PROJECT METALLURGIST

Manganese behavior in
Cobalt electrowinning cell
Thermodynamic study

KAFUMBILA KASONTA JOSEPH

2024
Manganese behavior in Cobalt electrowinning cell: Thermodynamic study
© Joseph Kafumbila 2024
[email protected]

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 Process simulation
Chemical engineering can be defined from many different aspects. However, all
the scientists and professionals agree that the process is the center of it. To make a
distinction from any other discipline, the role of chemical engineering could be defined
with its purpose to develop, design, construct, control, optimize and mange any process
involving physical and/or chemical changes and make this process profitable.

Process simulation as discipline uses mathematical models as basis for analysis

prediction, testing, detection of a process behavior unrelated to whether the process is
existing in reality or not. Process simulation is there to increase the level of knowledge
for a particular process and chemical engineering in general.

So, when those two concepts are put together, we can look into the chemical
engineering as a discipline defining how the process should be developed and
simulation as the tool helping us to explore the options. Chemical engineering needs to
know how the process should be designed while chemical engineers use the simulation
to explore all the process design options and define the optimal one.

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 Abstract
This publication finds the realistic mechanism of Manganese electrodeposition
at the anode as sludge in Cobalt electrowinning cell. Cobalt starts to plat at the anode as
CoOOH because of the high Cobalt concentration in solution. After CoOOH oxidizes
Manganese into MnOOH. At the end MnOOH reacts with acid to produce Manganese
dioxide. The increase in Manganese concentration in the Cobalt solution decreases the
Grade of Cobalt in the anodic sludge. The use of the Realistic Simulation Program base
on the thermodynamic equilibrium of soluble species allows modeling the Cobalt
electrowinning cell. The modeling of Cobalt electrowinning cell shows that there are two
anodic potential, the first anodic potential depends on the external power and it is
potential of metallic anode. The second anodic potential depends on the composition of
soluble species in front of the anode which is fixed by the kinetic of oxidation of water
into oxygen and it is the potential of solution.

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 Contents

1. Cobalt electrowinning 9
1.1. Modeling configuration of electrowinning cell 9
1.2. Cathode 10
1.2.1. First group of chemical reactions 10
1.2.2. Second group of chemical reactions 18
1.3. Anodic reaction 22
1.3.1. First group of chemical reactions 22
1.3.2. Second group of chemical reactions 30
1.4. Precipitation of MnOOH into solution 33
1.4.1. Location of MnOOH precipitation into solution 33
1.4.2. Chemical reactions 34
1.5. Cell voltage 34
1.5.1. Reversible voltage 35
1.5.2. Over potential of Cobalt on the cathode 35
1.5.3. Over potential of oxygen on the anode 35
1.5.4. Electrode contact resistance voltage drop 36
1.5.5. Electrode internal resistance voltage drop 36
1.5.6. Electrolyte resistance voltage drop 36
1.5.7. Energy consumption 36
2. Thermodynamic 37
2.1. Equilibrium condition 37
2.1.1. Thermodynamic system 37
2.1.2. Gibbs free energy 37
2.1.3. General equilibrium condition 39
2.1.4. Standard equilibrium constant 40
2.2. Free Gibbs energy at elevated temperature 41
2.2.1. Compound (solid, gas and soluble in solution) 41
2.2.2. Soluble compound without heat capacity 41
2.2.3. Chemical reaction without heat capacity 42
2.3. Precipitation process 42
2.3.1. Definition 42

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 2.3.2. Precipitation – condition 42
2.4. Free acid concentration in Cobalt electrowinning electrolyte 43
2.4.1. First free acid concentration 43
2.4.2. Second free acid concentration 45
2.5. Activity of soluble species 45
2.5.1. Ionic strength 45
2.5.2. Water activity 45
2.5.3. Activity coefficients 46
3. Eh-pH diagram of Mn-Water system 48
3.1. Overall equilibrium diagram 48
3.1.1. Definition 48
3.1.2. Thermodynamic conditions 48
3.1.3. Construction step of E-pH diagram 49
3.1.4. Boundary of two solid compounds 49
3.1.5. Concentrations of other soluble compounds 50
3.1.6. Boundary of aqueous solution and solid compounds 50
3.1.7. Boundary of two soluble compounds 51
3.2. Overall equilibrium diagram with heterogeneous solid solution 52
3.2.1. Thermodynamic conditions 52
3.2.2. Boundary of two solid compounds 52
3.3. Assumptions on Eh-pH diagram of Mn-Water system 53
3.4. Overall Eh-pH diagram of Mn-water system 54
3.4.1. Thermodynamic Data 54
3.4.2. Overall diagram of Mn-Water system 54
4. Mass balance of Cobalt electrowinning circuit – Anode potential at
saturation concentration of Mn(III) 57
4.1. Flow diagram 57
4.2. Problematic 58
4.3. Design criteria 58
4.3.1. Inlet solution 58
4.3.2. Down flow solution 60
4.3.3. Bottom mixed solution 60
4.3.4. Electrode inlet solution 60
4.3.5. Inlet cathodic up flow solution 62
4.3.6. Outlet cathodic up flow solution 63
4.3.7. Inlet anodic up flow solution 66

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 4.3.8. Outlet anodic up flow solution 66
4.3.9. Top mixed solution 70
4.3.10. Electrode outlet solution 70
4.3.11. Outlet solution 73
4.4. Mass balance 73
4.4.1. System A 73
4.4.2. System B 75
4.5. Observations 77
5. Mass balance of Cobalt electrowinning circuit – Anode potential at
saturation concentration of Co(III) 78
5.1. Flow diagram 78
5.2. Problematic 78
5.3. Design criteria 78
5.3.1. Outlet anodic up flow solution 78
5.4. Mass balance 79
5.4.1. System A 79
5.4.2. System B 81
5.5. Observations 84
6. Mass balance of Cobalt electrowinning circuit – Anodic potential at value of
Manganese current efficiency 85
6.1. Problematic 85
6.2. Flow diagram 86
6.3. Design criteria 86
6.3.1. Outlet anodic up flow solution 86
6.4. Mass balance 86
6.4.1. System A 86
6.4.2. System B 89
6.5. Observations 91
7. Mass balance of Cobalt electrowinning circuit – Anode potential of solution
in front of anode surface and Anode potential of metallic anode at Cobalt
saturation concentration 92
7.1. Problematic 92
7.2. Flow diagram 92
7.3. Design criteria 92
7.3.1. Outlet anodic up flow solution 92
7.4. Mass balance 93
7.4.1. System A 93

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 7.4.2. System B 95
7.5. Observations 98
8. Mass balance of Cobalt electrowinning circuit – Anode potential of solution
in front of anode surface, Anode potential of metallic anode and Cobalt
adsorption onto Manganese solid surface 99
8.1. Problematic 99
8.2. Flow diagram 99
8.3. Design criteria 99
8.3.1. Outlet anodic up flow solution 99
8.4. Mass balance 100
8.4.1. System A 100
8.4.2. System B 103
8.5. Observations 105
9. Mass balance of Cobalt electrowinning circuit – Anode potential of solution
in front of anode surface, Anode potential of metallic anode, Cobalt
adsorption into Manganese solid and electrodeposition of CoOOH on the
anode 107
9.1. Problematic 107
9.2. Flow diagram 107
9.3. Design criteria 107
9.4. Mass balance 108
9.4.1. System A 108
9.4.2. System B 110
9.5. Observations 113
10. Mass balance of Cobalt electrowinning circuit – Anode potential of solution
in front of anode surface, Anode potential of metallic anode, Cobalt
adsorption into Manganese solid, electrodeposition of CoOOH on the anode
and Oxidation of Manganese by CoOOH 114
10.1. Problematic 114
10.2. Flow diagram 114
10.3. Design criteria 114
10.4. Mass balance 116
10.4.1. System B 116
10.5. Observations 118
11. Mass balance of Cobalt electrowinning circuit – Anode potential of solution
in front of anode surface, Anode potential of metallic anode, Cobalt
adsorption into Manganese solid and electrodeposition of CoOOH on the
anode with a known oxygen anodic current efficiency 120
11.1. Problematic 120

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 11.2. Flow diagram 120
11.3. Design criteria 120
11.4. Mass balance 120
11.4.1. System B 120
11.5. Observations 123
12. References 124

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1. Cobalt electrowinning

1.1. Modeling configuration of electrowinning cell

Figure (1.1) and (1.2) show the hydrodynamic of electrowinning cell. The tracer
test shows that (A.C. Scott et al, 1987; Mahjabin Najminoori at al, 2015):

 Inlet solution goes to the bottom of the cell.

 Bottom cell solution rises through the electrodes to the top of the cell
into two up-flows. The first up-flow is near of the cathode surface. At the
cathode surface metal is plated, lowering the concentration and
decreasing the solution density. This causes solution to naturally rise
near the surface of the cathode. In the case there is hydrogen evolution
on the cathode surface, this increases the velocity of up-flow near the
cathode surface. The second up-flow is near of anode surface. At the
anode surface oxygen gas is evolved. This gas pushes up solution as it
rises.
 The cathode and anode up-flows are mixed at the top of the cell and
mixed solution is the outlet solution of the cell.
 One part of the top mixed solution is recycled to the bottom of the cell
between the two up-flows. The recycled solution (down-flow) and inlet
solution are mixed at the bottom of the cell. The ratio of flowrates of
down-flow and inlet solution varies from 2 to 9. This ratio increases with
the increase of current density. The bottom mixed solution gives the
chemical composition of the two up-flows (near cathode and anode).
 There is electrical neutrality of solution at each place of cell solution. In
the electrowinning cell of metal in presence of acid, most of the electrical
current in solution is carried by hydrogen ions. The hydrogen ions are
migrated from anode to cathode. There is an increase in acidity to the
cathode.

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 Figure 1.1: Hydrodynamic of electrowinning cell: Inlet and outlet solution

Figure 1.2: Hydrodynamic of electrowinning cell: up and down flows between electrodes

1.2. Cathode

1.2.1. First group of chemical reactions

1.2.1.1. Chemical reactions

In solution containing Cobalt and Manganese, the first group is constituted with
electrochemical reactions that appear due to decreasing of cathodic potential. These
electrochemical reactions are the following:

 Cobalt plating on the cathode

Co+2 + 2e− = Coo (1.a)

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  Hydrogen evolution on the cathode

2H + + 2e− = H2 ‘ (1.b)

 Co+3 reduction to Co+2

Co+3 + e− = Co+2 (1.c)

 Mn+3 reduction to Mn+2

Mn+3 + e− = Mn+2 (1.d)

 MnO−
4 reduction to Mn
+2

MnO− + − +2
4 +8H +5e =Mn +4H2 O (1.e)

1.2.1.2. Thermodynamic

1.2.1.2.1. Reaction (1.a)

°
The redox potential of reaction (1.a) is given by Equation (1.1). Where “Eh(1.a) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “2” is the number of electron, and “a(Co+2 )” is the activity of
Co+2 ion.

° R∗T∗2.303
Eh(1.a) =Eh(1.a) + *log(a(Co+2 ) ) (1.1)
2∗F

1.2.1.2.2. Reaction (1.b)

°
The redox potential of reaction (1.b) is given by Equation (1.2). Where “Eh(1.b) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “2” is the number of electron, “a(H+ ) ” is the activity of hydrogen ion and
“P(H2 ) ” is the partial pressure of hydrogen gas (1 atm).

