Overall Equilibrium Diagram of Cu Co MG Fe Al Sulfate Sulfane Water System

METALLURGIST
Overall equilibrium diagram

of Cu-Co-Mg-Fe-Al-Sulfate-
Sulfane-water system
Copper sulfide selective precipitation
Kafumbila Kasonta Joseph
August 2020
Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-Sulfane-Water system: Copper
sulfide selective precipitation
© 2020 Joseph Kafumbila
jokafumbila@hotmail.com
Joseph Kafumbila Page 1

Contents
1. EQUILIBRIUM CONDITION OF E-PH DIAGRAM SYSTEM 6
1.1. THERMODYNAMIC SYSTEM 6

1.2. GIBBS FREE ENERGY 6
1.2.1. DEFINITION 6
1.2.2. CHEMICAL POTENTIAL ENERGY 7
1.2.3. ELECTROCHEMICAL POTENTIAL ENERGY 7
1.3. GENERAL EQUILIBRIUM CONDITION 8
1.4. STANDARD EQUILIBRIUM CONSTANT 8
2. ACTIVITY OF SUBSTANCES 10
2.1. ACTIVITY OF SOLUBLE SUBSTANCES 10

2.1.1. IONIC STRENGTH 10
2.1.2. ACTIVITY SCALES 10
2.1.3. MEAN ION ACTIVITY COEFFICIENTS 11
2.1.4. FREE ION ACTIVITY COEFFICIENTS 12
2.2. ACTIVITY OF SOLID SUBSTANCES 14
2.2.1. PURE SOLID PHASE 14
2.2.2. MIXED SOLID PHASES 14
3. TRANSITION ZONE 16
3.1. CONCEPT 16
3.2. PURE PHASE 16
3.3. SOLID SOLUTION 16
4. ESTIMATION OF FREE GIBBS ENERGY FROM EXPERIMENTAL DATA 18
5. SOLUBILITY CURVE 23
5.1. CONCEPT 23
5.2. PURE SOLID PHASE 23
5.3. IDEAL MIXED SOLID PHASE 28
6. KINETIC ASPECT OF METAL PRECIPITATION 34
6.1. PRECIPITATION REACTION 34

6.1.1. NUCLEATION 34
6.1.2. GROWTH 35
7. POURBAIX EH – PH DIAGRAM 36
7.1. DEFINITION 36
7.2. MODEL OF EH-PH DIAGRAM 36
7.3. THERMODYNAMIC CONDITIONS 37
7.4. CONSTRUCTION STEP OF EH-PH DIAGRAM 37
7.5. BOUNDARY EQUATION 38
7.6. CONVENTION OF THE BOUNDARY 38
8. OVERALL EQUILIBRIUM DIAGRAM 40
8.1. DEFINITION 40
8.2. THERMODYNAMIC CONDITIONS 40
8.3. CONSTRUCTION STEP OF EH-PH DIAGRAM 40
8.4. BOUNDARY OF TWO SOLID COMPOUNDS 41
8.5. CONCENTRATIONS OF OTHER SOLUBLE COMPOUNDS 42
8.6. BOUNDARY OF AQUEOUS SOLUTION AND SOLID COMPOUNDS 42
8.7. BOUNDARY OF TWO SOLUBLE COMPOUNDS 42
9. OVERALL EQUILIBRIUM DIAGRAM OF WATER SYSTEM 44
10. OVERALL EQUILIBRIUM DIAGRAMS OF METAL-WATER SYSTEM WITHOUT AQUEOUS COMPLEXES 46
10.1. OVERALL EQUILIBRIUM DIAGRAM OF CU-WATER SYSTEM 46

10.2. OVERALL EQUILIBRIUM DIAGRAM OF CO-WATER SYSTEM 48
10.3. OVERALL EQUILIBRIUM DIAGRAM OF MG-WATER SYSTEM 50
10.4. OVERALL EQUILIBRIUM DIAGRAM OF FE-WATER SYSTEM 51
10.5. OVERALL EQUILIBRIUM DIAGRAM OF AL-WATER SYSTEM 53
11. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-WATER SYSTEM WITHOUT AQUEOUS

COMPLEXES 56
12. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-WATER SYSTEM WITH AQUEOUS COMPLEXES 58
13. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-WATER SYSTEM 67
14. OVERALL EQUILIBRIUM DIAGRAM OF SULFANE-WATER SYSTEM 78
14.1. THERMODYNAMIC 78
14.1.1. METAL SULFIDE PRECIPITATION REACTION 78
14.2. REACTION PATHWAYS OF METAL SULFIDE PRECIPITATION 84
15. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-CASE A 87

15.1. TOTAL CONCENTRATION OF SULFUR IN SULFANE COMPOUNDS 87
15.2. MODELS 87
15.3. MODEL 1 87
15.4. MODEL 2 97
15.5. OBSERVATIONS 104
16. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-CASE B 105
16.1. TOTAL CONCENTRATION OF SULFUR IN SULFANE COMPOUNDS 105

16.2. MODEL 1 105
16.3. MODEL 2 107
17. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM – CASE C 110
17.1. MAXIMUM VALUE OF EH 110

17.1.1. MODEL 1 110
17.1.2. MODEL 1 112
17.2. MINIMUM VALUE OF EH 114
17.2.1. MODEL 1 114
18. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM –CASE D 117
18.1. EFFECT OF AQUEOUS SPECIES ACTIVITY ON MAXIMUM AND MINIMUM EH 117

18.2. MAXIMUM VALUE OF EH 117
18.3. MINIMUM VALUE OF EH 119
19. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM –CASE E 122
19.1. SOLUBILITY CURVE OF COPPER 122

19.2. MODEL 1 122
19.3. MODEL 2 123
20. REFERENCES 124

Summary
Selective copper sulfide precipitation done at OMG Kokkola, in Finland, produces the
copper sulfide at pH 1.8 with hydrogen sulfide. The initial concentrations of metals are 27,7g/L
Co, 24.6g/L Cu, 17.1 g/L Ni, 1g/L Zn and 5.4g/L Fe. The concentration of Cu in the solution after
precipitation is 1.1g/L. The grades of metals in the precipitate are 0.9% Co, 0.5% Ni, 63.2% Cu
and 0.03% Zn. The sulfide of copper is essentially CuS (Gecamines).
E-pH diagram of Cu-S-Water shows that Cu2 S must precipitate before CuS (Hsim-Hsiung
Huang, 2016). Therefore Eh-pH diagram of Cu-S-Water system is done base on the evidence that
oxidation of sulfide soluble compounds produces elemental sulfur and the oxidation of elemental
sulfur produces sulfate soluble compounds (I. Piugdomenech et al, 2000). In consequence the S-
Water system contains two systems: sulfate-water system and Sulfide-water system. The soluble
compounds of these two systems are not thermodynamically in equilibrium (J.Kafumbila, 2018).
Therefore E-pH diagrams of Cu-sulfane-water system, Co-sulfane-water system and Fe-

sulfane-water system are done in equilibrium state separately. The thermodynamic study shows
that for any pH on Eh-pH diagram Eh is determined by the couple (H2 S/S ° ). In consequence the
total concentration of sulfur in sulfane compounds increases when Eh value decreases (J.
Kafumbila, 2019).
This publication introduces metastable state during precipitation of metal sulfide with
H2 S. In the metastable state there is not oxidation of sulfide in elemental sulfur and polysulfide.
In consequence Eh is not determined by the couple (H2 S/S ° ). During metastable state there is
precipitation of metal sulfide. In the same time there is oxidation of sulfide in elemental sulfur
and polysulfide to reach the equilibrium state where Eh is determined by the couple (H2 S/S ° ).
Oxidation of sulfide in elemental sulfur decreases the concentration of sulfide in solution. In
consequence there is dissolution of metal sulfide and precipitation of metal polysulfide. The
change from metastable state to stable state depends on sulfide oxidation kinetic.
The thermodynamic study of selective precipitation of copper, cobalt and iron from
leach solution is done by establishing overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-
Sulfane-Water system in metastable and stable states. The leach solution contains 10 g/L Cu, 14
g/L Co, 2 g/L Fe, 2.81 g/L Mg and 1.44 g/L Al at pH 1.5 and 25°C. The concentration of copper
after sulfide precipitation is about 0.1 g/L. The results shows that in the range of Eh from 0.42V
to 0.5V at pH 1.5 and 25°C, it is possible to selectively precipitate copper sulfide from leach
solution and to produce pure CuS.

1. Equilibrium condition of E-pH diagram system
1.1. 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.
1.2. Gibbs free energy
1.2.1. 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 (1.1). “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 (1.2). “E” is the internal energy, “P” is the pressure and “V” is the volume.
G=H-T*S (1.1)
H=E+PV (1.2)
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.
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 will be in a state of stable equilibrium if it has the lowest possible
value of the Gibbs free energy given by Equation (1.3).
dG = 0 (1.3)
In E-pH diagram system, the free internal energy of the system will vary 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 the E-pH
diagram system, the variation of free interne energy is due, generally, to the existence of
chemical reaction in the system.

1.2.2. 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 will increase by “dn” and the total free energy of the system will also
increase by a small amount “dG”. “dG” is proportional to the molar quantity “dn” added. This
relation is given by Equation (1.4).
dG=μ*dn (1.4)
The proportionality constant (μ) is called the chemical potential. The chemical potential
depends on the temperature, pressure and the composition of the phase. Equation (1.5) gives
the relationship between chemical potential and composition.
μ=μ° + R*T*2.303*Log(a) (1.5)
“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.
The activity of a gas “i” in a mixture of gases is given by Equation (1.6). “fi ” is the
fugacity, “Pi” partial pressure of gas “i” and “Po ” is standard pressure (1bar). The activity of a
soluble substance in the solvent is given by Equation (1.7). “γi ” is the activity coefficient, “Ci ” is
the concentration of soluble substance “i” in the solvent and “C0 ” is the standard concentration
(1 moL/L). The activity of a solvent is 1. The activity of a solid in a mixture of solids is given by
Equation (1.8). Where “Xi ” is the molar fraction of a solid “i”.
f ∗Pi
ai = iP (1.6)
0
γi ∗Ci
ai = (1.7)
C0
ai =Xi (1.8)
1.2.3. 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 will increase by “dn” and the total free energy of the system will increase by a small
quantity “dG”. “dG” is proportional to the molar quantity of charge “dn” added. This relation is

given by Equation (1.9). “z” is the charge, “F” is faraday constant (96485 C/moL) and “E” is
electrochemical potential (V).
dG=Z*F*E*dn (1.9)
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 (1.10).
dG=-F*E*dn (1.10)
The variation in internal energy (dG) due to the variation of the molar quantity of
electronic charge is called the electrochemical potential energy.
1.3. General equilibrium condition
In the closed system, there is reversible chemical reaction given by the chemical reaction
(a.1). “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 (a.1)
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 (1.11) 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 (1.12). 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 (1.11)
dGep = υe *F*E (1.12)
The equilibrium condition of the chemical reaction (a.1) is given by Equation (1.13).
dGcp + dGep = 0 (1.13)
1.4. Standard equilibrium constant
In aqueous solution, there is reversible chemical reaction between soluble compounds

given by the chemical reaction (a.1). “υp ” is the stoichiometry coefficient of the substance “p” and
“A”, “B”, “C” and “D” are the chemical substances. The equilibrium condition of the chemical
reaction (a.1) is given by Equation (1.14).
υa A + υb B +υe e− = υc C + υd D (a.1)
dGcp +dGep = υc *μC + υd *μD - υa *μA - υb *μB +υe *F*E =0 (1.14)
Combination of Equations (1.5) and (1.14) gives Equation (1.15).
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 (1.15)
aAA x aBB
The standard equilibrium constant is given by Equation (1.16) at a given temperature

°
(T ).
υ υ
ac c x aDD
K °(T° ) = υ υ (1.16)
aAA x aBB
If υe is equal to zero, Equation (1.17) gives the value of the logarithm of the standard
equilibrium constant. ΔG° is given by Equation (1.18).
ΔG°
log(K °(T° ) ) = - 2.303𝑅𝑇 (1.17)
ΔG° =υC μ°C +υD μ°D − υA μ°A − υB μ°B (1.18)
If υe is not equal to zero, Equation (1.19) gives the relationship between the logarithm of
standard equilibrium constant and the redox potential. E ° (Standard redox potential) is given by
Equation (1.20).
2.303RT
*log(K °(T° ) ) = E ° - E (1.19)
υe ∗F
ΔG°
E ° =- υ (1.20)
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 (1.21) 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° ) ) - 2.303R (T - T° ) - 2.303RT ∫T° ΔCp° dT + 2.303R ∫T°
(T )
dT (1.21)
T

2. Activity of substances
2.1. 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 (2.1). “γA ” is activity
coefficient and CA is the concentration (mol/kg water or mol/L) of soluble compound.
aA = γA * CA (2.1)
2.1.1. Ionic strength
The ionic strength (I) of the solution is the first to know because the electrostatic
interactions depend on the concentration of charge. The value of ionic strength is calculated
using Equation (2.2). “Zn ” is the charge of soluble compounds “n” and “Cn ” is the concentration of
soluble compounds “n”. The ionic strength has concentration units.
1
I=2 x ∑n Zn2 ∗ Cn (2.2)
2.1.2. Activity scales
2.1.2.1. Concept
The free energy change for an infinitely small change in concentration is called the chemical
potential. The chemical potential for gaseous, aqueous and solid solutions is given by Equation
(1.5). The combination of Equations (1.5) and (2.1) gives Equation (2.3).
μA =μ°A + R*T*2.303*Log(CA ) + R*T*2.303*Log(γA ) (2.3)
For aqueous solutions it is the unobtainable hypothetical situation where both the
concentration (CA ), and activity coefficient (γA ) are equal to one. Then μA =μ°A . The reference
state is the solution limit where activity coefficient is equal to one. There are two main activity
scales.

2.1.2.2. Infinite dilution scale
On the infinite dilution scale γA  1 as the concentration of all salts approaches zero.
The reference state is chosen to be an infinitely dilute aqueous solution. The standard state is a
hypothetical solution with CA =aA =1 (ideal behavior). γA =1 at infinite dilution and decreases as
concentration increases.
2.1.2.3. Ionic medium scale
This is the situation where there is a swamping electrolyte that has a much higher
concentration than the solutes of interest, and the total concentration of swamping electrolyte is
constant. For this case the activity coefficient goes to 1 in this ionic medium. The reference state
is the ionic medium. Standard states are chosen so that γA =CA /𝐶𝐴°  1 when 𝐶𝐴°  0 in the ionic
medium.
2.1.3. Mean ion activity coefficients
Mean ion activity coefficients are determined experimentally and represent the average
effects of all ions in the solution. The symbol for the mean ion activity coefficients is γ±.
Example: γ±NaCl
The chemical potential for Na+ and Cl− are written using Equations (2.4) and (2.5).
μ(Na+) = μ°(Na+) + RTln(C(Na+) ) + RTln(γ(Na+) ) (2.4)
μ(Cl−) = μ°(Cl−) + RTln(C(Cl−) ) + RTln(γ(Cl−) ) (2.5)
The total free energy is written as the sum (Equation 2.6).
GT = μ(Na+) + μ(Cl−) = μ°(Na+) + μ°(Cl−) + RTln(C(Na+) *C(Cl−) ) + RTln(γ(Na+) *γ(Cl−) ) (2.6)
For the average contribution the free energy is divided by two (Equation 2.7) or
Equation (2.8).
GT (µ(Na+ ) + µ(Cl−) ) (µ°(Na+) + µ°(Cl−) )

= = + RTln((C(Na+) ∗ C(Cl−) )(1/2)) + RTln((γ(Na+) ∗ γ(Cl− ) )(1/2) ) (2.7)
2 2 2
μ ± = μ° ± + RTln(C±) + RTln(γ±) (2.8)

The mean activity coefficient (γ±) of an electrolyte solution is the geometrical mean of
the activity coefficients of the ions in the solution. Thus for a solution containing “t” mol ions, “p”
mol of ion “p” Equation (2.9) gives the mean activity coefficient (K. Thomsen, 1997).
1
Ln(γ±) = t ∑ p ln(γp ) (2.9)
2.1.4. Free ion activity coefficients
There are several theoretically based expressions that can be used to estimate single ion
activity coefficients. However each is only good for a limited range of ionic strength.
2.1.4.1. Debye-Huckel Equations
Equation (2.10) gives the value of free ion activity coefficients. Its range is limited to I<
0.01. “I” is the ionic strength (mol/L), “Zp ” is the charge of ion “p” and “A” is constant and its
value is equal to 0.509 at 25°C.
Log(γp ) = - A (Zp )2 √I (2.10)
2.1.4.2. Extended Debye-Huckel Equations
0.1. “I” is the ionic strength (mol/L), “Zp ” is the charge of ion “p” and “A” is a constant and its
value is equal to 0.509 at 25°C. “B” is a constant and its value is 0.33 108 . “ap ” is the ion size
parameter in cm. Table (2.1) gives the value of “ap ”(J. Kielland, 1937).
Table 2.1: Ion size parameter for some inorganic compounds
Ion size ions

parameter
(cm)
11 10−8 Th+4 , Zr +4 , Ce+4 , Sn+4
9 10−8 H + , Al+3 , Fe+3, La+3, Ce+3 , Cr +3, Sc +3, Y +3 , In+3 , Pr +3 , Nd+3 , Sm+3
8 10−8 Mg +2 , Be+2
6 10−8 Ca+2 , Zn+2, Cu+2, Sn+2, Mn+2, Fe+2, Ni+2 , Co+2 , Li+
5 10−8 Ba+2 , Sr +2 , S −2, Ra+2 , Cd+2, Hg +2 , S2 O4−2, WO−2 4
4.5 10−8 Pb+2, CO−2 −2
3 , SO3 , MoO4
−2
4.5-4 10−8 Na+ , CdCl+ , ClO2− , IO3− , HCO3− , HSO− −

