Fe+2 ) (7.66)
2.303*3*R*T*log(mSFe19 *γ2 )= μFe19 +8μ(H+) -2*F*E-4μ(H2 O) -2μO (Fe+2 ) (7.68)
2.303*R*T*log(mSFe20 *γ2 )= μFe20 +2μ(Al+3 ) -4μ(SO−2
4 )
-22μ(H2 O) -μO (Fe+2 ) (7.69)
2.303*R*T*log(mSFe21 *γ2 )= μFe21 +2μ(Al+3 ) -4μ(H2 O) -μO(Fe+2 ) (7.70)
2.303*2*R*T*log(mFe22 *γ2 )= μFe22 +4μ(H+) -μ(H4 SiO4) -2μO
S
(Fe+2 ) (7.71)
S O
2.303*R*T*log(mFe23 *γ2 )= μFe23 +2μ(H+) -2μ(H2 O) -μ(Fe+2 ) (7.72)
At equilibrium the value of iron saturation concentration (mSFe ) is fixed by this

constraint (Equation 7.73). This constraint fixes also the value of molar fraction of each solid
in the iron precipitate.
mSFe =mSFe1 =mSFe2 =mSFe3 =mSFe4 =mSFe5 =mSFe6 =mSFe7 =mSFe8 =mSFe9 =mSFe10 =mSFe11 =mSFe12 =
mSFe13 =mSFe14 =mSFe15 =mSFe16 =mSFe17 =mSFe18 =mSFe19 =mSFe20 =mSFe21 =mSFe22 =mSFe23 (7.74)
The chemical potentials of Co+2 , Cu+2, Mn+2, Zn+2, Al+3, H + , SO4 −2 , PO4 −3, SO3 −2 and
H4 SiO4 are given respectively by Equation from (7.36) to (7.45). The total saturation
concentration of iron (FeST ) is given by equation (7.46).

Figure (7.5) shows the total iron concentration in the secondary leach solution from
pilot plant and from modelling for each date. Figure (7.6) shows the total iron concentration
in the secondary leach solution from pilot plant and from modelling versus pH where the
range of Eh 0.57V - 0.58V (industrial Eh range). Figure (7.7) shows the total iron
concentration in the secondary leach solution from pilot plant and from modelling versus Eh
where the range of pH 1.35-1.65 (industrial Eh range). Figures (7.8) and (7.9) give the molar
fractions of solid compounds versus date.
The general formula of iron solid compound that can precipitate from pilot plant
solution is (Fe+2 )a Feb (SO4 )c (PO4 )d Oe (OH)f (H2 O)g . Figures (7.10) and (7.11) give the values
of constants a, b, c, d, e, f, and g versus date. The average general formula during the
commissioning period of the pilot plant is the following:
(Fe+2 )0.876 Fe4.174 (SO4 )5.781 (PO4 )0.006 O0.330 (OH)2.035 (H2 O)19.414
versus date

versus pH (Eh 0.57-0.58V)
versus Eh (pH 1.35-1.65)

Figure 7.8: Molar fractions of solid compounds versus date
Figure 7.9: Molar fractions of solid compounds versus date

Figure 7.10 : Values of constans versus date
Figure 7.11 : Values of constans versus date

7.3.4. Observations
The observations shows that :
 The total concentration of iron in the secondary leach solution of pilot plant is
near of the iron saturation concentration.
 The iron saturation concentration decreases from 2 to 1 g/kg water when pH
increases from 1.3 to 1.9 in the range of Eh 0.57 -0.58V (industrial range.
 The iron saturation concentration decreases from 2.5 to 0.25 g/kg water when
Eh increases from 0.56 to 0.64v in the range of pH 1.35-1.65.
 The iron can precipitate as Fe+2 Fe4 (SO4 )6 (OH)2 . 20H2 O (Copiapite) in the
range of pH 1.35-1.65 and in the range of Eh 0.57 -0.58V.