R∗T∗2.303 (𝑎(H+ ) )2
°
Eh(1.b) =Eh(1.b) + *log( ) (1.2)
2∗F P(H2 )

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1.2.1.2.3. Reaction (1.c)

°
The redox potential of reaction (1.c) is given by Equation (1.3). Where “Eh(1.c) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “a(Co+3 ) ” is the activity of Co+3 ion and “a(Co+2 ) ” is the activity of Co+2
ion.

R∗T∗2.303 a +3 )
°
Eh(1.c)=Eh(1.c) + *log(a(Co ) (1.3)
F (Co+2 )

1.2.1.2.4. Reaction (1.d)

°
The redox potential of reaction (1.d) is given by Equation (1.4). Where “Eh(1.d) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mole*K), “F” is Faraday
constant (96485 c/mole), “a(Mn+3 ) ” is the activity of Mn+3 ion and “a(Mn+2 ) ” is the
activity of Mn+2 ion.

R∗T∗2.303 a +3 )
°
Eh(1.d) =Eh(1.d) + *log(a(Mn ) (1.4)
F (Mn+2 )

1.2.1.2.5. Reaction (1.e)

°
The redox potential of reaction (1.e) is given by Equation (1.5). Where “Eh(1.e) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “𝑎(MnO−4 ) ” is the activity of MnO− +
4 ion, “𝑎(H+ ) ” is the activity of H ion,
“a(Mn+2 ) ” is the activity of Mn+2 ion and “aw ” is the activity of water.

R∗T∗2.303 𝑎(MnO− ) ∗(𝑎(H+ ) )8

° 4
Eh(1.e) =Eh(1.e) + *log( ) (1.5)
5∗F 𝑎(Mn+2 ) ∗(𝑎𝑤 )4

1.2.1.3. Kinetic

1.2.1.3.1. Reaction (1.a)

Figure (1.3) gives the polarization curve of cobalt plating where Ec (cathodic
potential) is a function of log (i) (current density).

The Tafel line is ranged between log(i1 ) and log(i2 ). On the Tafel line, the cobalt
plating rate is controlled by electron transfer. “il ” is limit current density. Cobalt plating
rate is controlled by the cobalt ion mass transfer to the cathode. Between log(i2 ) and

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log(il ), the cobalt plating rate is controlled by the mixt regime (electron transfer and
cobalt ion mass transfer to the cathode). “io ” is exchange current density.

Figure 1.3: Polarization curve of Cobalt plating

A. Limit current density

Equation (1.6) gives the value of the Cobalt limiting current density from which
l
Cobalt powder starts to be produced. Where “ICo ” is the limiting current density (A/m2 ),
“z” is moles of electrons per mole of Cobalt, “F” is Faraday constant (96485 c/mole),
“k Co ” is the transfer coefficient (m/s) and “CCo ” is the bulk electrolyte of Cobalt
(mole/dm3).

l
ICo = z * F * k Co * CCo (1.6)

The value of mass transfer coefficient is depended on the electrolyte properties

and electrolyte agitation. Maximum current density that can be applied in industrial
operations is normally about 30-40% of the limiting current density. A rule-of-thumb is
that the ratio current density (A/m2) on metal concentration in spent electrolyte (g/L)
must be less than 10.

B. Tafel Equation

Equation (1.7) gives Tafel Equation of Cobalt plating. It has been observed that
the value of “b(1.a) ” depends on the nature of electrode and nature and concentrations of
active soluble compounds.

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 ρ(1.a) =a(1.a) +b(1.a) *log(i(1.a)) (1.7)

Equation (1.8) gives the over-potential of the chemical reaction (1.a). “ρ(1.a) ” is
Cobalt plating over-potential (V), “Eh(1.a) ” is redox potential of reaction (1.a) and “E(c) ” is
cathodic potential (V). It has been observed that the over-potential decreases with the
increase of temperature.

ρ(1.a) =E(c) -Eh(1.a) (1.8)

C. Plating mass

The mass of Cobalt deposited on the cathode is given by Faradays law. Faraday
law is given by Equation (1.9). Where “MCo ” is the mass of Cobalt (gram), “F” is the
Faraday constant (96485 c/mole), “58.93” is Cobalt molar mass (g/mole), “2” is moles of
electron per mole of Cobalt, “t” is the time when current has been applied (seconds) and
“I” is the current amperage (A).

1 58.93
MCo = F * *t*I (1.9)
2

1.2.1.3.2. Reaction (1.b)

It has been observed that for the reaction in which gas is evolved (hydrogen on
the cathode or the oxygen on the anode) the charge transfer kinetic is very slow because
of the mechanism (A.C. Scott et al, 1987). The mechanism of the hydrogen evolution has
three possible reaction steps (Andrzej Lasia, 2019):

H + +e− =Hads (Volmer reaction) (1.f)

H + +Hads +e− =H2 (Heyrovsky reaction) (1.g)

2Hads =H2 (Tafel reaction) (1.h)

These reactions can follow several different pathways on the cathode, most
consisting of two reaction steps: the Volmer-Tafel pathway, the Volmer-Heyrovsky
pathway, and the Tafel-Heyrovsky pathway.

Figure (1.4) gives the polarization curves of hydrogen evolution. Tafel line is
between log(ia ) and log(ib ).

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 Figure 1.4: Polarization curves of hydrogen evolution

A. Limit current density

Figure (1.4) shows that from log(ib ) the value of potential is exponential
function of log(i). The reason for this is presumably bubble formation that covers the
cathode active area and increases the over-potential. The cathode active area decreases
with the increase of current density (Chris van de Goor, 2015).

B. Tafel Equation

Equation (1.10) gives Tafel Equation of hydrogen evolution. It has been

observed that the value of “b(1.a)” depends on the nature of the electrode and pH. This
reaction takes places on all surface of cathode. At the same current density, the value of
b(1.a) is high at high pH in the range of pH less than 7.

ρ(1.b) =a(1.b) +b(1.b)*log(i(1.b) ) (1.10)

Equation (1.11) gives the over potential of the chemical reaction (1.b). “ρ(1.b)” is
hydrogen over-potential (V), “Eh(1.b) ” is redox potential of reaction (1.b) and “E(c) ” is
cathodic potential (V). It has been observed that the increase in temperature decreases
the over-potential at the same current density and pH.

ρ(1.b) =E(c) - Eh(1.b) (1.11)

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1.2.1.3.3. Reactions (1.c)

Due to low concentration of Co+3 the kinetic of reaction (1.c) is controlled by

the diffusion of ions to the cathode. Equation (1.12) gives the current density. Where
“i(Co+3 ) ” is the current density of soluble substance “Co+3”, “z” is moles of electrons per
mole of soluble substance “Co+3 ”, “F” is Faraday constant (96485 c/mole), “k (Co+3 )” is
the transfer coefficient (m/s) and “C(Co+3 ) ” is the bulk electrolyte of soluble substance
(mol/dm3).

i(Co+3 ) = z * F * k (Co+3 ) * C(Co+3 ) (1.12)

1.2.1.3.4. Reactions (1.d) and(1.e)

Figure (1.5) gives the polarization curve of reduction of Mn+3or MnO− 4 on the
cathode. Where Ec (cathodic potential) is a function of log (i) (current density).

The Tafel line is ranged between log(i1 ) and log(i2 ). On the Tafel line, the
reduction rate is controlled by electron transfer. “il ” is limit current density reduction
rate is controlled by the Mn+3or MnO− 4 ion mass transfer to the cathode. Between log(i2 )
and log(il ), the reduction rate is controlled by the mixt regime (electron transfer and
diffusion). “io ” is exchange current density.

Figure 1.5: Polarization curve of reduction of Mn+3 orMnO−

4 on the cathode

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 A. Limit current density

Equation (1.13) gives the value of the reduction limiting current density. Where
l
“I(p) ” is the limiting current density (A/m2 ) of Mn+3or MnO− 4 , “z” is moles of electrons
per mole of Mn+3or MnO− 4 , “F” is Faraday constant (96485 c/mol), “k (p) ” is the transfer
coefficient (m/s)of Mn+3 or MnO− +3
4 and “C(p) ” is the bulk electrolyte of Mn or MnO4
−

(mole/dm3).

l
I(p) = z * F * k (p) * C(p) (1.13)

The value of mass transfer coefficient is depended on the electrolyte properties

and electrolyte agitation.

B. Tafel Equation

Equation (1.14) gives Tafel Equation of reduction of Mn+3or MnO−

4.

ρ(1.d or e) =a(1.d or e) +b(1.d or e) *log(i(1.d or e) ) (1.14)

Equation (1.15) gives the over-potential of the chemical reaction (1.d or e).
“ρ(1.d or e) ” is reduction over-potential (V), “Eh(1.d or e)” is redox potential of reaction (1.d
or e) and “E(c) ” is cathodic potential (V).

ρ(1.d or e) =E(c) -Eh(1.d or e) (1.15)

1.2.1.3.5. Global

Equation (1.16) gives the current density which is the sum of current densities
used respectively for the chemical reactions from (1.a) to (1.e). Where “ic ” is cathodic
current density (A/m2).

ic =i(1.a) +i(1.b) +i(1.c)+i(1.d) +i(1.e) (1.16)

The values of current amperage and current efficiency are given by Equations
(1.17) and (1.18). Where “I” is the current amperage (A), “A” is the cathode active area
(m2) and “CE(1.a) ” is current efficiency.

I =i(c) *A (1.17)

i(1.a)
CE(1.a) = (1.18)
i(c)

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1.2.2. Second group of chemical reactions

1.2.2.1. Chemical reactions

At time t=0 when metal is immersed into the solution, there is an adsorption of
hydrogen ion on the active surface of the metal. On the active surface of Cobalt metal
there is a place where electron is in excess; hydrogen ions take these electrons and form
hydrogen gas. At this moment there is an electronic deficit in Cobalt metal structure.
There is another place on the active surface of Cobalt metal where Cobalt metal is
oxidized in Cobalt ion and releases electrons to fill the electronic deficit in the Cobalt
metal structure. It appears an electronic movement in the Cobalt metal from the place
where the metal is oxidized called anodic electrode to the place where hydrogen ion is
reduced called cathodic electrode. At this moment there is a polarization of the
electrochemical system.

The second group is constituted with electrochemical reactions of Cobalt

corrosion in acidic water (Cheng Tzong Hong, 1968). These electrochemical reactions
are the following:

2H + + 2e− = H2 ‘ (1.i)

Coo = Co+2 + 2e− (1.j)

1.2.2.2. Thermodynamic

Cobalt metal corrodes with the evolution of hydrogen. There are two half-
reactions as shown above. The redox potential of cathodic reaction is given by Equation
(1.19). The redox potential of anodic reaction is given by Equation (1.20).

R∗T∗2.303 (𝑎(H+ ) )2
°
Eh(1.i) =Eh(1.i) + *log( ) (1.19)
2∗F P(H2 )

R∗T∗2.303 a(Co+2 )
°
Eh(1.j) =Eh(1.j) + *log( ) (1.20)
2∗F aCo

1.2.2.3. Kinetic

1.2.2.3.1. Reaction (1.i)

It has been observed that for the reaction in which gas is evolved (hydrogen on
the cathode or the oxygen on the anode), the charge transfer kinetic is very slow

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because of the mechanism (A.C. Scott et al, 1987). The mechanism of the hydrogen
evolution has three possible reaction steps (Andrzej Lasia, 2019) (reactions (1.f), (1.g)
and (1.h)). These reactions can follow several different pathways on the cathode, most
consisting of two reaction steps: the Volmer-Tafel pathway, the Volmer-Heyrovsky
pathway, and the Tafel-Heyrovsky pathway.

Figure (1.6) gives the polarization curves of hydrogen evolution. Tafel line is
between log(ia ) and log(ib ).