3 , H2 PO4 , H2 AsO4
−
+2
4 10−8 SO−2 −2 −3 −2 −2 −2
4 , HPO4 , PO4 , Hg 2 , SeO4 , CrO4 , S2 O3 , S2 O6 , S2 O8
−2 −2
3.5 10−8 OH − , F − , NCS − , NCO− , HS − , ClO2− , ClO4− , BrO3− , IO4− , MnO−4

3 10−8 K + , Cl− , I− , NO3− , Br − , CN− , NO2−
2.5 10−8 Rb+ , Cs + , Tl+ , Ag + , NH4+

√I
Log(γp ) = - A (Zp )2 (1+a (2.11)
p B√I)
2.1.4.3. Davies Equation
0.5. “I” is the ionic strength (mol/L), “Zp ” is the charge of ion “p” and “A” is a constant and its
value is equal to 0.509 at 25°C.
√I
Log(γp ) = - A (Zp )2 [ (1+√I) -0.2I] (2.12)
2.1.4.4. Helgeson Equation
The calculations of individual ion activity coefficient have been approximated by

Equation (2.13) 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. “γp ” is the activity coefficient of soluble compound “p”, “Zp ” is
the electrical charge of compound “p” and “I” is the ionic strength (mol/kg of water). “A”, “B” and
“b” are temperature-dependent parameters. Table (2.2) gives values of parameters “A”, “B” and
“b” at 25°C (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).
Z2p A√I
Log(γp )= - (1+Bä√I) – log(1+0.018015*I)+b*I (2.13)
Table 2.2: values of A, B and b parameter at 25°C
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).
2.1.4.5. Activity of water
The activity of water (solvent) (𝑎𝑤 ) is given by Equation (2.14). “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 (2.14)

The calculations of osmotic coefficient have been approximated by Equation (2.15) (H.C.
Helgeson, 1969). The value of “u” is given by Equation (2.16). Table (2.3) gives values of
parameters “a”, “b”, “c” and “d” at 25°C. “A” comes from Debrye-Huckel equation for activity
coefficient and is function of temperature. The value of “A” is 0.5092 at 25°C. “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] + + + (2.15)
a3 ∗I 2 3 4
u=1+a*√I (2.16)
Table 2.3: values of a, b, c and d parameter at 25°C
a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4
2.2. Activity of solid substances
2.2.1. Pure solid phase
When a solid phase contains a single substance (salt, sulfide or hydrate), the activity of
solid phase is unity. Equation (2.17) coming from Equation (1.5) gives the chemical potential of
the solid phase.
μS = μ°S (2.17)
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 the molar fraction.
2.2.2. Mixed solid phases
2.2.2.1. Concept
If A and B are two solids which react to form a solid solution. The reaction (b.1) gives the
reaction between the solids A and B. The Free Gibbs energies of solid A and B in the solid
solution are given by Equations (2.18) and (2.19) where γA and γB are the activity coefficients
and XA and XB are molar fractions. The free Gibbs energy of the solid solution is given by
Equation (2.20).
αA + βB = Aα Bβ (b.1)
μA =μ°A +2.303*R*T.log(γA *XA ) (2.18)
μB =μ°B +2.303*R*T.log(γB *XB ) (2.19)
μ(Aα Bβ ) =XA *μA +XB *μB (2.20)
If the reaction is done in the ideal condition, the values of activity coefficients are one.
2.2.2.2. Example
Radium sulfate and barium sulfate can precipitate together in aqueous solution to form a
solid-solution (Raα , Baβ )SO4 . The reaction (b.2) gives the reaction between Radium sulfate and
barium sulfate where α and β are the molar fractions.
αRaSO4 + βBaSO4 = (Raα , Baβ )SO4 (b.2)
The aqueous solubility product K S of Radium sulfate for the reaction (b.3) is given by
Equation (2.21) (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,. “α”
is the molar fraction of each solid in the mixture and “γ” is the activity coefficient. In this case the
mixing reaction is done in non-ideal condition.
Ra+2 + SO−2
4 = RaSO4 (b.3)
a(Ra+2 ) ∗a(SO−2 ) a(Ra+2 ) ∗a(SO−2 )

Ks= 4
= 4
(2.21)
a(RaSO4 ) γ∗α

3. Transition zone
3.1. Concept
Each solid that precipitates from aqueous solution has a stability zone. Between two
stability zones, there is a transition zone where both solids precipitate. There are two cases:
 Solid compounds precipitate as pure phase in the transition zone.

 Solid compounds precipitate and react to form an ideal solid solution in
transition.
3.2. Pure phase
If solid is considered as pure phase, the precipitation of each solid phase in the mixed
precipitation must respect the precipitation condition (Equation 2.17). 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). Mass balance method for construction of E-pH diagram uses the same concepts (Hsin-
Hsiung Huang, 2016). In this case there is a juxtaposition of solid compounds.
Example: 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.
3.3. Solid solution
If C and D are two solids which react to form a solid solution in transition zone. The
reaction (c.1) gives the reaction between the solids C and D. The Free Gibbs energies of solid C
and D in the solid solution are given by Equations (3.1) and (3.2) where XC and XD are molar
fractions. The free Gibbs energy of the solid solution is given by Equation (3.3).
αC + βD = Cα Dβ (c.1)
μC =μ°C +2.303*R*T.log(XC ) (3.1)
μD =μ°D +2.303*R*T.log(XD ) (3.2)
μ(Cα Dβ ) =XC *μC +XD *μD (3.3)

Example: K-jarosite, Na-jarosite and H-jarosite can precipitate together in aqueous
solution to form a solid-solution K 0.77 Na0.03 (H3 O)0.2 Fe3 (SO4 )2 (OH)6. The reaction (b.5) gives
the reaction between K-jarosite, Na-jarosite and H-jarosite.
0.77(K-jarosite)+0.03(Na-jarosite)+0.2(H-jarosite) =K 0.77 Na0.03 (H3 O)0.2 Fe3 (SO4 )2 (OH)6 (b.5)
Table (3.1) gives standard Gibbs energies of K-jarosite, Na-jarosite, H-jarosite and
K 0.77 Na0.03 (H3 O)0.2 Fe3 (SO4 )2 (OH)6 (Clare Robinson, 2000).
Table 3.1: Standard Gibbs energies of Jarosite solid solutions at 25°C
Solid solution ΔG (kJ/mol) References

K-Jarosite -3309.8 Clare Robinson, 2000
Na-Jarosite -3256.8 Clare Robinson, 2000
H-Jarosite -3232.1 Clare Robinson, 2000
K 0.77 Na0.03 (H3 O)0.2 Fe3 (SO4 )2 (OH)6 -3293.5 Clare Robinson, 2000
By applying Equation (3.3) in ideal condition, the value of free Gibbs energy of solid
solution (K 0.77 Na0.03 (H3 O)0.2 Fe3 (SO4 )2 (OH)6) is around -3294.23 kJ/mol. This value is close to
the value given in Table (3.1). This solid solution can be considered as the ideal mixing of K-
jarosite, Na-jarosite, and H-jarosite.

4. Estimation of Free Gibbs energy from experimental data
For a given model of activities of soluble compounds, thermodynamic properties (ΔGf ,
ΔHf and Cp ) must fitted with the experimental data. In this case, Helgeson model of activity
coefficient is taken as the reference (H.C. Helgeson et al, 1981). Free Gibbs energies of formation
of solid compounds which have high value of solubility in water must be estimated using
experimental solubility data.
Example: Estimation of free Gibbs energy of MgSO4 . 7H2 O by considering Helgeson

model of activity coefficient and the aqueous solubility at 25°C (26.3 mass percent). Considering
Mg-sulfate-water system in equilibrium with MgSO4 . 7H2 O, the free Gibbs energy of MgSO4 . 7H2 O
is estimated using the following procedure:
- Ionic strength
The value of ionic strength is calculated using Equation (2.2). “Zn ” is the charge of
soluble compounds “n” and “Cn ” is the concentration of soluble compounds “n”. The ionic
strength has concentration units.
1
I=2 x ∑n Zn2 ∗ Cn (2.2)
- Helgeson Equation
Equation (4.1) gives the value of activity coefficient of soluble compound “p” having the value of
electrical charge of 𝑍𝑝 at 25°C. Equation (4.1) shows that activity coefficient depends on the
value of the electrical charge. Therefore 𝛾𝑍 is the value of activity coefficient of soluble
compound having absolute value of electrical charge Z (Z=1, 2, 3, ….).
𝑍 2 ∗0.509∗√I
Log(γZ )= - (1+1.22∗√I) – log(1+0.018015*I)+0.064*I (4.1)
unity at all values of ionic strength and temperature.
- Water
The chemical reaction (d.1) gives the water ionization reaction. Logarithm of the
equilibrium constant of the chemical reaction (d.1) 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 − (d.1)
The concentration mH2 is calculated using Equation (4.2) coming from the mass action
of the chemical reaction (d.1). The concentration mH1 is unknown value.
aw
mH2 =10(−13.998)* m 2
(4.2)
H1 ∗(γ1 )
The activity “aw ” is calculated from Equations from (4.3) to (4.5). “I” is ionic strength
and the value of ionic strength is given by Equation (2.2).
ln (aw ) = - 1.802*10−2*ϕ*∑i mi (4.3)
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 (4.4)
I
u=1+1.454√I (4.5)
- 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 chemical reactions (d.2) and (d.3) give the equilibrium reactions between SO4 −2
and the other soluble compounds. Table (4.1) gives the equilibrium constants of the chemical
reactions (d.2) and (d.3).
SO−2 + −
4 + H =HSO4 (d.2)
SO−2 +
4 +2H =H2 SO4 (d.3)
Table 4.1: Log(K) of sulfate-water system at 25°C
Chemical reactions logK Reference

d.2 1.99 MINTEQA2-V.4, 1999
d.3 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 soluble substances (H + and SO−2
4 ) using Equations (4.6) and (4.7) coming from
the mass actions of the chemical reactions from (d.2) to (d.3). The concentration mS1 is is
unknown value.
mSa2 =10(1.99)*mH1 *msa1 *γ2 (4.6)
mSa3 =10(0.08)*(mH1 )2*msa1 *γ2 *(γ1 )2 (4.7)
- Magnesium
The magnesium soluble substances are the following: Mg +2 , Mg(OH)+ , and MgSO4 . The
chemical reactions from (d.4) and (d.5) give the equilibrium reactions between Mg +2 and the
other soluble compounds. Table (4.2) gives the equilibrium constants of the chemical reactions
from (d.4) to (d.5).
Mg +2 + H2 O= Mg(OH)+ + H + (d.4)
Mg +2 + SO−2
4 = MgSO4 (d.5)
Table 4.2: Log(K) of Magnesium soluble compounds system at 25°C
Chemical reactions logK Reference

d.4 -11.397 MINTEQA2-V.4, 1999
d.5 2.36 MINTEQA2-V.4, 1999
The designation of concentration of soluble substances of magnesium soluble

compounds is the following:
Concentration of Mg +2 is mMg1 ,
Concentration of Mg(OH)+ is mMg2 ,
Concentration of MgSO4 is mMg3 ,
The concentrations of magnesium soluble substances are calculated as function of

concentration of soluble substances (Mg +2 , H + , and SO4 −2 ) using Equations from (4.8) and (4.9)
coming from the mass actions of the chemical reactions from (d.4) and (cd5).
mMg1 ∗γ2 ∗aw

mMg2 =10(−11.397) * (4.8)
mH1 ∗(γ1 )2
mMg3 =10(2.26) *mMg1 *mSa1 *(γ2 )2 (4.9)

The concentration mMg1 is unknown value.
- Constraints
Total concentration (Mg T ) of magnesium in solution (Equation 4.10) is equal to

solubility of magnesium in water (2.965 mol/kg).
Mg T =mMg1 +mMg2 +mMg3 (4.10)
The values of sum of positive charge (ChP) and sum of negative charge (ChN) are given
by Equation (4.11) and (4.12). The values of ChP and ChN are equals.
ChP=2*mMg1 +mMg2 +mH1 (4.11)
ChN=2*mS1 + mSa2 + mH2 (4.12)
The value of total concentration of sulfur (ST ) in solution is given by Equation (4.13).
The values of the total concentrations of magnesium (Mg T ) and sulfur (ST ) are equals.
ST = mSa1 +mSa2 +mSa3 +mMg3 (4.13)
The precipitation reaction of MgSO4 . 7H2 O is given by the chemical reaction (d.6).
Equilibrium condition of reaction (d.6) is given by Equation (4.14). The values of μ(Mg+2 ) , μ(SO−2
4 )
,
and μ(H2 O) are given by Equations (4.15), (4.16) and (4.17).
Mg +2 +SO−2
4 +7H2 O=MgSO4 . 7H2 O (d.6)
μ°(MgSO4 .7H2 O) =μ(Mg+2 ) +μ(SO−2

4 )
+7*μ(H2 O) (4.14)
μ(Mg+2 ) =μ°(Mg+2 ) +8.314*298.15*2.303*log(mMg1 *γ2 ) (4.15)
μ(SO−2
4 )
=μ°(SO−2 ) +8.314*298.15*2.303*log(mSa1 *γ2 ) (4.16)
4
μ(H2 O) =μ°(H2 O) +8.314*298.15*2.303*log(aw ) (4.17)
Table (4.3) gives the standard free Gibbs energies of Mg +2 , SO−2

4 , H2 O at 25°C.

Table 4.3: Standard free energy of formation at 25°C
Soluble species ΔG (kJ/mol) Reference

Mg +2 -454.8 NBS, Wagman et al, 1982
SO−2
4 -744.53 NBS, Wagman et al, 1982
H2 O -237.129 NBS, Wagman et al, 1982
Estimated standard free energy of formation of MgSO4 . 7H2 O is about -2872.092 kJ/mol
and equilibrium pH is about 6.65.

5. Solubility curve
5.1. Concept
On the Magnesium-sulfate-water system, the value of the magnesium solubility is

calculated from pH 1 to 10 by using the concept of pure solid phase and mixed solid phase.
5.2. Pure solid phase
- Solid phase
Magnesium-sulfate-water system contains two solid phases: MgSO4 . 7H2 O and

Mg(OH)2. The chemical reactions (d.6) and (e.1) give the precipitation reaction of MgSO4 . 7H2 O
and Mg(OH)2 respectively.
Mg +2 +SO−2
4 +7H2 O=MgSO4 . 7H2 O (d.6)
Mg +2 +2H2 O=Mg(OH)2+2H + (e.1)
Equilibrium conditions of reactions (d.6) and (e.1) are given by Equations (4.14) and
(5.1) respectively. The values of μ(SO−2
4 )
, μ(H+) and μ(H2 O) are given by Equations (4.16), (4.17)
and (5.2). The values of μ(A)(Mg+2 ) and μ(B)(Mg+2 ) are the chemical potentials of magnesium
calculated from equations (4.14) and (5.1) respectively. Table (5.1) gives standard chemical
potential of Mg +2 , SO−2
4 , H2 O, Mg(OH)2 and MgSO4 . 7H2 O at 25°
μ°(MgSO4 .7H2 O) =μ(A)(Mg+2 ) +μ(SO−2

4 )
+7*μ(H2 O) (4.14)
μ°(Mg(OH)2 ) +2*μ(H+) =μ(B)(Mg+2 ) +2*μ(H2 O) (5.1)
μ(SO−2
4 )
=μ°(SO−2 ) +8.314*298.15*2.303*log(mSa1 *γ2 ) (4.16)
4
μ(H2 O) =μ°(H2 O) +8.314*298.15*2.303*log(aw ) (4.17)
μ(H+) =8.314*298.15*2.303*log(mH1 *γ1 ) (5.2)


+2 -454.80
Mg NBS, Wagman et al, 1982
SO−2
4 -744.53 NBS, Wagman et al, 1982
Mg(OH)2 -831.992 Thermoddem
MgSO4 . 7H2 O -2872.092 Estimated -Chapter 4
- Water
equilibrium constant of the chemical reaction (d.1) is equal to -13.998 at 25°C (MINTEQA2-V.4,
H2 O = H + + OH − (d.1)
The concentration mH1 is given by Equation (5.3). The value of pH is a known value.
10−pH
mH1 = (5.3)
γ1
aw
mH2 =10(−13.998)* m 2 (4.2)
H1 ∗(γ1 )
ln (aw ) = - 1.802*10−2*ϕ*∑i mi (4.3)
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 (4.4)
I
u=1+1.454√I (4.5)

- Free sulfate
The free soluble compounds are the following: H2 SO4 , HSO4 − and SO4 −2 . The chemical
reactions (d.2) and (d.3) give the equilibrium reactions between SO4 −2 and the other soluble
compounds. Table (4.1) gives the equilibrium constants of the chemical reactions (d.2) and
(d.3).
SO−2 + −
4 + H =HSO4 (d.2)
SO−2 +
4 +2H =H2 SO4 (d.3)

following:
4 is mSa1 ,

the mass actions of the chemical reactions from (d.2) to (d.3).
mSa2 =10(1.99)*mH1 *msa1 *γ2 (4.6)
mSa3 =10(0.08)*(mH1 )2*msa1 *γ2 *(γ1 )2 (4.7)
by Equation (4.11) and (4.12). The values of ChP and ChN are equals. The value of mSa1 is
calculated from this constraint.
ChP=2*mMg1 +mMg2 +mH1 (4.11)
ChN=2*mSa1 + mSa2 + mH2 (4.12)
- Magnesium
from (d.4) to (d.5).
Mg +2 + H2 O= Mg(OH)+ + H + (d.4)