8. Loss of copper and cobalt in iron precipitates during
leaching
The iron concentration in le leach solution of copper and cobalt using open leach tanks
in the ranges of pH 1.4-1.8 and Eh 0.56 – 0.58V is near of iron saturation level. In consequence
there are two kinds of phemena that can cause the precipitation of iron during leaching of
copper and cobalt ores:
 first – the dissolution rate of iron and the loss of iron in the water balance bleed
give the iron concentration in the copper circuit less than the saturation
concentration; small variations of pH and Eh can cause the iron precipitation
during leaching. (Figure 8.1 – periods from July 6 to July 10, from July 14 to July
24 and from August 5 to August 10)
 Secend – the dissolution rate of iron and the los of iron in the water balance
bleed give the iron concentration in the copper circuit greater than the iron
saturation concentration. Iron will continuously precipitate during leaching.
(Figure 8.1 – period from August 19 to August 23)
Figure 8.1: Iron concentration in the leach solution versus date
In the ranges of pH 1.2-2.0 and Eh 0.56-0.58V, iron precipitates as coppiapite. The

copiapite group is a group of sulfates with mixed divalent-trivalent metal ions in the
composition with the formula AR 2 (SO4 )6 (OH)2 . 20H2 O where “A”(divalent metal ions)= Mg,
Fe, Mn, Co or Zn and “R”(trivalent metal ions)=Al, Fe or Cr (Jesica Murray, 2014). This means
that there is either the substitution of iron (II) by copper or cobalt in the copiapite or the co-

precipitation of cuprocopiapite and cobatocopiapite when iron precipitates during leaching.
Figure 8.2 shows the increase of copper grade in the leach residue on the period from July 14
to July 24. This increase can be due to the co-precipitation of copper and iron because the
average of pH is around 1.7 that can justified a good conditions of copper leaching. The
increase in cobalt grade in the residue can be due to the co-precipitation of cobalt and iron
and the bad conditions of cobalt leaching (Eh increases).
Figure 8.2: Copper and cobalt grade in leach residue versus date

9. Dissolution of cobalt (III)
9.1. Dissolution of cobalt (III) with SO2
It has been observed that Cobalt (III) reacts with sulfite species in absence of iron (R.C.
Hubli et al, 1997). The studies on the kinetic model of the dissolution of cobalt (III) are carried
out when soluble SO2 is used as the reducing reagents. By using the mathematical modelling
of the shrinking core model; the studies show that the kinetic model of the dissolution of
cobalt (III) is the shrinking core model and the rate controlling step is the diffusion of the
reducing reagent in the unreacted core. The rate of the dissolution of cobalt (III) increases
with increasing the concentration of sulfite species up to 0.025M.
9.2. Dissolution of cobalt (III) with ferrous
It has been observed that Cobalt (III) reacts with ferrous species in absence of sulfite
species (M. Rajaie et al, 2015).
9.3. Dissolution of cobalt (III) with ferrous and SO2
9.3.1. Materials and experimental methods
The sample of copper-cobalt ore other than pilot plant feed is collected from an
exploration site in Haut-Katanga province of the Democratic Republic of Congo. The sample of
copper-cobalt ore is pulverized to 80% passing 150 micron. Cobalt grade of the sample is
0.6%. Batch agitation leaching tests are performed using a 3 L glass reactor in which 1.0 kg of
the sample, pulped with synthetic raffinate solution at 20% (w/w), was continuously agitated
by means of an overhead stirrer. The stirrer speed is set so that adequate suspension of the
solids is achieved throughout each experiment. The synthetic raffinate contained 15 g/L of
sulfuric acid and desired concentration of ferrous. The pH and the Eh of slurry are monitored
and controlled continuously using a standard pH probe and Eh probe (Ag/AgCl). Each solid
sample is analyzed for cobalt. Samples are taken after 1, 2, 3, 4, 5 and 6 hours. These samples
are immediately filtered and washed with water. The solids are analyzed for cobalt.