Figure 1.6: Polarization curves of hydrogen evolution

A. Limit current density

Figure (1.6) shows that from log(ib ) the value of potential is exponential
function of log(i). The reason for this is presumably bubble formation that covers the
cathode active area and increases the over-potential. The cathode active area decreases
with the increase of current density (Chris van de Goor, 2015).

B. Tafel Equation

Equation (1.21) gives Tafel Equation of hydrogen evolution. It has been

observed that the value of “b(1.i)” depends on the nature of the electrode and pH. This
reaction takes places on a small surface of cathode. At the same current density, the
value of b(1.a) is high at high pH in the range of pH less than 7.

ρ(1.i) =a(1.i) +b(1.i) *log(i(1.i) ) (1.21)

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 Equation (1.22) gives the over potential of the chemical reaction (1.i). “ρ(1.i) ” is
hydrogen over-potential (V), “Eh(1.i) ” is redox potential of reaction (1.i) and “E(i) ” is
corrosion potential (V).

ρ(1.i) =E(i) - Eh(1.i) (1.22)

1.2.2.3.2. Reaction (1.j)

Figure (1.7) gives the polarization curve of dissolution of Cobalt. In this case
there is not limitation of current mass transfer of soluble substances. The dissolution is
characterized by the Tafel line.

Figure 1.7: Polarization curves of cobalt dissolution

Equation (1.23) gives Tafel Equation of cobalt dissolution. This reaction takes
places on small surface of anode.

ρ(1.j) =a(1.j) +b(1.j) *log(i(1.j) ) (1.23)

Equation (1.24) gives the over potential of the chemical reaction (1.j). “ρ(1.j) ” is
cobalt dissolution over-potential (V), “Eh(1.j) ” is redox potential of reaction (1.j) and
“E(i) ” is corrosion potential (V).

ρ(1.j) =E(i) - Eh(1.j) (1.24)

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1.2.2.3.3. Global polarization curves

Figure (1.8) gives the polarization curves of acidic corrosion of cobalt metal
during cobalt plating.

Figure 1.8: Polarization curves of acidic corrosion of cobalt metal

A. Cathodic potential

The redox potential decreases from redox potential (Eh(1.i)−(i) ) (when the global
current is zero) to the redox potential (Eh(1.i)−(c) ) (when the global current is corrosion
current (I(c) )).

B. Anodic potential

The anodic potential increases from redox potential (Eh(1.j)−(i) ) (when the
global current is zero) to the redox potential (Eh(1.j)−(c) ) (when the global current is
corrosion current (I(𝑐) )).

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 C. Cobalt cathode electrical resistance potential

The difference between Eh(1.i)−(c) and Eh(1.j)−(c) is the over-potential due to the
electrical resistance of Cobalt metal (Equation 1.25). Where “R” is the electrical
resistance of Cobalt metal.

Eh(1.i)−(c) -Eh(1.j)−(c) =R*Ic (1.25)

D. Global over-potential

The difference between Eh(1.i)−(i) and Eh(1.j)−(i) gives the global over-potential
(Equation 1.26). Where “ρ(1.i) ” is cathodic over-potential, “ρ(1.j) ” is anodic over-potential,
and “R” is the electrical resistance of the metal.

Eh(1.i)−(i) -Eh(1.j)−(i) =-ρ(1.i) + R*Icorr + ρ(1.j) (1.26)

1.2.2.4. Observation

The Cobalt corrosion rate in acidic solution increases with increasing

temperature. This phenomenon is due to the reduction of over-potential of hydrogen
evolution on Cobalt surface with increasing temperature (Cheng Tzong Hong, 1968).

The co-deposition of same impurities that present that decreases value of Tafel
slope of hydrogen evolution at corrosion current density can affect greatly the current
efficiency. In the case of Zinc, the co-deposition of these impurities (Co, Ni, Cu, Ge, Te, Sb
and Se) affects greatly the current efficiency.

1.3. Anodic reaction

1.3.1. First group of chemical reactions

1.3.1.1. Chemical reactions

In presence of manganese in the Cobalt electrowinning solution,

electrochemical reactions at the anode surface are given by the chemical reactions (1.k),
(1.l), (1.m), (1.n), (1.o), (1.p), (1.q), and (1.r).

 Oxygen evolution

2H2 O = 4H + + O2 + 4e− (1.k)

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  Oxidation of Co2+ to Co3+

Co2+ =Co3+ +e− (1.l)

 Oxidation of Co2+ to CoOOH

Co2+ +2H2 O=CoOOH+3H + +e− (1.m)

 Oxidation of Mn2+ to Mn3+

Mn2+ =Mn3+ +e− (1.n)

 Oxidation of Mn+2 to MnO−

4

Mn+2 +4H2 O =MnO− +

4 +8H +5e
−
(1.o)

 Oxidation of Mn+2 to MnOOH

Mn2+ +2H2 O=MnOOH+3H + +e− (1.p)

 Oxidation of Mn+2 to γ-MnO2

Mn2+ +2H2 O=γ-MnO2 +4H + +2e− (1.q)

 Oxidation of Mn+2 to δ-MnO2

Mn2+ +2H2 O=δ-MnO2 +4H + +2e− (1.r)

1.3.1.2. Thermodynamic

1.3.1.2.1. Reaction (1.k)

°
The redox potential of reaction (1.k) is given by Equation (1.27). Where “Eh(1.k) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “4” is the number of electron transferred , “P(O2 ) ” is the pressure of
oxygen gas, “aw ” is the activity of water and “a(H+ ) ” is the activity of
H + ion.

R∗T∗2.303 P(O2 ) ∗(a(H+ ) )4

°
Eh(2.i) =Eh(2.i) + 4∗F
*log( (aw )2
) (1.27)

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1.3.1.2.2. Reaction (1.l)

°
The redox potential of reaction (1.l) is given by Equation (1.28). Where “Eh(1.l) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mole*K), “F” is Faraday
constant (96485 c/mole), “a(Co+3 ) ” is the activity of Co+3 ion and “a(Co+2 )” is the activity
of Co+2 ion.

R∗T∗2.303 a +3 )
°
Eh(1.l) =Eh(1.l) + *log(a(Co ) (1.28)
F (Co+2 )

1.3.1.2.3. Reaction (1.m)

The redox potential of reaction (1.m) is given by Equation (1.29). Where

°
“Eh(1.m) ”is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday
constant (96485 c/mole), “a(H+) ” is the activity of H + ion, and “a(Co+2 ) ” is the activity of
Co+2 ion and “aw ” is the activity of water.

R∗T∗2.303 (a(H+ ) )3
°
Eh(1.m) =Eh(1.m) + *log(a 2 ) (1.29)
F (Co+2 ) ∗(aw )

1.3.1.2.4. Reaction (1.n)

°
The redox potential of reaction (1.n) is given by Equation (1.30). Where “Eh(1.n) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mole*K), “F” is Faraday
constant (96485 c/mole), “a(Mn+3 ) ” is the activity of Mn+3 ion and “a(Mn+2 ) ” is the
activity of Mn+2 ion.

R∗T∗2.303 a +3 )
°
Eh(1.n) =Eh(1.n) + *log(a(Mn ) (1.30)
F (Mn+2 )

1.3.1.2.5. Reaction (1.o)

°
The redox potential of reaction (1.o) is given by Equation (1.31). Where “Eh(1.o) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mole), “𝑎(MnO−4 ) ” is the activity of MnO− +
4 ion, “𝑎(H+ ) ” is the activity of H ion,
“a(Mn+2 ) ” is the activity of Mn+2 ion and “aw ” is the activity of water.

R∗T∗2.303 𝑎(MnO−) ∗(𝑎(H+ ) )8

° 4
Eh(1.o) =Eh(1.o) + *log( ) (1.31)
5∗F 𝑎(Mn+2 ) ∗(𝑎𝑤 )4

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1.3.1.2.6. Reaction (1.p)

°
The redox potential of reaction (1.p) is given by Equation (1.32). Where “Eh(1.p) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mol), “a(H+) ” is the activity of H + ion, and “a(Mn+2 )” is the activity of Mn+2 ion
and “aw ” is the activity of water.

R∗T∗2.303 (a(H+ ) )3
°
Eh(1.p) =Eh(1.p) + *log(a 2
) (1.32)
F (Mn+2 ) ∗(aw )

1.3.1.2.7. Reaction (1.q)

°
The redox potential of reaction (1.q) is given by Equation (1.33). Where “Eh(1.q) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mol*K), “F” is Faraday constant
(96485 c/mol), “a(H+) ” is the activity of H + ion, and “a(Mn+2 )” is the activity of Mn+2 ion
and “aw ” is the activity of water.

R∗T∗2.303 (a(H+ ) )4
°
Eh(1.q) =Eh(1.q) + *log(a 2 ) (1.33)
2∗F (Mn+2 ) ∗(aw )

1.3.1.2.8. Reaction (1.r)

°
The redox potential of reaction (1.r) is given by Equation (1.34). Where “Eh(1.r) ”
is the standard redox potential, “R” is equal to 8.314 (J/(mole*K), “F” is Faraday
constant (96485 c/mole), “a(H+) ” is the activity of H + ion, and “a(Mn+2 ) ” is the activity of
Mn+2 ion and “aw ” is the activity of water.

R∗T∗2.303 (a(H+ ) )4
°
Eh(1.r) =Eh(1.r) + *log(a 2
) (1.34)
2∗F (Mn+2 ) ∗(aw )

1.3.1.3. Kinetics

1.3.1.3.1. Reaction (𝐢(𝟏.𝐤) )

One of the more generally accepted pathways of oxygen evolution consists of

reactions (1.s), (1.t) and (1.u) (Fabbri, E. et al, 2014).

OH − =OHads +e− (1.s)

OH − +OHads =H2 O+e− +Oads (1.t)

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 2Oads =O2 (1.u)

Figure (1.9) gives the polarization curves of oxygen evolution. Tafel line is
ranged between log(i2 ) and log(i1 ).

Figure 1.9: Polarization curves of oxygen evolution

A. Limit current density

Figure (1.9) shows that from log(i2 ) the anodic potential increases
exponentially versus log(i). The reason for this is presumably bubble formation that
covers the anode active area and increases the over-potential. The anode active area
decreases with the increase of current density (Chris van de Goor, 2015).

B. Tafel Equation

Equation (1.35) gives Tafel Equation of oxygen evolution. It has been observed
that the value of “b(1.k) ” depends on the nature of the electrode and current density. The
value of b(1.k) on the oxide of Cobalt and manganese is less than the value on oxide of
Lead (A. N. Nikoloski et al, 2010 and Sönke Schmachtel et al, 2009).

ρ(1.k) =a(1.k) +b(1.k) *log(i(1.k) ) (1.35)

Equation (1.36) gives the over potential of the chemical reaction (1.k). “ρ(1.k) ” is
oxygen over-potential (V), “Eh(1.k) ” is redox potential of reaction (1.k) and “E(a) ” is

Joseph Kafumbila Page 26

anodic potential (V). It has been observed that the increase in temperature decreases
the over-potential at the same current density and pH.

ρ(1.k) =E(a) - Eh(1.k) (1.36)

1.3.1.3.2. Reaction (1.l)

Due to high concentration of Co+2 , the kinetic of reaction (1.l) is controlled by

electron transfer to the anode. Equation (1.37) gives Tafel Equation of cobalt oxidation.

ρ(1.l) =a(1.k)+b(1.l) *log(i(1.l) ) (1.37)

Equation (1.38) gives the over potential of the chemical reaction (1.l). “ρ(1.l) ” is
oxygen over-potential (V), “Eh(1.l)” is redox potential of reaction (1.l) and “E(a) ” is anodic
potential (V). It has been observed that the increase in temperature decreases the over-
potential at the same current density and pH.