Mg +2 + SO−2
4 = MgSO4 (d.5)


coming from the mass actions of the chemical reactions from (d.4) and (d.5).
mMg1 ∗γ2 ∗aw

mMg2 =10(−11.397) * (4.8)
mH1 ∗(γ1 )2
mMg3 =10(2.26) *mMg1 *mSa1 *(γ2 )2 (4.9)
The concentration mMg1 is minimum value between m(A)Mg1 and m(B)Mg1. m(A)Mg1 and
m(B)Mg1 are calculated from Equation (5.4) and (5.5) at a known value of pH
μ(𝐴)(Mg+2 ) =μ°(Mg+2 ) +8.314*298.15*2.303*log(m(A)Mg1*γ2 ) (5.4)
μ(𝐵)(Mg+2 ) =μ°(Mg+2 ) +8.314*298.15*2.303*log(m(B)Mg1*γ2 ) (5.5)
- Ionic strength
1
I=2 x ∑n Zn2 ∗ Cn (2.2)
- Helgeson Equation
Equation (4.1) gives the value of activity coefficient of soluble compound “p” having the
value of electrical charge of 𝑍𝑝 at 25°C. Equation (4.1) shows that activity coefficient depends on
the value of the electrical charge. Therefore 𝛾𝑍 is the value of activity coefficient of soluble
𝑍 2 ∗0.509∗√I
Log(γZ )= - (1+1.22∗√I) – log(1+0.018015*I)+0.064*I (4.1)

- Magnesium solubility

solubility of magnesium in water at a known value of pH
Figure (5.1) gives the solubility of magnesium in water at 25°C as a function of pH. The
zone below pH 8.91 is the stability zone of MgSO4 . 7H2 O and The zone above pH 8.91 is the
stability zone of Mg(OH)2.
Figure (5.1): Solubility of magnesium in water versus pH at 25°C

5.3. Ideal Mixed solid phase
This method is applied to solids having the same cation.
- Solid phase
Magnesium-sulfate-water system contains two solid phases: MgSO4 . 7H2 O and

Mg(OH)2. The chemical reactions (d.6) and (e.1) give the precipitation reaction of MgSO4 . 7H2 O
and Mg(OH)2 respectively.
Mg +2 +SO−2
4 +7H2 O=MgSO4 . 7H2 O (d.6)
Mg +2 +2H2 O=Mg(OH)2+2H + (e.1)
Equilibrium conditions of reactions (d.6) and (e.1) are given by Equations (5.6) and
(5.7) respectively. The values of μ(MgSO4 .7H2 O) and μ(Mg(OH)2 ) are given by Equations (5.8) and
(5.9) respectively at 25°C. X (MgSO4 .7H2 O) and X(Mg(OH)2 ) are molar fractions of MgSO4 . 7H2 O and
Mg(OH)2 respectively. Equation (5.10) gives molar fractions conditions. The values of μ(SO−2 4 )
,
μ(H+) and μ(H2 O) are given by Equations (4.16), (4.17) and (5.2). The values of μ(A)(Mg+2 ) and
μ(B)(Mg+2 ) are the chemical potentials of magnesium calculated from equations (5.6) and (5.7)
respectively. Table (5.1) gives standard chemical potential of Mg +2 , SO−2
4 , H2 O, Mg(OH)2 and
MgSO4 . 7H2 O at 25°
μ(MgSO4 .7H2 O) =μ(A)(Mg+2 ) +μ(SO−2

4 )
+7*μ(H2 O) (5.6)
μ(Mg(OH)2 ) +2*μ(H+) =μ(B)(Mg+2 ) +2*μ(H2 O) (5.7)
μ(MgSO4 .7H2 O) =μ°(MgSO4 .7H2 O)+8.314*298.15*2.303*log(X(MgSO4.7H2 O)) (5.8)
μ(Mg(OH)2 ) =μ°(Mg(OH)2 ) +8.314*298.15*2.303*log(X(Mg(OH)2 ) ) (5.9)
X(MgSO4.7H2O) + X(Mg(OH)2 )=1 (5.10)
μ(SO−2
4 )
=μ°(SO−2 ) +8.314*298.15*2.303*log(mSa1 *γ2 ) (4.16)
4
μ(H2 O) =μ°(H2 O) +8.314*298.15*2.303*log(aw ) (4.17)
μ(H+) =8.314*298.15*2.303*log(mH1 *γ1 ) (5.2)

- Water
equilibrium constant of the chemical reaction (c.1) is equal to -13.998 at 25°C (MINTEQA2-V.4,
H2 O = H + + OH − (d.1)
The concentration mH1 is given by Equation (5.3). The value of pH is a known value.
10−pH
mH1 = (5.3)
γ1
aw
mH2 =10(−13.998)* m 2
(4.2)
H1 ∗(γ1 )
ln (aw ) = - 1.802*10−2*ϕ*∑i mi (4.3)
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 (4.4)
I
u=1+1.454√I (4.5)
- Free sulfate
The free soluble compounds are the following: H2 SO4 , HSO4 − and SO4 −2 . The chemical
reactions (d.2) and (d.3) give the equilibrium reactions between SO4 −2 and the other soluble
compounds. Table (4.1) gives the equilibrium constants of the chemical reactions (d.2) and
(d.3).
SO−2 + −
4 + H =HSO4 (d.2)
SO−2 +
4 +2H =H2 SO4 (d.3)

following:
4 is mSa1 ,

the mass actions of the chemical reactions from (d.2) to (d.3).
mSa2 =10(1.99)*mH1 *msa1 *γ2 (4.6)
mSa3 =10(0.08)*(mH1 )2*msa1 *γ2 *(γ1 )2 (4.7)
by Equation (4.11) and (4.12). The values of ChP and ChN are equals. The value of mSa1 is
calculated from this constraint.
ChP=2*mMg1 +mMg2 +mH1 (4.11)
ChN=2*mSa1 + mSa2 + mH2 (4.12)
- Magnesium
from (c.4) to (c.5).
Mg +2 + H2 O= Mg(OH)+ + H + (d.4)
Mg +2 + SO−2
4 = MgSO4 (d.5)


coming from the mass actions of the chemical reactions from (d.4) and (d.5).
mMg1 ∗γ2 ∗aw

mMg2 =10(−11.397) * (4.8)
mH1 ∗(γ1 )2
mMg3 =10(2.26) *mMg1 *mSa1 *(γ2 )2 (4.9)
The concentration mMg1 is calculated from Equation (5.11). m(A)Mg1 and m(B)Mg1 are
calculated from Equation (5.4) and (5.5) at a known value of pH.
mMg1 =m(A)Mg1 =m(B)Mg1 (5.11)
μ(𝐴)(Mg+2 ) =μ°(Mg+2 ) +8.314*298.15*2.303*log(m(A)Mg1*γ2 ) (5.4)
μ(𝐵)(Mg+2 ) =μ°(Mg+2 ) +8.314*298.15*2.303*log(m(B)Mg1*γ2 ) (5.5)
- Ionic strength
1
I= x ∑n Zn2 ∗ Cn (2.2)
2
- Helgeson Equation
Equation (4.1) gives the value of activity coefficient of soluble compound “p” having the
value of electrical charge of 𝑍𝑝 at 25°C. Equation (4.1) shows that activity coefficient depends on
the value of the electrical charge. Therefore 𝛾𝑍 is the value of activity coefficient of soluble
𝑍 2 ∗0.509∗√I
Log(γZ )= - (1+1.22∗√I) – log(1+0.018015*I)+0.064*I (4.1)
- Magnesium solubility

solubility of magnesium in water at a known value of pH

Figure (5.2) gives the solubility of magnesium in water at 25°C as a function of pH.
Figure (5.3) gives molar fractions of MgSO4 . 7H2 O and Mg(OH)2 versus pH at 25°C
Figure (5.2): Solubility of magnesium in water versus pH at 25°C
The zone below pH 8.9 is the predominance zone of MgSO4 . 7H2 O and The zone above
pH 8.9 is the predominance zone of Mg(OH)2. On figure (5.3) the zone between 7.46 and 9.74 is
the transition zone where MgSO4 . 7H2 O and Mg(OH)2 are mixed.

Figure (5.3): Molar fractions of MgSO4 . 7H2 O and Mg(OH)2 versus pH at 25°C

6. Kinetic aspect of metal precipitation
6.1. Precipitation reaction
Precipitation reaction is crystallization process. A crystallization process means the

stabilization of a particular arrangement of atoms and/or molecules from reacting species
(solute as well as solvent molecules) at the supersaturation. The crystal structure of a solid
represents a stable state where the intermolecular interactions are optimized to provide the
most efficient packings (M. Singh et al, 2010).
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
(f.1).
Aα Bβ . nH2 O = αA + βB + nH2 O (f.1)
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 (6.1). The solubility product (K ps ) is given by Equation (6.2). “𝑎𝑖 ”
is the activity of ion “i”.
μ°𝑠 = αμA + βμB + nμw (6.1)
K ps = aA α ∗ aB β ∗ aw n (6.2)
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 6.3). 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 ∗aB β ∗aw n
SI = (6.3)
Kps
A crystallization process is characterized by two steps: Nucleation and Growth (M.

Singh et al, 2010).
6.1.1. Nucleation
Nucleation is defined as the formation of dispersed nuclei from a homogeneous solution

under supersaturation. Formation of a critical nucleus signals the separation of a solid phase
from the solution. Classical nucleation theory considers the existence of a critical nucleus,
corresponding to the maximum of energy versus radius curve. Supersaturation must occur, at
least, locally in nano or subnano volume to drive nucleation. Nucleus must continually form and
dissociate because of local concentration fluctuations. The sequence of events that occur during
the crystallization of solid from homogeneous solution is the following: Dissolved molecules –
complexes – clusters – critical nucleus – the minute crystal – single crystal or polycrystalline (M.
Singh et al, 2010).
6.1.2. Growth
Once the nucleus attains a critical size, a minute crystal with a particular lattice
structure is stabilized. Now the growth of the minute crystal is dominated by a different kinetics.
Here the rate of integration of aggregates into an existing lattice structure exceeds that rate of
releasing the aggregating molecules from surface. This process is driven by the local fluctuations
(M. Singh et al, 2010).
It violates no thermodynamic principles, that a minute crystal is the metastable phase

particularly in reactions near of ambient temperature. The metastable phases are predicted to
eventually decay to the stable phases, but eventually can be a very long time. The reaction
pathways are often determined by kinetics rather than by thermodynamics (W.B. White, 1997).

7. Pourbaix Eh – pH diagram
7.1. Definition
The Eh – pH diagram of a chemical element is a 2D graph representing the stability area

of the chemical form of this element in aqueous media as a function of redox potential (placed on
the ordinate) and pH (placed on the abscissa). The conventional Eh-pH also called Pourbaix
diagram is used for the corrosion application specially (M. Pourbaix, 1963). This type if diagram
shows the equilibrium condition for all possible redox reactions. In the field of metallic corrosion
the Pourbaix diagram is characterized by:
 Potential and pH on the axes

 Aqueous chemical systems
 Stability areas of both solid and dissolved species, but also gaseous species can be
included
 The concentration of dissolved compound is 10−6M and is the limit of corrosion.
 Ideal thermodynamic conditions (concentration is equal to activity).
 Three thermodynamic stability areas: immunity (the metal itself is the stable
phase and can therefore by definition not corrode), passivity (the existence area
where the metal is passivated by formation of a coating, usually a solid reaction
product like an oxide or a hydroxide) and corrosion (the state where the
thermodynamically stable species is a dissolved reaction product).
7.2. Model of Eh-pH diagram
Eh-pH diagram system is a closed system containing three phases. The gas phase is
constituted with one gas (or more), liquid phase is constituted with a solvent and one soluble
substance (or more) and solid phase is constituted with one solid (or more). The variation of the
free internal energy in the Eh-pH diagram system is due essentially to the chemical reaction.
In the closed system, there is reversible chemical reaction given by the chemical reaction
(g.1). “υp ” is the stoichiometry coefficient of the substance “p” and “A”, “B”, “C” and “D” are the
chemical substances.
υa A + υb B + υ(H+ ) H + + υe e− = υc C + υd D (g.1)
The equilibrium condition of the chemical reaction (e.1) is given by Equation (7.1).
υc *μC + υd *μD - υa *μA - υb *μB - υ(H+) *μ((H+ ) + υe *F*E = 0 (7.1)

The general equilibrium condition of the chemical reaction given by Equation (7.1)
shows that it is possible to establish Equation E=f(pH) for a chemical reaction. The value of pH
in Equation (E=f(pH)) is given by the chemical potential of hydrogen ion in water (Equation
7.2). Equation (7.3) gives the chemical potential of hydrogen ion in water.
( υa ∗µA + υb ∗µB −υc ∗µC − υd ∗µD ) υ(H+ )

E= - *R*T*2.303*pH (7.2)
υe ∗F υe ∗F
μH+ = -R*T*2.303*pH (7.3)
7.3. Thermodynamic conditions
The thermodynamic conditions of a conventional Eh-pH diagram are the following:
 Solid compound is pure. The activity of solid is equal to 1. The chemical potential of a
solid compound is given by Equation (7.4)
μ=μ° (7.4)
 The concentration is equal to activity. The chemical potential of a soluble compound is

given by Equation (7.5). “C” is the concentration of dissolved compound (mol/L or
mol/kg water).
μ=μ° + R*T*2.303*Log(C) (7.5)
 The partial pressure of hydrogen and oxygen gases is equal to 1Bar. The partial pressure
of other gases must be known.
.
7.4. Construction step of Eh-pH diagram
The construction steps of a conventional Eh-pH diagram of an element are the following:
 To identify all chemical compounds (solid, soluble and gas), that this element can form
with water or another soluble compound.
 To establish the chemical reaction between two chemical compounds.
 To establish the equilibrium conditions for each chemical reaction from that the
boundary Equation of the stability areas of the two chemical compounds is established.
 To stablish the Eh-pH diagram with the boundary Equation.
The first chemical compound taken as the reference must be the most acid and the most
oxidant. The stability area of the reference is located on the high and left corner of E-pH diagram.

7.5. Boundary Equation
The general equilibrium chemical reaction of two chemical compounds is given by the
chemical reaction (g.2). “A” and “B” are chemical compounds of the element. “C” is a soluble
compound that does not contain the element whose Eh-pH diagram is established.
υA *A + υH+ *H + + υe *e− + υC *C= υB *B (g.2)
Equation (7.6) gives the equilibrium condition of the chemical reaction (g.2).
υe *F*E+(υB *μB - υA *μA - υC *μC ) + υH+ *R*T*2.303*pH =0 (7.6)
Three possibilities arise from Equation (7.6):
 “𝜐𝑒 ”=0 – The boundary Equation of the stability areas of the two chemical compounds is
a vertical line on an E-pH diagram. Equation of the vertical line is given by Equation
(7.7).
(υB ∗µB − υA ∗µA − υC ∗µC )

pH= - (7.7)
υ(H+ ) ∗R∗T∗2.303
 “υH+ ”=0 – The boundary Equation of the stability areas of the two chemical compounds
is a horizontal line on an E-pH diagram. Equation of the horizontal line is given by
Equation (7.8).
(υB ∗µB − υA ∗µA − υC ∗µC )

Eh= - (7.8)
υe ∗F
 “υH+ ” and “𝜐𝑒 ” are not zero – The boundary Equation of the stability areas of the two
chemical compounds is an oblique line on an E-pH diagram. Equation of the oblique line
is given by Equation (7.9).
(υB ∗µB − υA ∗µA − υC ∗µC ) υ(H+ ) ∗R∗T∗2.303

Eh= - - *pH (7.9)
υe ∗F υe ∗F
7.6. Convention of the boundary
The concentration of soluble compounds follows the two agreements:
 The concentration of element for which the Pourbaix diagram is constructed is a constant
value. The concentration of each soluble compound is calculated from the concentration
of element.

 The total concentration in solution of element for which the Pourbaix diagram is
constructed is a constant value. The concentration of each soluble compound is calculated
from the total concentration of element in solution.
For the second agreement, the Pourbaix diagram of element goes together with the
predominance diagram of soluble compounds. The boundary between soluble compound and
solid is established in the predominance zone of soluble compound.

8. Overall equilibrium diagram
8.1. 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 E 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 E or as a function of E at
fixed value of pH.
8.2. 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 (7.4).
 The concentration of soluble compounds is the saturation concentration coming from
the precipitation reaction.
 At each point on E-pH diagram, one solid compound is in equilibrium with all soluble
compounds.
 The soluble compounds are in equilibrium each other.
 The partial pressures of hydrogen and oxygen gases are equal to 1Bar. The partial
pressure of other gases must be known.
8.3. Construction step of Eh-pH diagram
The conventional procedure of the construction of an overall equilibrium E-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.
8.4. 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 (h.1) and (h.2) give the precipitation
reactions of the two solids “A” and “B”).
υ1D *D + υ1H+ *H + + υ1e *e− + υ1C *C= υ𝐴 *A (h.1)
υ2D *D + υ2H+ *H + + υ2e *e− + υ2C *C= υB *B (h.2)
 To establish Equations giving the saturation concentrations of the reference from the
equilibrium conditions of the precipitation reactions (f.1) and (f.2). Equations (8.1) and
(8.2) gives the concentrations of soluble compound “D” established from the equilibrium
conditions of the chemical reactions (f.1) and (f.2).
υ1e ∗F (υA ∗µ°A − υ1D ∗µ°D − υ1c ∗µC ) υ1H+ ∗

Log([D])= υ *Eh+ + *pH (8.1)
1D ∗R∗T∗2.303 υ1D ∗R∗T∗2.303 υ1D

υ2e ∗F (υA ∗µ°A − υ2D ∗µ°D − υ2C ∗µC ) υ2H+ ∗
Log([D])= *Eh+ + *pH (8.2)
υ2D ∗R∗T∗2.303 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 (8.1) and (8.2) are equal.
8.5. Concentrations of other soluble compounds
The general equilibrium chemical reaction of a soluble compound with the reference is
given by the chemical reaction (g.3). “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.
υF *G + υH+ *H + + υe *e− + υC *C= υD *D (g.3)
Equation (8.3) 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([G])= υ *Eh+ *pH+ υD *Log([D]) + (8.3)
𝐺 ∗R∗T∗2.303 υ𝐺 𝐺 υG ∗R∗T∗2.303
8.6. 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 (8.1)) giving the saturation
concentration of soluble compound “D” is established. Equations (as Equation (8.3)) 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 “CtS ” that is
the known value. Equation (8.4) gives the total concentration of soluble compounds.
[D]+[G]+[H]= CtS (8.4)
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 respectively.
8.7. Boundary of two soluble compounds
The system contains two soluble compounds “D” and “G”. “C” is a soluble compound that
does not contain the element whose Eh-pH diagram is established. Equation of the boundary of
the two soluble compounds “D” and “G” is obtained as follows:
 To establish the chemical reactions between the two soluble compounds (Equation (g.3)).
 To establish Equation giving the concentration of one soluble compound as function of
the concentration of the other soluble compound, Eh and pH (Equation (8.3)).
 If the stoichiometry “υD ” and “υG ” are equal; the concentrations of the two soluble
compounds can be removed in the Equation (8.3).
 If the stoichiometry “υD ” and “υG ” are not equal; the concentrations of the two soluble
compounds cannot be removed in the Equation (8.3). There are two cases:
 First case: the two soluble compounds are in equilibrium with a solid compound.
a. To establish the precipitation reactions of the two soluble compounds with the solid
compounds.
b. To establish the Equations giving the saturation concentrations of the two soluble
compounds.
c. The equality of the two concentrations gives the boundary Equation of the soluble
compounds.
 Second case: the two soluble compounds are not in equilibrium with a solid compound.
a. If the soluble compounds are not in equilibrium with a solid; the total concentration of
the soluble compounds must be known.
b. To choice one soluble compound as a reference.
c. To establish Equations giving the concentration of others soluble compounds as a
function of the concentration of the reference, Eh and pH.
d. To establish Equation giving the sum of the concentrations of all soluble compounds as
function of the concentration of the reference, Eh and pH.
e. Second Equation is Equation giving the equality of the concentrations of the two soluble
compounds as a function of the concentration of the reference, Eh and pH.
f. To determine the value of pH for a known value of Eh, or the value of Eh for a known
value of pH from the two equations.