9.3.2. Results and discussion
The batch leaching test is conducted (pH of 1.5, the redox potential of 350 mV
(Ag/AgCl), ambient temperature and leach time of 6 hours). In the reactor of the batch leach
test, Na2S2O5 is used to maintain the redox potential value. The ferrous concentration in the
synthetic raffinate is varied from 0.5 to 3 g/L by adding ferrous sulfate. Figure (9.1) gives
grade of cobalt in the leach residue versus leach residence time.
Figure 9.1: Co grade in the leach residue versus leach residence time (pH 1.5,
temperature 25°C and redox potential 350 mV (Ag/AgCl) at different iron
concentration in solution
The results show that the grade of cobalt in the leach residue decreases with increasing
of the leaching residence time. Below cobalt grade in the leach residue of 0.053%; the rate of
the dissolution of cobalt is negligible (iron concentration of 2.5 and 3g/L). The rate of the
dissolution of cobalt increases with increasing iron concentration in the leach solution.
The main minerals of cobalt in the copper –cobalt ore from Democratic Republic of
Congo are: Heterogenite (CoOOH) and Kolwezite ((Cu, Co)2 CO3 (OH)2). The rate of the
dissolution of Kolwezite is fast like that of Malachite. Malachite leaching is taken to
completion in less than one hour (S.Y Seo et al, 2013). In the leach test, it assumes that the
cobalt that is remained in the leach residue after one hour is in form of Cobalt (III).

All kinetic models (Table 4.1) are plotted as a function of time (from the first hour of
leach residence time) for the experimental data. The plot gives a linear correlation for the first
order kinetic model (-ln(1-α)). Figure (9.2) gives the graph of the first order kinetic model.
Figure 9.2: Kinetic model (No. 1) versus time for experimental data at different values
of iron concentration (g/L) in solution
Kinetic model obtained when soluble SO2 is used alone as reducing reagent was the
shrinking core model. This means that dissolution of cobalt (III) is controlled by iron even
with low concentration during the leaching of copper-cobalt ore in the open tank in these
leach conditions. Soluble SO2 reduces ferric compounds to ferrous compounds. This means
that Iron is the catalyst of cobalt (III) dissolution with soluble SO2.
9.4. Mechanisms of cobalt (III) dissolution
In the secondary leach tanks, cobalt (III) dissolution rate depends on: cobalt (III)
reduction in Heterogenite, solution pH, distribution size and temperature.
There are two major mechanisms of cobalt (III) dissolution:
 Acidic dissolution - cobalt dissolves as cobaltic ion species:
 The protonation of surface oxygen atoms at acidic pH produces water.

The rate of protonation increases with increasing the acidity of solution
and temperature. The global reaction of protonation is controlled by
the chemical reaction (Ikram Boukerche et al, 2010). The protonation
breaks the Fe-O bond.
 Co(OH)+2 compound remains on the surface attached to the
heterogenite structure. The facility of Co(OH)+2 compound to form
strong complexes with anions (sulfate, sulfite, phosphate and silicate)
presented in solution promoting detachment of cobaltic compounds
into solution (Ikram Boukerche et al, 2010 and E. A. Yakusheva et al,
2012).
 The chemical reaction (9.a) gives the global reaction of acidic

dissolution of heterogenite.
CoOOH+2H + =Co(OH)+2+H2 O (9.a)
 The chemical reactions (9.b), (9.c), (9.d), (9.e) and (9.f) give the
conversion of cobaltic to cobaltous.
Co(OH)+2+Fe+2+2H + +2SO−2 +2
4 =FeH(SO4 )2 +Co + H2 O (9.b)
Co(OH)+2+Fe+2+H + +SO−2 + +2
4 =FeSO4 +Co + H2 O (9.c)
2Co(OH)+2+H3 SO3 =2Co+2+SO−2 +

4 +2H + H2 O (9.d)
2Co(OH)+2+HSO− +2 −2 +
3 =2Co +SO4 +H + H2 O (9.e)
Co(OH)+2+Cu+ +H + =Cu+2+Co+2 + H2 O (9.f)
 Reductive dissolution – cobalt dissolves as cobaltous ion species: the reduction

dissolution mechanism proposed in the publication is the following.
 Co3 O4 and CoOOH rich rocks are good electrical conductors. (Jian Wen
Wang et al, 2013).
 As in the case of goethite, the anodic electrode is located at one face and
cathodic electrode is located at different face; there is a potential
gradient between the two electrodes.
 The electron transport between the two electrodes takes place inside of
heterogenite.
 On the cathodic electrode, there are two simultaneous reactions: the

first reaction is the reduction of cobaltic ion in the heterogenite
structure and this process breaks the Co-O bond. The second reaction is
the protonation of oxygen surface atoms and process breaks the second