ρ(1.l) =E(a) - Eh(1.l) (1.38)

1.3.1.3.3. Reactions (1.n) and (1.o)

Figure (1.10) gives the polarization curve of oxidation of Mn+2 to Mn+3 or

MnO−4 on the anode. Where Ea (anodic potential) is a function of log (i) (current
density).

The Tafel line is ranged between log(i1 ) and log(i2 ). On the Tafel line, the
oxidation rate is controlled by electron transfer. “il ” is limit current density oxidation
rate is controlled by the Mn+2 ion mass transfer to the anode. Between log(i2 ) and
log(il ), the oxidation rate is controlled by the mixt regime (electron transfer and
diffusion). “io ” is exchange current density.

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 Figure 1.10: Polarization curve of oxidation of Mn+2 to Mn+3 or MnO−
4 on the anode

A. Limit current density

Equation (1.39) gives the value of the oxidation limiting current density. Where
l
“I(Mn +2 ) ”is the limiting current density (A/m2 ), “z” is moles of electrons per mole of
+2
Mn in reaction (1.n) or (1.o), “F” is Faraday constant (96485 c/mole), “k (Mn+2 ) ” is the
transfer coefficient (m/s) and “C(Mn+2 ) ” is the bulk electrolyte of Cobalt (mole/dm3).

l
I(Mn +2 ) = z * F * k (Mn+2 ) * C(Mn+2 ) (1.39)

The value of mass transfer coefficient is depended on the electrolyte properties

and electrolyte agitation.

B. Tafel Equation

Equation (1.40) gives Tafel Equation of oxidation of Mn+2.

ρ(1.n or o) =a(1.n or o)+b(1.n or o) *log(i(1.n or o) ) (1.40)

Equation (1.41) gives the over-potential of the chemical reaction (1.n or o).
“ρ(1.n or o) ” is oxidation over-potential (V), “Eh(1.n or o) ” is redox potential of reaction (1.n
or o) and “E(a) ” is anodic potential (V).

ρ(1.n or o) =E(a) -Eh(1.n or o) (1.41)

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1.3.1.3.4. Reaction (1.m), (1.p), (1.q) and (1.r)

The presence of Mn(III) in acidic solution in Zinc electrowinning cell shows that
the Mn(III) ion cannot disproportionate into Mn(II) and γ and δ MnO2 (Charles E. Abbey,
2019). MnOOH reacts with to produce Mn(II), and γ and δ MnO2 . There are two
pathways for Cobalt and Manganese oxidation into CoOOH and MnOOH respectively:

1. The direct oxidations of cobalt and manganese to CoOOH and MnOOH

respectively according to chemical reactions (1.m) and (1.p).

Co2+ +2H2 O=CoOOH+3H + +e− (1.m)

Mn2+ +2H2 O=MnOOH+3H + +e− (1.p)

2. First the oxidation of ions of Co (II) and Mn(II) to Co (III) and Mn(III)
respectively according to chemical reactions (1.l) and (1.n). When Co(III)
and Mn(III) concentrations reach the saturation concentration, Cobalt
and Manganese precipitate as CoOOH and MnOOH.

Co2+ =Co3+ +e− (1.l)

Mn2+ =Mn3+ +e− (1.n)

For the calculation of the material balance the second pathway is adopted.
Therefore the electrochemical reactions on the anode are:

 Oxygen evolution

2H2 O = 4H + + O2 + 4e− (1.k)

 Oxidation of Co2+ to Co3+

Co2+ =Co3+ +e− (1.l)

 Oxidation of Mn2+ to Mn3+

Mn2+ =Mn3+ +e− (1.n)

 Oxidation of Mn+2 to MnO−

4

Mn+2 +4H2 O =MnO− +

4 +8H +5e
−
(1.o)

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1.3.1.3.5. Global

Equation (1.42) gives the current density which is the sum of current densities
used respectively for the chemical reactions (1.k), (1.l), (1.n), and (1.o). Where “ia ” is
anodic current density (A/m2).

ia =i(1.k)+i(1.l) +i(1.n)+i(1.o) (1.42)

1.3.2. Second group of chemical reactions

1.3.2.1. Chemical reactions

 Co(III) reacts with water to produce CoOOH.

Co+3 +2H2 O=CoOOH + 3H + (1.v)

 Mn(III) reacts with water to produce MnOOH.

Mn+3 +2H2 O=MnOOH + 3H + (1.w)

 In acid media, MnOOH reacts with acid to produce δ-MnO2 and γMnO2 .

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

 In Cobalt solution, Cobalt is adsorbed on the surface of MnOOH, γMnO2

and δMnO2 . The adsorbed cobalt reacts with MnOOH, γMnO2 and δMnO2
according to reactions (1.z), (1.aa) and (1.ab).

MnOOH +Co+2 =CoOOH +Mn+2 (1.z)

𝛾MnO2 +2Co+2 +2H2 O=Mn+2 +2CoOOH+2H + (1.aa)

𝛿MnO2 +2Co+2 +2H2 O=Mn+2+2CoOOH+2H + (1.ab)

 In Cobalt solution, Manganese (II) reacts with CoOOH to produce MnOOH

according to the chemical reaction (1.ac).

CoOOH +Mn+2=MnOOH +Co+2 (1.ac)

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1.3.2.2. Thermodynamic

1.3.2.2.1. Reactions (1.x) and (1.y)

MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution. The chemical
potentials of solids in the heterogeneous solid solution are given by Equations (1.43),
(1.44) and (1.45). Equations (1.46), (1.47) and (1.48) give the chemical potential of
Mn+2, H + and H2 O.

μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (1.43)

μ(𝛿MnO2 ) =μ°(𝛿MnO2 ) +RTlog(X(𝛿MnO2 ) ) (1.44)

μ(𝛾MnO2 ) =μ°(𝛾MnO2 ) +RTlog(X(𝛾MnO2 ) ) (1.45)

μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (1.46)

μ(H+) =RTlog(C(H+ ) *γ(H+) ) (1.47)

μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (1.48)

Equation (1.49) gives the sum of molar fractions in heterogeneous solid

solution.

1=X(MnOOH)+X(𝛿MnO2 ) +X(𝛾MnO2 ) (1.49)

Equations (1.50) and (1.51) give the thermodynamic conditions.

μ(𝛿MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.50)

μ(𝛾MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.51)

1.3.2.2.2. Reaction (1.z), (1.aa) and (1ab)

CoOOH, MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution. The
chemical potentials of solids in the homogeneous solid solutions are given by Equations
(1.52), (1.53), (1.54) and (1.55). Equations (1.56), (1.57), (1.58) and (1.59) give the
chemical potential of Co+2, Mn+2, H + and H2 O.

μ(CoOOH) =μ°(CoOOH) +RTlog(X(CoOOH) ) (1.52)

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 μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (1.53)

μ(𝛿MnO2 ) =μ°(𝛿MnO2 )+RTlog(X(𝛿MnO2 ) ) (1.54)

μ( 𝛾MnO2 ) =μ°( 𝛾MnO2 ) +RTlog(X( 𝛾MnO2 ) ) (1.55)

μ(Co+2 ) =μ°(Co+2 ) +RTlog(C(Co+2 )*γ(Co+2 ) ) (1.56)

μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (1.57)

μ(H+) =RTlog(C(H+ ) *γ(H+) ) (1.58)

μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (1.59)

Equation (1.60) gives the sum of molar fractions in heterogeneous solid

solution.

1=X(MnOOH)+X(CoOOH)+X(𝛿MnO2 ) +X( 𝛾MnO2 ) (1.60)

Equations (1.61), (1.62) and (1.63) give the thermodynamic condition for
heterogeneous solid solution.

μ(𝛿MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.61)

μ(𝛾MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.62)

μ(MnOOH) +μ(Co+2 ) =μ(CoOOH) +μ(Mn+2 ) (1.63)

1.3.2.2.3. Reaction (1.ac)

CoOOH, MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution. The
chemical potentials of solids in the homogeneous solid solutions are given by Equations
(1.64), (1.65), (1.66) and (1.67). Equations (1.68), (1.69), (1.70) and (1.71) give the
chemical potential of Co+2, Mn+2, H + and H2 O.

μ(CoOOH) =μ°(CoOOH) +RTlog(X(CoOOH) ) (1.64)

μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (1.65)

Joseph Kafumbila Page 32

 μ(𝛿MnO2 ) =μ°(𝛿MnO2 )+RTlog(X(𝛿MnO2 ) ) (1.66)

μ( 𝛾MnO2 ) =μ°( 𝛾MnO2 ) +RTlog(X( 𝛾MnO2 ) ) (1.67)

μ(Co+2 ) =μ°(Co+2 ) +RTlog(C(Co+2 )*γ(Co+2 ) ) (1.68)

μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (1.69)

μ(H+) =RTlog(C(H+ ) *γ(H+) ) (1.70)

μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (1.71)

Equation (1.72) gives the sum of molar fractions in heterogeneous solid

solution.

1=X(MnOOH)+X(CoOOH)+X(𝛿MnO2 ) +X( 𝛾MnO2 ) (1.72)

Equations (1.73), (1.74) and (1.75) give the thermodynamic condition for
heterogeneous solid solution.

μ(𝛿MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.73)

μ(𝛾MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (1.74)

μ(CoOOH) +μ(Mn+2 ) =μ(MnOOH) +μ(Co+2 ) (1.75)

1.4. Precipitation of MnOOH into solution

1.4.1. Location of MnOOH precipitation into solution

The locations of MnOOH precipitation are:

 First - on the top cell solution in Cobalt electrowinning cell where the
outlet solutions of cathode and anode are mixed to form outlet cell
solution and recycled solution (down flow).
 Second – on the bottom cell solution in Cobalt electrowinning cell where
the inlet cell solution et the recycled solution (down flow) are mixed to
form inlet solution of cathode an anode (up flow)

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1.4.2. Chemical reactions

The redox potentials of couples (Co+3/Co+2), (Mn+3/Mn+2) and (MnO− +2

4 /Mn )
must be the same in the solution.

 The first possibility: the redox potentials of couple (Mn+3/Mn+2) is lower

than that of couple (MnO− +2
4 /Mn ), Mn
+2
reacts with MnO−
4 to Mn
+3

4Mn+2+MnO− + +3
4 +8H =5Mn +4H2 O (1.ad)

 The second possibility: the redox potentials of couple (Mn+3/Mn+2) is higher

than that of couple (MnO− +2
4 /Mn ), Mn
+3
disproportionate into MnO−4 and
+2
Mn

5Mn+3+4H2 O =4Mn+2+MnO−
4 +8H
+
(1.ae)

 The third possibility: the redox potentials of couple (Mn+3/Mn+2) is lower

than that of couple (Co+3 /Co+2 ), Mn+2 reacts with Co+3 to Mn+3 and Co+2

Mn+2 +Co+3=Mn+3+Co+2 (1.af)

 The fourth possibility: the redox potentials of couple (Mn+3 /Mn+2) is higher
than that of couple (Co+3 /Co+2 ), Mn+3 reacts with Co+2 to Mn+2 and Co+3

Mn+3 +Co+2=Mn+2+Co+3 (1.ag)

In the case where the concentration of Mn+3 increases in solution and reaches
the saturation concentration, Mn+3 reacts with water to produce MnOOH.

Mn+3 +2H2 O=MnOOH + 3H + (1.ah)

1.5. Cell voltage

The chemical reactions (1.a) on the cathode and (1.k) on the anode are used to
calculated the cell voltage.