9. Overall equilibrium diagram of Water system
Water system contains the following species: H2 O, H + , OH − , O2 (gas) and H2 (gas). The
boundaries of the stability zone of water are fixed by the chemical reactions (i.1) and (i.2).
O2 +4H + +4e− =2H2 O (i.1)
2H + +2e− =H2 (i.2)
By applying Equation (7.9) and taking partial pressures of O2 (gas) and H2 (gas) equal to
1bar, Equations (9.1) and (9.2) give boundary Equations of chemical reactions (i.1) and (i.2)
respectively at 25°C. Table (9.1) gives the standard chemical potentials of species at 25°C. Figure
(9.1) gives the overall equilibrium diagram of water system.
Figure (9.1): Overall equilibrium diagram of water system at 25C and partial pressures of
O2 (gas) and H2 (gas) equal to 1bar

Eh=1.229-0.059pH (9.1)
Eh= -0.059pH (9.2)

H+ 0.00 NBS, Wagman et al, 1982
O2 0.00 NBS, Wagman et al, 1982
H2 0.00 NBS, Wagman et al, 1982

10. Overall equilibrium diagrams of Metal-water system
without aqueous complexes
10.1. Overall equilibrium diagram of Cu-water system
Cu-water system without Cu aqueous complexes contains: soluble compounds (Cu+2

and Cu+ ) and solid compounds (Cu° , Cu2 O and Cu(OH)2). Cu+2 is taken as the reference. The
chemical reactions (j.1), (j.2) and (j.3) give respectively the precipitation reactions of solid
compounds with the reference.
Cu+2 + 2H2 O=Cu(OH)2 + 2H + (j.1)
2Cu+2 + H2 O+2e− =Cu2 O + 2H + (j.2)
Cu+2 +2e− =Cu° (j.3)
Table (10.1) gives the standard free Gibbs energies of formation at 25°C.
Soluble species ΔG (kJ/mol) References

+ 0.00
H NBS, Wagman et al, 1982
Cu+ 49.98 NBS, Wagman et al, 1982
Cu+2 65.49 NBS, Wagman et al, 1982
Cu° 0.00 NBS, Wagman et al, 1982
Values of logk of chemicals reactions (j.1) and (j.4) are given in Table (10.2).
2Cu+ + H2 O=Cu2 O + 2H + (j.4)
Table 10.2: logk at 25°C
Reactions logk References

j.1 -8.674 MINTEQA2-V.4, 1999
j.4 1.406 MINTEQA2-V.4, 1999
Equations (10.1), (10.2) and (10.3) give the saturation concentration of Cu+2 as function
of Eh and pH for the chemical reactions (j.1), (j.2) and (j.3) respectively at 25°C.
Log(m(Cu+2 ) )= -2pH-8.674 (Cu(OH)2) (10.1)

Log(m(Cu+2 ) )=16.989Eh-pH-3.43 (Cu2 O) (10.2)
Log(m(Cu+2 ) )=33.898Eh-11.504 (Cu° ) (10.3)
The soluble compounds of copper are the following: Cu+2 and Cu+ . The chemical
reaction (j.5) gives the equilibrium reaction between soluble compounds. Equation (10.4) gives
the relationship between the concentrations of soluble compounds. The total concentration of
copper (CuT ) (Equation 10.5) is equal to 0.002 mol/kg. m(Cu+2 ) and m(Cu+) are the concentration
of Cu+2 and Cu+ respectively.
Cu+2 +e− =Cu+ (j.5)
Log(m(Cu+) )=log(m(Cu+2 ) )-16.949Eh+2.725 (10.4)
CuT =m(Cu+2 ) +m(Cu+ ) (10.5)
Figure (10.1) gives overall equilibrium diagram of copper water system without copper
aqueous complexes at 25°C.
Figure (10.1): Overall equilibrium diagram of copper water system without copper

10.2. Overall equilibrium diagram of Co-water system
Co-water system without Co aqueous complexes contains: soluble compounds (Co+2 and
Co+3 ) and solid compounds (Co° , Co(OH)2, Co3 O4 and Co(OH)3). Co+2 is taken as the reference.
The chemical reactions (j.6), (j.7), (j.8) and (j.9) give respectively the precipitation reactions of
solid compounds with the reference.
Co(OH)3 + 3H + + e− =Co+2 + 3H2 O (j.6)
Co3 O4 + 8H + + 2e− =3Co+2 + 4H2 O (j.7)
Co+2 + 2H2 O=Co(OH)2 + 2H + (j.8)
Co+2 +2e− =Co° (j.9)

+ 0.00
Co+2 -54.4 NBS, Wagman et al, 1982
Co+3 134 NBS, Wagman et al, 1982
Co° 0.00 NBS, Wagman et al, 1982
Values of logk of chemicals reactions (j.8), (j.10) and (h.11) are given in Table (10.4).
Co+3 + 3H2 O=Co(OH)3 + 3H + (j.10)
Co+2 +2Co+3 + 4H2 O=Co3 O4 + 8H + (j.11)

j.8 -13.094 MINTEQA2-V.4, 1999
j.10 2.3009 MINTEQA2-V.4, 1999
j.11 10.4956 MINTEQA2-V.4, 1999
Equations (10.6), (10.7), (10.8) and (10.9) give the saturation concentration of Co+2 as
function of Eh and pH for the chemical reactions (j.6), (j.7), (j.8) and (j.9) respectively at 25°C.
Log(m(Co+2 ))= -16.949Eh-3pH+30.788 (Co(OH)3) (10.6)

Log(m(Co+2 ))=-11.299Eh-2.667pH+18.555 (Co3 O4 ) (10.7)
Log(m(Co+2 ))=-2pH+13.094 (Co(OH)2) (10.8)
Log(m(Co+2 ))=33.898Eh+9.556 (Co° ) (10.9)
The soluble compounds of cobalt are the following: Co+2 and Co+3 . The chemical
reaction (j.12) gives the equilibrium reaction between soluble compounds. Equation (10.10)
gives the relationship between the concentrations of soluble compounds. The total concentration
of cobalt (CoT ) (Equation 10.11) is equal to 0.238 mol/kg. m(Co+2 ) and m(Co+3 ) are the
concentration of Co+2 and Co+3 respectively.
Co+3 +e− =Co+2 (j.12)
Log(m(Co+3 ))=log(m(Co+2 ))+16.949Eh-33.096 (10.10)
CoT =m(Co+2 ) +m(Co+3 ) (10.11)
Figure (10.2) gives overall equilibrium diagram of cobalt water system without cobalt
Figure (10.2): Overall equilibrium diagram of cobalt water system without cobalt aqueous
complexes at 25°C.

10.3. Overall equilibrium diagram of Mg-water system
Mg-water system without Mg aqueous complexes contains: soluble compound (Mg +2 )

and solid compounds (Mg ° and Mg(OH)2). The chemical reactions (j.13) and (j.14) give
respectively the precipitation reactions of solid compounds with Mg +2 .
Mg +2 + 2H2 O=Mg(OH)2 + 2H + (j.13)
Mg +2 +2e− =Mg ° (j.14)
Table (10.5) gives the standard free Gibbs energies of formation at 25°C. Value of logk of
chemical reaction (j.13) is -16.844 (MINTEQA2-V.4, 1999).

Mg +2 -454.8 NBS, Wagman et al, 1982
Mg ° 0.00 NBS, Wagman et al, 1982
Equations (10.12) and (10.13) give the saturation concentration of Mg +2 as function of

Eh and pH for the chemical reactions (j.13) and (j.14) respectively at 25°C.
Log(m(Mg+2 ) )=-2pH+16.844 (Mg(OH)2) (10.12)
Log(m(Mg+2 ) )=33.898Eh+79.893 (Mg ° ) (10.13)
The total concentration of cobalt (Mg T ) (Equation 10.14) is equal to 0.116 mol/kg.
m(Mg+2 ) is the concentration of Mg +2 .
Mg T =m(Mg+2 ) (10.14)
Figure (10.3) gives overall equilibrium diagram of magnesium water system without
magnesium aqueous complexes at 25°C.

Figure (10.3): Overall equilibrium diagram of magnesium water system without
magnesium aqueous complexes at 25°C.
10.4. Overall equilibrium diagram of Fe-water system
Fe-water system without Fe aqueous complexes contains: soluble compounds (Fe+3 and
Fe+2) and solid compounds (Fe° , Fe(OH)2 , Fe+2 Fe2 O4and Fe(OH)3). Fe+2 is taken as the
reference. The chemical reactions (j.15), (j.16), (j.17) and (j.18) give respectively the
precipitation reactions of solid compounds with the reference.
Fe(OH)3 + 3H + +e− =Fe+2 + 3H2 O (j.15)
Fe+2 Fe2 O4 +8H + +2e− =3Fe+2 + 4H2 O (j.16)
Fe(OH)2 + 2H + =Fe+2 + 2H2 O (j.17)
Fe+2 +2e− =Fe° (j.18)


+ 0.00
Fe+2 -78.9 NBS, Wagman et al, 1982
Fe+3 -4.7 NBS, Wagman et al, 1982
Fe° 0.00 NBS, Wagman et al, 1982
Values of logk of chemicals reactions (j.17), (j.19) and (j.20) are given in Table (10.7).
Fe+3 + 3H2 O=Fe(OH)3 + 3H + (j.19)
Fe+2+2Fe+3 + 4H2 O=Fe3 O4 + 8H + (j.20)

j.17 -13.564 MINTEQA2-V.4, 1999
j.19 -3.191 MINTEQA2-V.4, 1999
j.20 -3.4028 MINTEQA2-V.4, 1999
Equations (10.14), (10.16), (10.17) and (10.18) give the saturation concentration of
+2
Fe as function of Eh and pH for the chemical reactions (j.15), (j.16), (j.17) and (j.18)
respectively at 25°C.
Log(m(Fe+2 ) )= -16.949Eh-3pH+16.234 (Fe(OH)3 ) (10.15)
Log(m(Fe+2 ) )=-11.299Eh-2.667pH+9.827 (Fe3 O4 ) (10.16)
Log(m(Fe+2 ) )=-2pH+13.564 (Fe(OH)2 ) (10.17)
Log(m(Fe+2 ) )=33.898Eh+13.86 (Fe° ) (10.18)
The soluble compounds of iron are the following: Fe+2 and Fe+3. The chemical reaction
(j.21) gives the equilibrium reaction between soluble compounds. Equation (10.19) gives the
relationship between the concentrations of soluble compounds. The total concentration of iron
(FeT ) (Equation 10.20) is equal to 0.036 mol/kg. m(Fe+2 ) and m(Fe+3 ) are the concentration of
Fe+2 and Fe+3 respectively.
Fe+3+e− =Fe+2 (j.21)
Log(m(Fe+3 ) )=log(m(Fe+2 ) )+16.949Eh-13.034 (10.19)

FeT =m(Fe+2 ) +m(Fe+3 ) (10.20)
Figure (10.4) gives the overall equilibrium diagram of iron water system without iron
Figure (10.4): overall equilibrium diagram of iron water system without iron aqueous
complexes at 25°C.
10.5. Overall equilibrium diagram of Al-water system
Al-water system without Al aqueous complexes contains: soluble compound (Al+3) and
solid compounds (Al° and Al(OH)3 ). The chemical reactions (j.22) and (j.23) give respectively the
precipitation reactions of solid compounds with Al+3.
Al+3 + 3H2 O=Al(OH)3 + 3H + (j.22)
Al+3 +3e− =Al° (j.23)
Table (10.8) gives the standard free Gibbs energies of formation at 25°C. Value of logk of
chemical reaction (j.22) is -10.8 (MINTEQA2-V.4, 1999).


Al+2 -485 NBS, Wagman et al, 1982
Al° 0.00 NBS, Wagman et al, 1982
Equations (10.21) and (10.22) give the saturation concentration of Al+3 as function of
Eh and pH for the chemical reactions (j.22) and (j.23) respectively at 25°C.
Log(m(Al+3 ))=-3pH+10.8 (Al(OH)3) (10.21)
Log(m(Al+3 ))=33.898Eh+127.797 (Al° ) (10.22)
The total concentration of cobalt (AlT ) (Equation 10.23) is equal to 0.053 mol/kg.
m(Al+3 ) is the concentration of Al+3.
AlT =m(Al+3 ) (10.23)
Figure (10.5) gives overall equilibrium diagram of aluminum water system without
aluminum aqueous complexes at 25°C.

Figure (10.5): overall equilibrium diagram of Al water system without Al aqueous
complexes at 25°C.

11. Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-water
system without aqueous complexes
Cu-Co-Mg-Fe-Al-water system without metal aqueous complexes contains is
juxtaposition of Cu-water, Co-water, Mg-water, Fe-water and Al-water systems. There are news
solid compounds that precipitate because of this juxtaposition. These news solid compounds are
the following: CuFe2 O4 , CoFe2 O4, and MgFe2 O4 in Fe-water system and FeAl2 O4 and
Mg 4 Al2 O7 . 10H2 O in the Al-water system.
Cu+2 , Co+2 , Mg +2 , Fe+2 and Al+3 are taken as the reference. The chemical reactions
(k.1), (k.2) and (k.3) give respectively the precipitation reactions of solid compounds with the
references in Fe-water system. The chemical reactions (k.4) and (k.5) give respectively the
precipitation reactions of solid compounds with the references in Al-water system.
CuFe2 O4 +8H + +2e− =2Fe+2 +Cu+2+ 4H2 O (k.1)
CoFe2 O4 +8H + +2e− =2Fe+2 +Co+2 + 4H2 O (k.2)
MgFe2 O4 +8H + +2e− =2Fe+2 +Mg +2 + 4H2 O (k.3)
Fe+2+2Al+3 +4H2 O= FeAl2 O4 +8H + (k.4)
Mg +2 +2Al+3+4H2 O=MgAl2 O4 +8H + (k.5)
Values of logk of chemicals reactions (k.1), (k.2), (k.3), (k.4) and (k.5) are given in Table
(11.1).

k.1 -9.5266 U.S. Department of Energy, 2004
k.5 -36.8476 MINTEQA2-V.4, 1999
Equations (11.1), (11.2) (11.3) give the saturation concentration of Fe+2 as function of
Eh and pH for the chemical reactions (k.1), (k.2), and (k.3) in Fe-water system respectively at
25°C.
Log(m(Fe+2 ) )=-16.949Eh-4pH-0.5log(m(Cu+2 ) )+17.811 (CuFe2 O4 ) (11.1)

Log(m(Fe+2 ) )=-16.949Eh-4pH-0.5log(m(Co+2 ) )+18.054 (CoFe2 O4 ) (11.2)
Log(m(Fe+2 ) )=-16.949Eh-4pH-0.5log(m(Mg+2 ) )+23.555 (MgFe2 O4 ) (11.3)
Equations (11.4), and (11.5) give the saturation concentration of Al+3 as function of Eh
and pH for the chemical reactions (k.4), and (k.5) in Al-water system respectively at 25°C.
Log(m(Al+3 ))=-4pH-0.5log(m(Fe+2 ) )+11.21 (FeAl2 O4 ) (11.4)
Log(m(Al+3 ))=-4pH-0.5log(m(Mg+2 ) )+18.4238 (MgAl2 O4 ) (11.5)
Figure (11.1) gives the overall equilibrium diagram of Cu-Co-Mg-Fe-Al water system
without aqueous complexes at 25°C (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe
and Blue line-Al).
Figure (11.1): Overall equilibrium diagram of Cu-Co-Mg-Fe-Al water system without aqueous
complexes at 25°C (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al).

12. Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-water
system with aqueous complexes
Overall equilibrium diagram with aqueous complexes is overall equilibrium diagram
without aqueous complexes in which aqueous complexes are added. Aqueous complexes for
each single overall equilibrium diagram are the following:
 Copper system
The soluble compounds of Cu-water system are: Cu+2, Cu(OH)+ , Cu(OH)2 , Cu(OH)− 3,
−2 +2 +2 + −
Cu(OH)4 , Cu2 (OH)2 , Cu3 (OH)4 , Cu , CuOH, Cu(OH)2 . The chemical reactions from (m.1) to
(m.8) give the complexation reactions of copper with water. Table (12.1) gives the logk of
chemical reactions from (m.1) to (m.8).

m.1 -7.497 MINTEQA2-V.4, 1999
m.2 -16.194 MINTEQA2-V.4, 1999
m.3 -26.878 MINTEQA2-V.4, 1999
m.4 -39.980 MINTEQA2-V.4, 1999
m.5 -10.594 MINTEQA2-V.4, 1999
m.6 -21.000 MINTEQA2-V.4, 1999
m.7 -11.600 Thermoddem
m.8 -16.100 Thermoddem
Cu+2 +H2 O=Cu(OH)+ +H + (m.1)
Cu+2 +2H2 O=Cu(OH)2+2H + (m.2)
Cu+2 +3H2 O=Cu(OH)−

3 +3H
+
(m.3)
Cu+2 +4H2 O=Cu(OH)−2

4 +4H
+
(m.4)
2Cu+2+2H2 O=Cu2 (OH)+2

2 +2H
+
(m.5)
3Cu+2 +4H2 O=Cu3 (OH)+2

4 +4H
+
(m.6)
Cu+ +H2 O= CuOH +H + (m.7)
Cu+ +2H2 O=Cu(OH)−

2 +2H
+
(m.8)

The designation of concentration (mol/kg water) of soluble compounds of copper 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)−24 is mCu5 ,
Concentration of Cu2 (OH)+2
2 is mCu6 ,
4 is mCu7 ,
+
Concentration of Cu is mCu8 ,
Concentration of CuOH is mCu9 ,
Concentration of Cu(OH)− 2 is mCu10 .
Equations from (12.1) to (12.8) give the concentrations of copper water complexes as
function of concentrations of Cu+2 and Cu+ . Equation (10.4) gives the concentration of Cu+ as a
function of concentration of Cu+2 .
Log(mCu2 )=log(mCu1 )+pH-7.497 (12.1)
Log(mCu3 )=log(mCu1 )+2pH-16.194 (12.2)
Log(mCu4 )=log(mCu1 )+3pH-26.278 (12.3)
Log(mCu5 )=log(mCu1 )+4pH-39.980 (12.4)
Log(mCu6 )=2log(mCu1 )+2pH-10.594 (12.5)
Log(mCu7 )=3log(mCu1 )+4pH-21.000 (12.6)
Log(mCu9 )=log(mCu8 )+pH-11.600 (12.7)
Log(mCu10 )=log(mCu8 )+2pH-16.100 (12.8)
Log(mCu8 )=log(mCu1 )-16.949Eh+2.725 (10.4)
Total concentration of copper (CuT ) is equal to 0.002 mol/kg water and it is given by
Equation (12.9).
CuT =mCu1 +mCu2 +mCu3 +mCu4 +mCu5 +2mCu6 +3mCu7 +mCu8 +mCu9 +mCu10 (12.9)

 Cobalt system
The soluble compounds of Co-water system are: Co+2, Co(OH)+ , Co(OH)2, Co(OH)− 3,
−2 +3 +4 − +3 +2
Co(OH)4 , Co2 (OH) , Co4 (OH)4 , CoOOH , Co , CoOH . The chemical reactions from (m.9) to
(m.16) give the complexation reactions of cobalt with water. Table (12.2) gives the logk of
chemical reactions from (m.9) to (m.16).
Co+2 +H2 O=Co(OH)+ +H + (m.9)
Co+2 +2H2 O=Co(OH)2+2H + (m.10)
Co+2 +3H2 O=Co(OH)−

3 +3H
+
(m.11)
Co+2 +4H2 O=Co(OH)−2

4 +4H
+
(m.12)
2Co+2+H2 O=Co2 (OH)+3+H + (m.13)
4Co+2+4H2 O=Co4 (OH)+4

4 +4H
+
(m.14)
Co+2 +2H2 O=CoOOH − +3H + (m.15)
Co+3 +H2 O=Co(OH)+2 +H + (m.16)

m.9 -9.697 MINTEQA2-V.4, 1999
m.10 -18.794 MINTEQA2-V.4, 1999
m.11 -31.491 MINTEQA2-V.4, 1999
m.12 -46.288 MINTEQA2-V.4, 1999
m.13 -10.997 MINTEQA2-V.4, 1999
m.14 -30.488 MINTEQA2-V.4, 1999
m.15 -32.092 MINTEQA2-V.4, 1999
m.15 -1.291 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of cobalt 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 ,
Concentration of Co(OH)−24 is mCo5 ,
Concentration of Co2 (OH)+3 is mCo6,

Concentration of Co4 (OH)+24 is mCo7 ,
−
Concentration of CoOOH is mCo8 ,
Concentration of Co(OH)+2 is mCo10 .
Equations from (12.10) to (12.18) give the concentrations of cobalt water complexes as
function of concentrations of Co+2 and Co+3 . Equation (10.10) gives the concentration of Co+3 as
a function of concentration of Co+2 .
Log(mCo2)=log(mCo1 )+pH-9.697 (12.10)
Log(mCo3)=log(mCo1 )+2pH-18.794 (12.12)
Log(mCo4)=log(mCo1 )+3pH-31.491 (12.13)
Log(mCo5)=log(mCo1 )+4pH-46.288 (12.14)
Log(mCo6)=2log(mCo1)+pH-10.997 (12.15)
Log(mCo7)=4log(mCo1)+4pH-30.488 (12.16)
Log(mCo8)=log(mCo1 )+3pH-32.092 (12.17)
Log(mCo10)=log(mCo9 )+pH-1.291 (12.18)
Log(mCo9)=log(mCo1 )+16.949Eh-33.096 (10.10)
Total concentration of cobalt (CoT ) is equal to 0.238 mol/kg water and it is given by
Equation (12.19).
CoT =mCo1+mCo2+mCo3+mCo4+mCo5+2mCo6 +4mCo7+mCo8+mCo9+mCo10 (12.19)
 Magnesium system
The soluble compounds of Mg-water system are: Mg +2 , and Mg(OH)+ . The chemical
reaction (m.17) gives the complexation reaction of magnesium with water. Table (12.3) gives
the logk of chemical reaction (m.17).
Mg +2 +H2 O=Mg(OH)+ +H + (m.17)


m.17 -11.397 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of magnesium is

the following:
Concentration of Mg(OH)+ is mMg2 .
Equation (12.20) gives the concentration of magnesium water complex as function of

concentration of Mg +2 .
Log(mMg2 )=log(mMg1 )+pH-11.397 (12.20)
Total concentration of magnesium (Mg T ) is equal to 0.116 mol/kg water and it is given
by Equation (12.21).
Mg T =mMg1 +mMg2 (12.21)
 Iron system
The soluble compounds of Fe-water system are: Fe+2, Fe(OH)+ , Fe(OH)2 , Fe(OH)− 3,
+3 +2 + − +4 +5
Fe , FeOH , Fe(OH)2 , Fe(OH)3, Fe(OH)4 , Fe2 (OH)2 , and Fe3 (OH)2 . The chemical reactions
from (m.18) to (m.26) give the complexation reactions of iron with water. Table (12.4) gives the
logk of chemical reactions from (m.18) to (m.26).
Fe+2+H2 O=Fe(OH)+ +H + (m.18)
Fe+2+2H2 O=Fe(OH)2 +2H + (m.19)
Fe+2+3H2 O=Fe(OH)−
3 +3H
+
(m.20)
Fe+3+4H2 O=Fe(OH)+2+4H + (m.21)
Fe+3+2H2 O=Fe(OH)+
2 +2H
+
(m.22)
Fe+3+3H2 O=Fe(OH)3 +3H + (m.23)
Fe+3+4H2 O=Fe(OH)−
4 +4H
+
(m.24)
2Fe+3+2H2 O=Fe2 (OH)+4

2 +2H
+
(m.25)

3Fe+3+4H2 O=Fe3 (OH)+5
4 +4H
+
(m.26)

m.18 -9.397 MINTEQA2-V.4, 1999
m.19 -20.494 MINTEQA2-V.4, 1999
m.20 -28.991 MINTEQA2-V.4, 1999
m.21 -2.187 MINTEQA2-V.4, 1999
m.22 -4.594 MINTEQA2-V.4, 1999
m.23 -12.560 MINTEQA2-V.4, 1999
m.24 -21.588 MINTEQA2-V.4, 1999
m.25 -2.854 MINTEQA2-V.4, 1999
m.26 -6.288 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of iron 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 ,
+3
Concentration of Fe is mFe5 ,
Concentration of Fe(OH)+2 is mFe6 ,
Concentration of Fe(OH)−4 is mFe9 ,
Concentration of Fe2 (OH)+4
2 is mFe10 ,
Concentration of Fe3 (OH)+5
4 is mFe11 .
Equations from (12.22) to (12.29) give the concentrations of iron water complexes as
function of concentrations of Fe+2 and Fe+3. Equation (10.19) gives the concentration of Fe+3 as
a function of concentration of Fe+2.
Log(mFe2 )=log(mFe1 )+pH-9.397 (12.22)
Log(mFe3 )=log(mFe1 )+2pH-20.494 (12.23)
Log(mFe4 )=log(mFe1 )+3pH-28.991 (12.23)
Log(mFe6 )=log(mFe5 )+pH-2.187 (12.24)
Log(mFe7 )=log(mFe5 )+2pH-4.594 (12.25)
Log(mFe8 )=log(mFe5 )+3pH-12.560 (12.26)

Log(mFe9 )=log(mFe5 )+4pH-21.588 (12.27)
Log(mFe10 )=2log(mFe5 )+2pH-2.854 (12.28)
Log(mFe11 )=3log(mFe5 )+4pH-6.288 (12.29)
Log(mFe5 )=log(mFe1 )+16.949Eh-13.034 (10.19)
Total concentration of iron (FeT ) is equal to 0.036 mol/kg water and it is given by
Equation (12.30).
FeT =mFe1 +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +2mFe10 +3mFe11 (12.30)
 Aluminum system
The soluble compounds of Al-water system are: Al+3, AlOH +2, Al(OH)+ 2 , Al(OH)3 , and
−
Al(OH)4 . The chemical reactions from (m.27) to (m.30) give the complexation reactions of
aluminum with water. Table (12.5) gives the logk of chemical reactions from (m.27) to (m.30).
Al+3 +4H2 O=Al(OH)+2+4H + (m.27)
Al+3 +2H2 O=Al(OH)+

2 +2H
+
(m.28)
Al+3 +3H2 O=Al(OH)3 +3H + (m.29)
Al+3 +4H2 O=Al(OH)−

4 +4H
+
(m.30)

m.27 -4.997 MINTEQA2-V.4, 1999
m.28 -10.094 MINTEQA2-V.4, 1999
m.29 -16.791 MINTEQA2-V.4, 1999
m.30 -22.688 MINTEQA2-V.4, 1999

The designation of concentration (mol/kg water) of soluble compounds of aluminum is
the following:
Concentration of Al+3 is mAl1 ,

Concentration of Al(OH)+2 is mAl2 ,
Concentration of Al(OH)3 is mAl4 ,
Concentration of Al(OH)−4 is mAl5 .
Equations from (12.31) to (12.29) give the concentrations of aluminum water

complexes as function of concentrations of Al+3 .
Log(mAl2 )=log(mAl1 )+pH-4.997 (12.31)
Log(mAl3 )=log(mAl1 )+2pH-10.094 (12.32)
Log(mAl4 )=log(mAl1 )+3pH-16.791 (12.33)
Log(mAl5 )=log(mAl1 )+4pH-22.688 (12.34)
Total concentration of aluminum (AlT ) is equal to 0.053 mol/kg water and it is given by
Equation (12.35).
AlT =mAl1 +mAl2 +mAl3 +mAl4 +mAl5 (12.35)
Figure (12.1) gives the overall equilibrium diagram of Cu-Co-Mg-Fe-Al water system
with aqueous complexes at 25°C (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al).

Figure (12.1): Overall equilibrium diagram of Cu-Co-Mg-Fe-Al water system with aqueous
complexes at 25°C (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al).

13. Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-
water system
Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-Water is overall equilibrium
diagram of Cu-Co-Mg-Fe-Al-Water in which compounds containing sulfate are added. Sulfate
compounds for each single overall equilibrium diagram are the following:
 Sulfate-water system
The soluble compounds of Sulfate-water system are: SO−2 −

4 , and HSO4 . The chemical
reaction (n.1) gives relationship between the two soluble compounds. Table (13.1) gives the
logk of chemical reaction (n.1).
H + +SO−2 −
4 =HSO4 (n.1)
Reaction logk References

n.1 1.99 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of sulfate soluble compounds is the

following:
4 is mSa1 ,
Concentration of HSO−4 is mSa2 .
Equation (13.1) gives the concentration of HSO− −2

4 as function of concentration of SO4 .
Log(mSa2 )=log(mSa1 )-pH+1.99 (13.1)
 Copper system
Sulfate compounds of Cu-sulfate water system are: solids (Cu2 SO4 , CuSO4 . 5H2 O,
Cu3 SO4 (OH)4, and Cu4 SO4 (OH)6)and soluble (CuSO4 ). Cu+2 is taken as the reference. The
chemical reactions from (n.2) to (n.5) give the precipitation reactions of solid compounds.
2Cu+2+SO−2 −
4 +2e =Cu2 SO4 (n.2)
Cu+2 +SO−2
4 +5H2 O=CuSO4 . 5H2 O (n.3)
3Cu+2+SO−2
4 +4H2 O=Cu3 SO4 (OH)4 +4H
+
(n.4)

4Cu+2 +SO−2
4 +6H2 O=Cu4 SO4 (OH)6 +4H
+
(n.5)
Values of logk of chemicals reactions from (n.3) to (n.5) and (n.6) are given in Table
(13.1).
2Cu+ + SO−2
4 =Cu2 SO4 (n.6)

n.2 2.64 MINTEQA2-V.4, 1999
n.3 -8.788 MINTEQA2-V.4, 1999
n.4 -15.222 MINTEQA2-V.4, 1999
n.5 1.95 MINTEQA2-V.4, 1999
Equations from (13.1) to (13.4) give the saturation concentration of Cu+2 as function of
Eh and pH for the chemical reactions from (n.2) to (n.5) respectively at 25°C.
Log(m(Cu1) )= 16.949Eh-0.5log(mSa1 )-3.702 (Cu2 SO4 ) (13.1)
Log((m(Cu1) )= -log(mSa1 )-2.64 (CuSO4 . 5H2 O) (13.2)
Log((m(Cu1) )= -1.333pH-0.333log(mSa1 )+2.929 (Cu3 SO4 (OH)4 ) (13.3)
Log((m(Cu1) )= -1.500pH-0.25log(mSa1 )+3.806 (Cu4 SO4 (OH)6) (13.4)
The soluble compound of copper is the following: CuSO4 . The chemical reaction (n.7)
gives the equilibrium reaction between CuSO4 and Cu+2. Value of logk of chemical reaction (n.7)
is given in Table (13.2).
Cu+2 +SO−2
4 =CuSO4 (n.7)

n.7 2.36 MINTEQA2-V.4, 1999

following:


Concentration of Cu(OH)−2
4 is mCu5 ,
2 is mCu6 ,
4 is mCu7 ,
+
Concentration of CuSO4 is mCu11 .
Equation (13.5) gives the concentration of CuSO4 as function of concentration of Cu+2.
Log(mCu11 )=log(mCu1 )+ log(mSa1 )+2.36 (13.5)
Equation (13.6).
CuT =mCu1 +mCu2 +mCu3 +mCu4 +mCu5 +2mCu6 +3mCu7 +mCu8 +mCu9 +mCu10 +mCu11 (13.6)
 Cobalt system
Sulfate compounds of Co-sulfate water system are: solids (CoSO4 . 6H2 O, and
Co4 SO4 (OH)6) and soluble (CoSO4 ). Co+2 is taken as the reference. The chemical reactions (n.8)
and (n.9) give the precipitation reactions of solid compounds.
Co+2 +SO−2
4 +6H2 O=CoSO4 . 6H2 O (n.8)
4Co+2+SO−2
4 +6H2 O=Co4 SO4 (OH)6 +4H
+
(n.9)
Values of logk of chemicals reactions (n.8) and (n.9) are given in Table (13.3).

n.8 2.473 MINTEQA2-V.4, 1999
n.9 -33.22 MINTEQA2-V.4, 1999
Equations (13.7) and (13.8) give the saturation concentration of Co+2 as function of Eh
and pH for the chemical reactions from (n.8) to (n.9) respectively at 25°C.
Log((m(Co1) )= -log(mSa1 )-2.473 (CoSO4 . 6H2 O) (13.7)
Log((m(Co1) )= -1.500pH-0.25log(mSa1 )+8.305 (Co4 SO4 (OH)6 ) (13.8)

The soluble compound of cobalt is the following: CoSO4 . The chemical reaction (k.10)
gives the equilibrium reaction between CoSO4 and Co+2. Value of logk of chemical reaction
(n.10) is given in Table (13.4).
Co+2 +SO−2
4 =CoSO4 (n.10)

n.10 2.30 MINTEQA2-V.4, 1999

following:

−
Concentration of Co(OH)+2 is mCo10 ,
Concentration of CoSO4 is mCo11,
Equation (13.9) gives the concentration of CoSO4 as function of concentration of Co+2 .
Log(mCo11)=log(mCo1 )+ log(mSa1 )+2.30 (13.9)
Equation (13.10).
CoT =mCo1+mCo2+mCo3+mCo4+mCo5+2mCo6+4mCo7 +mCo8+mCo9+mCo10+mCo11 (13.10)
 Magnesium system
Sulfate compounds of Mg-sulfate water system are: solid (MgSO4 . 7H2 O) and soluble
(MgSO4 ). Mg +2 is taken as the reference. The chemical reaction (n.11) gives the precipitation
reaction of solid compounds.
Mg +2 +SO−2
4 +7H2 O=MgSO4 . 7H2 O (n.11)
Value of logk of chemical reaction (n.11) is given in Table (13.5).


n.11 2.127 MINTEQA2-V.4, 1999
Equation (13.11) gives the saturation concentration of Mg +2 as function of Eh and pH

for the chemical reaction (n.11) respectively at 25°C.
Log((m(Mg1) )= -log(mSa1 )-2.127 (MgSO4 . 7H2 O) (13.11)
The soluble compound of Mg is the following: MgSO4 . The chemical reaction (n.12) gives
the equilibrium reaction between MgSO4 and Mg +2 . Value of logk of chemical reaction (n.12) is
given in Table (13.6).
Mg +2 +SO−2
4 =MgSO4 (n.12)

k.12 2.26 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of Mg is the

following:
Concentration of MgSO4 is mMg3 .
Equation (13.12) gives the concentration of MgSO4 as function of concentration of Mg +2 .
Log(mMg3 )=log(mMg1 )+ log(mSa1 )+2.26 (13.12)
Total concentration of magnesium (Mg T ) is equal to 0.116 mol/kg water and it is given
by Equation (13.13).
 Iron system
Sulfate compounds of Fe-sulfate water system are: solids (FeSO4 . 7H2 O, and
(H3 O)Fe3 (SO4 )2 (OH)6)(H-jarosite)) and soluble (FeSO4 , FeHSO+2 +
4 , FeH(SO4 )2 , Fe2 (SO4 )3 , FeSO4 ,
and Fe(SO4 )−2 ). Fe
+2
is taken as the reference. The chemical reactions (n.13) and (n.14) give the
precipitation reactions of solid compounds.