Co-O bond and cobalt ion is released into solution. The global cathodic
electrochemical reaction is given by the reaction (9.g). The cathodic
potential is given by Equation (9.1). “a(CoOOH) ” is the activity of CoOOH
in the heterogenite and “a(Co+2 −L) ” is the activity of cobaltous ion into
solution.
CoOOH + 3H + + e− =Co+2 + 2H2 O (9.g)
° 2.303∗R∗T a(CoOOH)
E(CoOOH−Co+2 )=E(CoOOH−Co+2 ) + *log(a ) (9.1)
F (Co+2 −L)
 On the anodic electrodes, the first step is the migration of reactants to

the heterogenite surface and adsorption of the reactants on the
heterogenite surface. The adsorptions of HSO− 3 and Fe
+2
are facilitated
by neutralization process of free electric charge on the heterogenite
surface. The second step is the reactions of oxidations of sulfite to
sulfate compounds and ferrous to ferric compounds on the surface of
Heterogenite and the electrons are transferred into the Heterogenite
structure. The main reaction is the oxidation of ferrous to ferric (9.i)
the anodic reactions of sulfite compounds are restricted by the
diffusion of sulfite compounds in the pores of heterogenite (R.C. Hubli
et al, 1997). Anodic potential is given by Equations (9.2).
Fe+2 =Fe+3 + e− (9.i)
2.303∗R∗T a +3 −L)
°
E(Fe+3 −Fe+2 )=E(Fe+3 −Fe+2 ) + *log(a(Fe ) (9.2)
F (Fe+2 −L)
 The cathodic potential moves to cathodic corrosion potential and the

difference between the two potentials is the cathodic over-potential
(ηc ). Equation (9.3) gives the relationship between cathodic over-
corr
ηc =E(CoOOH−Co +2 ) -E(CoOOH−Co+2 ) = a c -bc *log(Icorr ) (9.3)
 The anodic potentials move to anodic corrosion potentials and the

difference between the two potentials are the anodic over-potentials
(ηa ). when the anodic reactions are controlled by the electron transfer,
Equation (9.4) gives the relationship between over-potential and
corrosion current density.
(Fe+3 −Fe+2 ) corr (Fe+3 −Fe+2 ) (Fe+3 −Fe+2 ) (Fe+3 −Fe+2 )

η𝑎 =E(Fe+3 −Fe+2 ) -E(Fe+3 −Fe+2 ) =a a +ba *log(Icorr ) (9.4)

 The corrosion current density for each anodic reaction must be less the
limit current density. The limit current density is the corrosion current
density when the anodic reaction is controlled by the migration of
reactants to the electrode surface.
 Complexation of Fe+3into FeSO+ 4 or/and FeH(SO4 )2 decreases the

potential of anodic electrode of electrochemical reactions (9.i).
 The difference between the cathodic corrosion potential and the anodic
corrosion potential gives over-potential due to the electrical resistivity
of heterogenite (Equation (9.5)).
(Fe+3 −Fe+2 )
corr corr
E(CoOOH−Co +2 ) -E(Fe+3 −Fe+2 ) =R (Heterogenite) *Icorr (9.5)
 The anodic corrosion current density of ferrous compound is restricted

by value of the electrical conductivity of heterogenite.
 Figure (9.1) gives the graphic representation of the reduction

dissolution of Heterogenite with ferrous ion.