Equation (1.76) gives the value of operating cell voltage. Where “VRCo ” is the
reversible voltage, “ρ(1.a) ” is absolute value of cathode over-potential, “ρ(1.k)” is absolute
value of anode over-potential, “Vῼc ” is electrode contact resistance voltage drop, “VOῼi ”
is operating electrode internal resistance voltage drop, and “VOῼe ” is operating
electrolyte resistance voltage drop.

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 VOC = VRCo + ρ(1.a) + ρ(1.k) + Vῼc +VOῼi +VOῼe (1.76)

1.5.1. Reversible voltage

Reversible voltage (VRCo ) is given by Equation (1.77). Where “Eh(1.k) ” is the

electrode potential of the chemical reaction (1.k) and “Eh(1.a) ” is the electrode potential
of the chemical reaction (1.a).

VRCo = Eh(1.k) - Eh(1.a) (1.77)

1.5.2. Over potential of Cobalt on the cathode

Equation (1.78) gives the cathodic Cobalt over potential. Where “ρ(1.a) ” is Cobalt
over-potential (V) and “Iex ” is Cobalt exchange current density (A/m2 ), “b(1.a) ” is Tafel
slope and “I(1.a) ” is Cobalt current density (A/m2 ).

Iex
ρ(1.a) =b(1.a) *log(I ) (1.78)
(1.a)

The cathodic potential is given by Equation (1.79).

Eh(c) =Eh(1.a) +ρ(1.a) (1.79)

1.5.3. Over potential of oxygen on the anode

Equation (1.80) gives the anodic over potential of oxygen evolution. Where
“ρ(1.k) ” is oxygen over potential (V) and “I(1.k) ” is oxygen current density (A/m2 ), “b(1.k)”
is Tafel slope and “Iex ” is exchange current density (A/m2 ).

I(1.k)
ρ(1.k) =b(1.k) *log( ) (1.80)
Iex

The anodic potential is given by Equation (1.81).

Eh(a) =Eh(1.a) +ρ(1.k) (1.81)

Joseph Kafumbila Page 35

1.5.4. Electrode contact resistance voltage drop

In the modern Cobalt electrowinning cell-house, the range of electrode contact

voltage drop is from 5 to 25% of the total cell voltage. Electrode contact resistance
voltage drop is estimated at 10% of total cell voltage.

1.5.5. Electrode internal resistance voltage drop

Equation (1.82) gives the electrode internal resistance voltage drops. Where
“VOῼi ” is operating electrode internal resistance voltage drop (V), “Ic ” is the cathodic
current density (A/m2), “ῼc ” is the cathodic material resistivity (Ω-m), “Tc ” is the
thickness of cathode (m), “Ia ” is the anodic current density (A/m2), “ῼa ” is the anodic
material resistivity (Ω-m), and “Ta ” is the thickness of cathode (m), .
.
VOῼi = Ic * ῼc * Tc +Ia * ῼa * Ta (1.82)

1.5.6. Electrolyte resistance voltage drop

Equation (1.83) gives operating electrolyte resistance voltage drops. Where

“VOῼe ” is operating electrolyte resistance voltage drop (V), “Ic ” is the cathodic current
density (A/m2), “ῼel ” is the electrolyte resistivity (Ω-m), and “De ” is the distance face-to-
face between anode and cathode (m).

VOῼe = Ic * ῼel * De (1.83)

1.5.7. Energy consumption

The energy consumption for an electrowinning cell is calculated according to

Equation (1.84). Where “EC” is the energy consumption (kWh/kg), “Voc ” is the operating
cell voltage over the deposition cycle (V), “Ic ” is the cathodic current (A), “t” is time (s)
and “Mac ” is the deposit mass (g).

Voc ∗Ic ∗t
EC = (1.84)
MCo

Joseph Kafumbila Page 36

2. Thermodynamic

2.1. Equilibrium condition

2.1.1. 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.

2.1.2. Gibbs free energy

2.1.2.1. 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 (2.1). “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 (2.2). “E” is the internal energy, “P” is the
pressure and “V” is the volume.

G=H-T*S (2.1)

H=E+PV (2.2)

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 (2.3).

Joseph Kafumbila Page 37

 dG = 0 (2.3)

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.

2.1.2.2. 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 (2.4).

dG=μ*dn (2.4)

The proportionality constant (μ) is called the chemical potential. The chemical
potential depends on the temperature, pressure and the composition of the phase.
Equation (2.5) gives the relationship between chemical potential and composition.

μ=μ° + R*T*2.303*Log(a) (2.5)

“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/mole*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 (2.6). “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 (2.7). “γi ” is the activity
coefficient, “Ci ” is the concentration of soluble substance “i” in the solvent and “C0 ” is the
standard concentration (1 mole/L). The activity of a solvent is 1. The activity of a solid in
a mixture of solids is given by Equation (2.8). Where “Xi ” is the molar fraction of a solid
“i”.

f ∗Pi
ai = iP (2.6)
0

γi ∗Ci
ai = (2.7)
C0

Joseph Kafumbila Page 38

 ai =Xi (2.8)

2.1.2.3. 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 (2.9). “z” is the charge, “F” is faraday constant (96485
C/mole) and “E” is electrochemical potential (V).

dG=Z*F*E*dn (2.9)

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 (2.10).

dG=-F*E*dn (2.10)

The variation in internal energy (dG) due to the variation of the molar quantity
of electronic charge is called the electrochemical potential energy.

2.1.3. General equilibrium condition

In the closed system, there is reversible chemical reaction given by the chemical
reaction (2.a). “υi ” is the stoichiometry coefficient of the substance “i” and “A”, “B”, “C”
and “D” are the chemical substances.

υa A + υb B + υe e− = υc C + υd D (2.a)

At constant temperature and pressure, the chemical potential energy is the sum
of the chemical potential energy of products minus the sum of the chemical potential
energy of reactants. Equation (2.11) gives the chemical potential energy of chemical
reaction (1.a). “dGcp ” is the chemical potential energy of the chemical reaction (1.a) and
“μi ” is the chemical potential of the substance “i”. At constant temperature and pressure,
the electrochemical potential energy is given by Equation (2.12). 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 (2.11)

dGep =- υe *F*E (2.12)

Joseph Kafumbila Page 39

 The equilibrium condition of the chemical reaction (2.a) is given by Equation
(2.13).

dGcp + dGep = 0 (2.13)

2.1.4. Standard equilibrium constant

In aqueous solution, there is reversible chemical reaction between soluble

compounds given by the chemical reaction (2.a). “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 (2.a) is given by Equation (2.14).

υa A + υb B +υe e− = υc C + υd D (2.a)

dGcp +dGep = υc *μC + υd *μD - υa *μA - υb *μB -υe *F*E =0 (2.14)

Combination of Equations (2.5) and (2.14) gives Equation (2.15).

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 (2.15)
aAA x aBB

The standard equilibrium constant is given by Equation (2.16) at a given

temperature (T ° ).

υ υ
ac c x aDD
K °(T° ) = υ υ (2.16)
aAA x aBB

If υe is equal to zero, Equation (2.17) gives the value of the logarithm of the
standard equilibrium constant. ΔG° is given by Equation (2.18).

ΔG°
log(K °(T° ) ) = - 2.303RT (2.17)

ΔG° =υC μ°C +υD μ°D − υA μ°A − υB μ°B (2.18)

If υe is not equal to zero, Equation (2.19) gives the relationship between the
logarithm of standard equilibrium constant and the redox potential. E ° (Standard redox
potential) is given by Equation (2.20).

2.303RT
*log(K °(T° ) ) = E ° - E (2.19)
υe ∗F

ΔG°
E ° =- υ (2.20)
e ∗F

Joseph Kafumbila Page 40

2.2. Free Gibbs energy at elevated temperature

2.2.1. Compound (solid, gas and soluble in solution)

The free Gibbs energy of formation at elevated temperature of the compound,

for which heat capacity is available, can be calculated as a function of temperature using
° °
Equation (2.21) (Ignasi Puigdomenech et al, 1999). Where “G(T 2)
” and “G(T 1)
” are free
Gibbs energies of formation of the compound at temperature T2 and T1 respectively.
°
“S(T1)
” is the entropy of formation of the compound at temperatureT1 . “Cp° ” is the heat
capacity of the compound.

° ° ° T C°p T
G(T2)
=G(T1)
-S(T1)
*(T(2) -T(1) )- T(2) *∫T 2 dT+∫T 2 Cp° dT (2.21)
1 T 1

2.2.2. Soluble compound without heat capacity

For soluble compounds in solution, for which heat capacity is not available, free
Gibbs energy of formation at elevated temperature can be calculated using Equation
(°a) (°a)
(2.22). Where “S(T2 ) ” and “S(T1 ) ” are the absolute entropies of the soluble compound at
temperature T(2) and T(1) respectively.

° ° (°a) (°a) (T(2) −T(1) ) (°a) (°a)

G(T2)
=G(T1)
-(T(2) *S(T2 ) -T(1) *S(T1 ) )+ *(S(T2 ) -S(T1 ) ) (2.22)
ln(T(2) ⁄T(1) )

The absolute entropy of soluble compound at temperature T(2) can calculated

using Equation (2.23). Where “a” and “b” are constants that are unique for a given
temperature and class of soluble compound (Digby D. Macdonald et al, 1972)

(°a) (°a)
S(T2 ) =a+b*S(T1 ) (2.23)

The absolute entropy at 298.15°K is based on the scale where the entropy of
hydrogen ion (H + ) is -20.93 j/K.mol. Entropy of hydrogen ion in the conventional scale
at 298.15°K is 0.00j/K.mole. Entropy in conventional scale of soluble compound can be
transformed in the absolute scale by using Equation (2.24). Where “z” is soluble
compound electrical charge including the sign.

(°a) °
S(298.15) =S(298.15) -20.93*Z (2.24)

Joseph Kafumbila Page 41

2.2.3. Chemical reaction without heat capacity

For many chemical reactions there is a lack of heat capacity functions for all or
some of the species involved. Therefore approximation must be made. The simplest
assumption to be made is that the change of heat capacity of reaction is zero at all
temperatures (the standard molar enthalpy of reaction does not vary with temperature).
Equation (2.25) gives the values of equilibrium constant at temperature less than
373.15°K (Ignasi Puigdomenech et al, 1999). Where “K °(T) ” is equilibrium constant of
chemical reaction at temperature (T°K), “K °(298.15) ” is equilibrium constant of chemical
°
reaction at temperature (298.15°K), “ΔH(298.15) ” is the enthalpy of the chemical reaction
at 298.15°K, “T” is temperature in degree kelvin and “R” is equal to 8.314 (J/(mole*K).

ΔH°(298.15) 1 1
Log(K °(T) )=log(K °(298.15))+ R∗ln(10) *(298.15-T) (2.25)

2.3. Precipitation process

2.3.1. Definition

Precipitation reactions occur when cations and anions in aqueous solution

combine to form an insoluble ionic solid called precipitate. The precipitation is a
spontaneously and relatively fast crystallization process.

2.3.2. Precipitation – condition

In the close system, there is precipitation reaction given by the chemical

reaction (2.b). “υi ” is the stoichiometry coefficient of the substance “i” and “A”, “B”, “C”
and “D” are the chemical substances. “C” is the precipitate.

υa A + υb B + υe e− = υc C + υd D (2.b)

At constant temperature and pressure, Equation (2.26) gives thermodynamic

condition of precipitation reaction (2.b). This condition is called supersaturation.