Fe+2+SO−2
4 +6H2 O=FeSO4 . 7H2 O (n.13)
(H3 O)Fe3 (SO4 )2 (OH)6+5H + +3e− =3Fe+2+2SO−2

4 +7H2 O (n.14)
Values of logk of chemicals reactions (n.13) and (n.15) are given in Table (13.7).
3Fe+3+2SO−2
4 +7H2 O =(H3 O)Fe3 (SO4 )2 (OH)6 +5H
+
(n.15)

n.13 2.209 MINTEQA2-V.4, 1999
n.15 12.1 MINTEQA2-V.4, 1999
Equations (13.14) and (13.15) give the saturation concentration of Fe+2 as function of
Eh and pH for the chemical reactions from (n.13) to (n.14) respectively at 25°C.
Log((m(Fe1) )= -log(mSa1 )-2.209 (CoSO4 . 6H2 O) (13.14)
Log((m(Fe1) )=-16.949Eh-1.667pH-0.667log(mSa1 )+8.99 (H-jarosite) (13.15)
The soluble compounds of Fe are the following: FeSO4 , FeHSO+2

4 , FeH(SO4 )2 , Fe2 (SO4 )3 ,
+ −
FeSO4 , and Fe(SO4 )2 . The chemical reactions from (n.16) to (n.21) give the equilibrium
reactions between Fe sulfate complexes and Fe+2. Values of logk of chemical reactions from
(n.16) to (n.21) are given in Table (13.8).
Fe+2+SO−2
4 =FeSO4 (n.16)
Fe+3+H + +SO−2 +2
4 =FeHSO4 (n.17)
Fe+3+H + +2SO−2
4 =FeH(SO4 )2 (n.18)
2Fe+3+3SO−2
4 =Fe2 (SO4 )3 (n.19)
Fe+3+SO−2 +
4 =FeSO4 (n.20)
Fe+3+2SO−2 −
4 =Fe(SO4 )2 (n.21)


n.16 2.39 MINTEQA2-V.4, 1999
n.17 2.48 Thermoddem
n.20 4.05 MINTEQA2-V.4, 1999
n.21 5.38 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of Fe is the

following:

+3
Concentration of Fe(OH)+ 2 is mFe7 ,
Concentration of Fe2 (OH)+4 2 is mFe10 ,
Concentration of Fe3 (OH)+5 4 is mFe11 .
Concentration of FeSO4 is mFe12 .
Concentration of FeHSO+2 4 is mFe13 .
Concentration of FeH(SO4 )2 is mFe14 .
Concentration of Fe2 (SO4 )3 is mFe15 .
Concentration of FeSO+ 4 is mFe16 .
Concentration of Fe(SO4 )− 2 is mFe17 .
Equations from (13.16) to (13.21) give the concentration of Fe sulfate complexes as

function of concentration of Fe+2.
Log(mFe12 )=log(mFe1 )+ log(mSa1 )+2.39 (13.16)
Log(mFe13 )=log(mFe5 )-pH+ log(mSa1 )+2.48 (13.17)
Log(mFe14 )=log(mFe5 )-pH+ 2log(mSa1 )+7.49 (13.18)
Log(mFe15 )=2log(mFe5 )+ 3log(mSa1 )+8.02 (13.19)
Log(mFe16 )=log(mFe5 )+ log(mSa1 )+4.05 (13.20)
Log(mFe17 )=log(mFe5 )+ 2log(mSa1 )+5.38 (13.21)

Equation (13.22).
FeT =mFe1 +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +2mFe10 +3mFe11 +mFe12
+mFe13 +mFe14 +2mFe15 +mFe16 +mFe17 (13.22)
 Aluminum system
Sulfate compounds of Al-sulfate water system are: solids (Al2 (SO4 )3 . 6H2 O, and
Al4 (OH)10 SO4 ) and soluble (AlSO+ −
4 , and Al(SO4 )2 ). Al
+3
is taken as the reference. The chemical
reactions (n.22), and (n.23) give the precipitation reactions of solid compounds.
2Al+3+3SO−2
4 +6H2 O=Al2 (SO4 )3 . 6H2 O (n.22)
4Al+3+SO−2
4 +10H2 O=Al4 (OH)10 SO4 +10H
+
(n.23)
Values of logk of chemicals reactions (n.22), and (n.23) are given in Table (13.9).

n.22 -1.68 B.P.C. Grover et al, 2016
n.23 -22.7 MINTEQA2-V.4, 1999
Equations (13.23), and (13.24) give the saturation concentration of Al+3 as function of
Eh and pH for the chemical reactions (n.22), (n.23) and (n.24) respectively at 25°C.
Log((m(Al1) )= -1.500log(mSa1 )-0.840 (Al2 (SO4 )3 . 6H2 O) (13.23)
Log((m(Al1) )= -2.5pH-0.25log(mSa1 )-5.675 (Al4 (OH)10 SO4 ) (13.24)
The soluble compounds of Al are the following: AlSO+ −

4 , and Al(SO4 )2 . The chemical
reactions from (n.24) to (n.25) give the equilibrium reactions between Al sulfate complexes and
Al+3 . Values of logk of chemical reactions from (n.24) to (n.25) are given in Table (13.10).
Al+3 +SO−2 +
4 =AlSO4 (n.24)
Al+3 +2SO−2 −
4 =Al(SO4 )2 (n.25)


n.24 3.89 MINTEQA2-V.4, 1999
n.25 4.92 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of Al is the

following:
Concentration of Al+3 is mAl1 ,

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 .
Equations from (13.25) to (13.26) give the concentration of Al sulfate complexes as

function of concentration of Al+3 .
Log(mAl16)=log(mAl1 )+ log(mSa1 )+3.89 (13.25)
Log(mAl7 )=log(mAl1 )+ 2log(mSa1 )+4.92 (13.26)
Total concentration of aluminum (AlT ) is equal to 0.053 mol/kg water and it is given by
Equation (13.27).
AlT =mAl1 +mAl2 +mAl3 +mAl4 +mAl5 +mAl6 +mAl7 (13.27)
 Water system
Water system contains the following species: H2 O, H + , and OH − . Chemical reaction

(n.26) gives the relationship between H2 O, H + , and OH − .
H + +OH − =2H2 O (n.26)
Value of logk of chemical reaction (n.26) is given in Table (13.11).

n.27 13.998 MINTEQA2-V.4, 1999

The designation of concentration (mol/kg water) of soluble compounds of water is the
following:
Concentrations of H + and OH − are given by Equations (13.28) and (13.29).
Log(H + )=-pH (13.28)
Log(OH − )=-13.998+pH (13.29)
 Constraint on sulfate concentration
Total concentration of sulfur in free sulfate compounds (SaT ) is given by Equation

(13.30). SaT is fixed by the neutrality of the solution. Ratio of Ch+ (positive charge) onto Ch−
(negative charge) is equal to one. Values of Ch+ and Ch− are given by Equations (13.31) and
(13.32).
SaT =mSa1 +mSa2 (13.30)
Ch+ =mH1 +2mCu1 +mCu2 +2mcu6 +2mCu7 +mCu8 +2mCo1 +mCo2+3mCo6+2mCo7+3mCo9+2mCo10

+2mMg1 +mMg2 +2mFe1 +mFe2 +3mFe5 +2mFe6 +mFe7 +4mFe10 +5mFe11 +2mFe13 +mFe16 +
3mAl1 +2mAl2 +mAl3 +mAl6 (13.31)
Ch− =mH2 +2mCu4 +2mCu5 +2mcu10 +mCo4+2mCo5+mCo8 +mFe4 +mFe9 +mFe17 +mAl5 +2mAl7 +2
mSa1 +mSa2 (13.32)
Figure (13.1) gives the overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-water

system at 25°C (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and Blue line-Al).

Figure 13.1: Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-water system at 25°C (black
line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and Blue line-Al).

14. Overall equilibrium diagram of sulfane-water system
14.1. Thermodynamic
14.1.1. Metal sulfide precipitation reaction
General chemical reaction of metal sulfide precipitation is given by the reaction (o.1).
Equation (14.1) gives the saturation condition for the chemical reaction (o.1).
(−2)
αM (+n) + βSγ = M α Sλ (o.1)
(a )(α) ∗(a (−2) )(β)

(M(+n) ) (Sγ )
SI= (14.1)
KpS
Hydrogen sulfide readily dissolves in water and partially dissociates in sulfane. Equation
(14.2) gives the concentration of soluble hydrogen sulfide in water as a function of partial
pressure (Jing Ning et al; 2013). C(H2 S) is the concentration (mol/L) of hydrogen sulfide in water
at 25°C and P(H2 S) is the partial pressure (bars) of hydrogen sulfide.
C(H2 S) =0.097*P(H2 S) (14.2)
Table (14.1) gives a list of the first and second acid dissociation constants for sulfane
series from H2 S to H2 S8 . S −2 is called sulfide and Sn−2 (2<n<8) is called polysulfide.
Table 14.1: Acid dissociation constants for sulfane at 25°C
Sulfane pK1 pK 2 Reference

H2 S 7.02 17.1 R.J. Remick at al, 1983 and MINTEQA2-V.4, 1999
H2 S 2 5.0 9.7 R.J. Remick at al, 1983
H2 S 3 4.2 7.5 R.J. Remick at al, 1983
H2 S 4 3.8 6.3 R.J. Remick at al, 1983
H2 S 5 3.5 5.7 R.J. Remick at al, 1983
H2 S 6 3.2 5.2 R.J. Remick at al, 1983
H2 S 7 3.0 4.8 R.J. Remick at al, 1983
H2 S 8 2.9 4.4 R.J. Remick at al, 1983
Chemical reactions from (o.2) to (o.6) give the equilibrium reactions between sulfide
and polysulfide systems. Table (14.2) gives logK of the chemical reactions from (o.2) to (o.6) at
25°C.

HS − + S ° =S2−2 + H + (o.2)
HS − + 2S ° =S3−2 + H + (o.3)
HS − + 3S ° =S4−2 + H + (o.4)
HS − + 4S ° =S5−2 + H + (o.5)
HS − + 5S ° =S6−2 + H + (o.6)
Table 14.2: logK of chemical reactions from (o.2) to (o.6) at 25°C
Reactions logk Reference

o.2 -11.7828 MINTEQA2-V.4, 1999
o.3 -10.7667 MINTEQA2-V.4, 1999
o.4 -9.9608 MINTEQA2-V.4, 1999
o.5 -9.3651 MINTEQA2-V.4, 1999
o.6 -9.881 MINTEQA2-V.4, 1999
Data from Tables (14.1) and (14.2) give the free Gibbs energies of formation of sulfide
and polysulfide species in water at 25°C (Table 14.3).
Table 14.3: Free Gibbs energies of formation of sulfide and polysulfide species in water at 25°C
Species Gibbs energy References

(kJ/mol)
H2 S -27.995 Calculated
HS − 12.08 NBS, Wagman et al, 1982
S −2 109.699 Calculated
H2 S 2 -4.573 Calculated
HS2− 23.970 Calculated
S2−2 79.345 Calculated
H2 S 3 6.689 Calculated

Sulfane-water system contains: solid (elemental sulfur) and soluble compounds (species
in Table 14.3). H2 S is taken as the reference. The chemical reaction (o.7) gives the precipitation
reactions of solid compounds with the reference.
S ° + 2H + +2e− =H2 S (o.7)

+ 0.00
Equation (14.3) gives the saturation concentration of H2 S as function of Eh and pH for

the chemical reaction (l.7) at 25°C.
Log(m(H2 S))= -33.898Eh-2pH+4.918 (14.3)
The soluble compounds of Sulfane-water system are given in Table (14.3). The chemical
reactions from (o.8) to (o.24) give reactions between of H2 S with other species.
HS − +H + =H2 S (o.8)
S −2+2H + =H2 S (o.9)
H2 S2 +2H + +2e− =2H2 S (o.10)
HS2− +3H + +2e− =2H2 S (o.11)
S2−2+4H + +2e− =2H2 S (o.12)
H2 S3 +4H + +4e− =3H2 S (o.13)
HS3− +5H + +4e− =3H2 S (o.14)
S3−2+6H + +4e− =3H2 S (o.15)
H2 S4 +6H + +6e− =4H2 S (o.16)
HS4− +7H + +6e− =4H2 S (o.17)
S4−2+8H + +6e− =4H2 S (o.18)

H2 S5 +8H + +8e− =5H2 S (o.19)
HS5− +9H + +8e− =5H2 S (o.20)
S5−2+10H + +8e− =5H2 S (o.21)
H2 S6 +10H + +10e− =6H2 S (o.22)
HS6− +11H + +10e− =6H2 S (o.23)
S6−2+12H + +10e− =6H2 S (o.24)
The designation of concentration (mol/kg water) of sulfane compounds is the following:
Concentration of H2 S is mSi1 ,
Concentration of HS − is mSi2 ,
Concentration of S −2 is mSi3 ,
Concentration of H2 S2 is mSi4 ,
Concentration of HS2− is mSi5 ,
Concentration of S2−2 is mSi6 ,
Concentration of S6−2 is mSi18 .
Equations from (14.4) to (14.20) give the concentrations of sulfane compounds as

function of concentration of H2 S.
Log(mSi2 )=log(mSi1 )+pH-7.02 (14.4)
Log(mSi3 )=log(mSi1 )+2pH-24.32 (14.5)
Log(mSi4 )=2log(mSi1 )+33.898Eh+2pH-9.032 (14.6)

Total concentration of sulfur in free sulfane compounds (SiT ) is given by Equation

(14.21).
SiT =mSi1 +mSi2 +mSi3 +2mSi4 +2mSi5 +2mSi6 +3mSi7 +3mSi8 +3mSi9 +4mSi10 +4mSi11 +4mSi12 +5
mSi13 +5mSi14 +5mSi15 +6mSi16 +6mSi17 +6mSi18 (14.21)
For total concentration of sulfur in free sulfane compounds (SiT ) equals to 0.1 mol/kg
water, Figure (14.1) gives overall equilibrium diagram of sulfane-water system at 25°C. Buckley
and Hamilton arrived at the same picture of Eh-pH diagram of sulfane system in 1987 (Thomas
Provijn, 1993).
It has been observed that in the bottle where there is a saturation of H2 S in presence of
solid sulfur, the redox potential that is measured by electrode is equal to value given by the
chemical reaction (o.7). The presence of thiosulfate and sulfite does not have a significant effect
on the redox potential (Art. A. Migdisov, 1993). On Figure (14.1), the line giving the redox
potential from the chemical reaction (o.7) is the redox potential line of sulfane-water system.