Figure (9.1): Tafel curves of reductive dissolution of heterogenite with ferrous ion

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Appendix

Table A-1: Chemical composition of secondary leach solution (mol/kg water)
July 3 July 4 July 5 July 6 July 7 July 8 July 9 July 10 July 11

Eh(V) 0.584 0.587 0.578 0.567 0.570 0.569 0.595 0.622 0.585
pH 1.840 1.800 1.770 1.750 1.832 1.810 1.960 1.542 1.440
P 0.0159 0.0178 0.0171 0.0184 0.0184 0.0190 0.0197 0.0204 0.0203
Ca 0.0189 0.0178 0.0165 0.0194 0.0185 0.0185 0.0175 0.0167 0.0167
Mg 0.0808 0.0866 0.0863 0.0938 0.0936 0.0974 0.1020 0.1018 0.1075
Al 0.0285 0.0410 0.0412 0.0474 0.0467 0.0463 0.0465 0.0480 0.0485
Zn 0.0149 0.0163 0.0154 0.0181 0.0182 0.0175 0.0174 0.0185 0.0194
Mn 0.0719 0.0777 0.0755 0.0824 0.0798 0.0817 0.0850 0.0803 0.0899
Cu 0.0490 0.0667 0.0478 0.0611 0.0526 0.0581 0.0774 0.0926 0.0989
Co 0.1672 0.1867 0.1795 0.1931 0.1935 0.2000 0.2073 0.2148 0.2137
Fe 0.0193 0.0198 0.0191 0.0202 0.0215 0.0244 0.0336 0.0314 0.0307
Si 0.0410 0.0335 0.0335 0.0384 0.0382 0.0385 0.0413 0.0402 0.0406

Eh(V) 0.562 0.570 0.538 0.562 0.602 0.576 0.587 0.620 0.668
pH 1.570 1.660 1.920 2.040 1.540 1.660 1.670 1.720 1.700
P 0.0172 0.0147 0.0154 0.0157 0.0169 0.0168 0.0151 0.0150 0.0136
Ca 0.0143 0.0169 0.0187 0.0182 0.0174 0.0190 0.0181 0.0171 0.0152
Mg 0.0828 0.0756 0.0797 0.0724 0.0782 0.0805 0.0784 0.0781 0.0814
Al 0.0348 0.0356 0.0391 0.0369 0.0404 0.0381 0.0369 0.0370 0.0349
Zn 0.0168 0.0158 0.0178 0.0177 0.0176 0.0193 0.0152 0.0171 0.0176
Mn 0.0750 0.0734 0.0788 0.0770 0.0789 0.0820 0.0714 0.0688 0.0626
Cu 0.1112 0.0722 0.0561 0.0753 0.0686 0.0745 0.0865 0.0770 0.0899
Co 0.1810 0.1541 0.1615 0.1646 0.1782 0.1766 0.1584 0.1574 0.1425
Fe 0.0237 0.0213 0.0213 0.0255 0.0336 0.0302 0.0262 0.0184 0.0075
Si 0.0320 0.0296 0.0344 0.0327 0.0335 0.0335 0.0323 0.0329 0.0320

Eh(V) 0.641 0.596 0.624 0.615 0.603 0.596 0.571 0.559 0.591
pH 1.610 1.670 1.730 1.450 1.600 1.380 1.360 1.520 1.400
P 0.0126 0.0141 0.0136 0.0100 0.0103 0.0118 0.0110 0.0119 0.0127
Ca 0.0158 0.0173 0.0161 0.0148 0.0146 0.0190 0.0175 0.0177 0.0167
Mg 0.0715 0.0705 0.0728 0.0538 0.0497 0.0616 0.1250 0.0671 0.0576
Al 0.0324 0.0332 0.0333 0.0260 0.0241 0.0273 0.0289 0.0317 0.0298
Zn 0.0178 0.0170 0.0183 0.0131 0.0114 0.0133 0.0127 0.0132 0.0130
Mn 0.0598 0.0744 0.0624 0.0469 0.0409 0.0498 0.0477 0.0526 0.0503
Cu 0.1045 0.0965 0.0866 0.0711 0.0779 0.0792 0.0625 0.0675 0.0405
Co 0.1320 0.1479 0.1434 0.1053 0.1085 0.1238 0.1159 0.1252 0.1331
Fe 0.0174 0.0216 0.0103 0.0043 0.0041 0.0101 0.0111 0.0136 0.0144
Si 0.0297 0.0296 0.0301 0.0239 0.0228 0.0263 0.0262 0.0270 0.0234