ΔG=ΔGc +ΔGs -ΔGM <0 (2.26)

“ΔGc ” is the chemical potential energy of the chemical reaction (2.b) and the
value is given by Equation (2.27). Where “μi ” is the chemical potential of the substance
“i”, “F” is faraday constant and “E” is the redox potential.

ΔGc = (υc *μC + υd *μD )-(- υe *F*E + υa *μA + υb *μB ) (2.27)

Joseph Kafumbila Page 42

 “ΔGs ” is the surface energy on the precipitate and the value is given by Equation
(2.28). Where “σ” is surface energy of precipitate and “A” is molar surface area of
precipitate.

ΔGs =σ*A (2.28)

“ΔGM ” is the internal energy consumed due to the path of the reaction
mechanism. The mechanism of precipitation of precipitation reaction contains two
steps. The first step is the nucleation. Nucleation is commonly defined as the formation
of the first thermodynamically stable solid. The second step is the growth. Growth is
when the thermodynamically stable nuclei grow into larger particles by deposition of
solute from the supersaturated solution.

Evaluation of values of “ΔGs ” and “ΔGM ” depends on the knowledge of the size of
particles and the path way of the chemical reaction. Therefore Equation (2.29) gives the
simplest supersaturation coming only from variation of chemical potential of products
and reactants.

ΔGc <0 (2.29)

2.4. Free acid concentration in Cobalt electrowinning

electrolyte

2.4.1. First free acid concentration

The pure solution of Cobalt in sulfate medium contains the following soluble
substances: H + , Co+2 , HSO− −2
4 , SO4 , H2 SO4 and CoSO4 . The chemical reaction (2.c), (2.d)
and (2.e) give the equilibrium reactions of soluble compounds.

H + +SO−2 −
4 =HSO4 (2.c)

2H + +SO−2
4 =H2 SO4 (2.d)

Co+2 +SO−2
4 =CoSO4 (2.e)

pH and total Cobalt concentration are known values. Equation (2.30) and
(2.31) gives the concentration of H + (C( H+) ) and total Cobalt concentration (C( CoT) ).
Where “γ( p) ” is activity coefficient of soluble compound “p” and “C( p) ” is the molar
concentration of soluble compound “p”.

Joseph Kafumbila Page 43

 10(−pH)
C( H+) = (2.30)
γ( H+ )

C( CoT) =C(Co+2 )+C( CoSO4) (2.31)

The concentration of CoSO4 (C( CoSO4 )) is given by Equation (2.32). Where

“K ( 2.e) ” is equilibrium constant of chemical reaction (2.e). The concentration of HSO−
4
(C( HSO−4 ) ) and H2 SO4 (C(H2 SO4 )) are given by Equations (2.33) and (2.34).

γ(Co+2 ) ∗γ( SO−2 )

C( CoSO4 ) =K ( 2.e) *C(Co+2 ) *C(SO−2
4 )
* 4
(2.32)
γ( C( CoSO ))
4

γ(H+ ) ∗γ( SO−2 )

C(HSO−4 ) =K ( 2.c)*C(H+) *C(SO−2
4 )
* 4
(2.33)
γ( C − ))
(HSO4

(C(H+ ) )2 ∗γ( SO−2 )

C(H2 SO4 ) =K ( 2.d) *(C(H+) )2 *C(SO−2
4 )
* 4
(2.34)
γ( C(H SO ))
2 4

Equation (2.35) gives the electrical neutrality of solution. The resolution of

Equations (2.31), (2.32), (2.33), (2.34) and (2.35) gives the values of C(Co+2 ) ; C( CoSO4 ),
C(HSO−4 ), C(H2 SO4 ) and C(SO−2
4 )
.

C(H+ ) +2C(Co+2 )=C(HSO−4 )+2C(SO−2

4 )
(2.35)

Hydrogen ions (H + ) are in electrical charge equilibrium with anion (HSO− 4 ).

Equation (2.36) gives the concentration (G(H2 SO4)) (g/L) of free acid is solution. Where
“98.075” is molar mass of H2 SO4 . Equation (2.37) gives the total sulfur concentration
(G(ST) ). Where “32.065” is molar mass of sulfur.

G(H2 SO4) =(C( H+) +C(H2 SO4 ) )*98.075 (2.36)

G(ST) )=( C( CoSO4) +C(HSO−4 ) +C(H2 SO4 ) +C(SO−2

4 )
)*32.065 (2.37)

This value of acid concentration in solution obtained by using Equation (2.36) is

used in Realistic Simulation Program (J. Kafumbila (1), 2023), by R. Breckpot and by
Umicore Cobalt electrowinning design (J. Kafumbila (2), 2023).

Joseph Kafumbila Page 44

2.4.2. Second free acid concentration

The pure solution of Cobalt in sulfate medium contains the following soluble
substances: H2 SO4 and CoSO4 . Equation (2.38) gives the concentration (G(H2 SO4 )) (g/L)
of free acid is solution. Where “G(ST) ” is total concentration of sulfur in solution (g/L),
“G(CoT) ” is total concentration of Cobalt in solution (g/L), “58.93” is molar mass of
Cobalt.

32.065 98.075
G(H2 SO4) =(G(sT ) - G(CoT) * 58.93 )*32.065 (2.38)

This value of acid concentration in solution obtained by using Equation (1.38) is

equal to the analytical free acid concentration obtained from chemical analysis
laboratory. This is used in the design of Cobalt electrowinning unit operation of Mintek
(South Africa), FQM (Australia), Luilu-Gecamines (DRC), Chambishi (Zambia) and
Nkana (Zambia)( J. Kafumbila (2), 2023).

2.5. Activity of soluble species

2.5.1. Ionic strength

The ionic strength of the system is given by Equation (2.39). Where “Ci ” is the
concentration (mol/L) of soluble compounds “i” and “Zi ” is electrical charge of the
soluble compounds “i”.

1
I = 2x∑ Ci ∗ Zi2 (2.39)

2.5.2. Water activity

The activity of water (solvent) (aw ) is given by Equation (2.40). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “mi ” is the
concentration (mole/kg water) of soluble compounds (Charles E. Harvie et al, 1984). In
this case, the concentrations of soluble compounds are very low; in consequence the
molarity is close to the molarity. Equation (2.40) becomes Equation (2.41).

W
ln (aw ) = - 1000 *ϕ *∑i mi (2.40)

W
ln (aw ) = - 1000 *ϕ *∑i Ci (2.41)

Joseph Kafumbila Page 45

 The calculations of osmotic coefficient have been approximated by Equation
(2.42) (H.C. Helgeson, 1969). The value of “u” is given by Equation (2.43). Table (2.1)
gives values of parameters “a”, “b”, “c” and “d” at different temperatures. “A” comes from
Debrye-Huckel Equation for activity coefficient and is function of temperature. The value
of “A” is in Table (2.2). “I” is the ionic strength (mole/kg of water). In this case, the ionic
strength is given in mole/L.

2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) -u] + + + (2.42)
a3 ∗I 2 3 4

u=1+a*√I (2.43)

Table 2.1: values of a, b, c and d

Temperature (°C) a b c d
25 1.454 0.02236 9.38*10−3 -5.362*10−4
100 1.555 0.03648 6.437*10−3 -7.132*10−4
200 1.623 0.04589 4.522*10−3 -8.312*10−4

2.5.3. Activity coefficients

Activity of soluble compound “I” in water is given by Equation (2.44). “γi ” is

activity coefficient and Ci is the concentration (mole/L) of soluble compound.

ai = γi * Ci (2.44)

The calculations of individual ion activity coefficient have been approximated by

Equation (2.45) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. Helge son et al, 1981)
and suitable for overall equilibrium diagram calculations. “γi ” Is the activity coefficient
of soluble compound “I”, “Zi ” is the electrical charge of compound “i” and “I” is the ionic
strength (mole/kg of water) (in this case ionic strength is given in mole/L). “A”, “B” and
“b” are temperature-dependent parameters. Table (2.2) gives values of parameters “A”,
“B” and “b” at different temperatures (B. Beverskog et al, 1998). “ä” is a distance of
closest approach, which may be taken to be equal to that of NaCl (3.72 10−10m).

Z2 A√I
Log(γi )= - (1+Bä√I)
i
– log(1+0.018015*I)+b*I (2.45)

Joseph Kafumbila Page 46

 Table 2.2: values of A, B and b parameter

Temperature (°C) A B b
25 0.509 0.328 0.064
100 0.600 0.342 0.076
150 0.690 0.353 0.065
200 0.81 0.361 0.046

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 (mole/kg of water) (H.C. Helgeson
et al, 1981).

Joseph Kafumbila Page 47

3. Eh-pH diagram of Mn-Water system

3.1. Overall equilibrium diagram

3.1.1. 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.

3.1.2. Thermodynamic conditions

The thermodynamic conditions of an overall equilibrium diagram are the

following:

 The solid compound is pure. The activity of solid is equal to 1. The chemical
potential of a solid compound is given by Equation (3.1).

μ=μ° (3.1)

 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 pressure of hydrogen and oxygen gases is equal to 1Bar. The partial
pressure of other gases must be known.
 The activity coefficient can be added in the chemical potential calculation if
there is an adequate model.

Joseph Kafumbila Page 48

3.1.3. Construction step of E-pH diagram

The new 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, E 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, E 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 E
and pH; the ratios of the concentrations of soluble compounds on the sum of the
concentrations of soluble compounds can be calculated.

3.1.4. 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 E-pH diagram is established. Equation of the boundary of the
two solids “A” and “B” is obtained as follows:

 “D” is a soluble compound and it is the reference.

 To establish the precipitation reactions between the reference “D” and the two
solid compounds “A” and “B” (the chemical reactions (3.a) and (3.b) give the
precipitation reactions of the two solids “A” and “B”).

Joseph Kafumbila Page 49

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

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

 To establish Equations giving the saturation concentrations of the reference

from the equilibrium conditions of the precipitation reactions (3.a) and (3.b).
Equations (3.2) and (3.3) gives the concentrations of soluble compound “D” (CD )
established from the equilibrium conditions of the chemical reactions (3.a) and
(3.b).

υ1e ∗F (υA ∗μ°A − υ1D ∗μ°D − υ1c ∗μC ) υ1H+ ∗

Log(CD )= υ *E+ + *pH (3.2)
1D ∗R∗T∗2.303 υ1D ∗R∗T∗2.303 υ1D

υ2e ∗F (υA ∗μ°A − υ2D ∗μ°D − υ2C ∗μC ) υ2H+ ∗

Log(CD )= υ *E+ + *pH (3.3)
2D ∗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 (3.2) and (3.3) are equal.

3.1.5. Concentrations of other soluble compounds

The general equilibrium chemical reaction of a soluble compound with the

reference is given by the chemical reaction (3.c). “G” is the soluble compound and “D” is
the reference. “C” is a soluble compound that does not contain the element whose E-pH
diagram is established.

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

Equation (3.4) gives the concentration of soluble compound “G” as a function of

the concentration of the reference, E and pH. The concentration of soluble compound “C”
is known.

υe ∗F υ1H+ ∗ υ ∗ (υD ∗μ°D − υG ∗μ°𝐺 − υc ∗μC )

Log(CG )= υ *E+ *pH+ υD *Log(CD ) + (3.4)
𝐺 ∗R∗T∗2.303 υ𝐺 𝐺 υG ∗R∗T∗2.303

3.1.6. Boundary of aqueous solution and solid compounds

The system contains soluble compounds “D”, “G” and “H” and solid compound
“A”. The soluble compound “D” is the reference. Equation (as Equation (3.2)) giving the
saturation concentration of soluble compound “D” is established. Equations (as Equation
(3.4)) giving the concentration of other soluble compounds as function of the
concentration of the reference, E and pH are established.