Figure (14.2) gives molar fractions of soluble compounds of sulfane water system on the
redox potential line as function of pH at 25°C for SiT equals to 0.1 mol/kg water. The activity of
(−2)
Sγ depends on pH and redox potential.
Figure (14.1): Overall equilibrium diagram of sulfane-water system at 25°C for SiT =0.1mol/kg

Figure (14.2): Molar fractions of compounds of sulfane-water system at 25°C on the redox
potential line for SiT =0.1mol/kg
14.2. Reaction pathways of metal sulfide precipitation
A reactor is considered as a closed system. The reactor is characterized by Eh, pH,

temperature (ambient) and chemical composition given by overall equilibrium diagram (Figure
13.1). H2 S is injected in the reactor, the reaction pathways are the following:
1. In acidic zone, there are dissociation of H2 S according to the reactions (o.25) and (o.26).
In alkaline zone, H2 S reacts with OH − according to the reactions (o.27) and (o.28).
H2 S=HS − +H + (o.25)
HS − =S −2+H + (o.26)
H2 S+OH − =HS − +H2 O (o.27)
HS − +OH − =S −2+H2 O (o.28)

2. HS − reacts with free soluble metal species to form soluble sulfide complexes according to
the general reaction (o.29) (Vutiswa Dube, 2015).
(αn−β)
αM (+n) + βHS − = Mα (HS)β (o.29)
3. Depending on the saturation index and pH, there are three mechanisms of metal sulfide
precipitation (Vutiswa Dube, 2015). Notice that CuS precipitation has very fast kinetic
(Aysel sen et al, 2016):
o The soluble sulfide complexes lose protons and metal precipitates as metal sulfide
according to the reaction (o.30).
(αn−β)
Mα (HS)β =Mα Sβ+βH + (o.30)
o The soluble sulfide complexes react with free soluble metal to form metal sulfide
according to the reaction (o.31).
(αn−β)
Mα (HS)β +λM (+n) =Mλ Sβ+βH + (o.31)
o S −2 reacts with free soluble metal species to form metal sulfide according to the
reaction (o.32).
αM (+n) + βS −2 = Mα Sβ (o.32)
4. The concentration of free soluble metal decreases in the system because of formation of
soluble sulfide complexes and metal sulfide. Therefore depending on the value of complex
constant, there are dissociations of aqueous metal complexes and other soluble
complexes and depending on the saturation index there are dissolutions of salts,
hydroxides and hydrosulfates.
5. Due to presence of soluble oxygen, ferric, copper and manganese in the system, S −2 is
oxidized in elemental sulfur and polysulfide according to the half electrochemical
reactions (o.33) and (o.34). If Eh is high enough, elemental sulfur can be oxidized in
thiosulfate and/or sulfate (I. Piugdomenech et al, 2000). The rate of the oxidation
reaction of S −2 with soluble oxygen is slow at ambient temperature (Art. A. Migdisov,
1993). The oxidation of S −2 by oxygen is catalyzed iron, copper and manganese in the
system. Oxygen oxidizes ferrous to ferric and ferric oxidizes S −2 to elemental sulfur and
polysulfide (George W. Luther III et al, 2011).
S ° +2e− =S −2 (o.33)
Sλ−2+(2λ-2)e− =λS −2 (o.34)

6. Sλ−2 reacts with free soluble metal species to form soluble polysulfide complexes
according to the reaction (o.35) (Vutiswa Dube, 2015).
(αn−2β)
αM (+n) + β𝑆𝜆−2 = Mα (Sλ )β (o.35)
7. Depending on the saturation index, Sλ−2 reacts with free soluble metal species to form
polysulfide according to the reaction (o.36).
(−2)
αM (+n) + βSλ = M α Sλ (o.36)
8. The oxidation of S −2 into S ° and Sλ−2 decreases the concentration of S −2 in the system.
Therefore there are dissolutions, depending on the saturation index, of metal sulfides
and sometimes precipitations of salts, hydroxides and hydrosulfates.

sulfane-Case A
15.1. Total concentration of sulfur in sulfane compounds
Total concentration of sulfur in sulfane compounds is 0.1 mol/kg
15.2. Models
Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-Sulfane-water system is overall

equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-water system in which H2 S is added to reach a
certain value of total concentration of sulfur in free soluble sulfane compounds.
Construction of overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-Sulfane-water

system is done in two models. The first model contains steps from 1 to 4 of reaction pathways of
metal sulfide precipitation. This system appears when H2 S or sulfide salts are introduced in the
system quickly and there is not enough time to reach the equilibrium. The rate of precipitation
of metal sulfide is greater than the oxidation of sulfide in polysulfide. The second model contains
steps from 1 to 9 of reaction pathways. This system appears firstly when H2 S is introduced in the
system slowly for example the production of H2 S by decomposition of NH2 SCNH2 in water
according to the reaction (p.1). The rate of precipitation of metal sulfide is in competition with
the rate of oxidation of H2 S in polysulfide. This system appears secondly when the time is given
to the system to reach the equilibrium. These two systems have observed experimentally (O.O.
Balayeva et al, 2016).
NH2 SCNH2 +2H2 O=H2 S+2NH3 +CO2 (p.1)
15.3. Model 1
Sulfane compounds for each single overall equilibrium diagram are the following:
 Sulfane-water system
The soluble compounds of Sulfane-water system are: H2 S, HS − , and S −2 . H2 S is taken as

the reference. The chemical reactions (o.8) and (o.9) give relationship between the soluble
compounds and the reference.
HS − +H + =H2 S (o.8)
S −2+2H + =H2 S (o.9)

Equations from (14.4) and (14.5) give the concentrations of sulfane compounds as
Log(mSi2 )=log(mSi1 )+pH-7.02 (14.4)
Log(mSi3 )=log(mSi1 )+2pH-24.32 (14.5)

(15.1).
SiT =mSi1 +mSi2 +mSi3 (15.1)
 Copper system
Sulfide compounds of Cu-sulfide-water system are: solids (Cu2 S, and CuS) and soluble
(Cu(HS)− −
3 , CuHS, and Cu(HS)2 ). Cu
+2
is taken as the reference. The chemical reactions from (p.2)
to (p.3) give the precipitation reactions of solid compounds.
2Cu+2+H2 S+2e− =Cu2 S+2H + (p.2)
Cu+2 +H2 S=CuS+2H + (p.3)
Values of free Gibbs energies of formation at 25°C of copper sulfide compounds are
given in Table (15.1).
Table 15.1: Free energy of formation at 25°C
Reactions ΔG (kj/mol) References

Cu2 S -86.2 NBS, Wagman et al, 1982
CuS -53.6 NBS, Wagman et al, 1982
Equations from (15.2) to (15.3) give the saturation concentration of Cu+2 as function of
Eh and pH for the chemical reactions from (p.2) to (p.3) respectively at 25°C.
Log(m(Cu1) )= 16.949Eh-pH-0.5log(mSi1 )-16.617 (Cu2 S) (15.2)
Log((m(Cu1) )= -2pH-log(mSi1 )-15.957 (CuS) (15.3)

Sulfide soluble compound of copper are the following: Cu(HS)− −
3 , CuHS, and Cu(HS)2 . The
chemical reactions from (p.4) to (p.6) give the equilibrium reaction between soluble sulfide
compounds and Cu+2 .
Cu+2 +3H2 S =Cu(HS)−

3 +3H
+
(p.4)
Cu+2 +H2 S+e− =CuHS +H + (p.5)
Cu+2 +2H2 S+e− =Cu(HS)−

2 +2H
+
(p.6)
Values of logk of chemical reactions from (p.7) to (p.9) are given in Table (15.2).
Cu+2 +3HS − =Cu(HS)−

3 (p.7)
Cu+ +HS − =CuHS (p.8)
Cu+ +2HS − =Cu(HS)−

2 (p.9)

p.7 25.9 MINTEQA2-V.4, 1999
p.8 13.39 Thermoddem
p.9 17.4 Thermoddem

following:

2 is mCu6 ,
4 is mCu7 ,
+
Concentration of CuSO4 is mCu11 .
Concentration of Cu(HS)−3 is mCu12 .
Concentration of CuHS is mCu13 .
Concentration of Cu(HS)−2 is mCu14 .

Equations from (15.4) to (15.6) give the concentration of soluble sulfide compounds as
function of concentration of Cu+2 .
Log(mCu12 )=3pH+log(mCu1 )+ 3log(mSi1 )+4.84 (15.4)
Log(mCu13 )=-16.949Eh+pH+log(mCu1 )+log(mSi1 )+9.113 (15.5)
Log(mCu14 )=-16.949Eh+2pH+log(mCu1 )+2log(mSi1 )+6.094 (15.6)
Equation (15.7).
CuT =mCu1 +mCu2 +mCu3 +mCu4 +mCu5 +2mCu6 +3mCu7 +mCu8 +mCu9 +mCu10 +mCu11
+mCu12 +mCu13 +mCu14 (15.7)
 Cobalt system
Sulfide compounds of Co-sulfide-water system are: solids (CoS, Co3 S4 , and Co2 S3) and
soluble (Co(HS)+ , and Co(HS)2 ). Co+2 is taken as the reference. The chemical reactions from
(p.10) to (p.12) give the precipitation reactions of solid compounds.
Co+2 +H2 S=CoS+2H + (p.10)
Co3 S4 +8H + +2e(-)=3Co+2 +4H2 S (p.11)
Co2 S3 +6H + +2e(-)=2Co+2 +3H2 S (p.12)
Values of free Gibbs energies of formation at 25°C of cobalt sulfide compounds are given
in Table (15.3).

CoS -95.395 NBS, Wagman et al, 1982
Co3 S4 -348.95 NBS, Wagman et al, 1982
Co2 S3 -193.41 Calculated from logk
Equations from (15.7) to (15.9) give the saturation concentration of Co+2 as function of
Eh and pH for the chemical reactions from (p.10) to (p.12) respectively at 25°C.
Log((m(Co1) )= -2pH-log(mSi1 )-2.277 (CoS) (15.7)

Log(m(Co1))= -11.299Eh-2.667pH-1.333log(mSi1 )-4.319 (Co3 S4) (15.8)
Log(m(Co1))= -16.949Eh-3.000pH-1.500log(mSi1 )-0.055 (Co2 S3) (15.9)
Sulfide soluble compound of cobalt are the following: Co(HS)+, and Co(HS)2. The
chemical reactions from (p.13) to (p.14) give the equilibrium reaction between soluble sulfide
compounds and Co+2 .
Co+2 +H2 S=Co(HS)+ +H + (p.13)
Co+2 +2H2 S=Co(HS)2 +2H + (p.14)
Co+2 +HS − =Co(HS)+ (p.15)
Co+2 +2HS − =Co(HS)2 (p.16)


following:

−
Concentration of Co(OH)+2 is mCo10 ,
Concentration of CoSO4 is mCo11,
Concentration of Co(HS)+ is mCo12 ,
Concentration of Co(HS)2 is mCo13 ,
Equations (15.10) and (15.11) give the soluble sulfide compounds as function of
concentration of Co+2 .

Log(mCo12)=pH+log(mCo1)+log(mSi1 )-1.35 (15.10)
Log(mCo13)=2pH+log(mCo1)+2log(mSi1 )-5.27 (15.11)
Equation (15.12).
CoT =mCo1+mCo2+mCo3+mCo4+mCo5+2mCo6+4mCo7 +mCo8+mCo9+mCo10+mCo11 +mCo12+

mCo13 (15.12)
 Iron system
Sulfide compounds of Fe-sulfide-water system are: solids (FeS, CuFeS2 Fe3 S4) and
soluble (Fe(HS)2 and Fe(HS)− 3 ). Fe
+2
is taken as the reference. The chemical reactions from
(p.17) to (p.19) give the precipitation reactions of solid compounds.
Fe+2+H2 S=FeS+2H + (p.17)
Fe+2+Cu+2 +2H2 S=CuFeS2 +4H + (p.18)
Fe3 S4+8H + +2e(-)=3Fe+2+4H2 S (p.19)
Values of free Gibbs energies of formation at 25°C of iron sulfide compounds are given in
Table (15.5).

FeS -100.40 NBS, Wagman et al, 1982
CuFeS2 -187.71 NBS, Wagman et al, 1982
Fe3 S4 -306.43 NBS, Wagman et al, 1982
Equations from (15.13) to (15.15) give the saturation concentration of Fe+2 as function
of Eh and pH for the chemical reactions from (p.17) to (p.19) respectively at 25°C.
Log((m(Fe1) )= -2pH-log(mSi1 )-1.138 (FeS) (15.13)
Log((m(Fe1) )= -2pH-log(m(Cu1) )-2log(mSi1 )-20.724 (CuFeS2 ) (15.14)
Log(m(Fe1) )= -11.299Eh-2.667pH-1.333log(mSi1 )+2.474 (Fe3 S4) (15.15)
Sulfide soluble compound of iron are the following: Fe(HS)2 and Fe(HS)− 3 . The chemical
reactions from (p.20) to (p.21) give the equilibrium reaction between soluble sulfide compounds
and Fe+2.

Fe+2+2H2 S=Fe(HS)2 +2H + (p.20)
Fe+2+3H2 S=Fe(HS)−
3 +3H
+
(p.21)
Fe+2+2HS − =Fe(HS)2 (p.22)
Fe+2+3HS − =Fe(HS)−
3 (p.23)

p.22 8.95 MINTEQA2-V.4, 1999
p.23 10.99 MINTEQA2-V.4, 1999
The designation of concentration (mol/kg water) of soluble compounds of Fe is the

following:

+3
Concentration of Fe(OH)+ 2 is mFe7 ,
Concentration of Fe2 (OH)+4 2 is mFe10 ,
Concentration of Fe3 (OH)+5 4 is mFe11 .
Concentration of FeSO4 is mFe12 .
Concentration of FeHSO+2 4 is mFe13 .
Concentration of FeH(SO4 )2 is mFe14 .
Concentration of Fe2 (SO4 )3 is mFe15 .
Concentration of FeSO+ 4 is mFe16 .
Concentration of Fe(SO4 )− 2 is mFe17 .
Concentration of Fe(HS)2 is mFe18 .
Concentration of Fe(HS)− 3 is mFe19 .
Equations from (15.16) to (15.17) give the concentration of soluble sulfide compounds
as function of concentration of Fe+2.
Log(mFe18 )=2pH+log(mFe1 )+2log(mSi1 )-5.09 (15.16)

Log(mFe19 )=3pH+log(mFe1 )+3log(mSi1 )-10.07 (15.17)
Equation (15.18).
FeT =mFe1 +mFe2 +mFe3 +mFe4 +mFe5 +mFe6 +mFe7 +mFe8 +mFe9 +2mFe10 +3mFe11 +mFe12
+mFe13 +mFe14 +2mFe15 +mFe16 +mFe17 +mFe18 +mFe19 (15.18)
 Constraint on sulfate concentration
Total concentration of sulfur in free sulfate compounds (SaT ) is given by Equation

(13.32). SaT is fixed by the neutrality of the solution. Ratio of Ch+ (positive charge) onto Ch−
(negative charge) is equal to one. Values of Ch+ and Ch− are given by Equations (15.19) and
(15.20).
SaT =mSa1 +mSa2 (13.32)
Ch+ =mH1 +2mCu1 +mCu2 +2mcu6 +2mCu7 +mCu8 +2mCo1 +mCo2+3mCo6+2mCo7+3mCo9+2mCo10

+2mMg1 +mMg2 +2mFe1 +mFe2 +3mFe5 +2mFe6 +mFe7 +4mFe10 +5mFe11 +2mFe13 +mFe16 +
3mAl1 +2mAl2 +mAl3 +mAl6 +mCo12 (15.19)
Ch− =mH2 +2mCu4 +2mCu5 +2mcu10 +mCo4+2mCo5+mCo8 +mFe4 +mFe9 +mFe17 +mAl5 +2mAl7 +2
mSa1 +mSa2 +mCu12 +mCu14 +mFe19 (15.20)
Figure (15.1) gives the overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-sulfane-

water system at 25°C from model 1 (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al).
Figures (15.2), (15.3) and (15.4) give respectively total concentrations of Copper, Cobalt
and Iron; the molar fractions of soluble compounds at pH 1.5 as function of Eh and boundaries of
solid compounds at pH 1.5.

Figure 15.1: Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-sulfane-water system at
25°C from model 1 (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al)

Figure 15.2: Total concentration of copper, molar fractions of soluble compounds and
boundaries of solid compounds at 25°C and pH 1.5 from model 1 versus Eh
Figure 15.3: Total concentration of cobalt, molar fractions of soluble compounds and boundaries
of solid compounds at 25°C and pH 1.5 from model 1 versus Eh

Figure 15.4: Total concentration of iron, molar fractions of soluble compounds and boundaries of
solid compounds at 25°C and pH 1.5 from model 1 versus Eh
15.4. Model 2
Overall equilibrium diagram Model (2) is the overall equilibrium Model (1) that reaches
the equilibrium state. Sulfane compounds for each single overall equilibrium diagram are the
following:
 Sulfane-water system
Sulfane-water system contains: solid (elemental sulfur) and soluble compounds (species
in Table 14.3). H2 S is taken as the reference. The chemical reaction (o.7) gives the precipitation
reactions of solid compounds with the reference.
S ° + 2H + +2e− =H2 S (o.7)
Equation (14.3) gives the saturation concentration of H2 S as function of Eh and pH for

the chemical reaction (o.7) at 25°C.
Log(m(H2 S))= -33.898Eh-2pH+4.918 (14.3)
The soluble compounds of Sulfane-water system are given in Table (14.3). The chemical
reactions from (o.8) to (o.24) give reactions between of H2 S with other species.

HS − +H + =H2 S (o.8)
S −2+2H + =H2 S (o.9)
H2 S2 +2H + +2e− =2H2 S (o.10)
HS2− +3H + +2e− =2H2 S (o.11)
S2−2+4H + +2e− =2H2 S (o.12)
H2 S3 +4H + +4e− =3H2 S (o.13)
HS3− +5H + +4e− =3H2 S (o.14)
S3−2+6H + +4e− =3H2 S (o.15)
H2 S4 +6H + +6e− =4H2 S (o.16)
HS4− +7H + +6e− =4H2 S (o.17)
S4−2+8H + +6e− =4H2 S (o.18)
H2 S5 +8H + +8e− =5H2 S (o.19)
HS5− +9H + +8e− =5H2 S (o.20)
S5−2+10H + +8e− =5H2 S (o.21)
H2 S6 +10H + +10e− =6H2 S (o.22)
HS6− +11H + +10e− =6H2 S (o.23)
S6−2+12H + +10e− =6H2 S (o.24)

Concentration of S6−2 is mSi18 .
Equations from (14.4) to (14.20) give the concentrations of sulfane compounds as

Log(mSi2 )=log(mSi1 )+pH-7.02 (14.4)
Log(mSi3 )=log(mSi1 )+2pH-24.32 (14.5)


(14.21).
SiT =mSi1 +mSi2 +mSi3 +2mSi4 +2mSi5 +2mSi6 +3mSi7 +3mSi8 +3mSi9 +4mSi10 +4mSi11 +4mSi12 +5
mSi13 +5mSi14 +5mSi15 +6mSi16 +6mSi17 +6mSi18 (14.21)
 Cobalt system
Polysulfide compound of Co-sulfide-water system is: solid (CoS2 ). Co+2 is taken as the
reference. The chemical reaction from (p.24) gives the precipitation reaction of solid compound.
CoS2 +4H + +2e(-)=Co+2+2H2 S (p.24)
Value of free Gibbs energy of formation at 25°C of cobalt polysulfide compound is given
in Table (15.7).

CoS2 -145.6 NBS, Wagman et al, 1982
Equation from (15.21) gives the saturation concentration of Co+2 as function of Eh and
pH for the chemical reaction (p.24) at 25°C.
Log(m(Co1))= -33.898Eh-4pH-2log(mSi1 )-6.186 (CoS2 ) (15.21)
 Iron system
Polysulfide compound of Fe-sulfide-water system is: solid (FeS2). Co+2 is taken as the
reference. The chemical reaction from (p.25) gives the precipitation reaction of solid compound.
FeS2+4H + +2e(-)=Fe+2+2H2 S (p.25)
Value of free Gibbs energy of formation at 25°C of iron polysulfide compound is given in
Table (15.8).