July 30 July 31 August 1 August 2 August 3 August 4 August 6 August 7 August 8

Eh(V) 0.562 0.5600 0.565 0.575 0.572 0.590 0.590 0.584 0.574
pH 1.660 1.530 1.520 1.550 1.540 1.460 1.350 1.380 1.440
P 0.0132 0.0106 0.0118 0.0140 0.0135 0.0202 0.0188 0.0146 0.0156
Ca 0.0171 0.0138 0.0142 0.0155 0.0140 0.0176 0.0169 0.0159 0.0186
Mg 0.0610 0.0492 0.0555 0.0640 0.0628 0.0867 0.0885 0.0627 0.0739
Al 0.0281 0.0244 0.0270 0.0322 0.0372 0.0431 0.0438 0.0357 0.0371
Zn 0.0153 0.0121 0.0131 0.0149 0.0142 0.0200 0.0184 0.0168 0.0169
Mn 0.0578 0.0462 0.0504 0.0585 0.0612 0.0871 0.0861 0.0679 0.0724
Cu 0.0693 0.0594 0.0663 0.0625 0.0698 0.1006 0.1422 0.0801 0.0934
Co 0.1384 0.1114 0.1244 0.1469 0.1423 0.2122 0.1981 0.1539 0.1639
Fe 0.0188 0.0152 0.0163 0.0190 0.0176 0.0230 0.0245 0.0225 0.0233
Si 0.0255 0.0204 0.0209 0.0262 0.0253 0.0380 0.0385 0.0298 0.0314
August 9 August 10 August 11 August 12 August 13 August 14 August 15 August 16

Eh(V) 0.583 0.596 0.582 0.575 0.564 0.567 0.577 0.573
pH 1.350 1.420 1.390 1.370 1.400 1.320 1.300 1.370
P 0.0179 0.0161 0.0163 0.0165 0.0169 0.0173 0.0192 0.0203
Ca 0.0182 0.0181 0.0177 0.0190 0.0190 0.0203 0.0183 0.0190
Mg 0.0804 0.0746 0.0768 0.0740 0.0776 0.0808 0.0933 0.0981
Al 0.0391 0.0369 0.0391 0.0383 0.0385 0.0428 0.0454 0.0494
Zn 0.0223 0.0218 0.0201 0.0176 0.0181 0.0180 0.0186 0.0193
Mn 0.0774 0.0736 0.0714 0.0693 0.0703 0.0682 0.0724 0.0811
Cu 0.0575 0.0624 0.0660 0.0862 0.0646 0.0657 0.0651 0.0737
Co 0.1880 0.1697 0.1711 0.1736 0.1780 0.1814 0.2014 0.2131
Fe 0.0275 0.0261 0.236 0.0226 0.0242 0.0254 0.0278 0.0300
Si 0.0350 0.0329 0.0348 0.0320 0.0341 0.0368 0.0394 0.0417
August 17 August 18 August 19 August 20 August 21 August 22 August 23

Eh(V) 0.569 0.577 0.568 0.574 0.576 0.573 0.577
pH 1.380 1.310 1.400 1.400 1.300 1.350 1.370
P 0.0206 0.0210 0.0233 0.0220 0.0207 0.0197 0.0177
Ca 0.0173 0.0174 0.0177 0.0173 0.0187 0.0166 0.0151
Mg 0.1041 0.1040 0.1071 0.1167 0.1046 0.0977 0.0919
Al 0.0507 0.0513 0.0539 0.0532 0.0526 0.0466 0.0415
Zn 0.0196 0.0208 0.0202 0.0207 0.0199 0.0162 0.0149
Mn 0.0830 0.0866 0.0968 0.0914 0.0914 0.0769 0.0704
Cu 0.0776 0.0668 0.0865 0.0983 0.1021 0.0455 0.0629
Co 0.2163 0.2212 0.2449 0.2308 0.2178 0.2068 0.1863
Fe 0.0302 0.0306 0.0334 0.0346 0.0365 0.0346 0.0330
Si 0.0430 0.0424 0.0452 0.0449 0.0434 0.0390 0.0364

Iron Precipitation During Leaching of Copper and Cobalt Ores - Geochemical Modelling