Joseph Kafumbila Page 50

 The total concentration of soluble compounds (“D”, “G” and “H”) is equal to “CtS ”
that is the known value. Equation (3.5) gives the total concentration of soluble
compounds.

CD +CG +CH = CtS (3.5)

In the stability area of a giving solid compound; at known value of E or at known

value of pH, the value of pH or the value of E can be calculated.

3.1.7. 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 E-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 (3.c)).
 To establish Equation giving the concentration of one soluble compound as
function of the concentration of the other soluble compound, E and pH (Equation
(3.4)).
 If the stoichiometry “υD ” and “υG ” are equal; the concentrations of the two
soluble compounds can be removed in the Equation (3.4).
 If the stoichiometry “υD ” and “υG ” are not equal; the concentrations of the two
soluble compounds cannot be removed in the Equation (3.4). 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.

Joseph Kafumbila Page 51

 c. To establish Equations giving the concentration of others soluble compounds as
a function of the concentration of the reference, E and pH.
d. To establish Equation giving the sum of the concentrations of all soluble
compounds as function of the concentration of the reference, E and pH (First
Equation)
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, E and pH.
f. To determine the value of pH for a known value of E, or the value of E for a
known value of pH from the two equations.

3.2. Overall equilibrium diagram with heterogeneous solid

solution

3.2.1. Thermodynamic conditions

The thermodynamic conditions of an overall equilibrium diagram with

heterogeneous solid solution are the following:

 The precipitate is the mixture of solid compounds that are thermodynamically

stables.
 The activity of the thermodynamically stable solid compound in the precipitate
is the molar fraction. The chemical potential of stable solid compounds is given
by Equation (3.6). “X” is the molar fraction.

μ=μ° + R*T*2.303*Log(X) (3.6)

 The stable solid compounds in the precipitate are individually in equilibrium

with all soluble compounds
 The liquid phase contains solvent and ions.
 The concentration of soluble compounds is the saturation concentration coming
from the precipitation reaction.
 The soluble compounds are in equilibrium each other.
 The partial pressure of hydrogen and oxygen gases is equal to 1Bar. The partial
pressure of other gases must be known.
 The activity coefficient can be added in the chemical potential calculation if
there is an adequate model.

3.2.2. Boundary of two solid compounds

The system contains three soluble compounds “A”, “B” and “C” and two solid
compounds “D” and “G”. The two soluble compounds “A” and “B” react to give the solid

Joseph Kafumbila Page 52

compound “D” according to the precipitation reaction (3.d) and the two soluble
compounds “A” and “C” react to give the solid compound “G” according to the
precipitation reaction (3.e).

υ1A *A + υ1H+ *H + + υ1e *e− + υB *B= υ𝐷 *D (3.d)

υ2A *A + υ2H+ *H + + υ2e *e− + υC *C= υG *G (3.e)

The chemical potentials of the soluble compound “A” calculated from the
precipitation reactions (3.d) and (3.e) are given by Equations (3.7) and (3.8).

υ υ υ υ1H+ υ
μ1A =υ D *μ°D - υ B *μB + υ D *R*T*2.303*Log(X D) + υ1A
*R*T*2.303*pH + υ 1e *F*E (3.7)
1A 1A 1A 1A

υ𝐺 υC υG υ + υ
μ2A = *μ° - *μ + *R*T*2.303*Log(X G ) + 2H *R*T*2.303*pH + 2e *F*E (3.8)
υ2A G υ2A C υ2A υ2A υ2A

"XD " and "XG " are the molar fractions of the solid compounds “D” and “G” in the
heterogeneous solid solution.

The equilibrium constraints are given by Equations (3.9) and (3.10).

μ1A =μ2A (3.9)

XD + XG =1 (3.10)

The coordinates (E;pH) of the boundary of the predominance areas of the two
solid compounds are obtained when “XD ” is equal to “XG ”. In this condition; at a known
value of E, pH becomes a variable or at a known value of pH, E becomes a variable.

3.3. Assumptions on Eh-pH diagram of Mn-Water system

The pathways are first the oxidation of ions Mn(II) to Mn(III). When Mn(III)
concentration reaches the saturation concentration, Manganese precipitate as MnOOH.
MnOOH reacts with acid to produce Mn(II), and γ and δ MnO2 in the presence of acid.

The assumption is that:

 Firstly, MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution in

which all solid compounds are thermodynamically in equilibrium with
soluble species. Mn-Water system contains Manganese Metal, Mn(OH)2, and
heterogeneous solid solution having MnOOH, 𝛿MnO2 and 𝛾MnO2 as solid
compounds. This system is called system A.

Joseph Kafumbila Page 53

  Secondly, MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution
in which only MnOOH is thermodynamically in equilibrium with soluble
species. Mn-Water system contains Manganese Metal, Mn(OH)2, and
heterogeneous solid solution having MnOOH, 𝛿MnO2 and 𝛾MnO2 as solid
compounds. This system is called system B.

3.4. Overall Eh-pH diagram of Mn-water system

3.4.1. Thermodynamic Data

Table 3.1: Thermodynamic data of compounds

G° H° S° Cp° Reference
J/mole J/mole J/mole J/mole
H+ 0 0 0 0 CoData
H2 0 0 130.684 28.824 CoData
O2 0.00 0.00 205.138 29.355 CoData
H2 O -237130.0 -285830.0 69.91 75.291 CoData
Co° 0 0 30.04 24.8 CoData
Co+2 -54400.0 -58200.0 -113.0 CoData
Co+3 134000.0 92000.0 -305.0 CoData
CoOOH -382099 -437140 -184.624 Cp° =f(T) Tian Qing-hua et al, 2015
Mn+2 -228100 -220800 -73.6 50.0 CoData
MnO4− -447200.0 -541400.0 191.2 -82.0 CoData
a:Wenhao et al, 2019
MnOOH -557683.3(a) -635000.0(b)
b:E.Z. Carlson et al
a: Wenhao et al, 2019
γMnO2 -461873.7(a) 68.78(b) 70.14(b) b: Chunsheng Zhou et al,2018
a: Wenhao et al, 2019
δMnO2 -459944.0(a) 411.37(b) 350.77(b) b: Chunsheng Zhou et al,2018

1.055∗109
Cp° (CoOOH)=4.237*104 -140.8*T+0.1332*T 2 - T2

Mn+3 + e− = Mn+2 (1.d)

Table 3.2: log(k) and enthalpy change of reaction (1.d)

Reaction Log(k) 𝛥H ° Reference

J/mole
1.d 25.51 -107973.0 WATEQ4F

3.4.2. Overall diagram of Mn-Water system

Figures (3.1) and (3.2) give respectively the overall diagrams of system A and
system B at 60°C. Red lines give the solid predominance area, green lines give soluble

Joseph Kafumbila Page 54

species predominance area, bleu lines gives water stability area and black lines gives
total concentrations of Manganese in solution as function of pH and Eh.

Figure 3.1: Overall diagram of system A at 60°C

Joseph Kafumbila Page 55

 Figure 3.2: Overall diagram of System B at 60°C

The difference between the two Figures is the position of the soluble and solid
boundary line in predominance areas of MnOOH and δMnO2 .

Joseph Kafumbila Page 56

4. Mass balance of Cobalt electrowinning circuit –
Anode potential at saturation concentration of
Mn(III)

4.1. Flow diagram

Figure (4.1) shows the hydrodynamic between cathode and anode.

Figure 4.1: Flow diagram showing flow between cathode and anode

Abbreviations:

IS: Inlet solution.

DFS: Down flow solution.
BMS: Bottom mixed solution (IS+DFS).
EIS: Electrode inlet solution (BMS after precipitation of BSS and Redox potential
balancing).
BSS: Bottom solution sludge.
ICUFS: Inlet cathodic up flow solution.

Joseph Kafumbila Page 57

 IAUFS: Inlet anodic up flow solution.
OCUFS: Outlet cathodic up flow solution.
OAUFS: Outlet anodic up flow solution.
TMS: Top mixed solution (OCUFS+OAUFS)
EOS: Electrode outlet solution (TMS after precipitation of TSS and Redox
potential balancing).
TSS: Top solution sludge.
OS: Outlet solution.
CC: Cathodic Cobalt.
AS: Anode sludge.

4.2. Problematic
The precipitation of Manganese at the anode is start when Mn(III) reaches the
saturation concentration. The saturation concentration is reached with reaction (1.w).

Mn+3 +2H2 O=MnOOH + 3H + (1.w)

4.3. Design criteria

4.3.1. Inlet solution

 Composition of inlet solution:

o Temperature: 60°C
o Flow rate: 1.0 m3/h
o pH: 2.0 (to have a ductile cobalt cathode)
o Total cobalt concentration: 60g/L
o Total Manganese concentration: 4g/l.
o Redox potential: Solution in equilibrium with oxygen in Air. “Es” is
°
redox potential of solution (v), “Eoxy(60°C) ” is standard redox
potential of oxidation of water into oxygen at 60°C (1.224v), “a(H+ ) ”
is hydrogen ion activity, “aw ” is water activity and “P(O2 ) ” is oxygen
partial pressure in Air (0.21bar).

2H2 O = 4H + + O2 + 4e− (1.k)

8.314∗333.15∗2.303 (a(H+ ) )4 ∗P(O2 )

°
Es =Eoxy(60°C) + *log( ) (4.1)
4∗96485 (aw )2

Joseph Kafumbila Page 58

  Complexation reactions

H + +SO−2 −
4 =HSO4 log(k)=2.395 at 60°C (4.a)

Log(a(HSO−4 ))=log(k (4.a) )+ log(a(H+) )+ log(a(SO−2

4 )
) (4.2)

Co2+ +SO−2
4 =CoSO4 log(k)=2.414 at 60°C (4.b)

Log(a(CoSO4 ))=log(k (4.b) )+ log(a(Co+2 ))+ log(a(SO−2

4 )
) (4.3)

Mn2+ +SO−2
4 =MnSO4 log(k)=2.417 at 60°C (4.c)

Log(a(MnSO4 ))=log(k (4.c))+ log(a(Mn+2 ))+ log(a(SO−2

4 )
) (4.3)

 Equilibrium concentrations of Co+3 , Mn+3, MnO− −2

4 and MnO4 .

Co+3 + e− = Co+2 (4.d)

μ(Co+3 ) =μ(Co+2 ) +96485*Es (4.4)

Mn+3 + e− = Mn+2 (4.e)

μ(Mn+3 ) =μ(Mn+2 ) +96485*Es (4.5)

MnO− + − +2
4 +8H +5e =Mn +4H2 O (4.f)

μ(MnO−4 ) +8μ(H+) =μ(Mn+2 ) +4μ(H2 O) +5*96485*Es (4.6)

 Activity coefficient of soluble compounds at 60°C

Z2 0.544√I
Log(γi )= - (1+1.245√I)
i
– log(1+0.018015*I)+0.073*I (4.7)

 Water activity at 60°C

0.366 1
ϕ=1- *[u -2ln(u) -u] +1.485*10−2 + 5.325*10−3*I2 -4.712*10−4 (4.8)
I

u=1+1.507*√I (4.9)

 Concentration of soluble sulfur:

The electrical neutrality of solution.

Joseph Kafumbila Page 59
4.3.2. Down flow solution

 Flow rate: “VIS ” is inlet solution flow rate and “VDFS ” is down flow
solution flow rate

VDFS =9*VIS (4.11)

4.3.3. Bottom mixed solution

 BMS is the mixture of IS and DFS

 Quantity respectively of CoT, MnT, S, CoSO4 , Co+3, MnSO4, Mn+3, and

MnO−4 in BMS is the sum of the quantities in IS and DFS.