FeS2 -160.2 NBS, Wagman et al, 1982

Equation from (15.22) gives the saturation concentration of Fe+2 as function of Eh and
pH for the chemical reaction (m.25) at 25°C.
Log(m(Fe1) )= -33.898Eh-4pH-2log(mSi1 )-4.446 (FeS2) (15.22)
Figure (15.5) gives the overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-sulfane-

water system at 25°C from model 2 (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al).
Figures (15.6), (15.7), (15.8) and (15.9) give respectively total concentrations of
Copper, Cobalt, Iron and sulfane, the molar fractions of soluble compounds and boundaries of
solid compounds at pH 1.5 as function of Eh.
Figure 15.5: Overall equilibrium diagram of Cu-Co-Mg-Fe-Al-Sulfate-sulfane-water system at

25°C from model 2 (black line-Cu, Green line-Co, Purple line-Mg, Red line-Fe and
Blue line-Al)

of solid compounds at 25°C and pH 1.5 from model 2 versus Eh

solid compounds at 25°C and pH 1.5 from model 1 versus Eh
Figure 15.9: Total concentration of sulfane, molar fractions of soluble compounds and

15.5. Observations
The differences between the results of Model (1) and Model (2) are the following:
 The precipitation of cobalt and iron polysulfide takes place around the equilibrium
potential of sulfane water system.
 Above the equilibrium potential of sulfane water system, there dissolution of metal
sulfide and precipitation of hydroxide or hydrosulfate because the concentration of
sulfide decreases when potential increases.

sulfane-Case B
16.1. Total concentration of sulfur in sulfane compounds
Total concentration of sulfur in sulfane compounds is decreased from 0.1 to 10−6

mol/kg
16.2. Model 1
Figures (16.1), (16.2) and (16.3) give respectively total concentrations of Copper, Cobalt
and Iron; the molar fractions of soluble compounds at pH 1.5 as function of Eh and boundaries of
solid compounds at pH 1.5 for model (1).
boundaries of solid compounds at 25°C and pH 1.5 from model 2 versus Eh for
model (1)

of solid compounds at 25°C and pH 1.5 from model 2 versus Eh for model (1)
solid compounds at 25°C and pH 1.5 from model 1 versus Eh for model (1)

16.3. Model 2
solid compounds at pH 1.5 as function of Eh for model (2).
model (2)


16.4. Observations
When the total concentration of sulfur in the sulfane compounds decreases from 0.1 to
−6
10 mol/kg:
 Iron sulfides do not precipitate at pH in the model (1). This means that it is
possible to precipitate metal sulfide selectively by controlling the total
concentration of sulfur in the sulfane compounds at certain value of pH.
 The polysulfide of cobalt precipitates and cobalt sulfides disappear in the system
between model (1) and model (2).
 Eh equilibrium potential of sulfane water system moves from 0.086 to 0.234V in
the model (2).
 Eh equilibrium potential of sulfane water system remains inside of CuS
precipitation zone.

sulfane-water system – Case C
17.1. Maximum value of Eh
17.1.1. Model 1
In the model (2), the Eh equilibrium potential of sulfane water system is moved to the
potential (Eh 0.506V - (figure 16.4)). Above this Eh value, the concentration of copper in solution
is high than the target value (0.002 mol/kg) at pH 1.5.
model (2)


Figure (17.1) show that when equilibrium Eh of sulfane water system reaches 0.506V,
The concentration of sulfur in sulfane compounds is around 5.881*10−16 mol/kg.. This Eh is in a
stability zone of CuS but Eh of the boundary of the stability zones of Cu2 S and CuS is about
0.393V at pH 1.5. At this Eh, there is not precipitation of polysulfides of cobalt and iron in the
model (2).
17.1.2. Model 1
The model (1) is constructed with the total concentration of sulfur in the sulfane
compounds found in the model (2). Figures (17.5), (17.6) and (17.7) give respectively total
concentrations of Copper, Cobalt and Iron; the molar fractions of soluble compounds at pH 1.5 as
function of Eh and boundaries of solid compounds at pH 1.5 for model (1).

model (1)

The results show that, at Eh of 0.506V, the copper precipitates as CuS. The boundary of
the stability zones of Cu2 S and CuS is at Eh about 0.393V at pH 1.5 in the model (1).
The maximum value of Eh above that copper concentration in solution is high than 0.002
mol/kg is 0.506V at pH 1.5.
17.2. Minimum value of Eh
17.2.1. Model 1
The minimum value of Eh of copper precipitation is the Eh where cobalt starts to

precipitate as polysulfide. In the model (2), the Eh equilibrium potential of sulfane water system
is moved to Eh value. Below this Eh value, cobalt starts to precipitate as cobalt polysulfide.

model (2)

Figure 17.10: Total concentration of iron, molar fractions of soluble compounds and boundaries
Eh value below that cobalt starts to precipitates as cobalt polysulfide is 0.429V at pH 1.5
and the total concentration of sulfur in the sulfane compounds is about 2.463*10−13 mol/kg. This
Eh value is inside of the stability zone of CuS.

sulfane-water system –Case D
18.1. Effect of aqueous species activity on maximum and minimum Eh
The presence of other aqueous species in the solution can change the solubility of H2 S in
solution. Helgeson Equation of activity (chapter 2.1.4.4) and water activity (chapter 2.1.4.5.) are
applied to Model (2). The example of application of Helgeson Equation of activity and water
activity is in this publication (J. Kafumbila, 2020).
18.2. Maximum value of Eh
model (2)


The maximum value of Eh obtained with activity of soluble compounds is 0.500V. This
value is close the maximum Eh about 0.506V obtained without activity of soluble compounds.
The concentration of sulfur in sulfane compounds is around 9.659*10−16 mol/kg. This Eh is
inside of CuS stability zone.
18.3. Minimum value of Eh

model (2)

When activity of soluble compounds is applied in the model (2), Eh value below that
cobalt starts to precipitates as cobalt polysulfide is 0.421V and the total concentration of sulfur
in the sulfane compounds is about 4.285*10−13mol/kg. This Eh value is inside of the stability
zone of CuS.

sulfane-water system –Case E
19.1. Solubility curve of copper
The solubility curve developed in chapter (5) is applied to copper sulfide selective
precipitation. Here the solubility curve is established with mixed precipitation concept without
activity of soluble compounds. The solubility curve is established around the maximum Eh giving
the desired copper concentration in the solution after precipitation. Eh value is 0.506V and the
total concentration of sulfur in the sulfane compounds is 5.881*10−16mol/kg are used. The
concentration of other metals remains the same.
19.2. Model 1
Figure (19.1) gives the molar fractions of solid compounds in the mixture and the
solubility curve of copper in model (1) at pH 1.5.
Figure (19.1): Molar fractions of solid compounds in the mixture and the solubility curve of
copper in model (1) at pH 1.5.

19.3. Model 2
Figure (19.2) gives the molar fractions of solid compounds in the mixture and the
solubility curve of copper in model (2) at pH 1.5.
Figure (19.2): Molar fractions of solid compounds in the mixture and the solubility curve of
copper in model (2) at pH 1.5.
19.4. Observations
Figures (19.1) and (19.2) show that:
 Above Eh of 0.506V, CuS is instable because of reduction of concentration of

sulfide due to oxidation into elemental sulfur and polysulfide.
 Below Eh of 0.506V, CuS is stable.
 At Eh of 0.506V, it possible to obtain pure CuS.

20. References
Gecamines, Visit report to OMG-kokkola and Outokumpu, Department of Metallurgical
research, 2000.
Hsin-Hsiung Huang, The Eh-pH diagram and its advances, Metals, 2016.
I. Piugdomenech et al, Thermodynamic data for copper: Implications for the corrosion of
copper under repository conditions, Technical Report, SKB, August 2000.
Joseph Kafumbila, Upgrading of E-pH diagram of Cu-S-Water system by associating the

theories of mixed precipitation of solids in aqueous solution and hydrothermal, technical
report, Researchgate, 2018
Joseph Kafumbila, Selective sulfide precipitation of copper, cobalt and iron from leach
solution: Thermodynamic study, Presentation, Researchgate, 2019.
I. Puigdomenech et al, Temperature corrections to thermodynamic data and Enthalpy

calculations, NEA, October 1999.
K. Thomsen, Aqueous electrolytes model parameters and process simulation, Thesis,

Technical University of Denmark, 1997.
J. Kielland, Individual activity coefficients of ions in aqueous solutions, J. Am. Chem. 1937
H.C. Helgeson et al, Theoretical prediction of the thermodynamic behavior of aqueous

electrolytes at high pressures and temperatures: IV calculation of activity coefficients,
osmotic coefficients, and apparent molal and standard and relative partial molal properties
to 600°C and 5 KB, American Journal of Science, Vol. 281, December, 1981, PP 1249-1516.
Bjorn Beverskog et al, Pourbaix diagrams for the system copper – chlorine at 5 – 100°C, SKI
Rapport 98:19, April 1998.
Charles E. Harvi et al, The prediction of mineral solubilities in natural water: Na-K-Mg-Ca-H-
Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C, Geochemical et
Cosmochimica Acta (1984) Vol. 48 pp 723-751.
H.C. Helgeson, Thermodynamics of hydrothermal systems at elevated temperatures and

pressures, American Journal of Science 267, 1969, 729-804.

W.T. Thompson et al, Pourbaix diagrams for multi-element systems, Uhlig’s corrosion
handbook Edition, Edited by R. Winston, 2000.
V.L. Vinograd et al, Thermodynamics of the solid solution – aqueous solution system (Ba, Sr,
Ra)SO4 + H2O. I. The effect of Strontium content on radium uptake by barite, Applied
Geochemistry 89 (2018) 59-74.
P.S.O. Beltrao et al, A reliable procedure to predict salt precipitation in pure phases, Brazilian
Journal of Chemical Engineering, Vol. 27, No 1, 2010.
O.O. Balayeva et al, Synthesis and characterization of cobalt sulfide/FNBR nanocomposites

by silar method, Journal of ovonic research, Vol. 12, No. 6, 2016.
Clare Robinson, The role of jarosite and copiapite in the chemical evolution of acid drainage
waters, Richmond Mine, Iron Mountain, California, Thesis, Queen’ university, 2000
M. Singh et al, Crystallization of copper (II) sulfate based minerals and MOF from solution:
Chemical insights into the supramolecular interactions, J. Chem. Sci., Vol. 122, No. 5, 2010.
W.B. White, Thermodynamic equilibrium, Kinetics, Activation barriers, and reaction

mechanisms for chemical reactions in Karst Terrains, Environmental Geology 20 (1/2) Mach
1997.
Vuyiswa Dube, Study of selective removal of CoS and NiS during purification of MnSO4
electrolyte, thesis, university of Cape Town, 2015.
M. Pourbaix, Atlas d’équilibres électrochimiques à 25°C, Gauthier and CEBELCOR, 1963.
Rutio-Luo, Overall equilibrium diagrams for hydrometallurgical systems: copper-NH3-H2O

system, Elsevier science publishers, 1978.
D.D. Wagman et al, The NBS Tables of chemical thermodynamic properties, selected values
for inorganic and 𝐶1 and 𝐶2 organic substances in SI units, Journal of physical and chemical
reference Data, 11, (supplement No 2), 2-276-2-282. Washington D.C.: American chemical
society (1982).
U.S. Department of Energy, Qualification of thermodynamic Data for geochemical modelling

of mineral – water interactions in dilute systems, 2004.
B.P.C. Grover et al, Mineralogy and geochemistry of efflorescent minerals on mine tailings
and their potential impact on water chemistry, Environ Sci Pollut Res (2016) 23: 7338-7348.
Jing Ning et al, Thermodynamic study of hydrogen sulfide corrosion of Mild Steel, Corrosion
– Vol.70(2014) p: 375-389.

R.J. Remick and E.H. camara, Electrochemistry of the sulfide/polysulfide couple, LBC, 1983.
Thomas Provijn, Electrochemical recovery of sodium and sulfur species from spent caustic
streams, thesis – Universiteit Gent, 2015.
Art. A. Migdisov, Low-Temperature hydrothermal experiments on the H2S-H2O-Sc system,

Geochemistry international, 30(4), 1993.
Aysel Sen et al, Selective sulphide precipitation of Copper, Nickel and Zinc from industrial
wastewater, 18th International Metallurgy and Material Congress, 2016, pp 363-366.
George W. Luther III et al, Thermodynamics and kinetics of sulfide oxidation by oxygen: a
look at inorganically controlled reactions and biologically mediated processes in the
environment, Frontiers in Microbiology, 2011.
J. Kafumbila, Iron precipitation during leaching of copper and cobalt ores: Geochemical
modeling, Technical report, Researchgate, 2020

Overall Equilibrium Diagram of Cu Co MG Fe Al Sulfate Sulfane Water System

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METALLURGIST

Overall equilibrium diagram

Joseph Kafumbila Page 1

1. EQUILIBRIUM CONDITION OF E-PH DIAGRAM SYSTEM 6

1.1. THERMODYNAMIC SYSTEM 6

2.1. ACTIVITY OF SOLUBLE SUBSTANCES 10

4. ESTIMATION OF FREE GIBBS ENERGY FROM EXPERIMENTAL DATA 18

6. KINETIC ASPECT OF METAL PRECIPITATION 34

6.1. PRECIPITATION REACTION 34

8. OVERALL EQUILIBRIUM DIAGRAM 40

9. OVERALL EQUILIBRIUM DIAGRAM OF WATER SYSTEM 44

10. OVERALL EQUILIBRIUM DIAGRAMS OF METAL-WATER SYSTEM WITHOUT AQUEOUS COMPLEXES 46

10.1. OVERALL EQUILIBRIUM DIAGRAM OF CU-WATER SYSTEM 46

11. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-WATER SYSTEM WITHOUT AQUEOUS

12. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-WATER SYSTEM WITH AQUEOUS COMPLEXES 58

13. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-WATER SYSTEM 67

14. OVERALL EQUILIBRIUM DIAGRAM OF SULFANE-WATER SYSTEM 78

15. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-CASE A 87

Joseph Kafumbila Page 3

16. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-CASE B 105

16.1. TOTAL CONCENTRATION OF SULFUR IN SULFANE COMPOUNDS 105

17. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM – CASE C 110

17.1. MAXIMUM VALUE OF EH 110

18. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM –CASE D 117

18.1. EFFECT OF AQUEOUS SPECIES ACTIVITY ON MAXIMUM AND MINIMUM EH 117

19. OVERALL EQUILIBRIUM DIAGRAM OF CU-CO-MG-FE-AL-SULFATE-SULFANE-WATER SYSTEM –CASE E 122

19.1. SOLUBILITY CURVE OF COPPER 122

20. REFERENCES 124

Joseph Kafumbila Page 4

Therefore E-pH diagrams of Cu-sulfane-water system, Co-sulfane-water system and Fe-

Joseph Kafumbila Page 5

1.1. Thermodynamic system

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

1.2. Gibbs free energy

Joseph Kafumbila Page 6

μ=μ° + R*T*2.303*Log(a) (1.5)

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

1.2.3. Electrochemical potential energy

Joseph Kafumbila Page 7

1.3. General equilibrium condition

dGcp = υc *μC + υd *μD - υa *μA - υb *μB (1.11)

dGep = υe *F*E (1.12)

dGcp + dGep = 0 (1.13)

1.4. Standard equilibrium constant

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 (1.14)

Combination of Equations (1.5) and (1.14) gives Equation (1.15).

The standard equilibrium constant is given by Equation (1.16) at a given temperature

ΔG° =υC μ°C +υD μ°D − υA μ°A − υB μ°B (1.18)

Joseph Kafumbila Page 9

2.1. Activity of soluble substances

2.1.1. Ionic strength

2.1.2. Activity scales

μA =μ°A + R*T*2.303*Log(CA ) + R*T*2.303*Log(γA ) (2.3)

Joseph Kafumbila Page 10

2.1.2.3. Ionic medium scale

2.1.3. Mean ion activity coefficients

μ(Na+) = μ°(Na+) + RTln(C(Na+) ) + RTln(γ(Na+) ) (2.4)

μ(Cl−) = μ°(Cl−) + RTln(C(Cl−) ) + RTln(γ(Cl−) ) (2.5)

The total free energy is written as the sum (Equation 2.6).

GT = μ(Na+) + μ(Cl−) = μ°(Na+) + μ°(Cl−) + RTln(C(Na+) *C(Cl−) ) + RTln(γ(Na+) *γ(Cl−) ) (2.6)

GT (µ(Na+ ) + µ(Cl−) ) (µ°(Na+) + µ°(Cl−) )

μ ± = μ° ± + RTln(C±) + RTln(γ±) (2.8)

μ=μ° + RT2.303*Log(a) (1.5)

dGcp = υc μC + υd μD - υa μA - υb μB (1.11)

dGep = υe FE (1.12)

dGcp +dGep = υc μC + υd μD - υa μA - υb μB +υe FE =0 (1.14)

μA =μ°A + RT2.303Log(CA ) + RT2.303Log(γA ) (2.3)

GT = μ(Na+) + μ(Cl−) = μ°(Na+) + μ°(Cl−) + RTln(C(Na+) C(Cl−) ) + RTln(γ(Na+) γ(Cl−) ) (2.6)

μA =μ°A +2.303RT.log(γA *XA ) (2.18)

μB =μ°B +2.303RT.log(γB *XB ) (2.19)

μ(Aα Bβ ) =XA μA +XB μB (2.20)

μC =μ°C +2.303RT.log(XC ) (3.1)

μD =μ°D +2.303RT.log(XD ) (3.2)

μ(Cα Dβ ) =XC μC +XD μD (3.3)

ln (aw ) = - 1.80210−2ϕ*∑i mi (4.3)

mSa2 =10(1.99)mH1 msa1 *γ2 (4.6)

mSa3 =10(0.08)(mH1 )2msa1 γ2 (γ1 )2 (4.7)

mMg3 =10(2.26) mMg1 mSa1 *(γ2 )2 (4.9)

μ(Mg+2 ) =μ°(Mg+2 ) +8.314298.152.303log(mMg1 γ2 ) (4.15)

μ(H2 O) =μ°(H2 O) +8.314298.152.303*log(aw ) (4.17)