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Iron Precipitation During Leaching of Copper and Cobalt Ores - Geochemical Modelling

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INDEPENDENT METALLURGIST

Kafumbila Kasonta Joseph

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2.1. Pilot plant description

Figure 2.1: Flow diagram of copper plant of pilot plant

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Secondary Cu SX consists only of an extraction stage, designed to strip any residual

2.2. Pilot plant results

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The results show that:

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Figure 2.8: Redox potential (mV) (Ag/AgCl) and pH versus date

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3.1. Thermodynamic system

A thermodynamic system is a constituent or, group of constituents, which is isolated

3.2. Gibbs free energy

3.2.2. Equilibrium of a closed system

A closed system is considered to be in equilibrium when it is in its most stable state

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3.2.3. Chemical potential energy

μ=μ° + R*T*2.303*log(a) (3.5)

“μ° ” is standard chemical potential of a substance at constant temperature and

3.2.4. Electrochemical potential energy

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3.3. General equilibrium condition

In aqueous precipitation system, there is reversible chemical reaction given by the

dGcp = υc *μC + υd *μD - υa *μA - υb *μB (3.8)

dGep = υe *F*E (3.9)

dGcp + dGep = 0 (3.10)

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In aqueous solution, there is reversible chemical reaction between soluble compounds

dGcp +dGep = υc *μC + υd *μD - υa *μA - υb *μB +υe *F*E =0 (3.11)

Combination of Equations (3.5) and (3.11) gives Equation (3.12).

The standard equilibrium constant is given by Equation (3.13) at a given temperature

ΔG° =υC μ°C +υD μ°D − υA μ°A − υB μ°B (3.15)

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3.5. Activity of substances

3.5.1. Activity of soluble substances

The calculations of individual ion activity coefficient have been approximated by

Table 2: values of A, B and b parameter at 298.15K

The calculations of osmotic coefficient have been approximated by Equation (3.24)

2.303∗A 1 b∗I 2c∗I2 3d∗I3

Table 4: values of a, b, c and d parameter at 298.15K

3.5.2. Activity of solid substances

3.5.2.1. Pure solid phase

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- When solid substances are precipitated, each solid substance is considered as

Aα Bβ . nH2 O = αA + βB + nH2 O (3.c)

μ°𝑠 = αμA + βμB + nμw (3.27)

K ps = aA α xaB β xaw n (3.28)

3.5.2.2. Mixed solid phases

a(Ra+2 ) ∗a(SO−2 ) a(Ra+2 ) ∗a(SO−2 )

μ𝑠 =μ°𝑠 +2.303RTlog(γ*X) (3.31)

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0.25 CuS + 0.75Cu2 S = Cu1.75 S (3.e)

μ°reactants = 0.25*μ°CuS + 0.75*μ°Cu2 S (3.32)

μmixing =μ°reactants +2.303*R*T*(0.25*log(0.25*γCuS )+0.75*log(0.75*γCu2 S ) (3.33)

μ𝑠 =μ°𝑠 +2.303RTlog(X) (3.34)

3.6. Overall equilibrium diagram

μ=μ° + RT2.303*log(a) (3.5)

dGcp = υc μC + υd μD - υa μA - υb μB (3.8)

dGep = υe FE (3.9)

dGcp +dGep = υc μC + υd μD - υa μA - υb μB +υe FE =0 (3.11)

μ°reactants = 0.25μ°CuS + 0.75μ°Cu2 S (3.32)

μmixing =μ°reactants +2.303RT*(0.25log(0.25γCuS )+0.75log(0.75γCu2 S ) (3.33)

υ1D D + υ1H+ H + + υ1e e− + υ1C C= υ𝐴 *A (3.f)

υ2D D + υ2H+ H + + υ2e e− + υ2C C= υB *B (3.g)

υG G + υH+ H + + υe e− + υC C= υD *D (3.h)

R g =R r - R o = k r Cr - k o Co (4.6)

Ig =-nFR g =nF(k o Co -k r Cr ) (4.10)

ln (aw1 ) = - 1.80210−2 ϕ*N (6.3)