 Quantity of Co+2 in BMS is quantity of COT minus quantity of CoSO4 in

BMS.

 Quantity of Mn+2 in BMS is quantity of MnT minus the sum of quantities

of Mn+3, and MnO−4 in BMS.

 Mass balances of sulfur and electrical charge neutrality allow having the
concentrations of H + , SO−2 −
4 , HSO4 in BMS.

This step is added to visualize the redox potential of couples (Co+3 /Co+2 ),
(Mn+3 /Mn+2 ), and (MnO− +2
4 /Mn )

4.3.4. Electrode inlet solution

EIS is BMS after sulfate balancing, redox potential balancing and precipitation of
BSS.
 During the sulfate balancing the free sulfate must be in equilibrium with
soluble Cobalt and Manganese sulfate complexes according to chemical
reactions (4.a), (4.b) and (4.c).

H + +SO−2 −
4 =HSO4 log(k)=2.395 at 60°C (4.a)

Co2+ +SO−2
4 =CoSO4 log(k)=2.414 at 60°C (4.b)

Mn2+ +SO−2
4 =MnSO4 log(k)=2.417 at 60°C (4.c)

Joseph Kafumbila Page 60

  During the redox potential balancing, the redox potential of couples
(Co+3 /Co+2 ), (Mn+3/Mn+2), and (MnO− +2
4 /Mn ) must be equal.

o Co+3 and Mn+2 react to produce Co+2 and Mn+3 or Co+2 and Mn+3
react to produce Co+3 and Mn+2.

Mn+2+Co+3 =Mn+3+Co+2 (1.ae)

Mn+3+Co+2 =Mn+2+Co+3 (1.af)

o Mn+2 and MnO− 4 react to produce Mn

+3
or Mn+3 disproportionate
into Mn+2 and MnO−4.

4Mn+2+MnO− + +3
4 +8H =5Mn +4H2 O (1.ac)

5Mn+3+4H2 O =4Mn+2 +MnO−

4 +8H
+
(1.ad)

 In Case where there is production of Mn+3, MnOOH can precipitate when

the Mn+3 concentration reaches the saturation concentration. In acid
media, MnOOH reacts with acid to produce δ-MnO2 and γMnO2 .

Mn+3+2H2 O=MnOOH + 3H + (1.w)

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

o Equation (4.12) gives the saturation concentration of Mn+3

C(Mn+3 )
8.314*333.15*2.303*log( )=μ(MnOOH) +3μ(H+) -2μ(H2 O) -μ°(Mn+3 ) (4.12)
γ3

o Molar fraction of MnOOH, γMnO2 and δMnO2 in the

heterogeneous solid solution. The chemical potentials of MnOOH,
γMnO2 and δMnO2 in the solid are given by Equations (4.13),
(4.14), and (4.15). Where X(MnOOH), X(γMnO2 ) and X ((δMnO2 ) are the
molar fractions of MnOOH, γMnO2 and δMnO2.

μ(MnOOH) =μ°(MnOOH)+8.314*333.15*2.303*log(X(MnOOH) ) (4.13)

μ(γMnO2 ) =μ°(γMnO2) +8.314*333.15*2.303*log(X(γMnO2 )) (4.14)

μ(δMnO2) =μ°(δMnO2 )+8.314*333.15*2.303*log(X(δMnO2 )) (4.15)

Joseph Kafumbila Page 61

 o The first constraint is given by Equation (4.16)

1=X(MnOOH)+X(𝛿MnO2 ) +X(𝛾MnO2 ) (4.16)

o The second and third constraints are given by Equations (4.17)

and (4.18) that give the thermodynamic equilibrium of chemical
reactions (1.x) and (1.y)

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

μ(𝛿MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH)+2*μ(H+) (4.17)

μ(𝛾MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (4.18)

In system A, the value of μ(MnOOH) in Equation (4.12) is given by Equation

(4.13). Where μ°(MnOOH) is the standard chemical potential of MnOOH at 60°C (-
561898.46 j/mole) and X (MnOOH) is molar fraction of MnOOH in the heterogeneous solid
solution (MnOOH, γMnO2 and δMnO2).

In system B, the value of μ(MnOOH) is given by Equation (4.19).

μ(MnOOH) =μ°(MnOOH) (4.19)

The values of μ(H+) and μ(H2 O) are given by Equations (4.20) and (4.21). Where
μ°(H2 O) is standard chemical potential of water at 60°C (-239725.80 j/mole).

μ(H+) =8.314*333.15*2.303*log(C(H+) *γ1 ) (4.20)

μ(H2 O) =μ°(H2 O) +8.314*333.15*2.303*log(aw ) (4.21)

4.3.5. Inlet cathodic up flow solution

 Flow rate: “V(ICUFS) ” is the inlet cathodic up flow solution flow rate

V(ICUFS) =1/2*(VEIS ) (4.22)

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4.3.6. Outlet cathodic up flow solution

 Over potential: -0.8V (assumed)

The cathodic over-potential increases with the increase of current

density. For Nickel, the values of Tafel slope and exchange current
density are 120mV and 2*10−5 at 25°C in 1MNiSO4 . This means that at
current density of 300A/m2 (average cobalt electrowinning current
density) the cathodic over-potential is equal to -0.86V. The assumption is
that the over-potential of Cobalt on the cathode is close to that of Nickel.

°
 Cobalt potential at 60°C: “a(Co+2 )” is the activity of Co+2 and “E(Co+2 ) ” is

standard potential of Cobalt at 60°C (-0.249V)

Co+2 + 2e− = Coo (1.a)

° 8.314∗333.15∗2.303
E(Co+2 ) =E(Co +2 ) + *log(a(Co+2 ) ) (4.23)
2∗96485

 Cathodic potential: “Ec ”

Ec =E(Co+2 ) -0.8 (4.24)

 Complexation reactions

Same as Inlet solution

 Equilibrium concentrations of Co+3 , Mn+3, MnO− −2

4 and MnO4 .

Same as Inlet solution: Ec takes the place of Es

 Activity coefficient of soluble compounds at 60°C

Same as Inlet solution

 Water activity at 60°C

Same as Inlet solution

Joseph Kafumbila Page 63

  Mass of Cobalt cathode: M(CC)

Quantity of total Cobalt in inlet cathodic up flow minus quantity in outlet

cathodic up flow.

The total concentration of Cobalt in the outlet solution (OS) is a known

value.

c
 Mass of Co+3 reduces to Co+2 : M(Co +3 )

Quantity of Co+3 in inlet cathodic up flow minus quantity in outlet

cathodic up flow.

c
 Mass of Mn+3 reduces to Mn+2: M(Mn +3 )

Quantity of Mn+3 in inlet cathodic up flow minus quantity in outlet

cathodic up flow.

c
 Mass of MnO− +2
4 reduce to Mn : M(MnO−
4)

Quantity of MnO− 4 in inlet cathodic up flow minus quantity in outlet

cathodic up flow.

 Current efficiencies:

C C C C C
CE(CC) +CE(H 2)
+CE(Co +3 ) +CE(Mn+3 ) +CE(MnO− ) =100%
4
(4.25)

C
o Current efficiency: CE(CC) is unknown value

C
o Current efficiency: CE(H 2)

Figure (4.2) gives the current efficiency of hydrogen at 60°C (R. Breckpot et al
1969).

C
CE(H 2)
=-17.333pH 3 +12pH 2 -7.6667pH+93 (pH<1.5) (4.26)

C
CE(H 2)
=-12pH 3 +108pH 2 -327pH+338 (pH>1.5) (4.27)

Joseph Kafumbila Page 64

Figure (4.2): Hydrogen current efficiency during cobalt electrowinning at 60°C

C
o Current efficiency: CE(Co +3 ) – “58.93” is molar mass of cobalt, “1”

is number electron in reaction (1.c) and “2” is number electron in

reaction (1.a).

Co+2 + 2e− = Coo (1.a)

Co+3 + e− = Co+2 (1.c)

Mc +3 1 58.93
C (Co ) C
CE(Co +3 ) = * * *CE(CC) (4.28)
58.93 2 M(CC)

C
o Current efficiency: CE(Mn +3 ) – “54.94” is molar mass of
manganese, “1” is number electron in reaction (1.d) and “2” is
number electron in reaction (1.a).

Co+2 + 2e− = Coo (1.a)

Mn+3 + e− = Mn+2 (1.d)

Mc
C (Mn+3 ) 1 58.93 C
CE(Mn +3 ) = *2*M *CE(CC) (4.29)
54.94 (CC)

Joseph Kafumbila Page 65

 C −
o Current efficiency: CE(MnO − ) – “118.94” is molar mass of MnO4 ,
4
“5” is number electron in reaction (1.e) and “2” is number
electron in reaction (1.a).

Co+2 + 2e− = Coo (1.a)

MnO− + − +2
4 +8H +5e =Mn +4H2 O (1.e)

Mc(MnO−) 5 58.93
C C
CE(MnO −) =
4
*2*M *CE(CC) (4.30)
4 118.94 (CC)

 Mass of H2 : M(H2 )

Co+2 + 2e− = Coo (1.a)

2H + + 2e− = H2 ‘ (1.b)

CEC
(H ) 2.014 2
𝑎
M(H2 ) = CEC 2 *58.93*2b *M(CC) (4.31)
(CC)

Where “2𝑎 ” is number of electrons in the reaction (1.a) and “2𝑏 ” is number of
electrons in the reaction (1.b)

 pH of outlet cathodic up flow solution:

Quantity of soluble sulfur in inlet cathodic up flow solution is equal to

quantity of soluble sulfur in outlet cathodic up flow solution

4.3.7. Inlet anodic up flow solution

 Flow rate: “V(IAUFS) ” is the inlet anodic up flow solution flow rate

V(IAUFS) =1/2*(VEIS ) (4.32)

4.3.8. Outlet anodic up flow solution

 Oxygen potential at 60*C: “a(H+) ” is the activity of H + , “aw ” is the activity

of water, “PO2 ” is pressure of oxygen in the bubble on the anode (around
°
1bar) and “E(O 2)
” is standard potential of oxygen at 60°C (1.224V)

2H2 O = 4H + + O2 + 4e− (1.k)

Joseph Kafumbila Page 66

 8.314∗333.15∗2.303 (a(H+ ) )4 ∗PO2
°
E(O2 ) =E(O 2)
+ *log( ) (4.33)
4∗96485 (aw )2

 Complexation reactions

Same as Inlet solution

 Equilibrium concentrations of Co+3 , Mn+3, MnO− −2

4 and MnO4 .

Same as Inlet solution: Ea takes the place of Es

 Activity coefficient of soluble compounds at 60°C

Same as Inlet solution

 Water activity at 60°C

Same as Inlet solution

a
 Mass of Co+2 oxidizes to Co+3 : M(Co +3 )

Quantity of Co+3 in outlet anodic up flow minus quantity in inlet anodic

up flow.

a
 Mass of Mn+2 oxidizes to Mn+3: M(Mn +3 )

Quantity of Mn+3 in outlet anodic up flow minus quantity in inlet anodic

up flow.

a
 Mass of Mn+2 oxidizes to MnO−
4 : M(MnO−
4)

Quantity of MnO−
4 in outlet anodic up flow minus quantity in inlet anodic
up flow.

 Current efficiencies:

a a a a
CE(O 2)
+CE(Co +3 ) +CE(Mn+3 ) +CE(MnO− ) =100%
4
(4.34)

a
o Current efficiency: CE(Co +3 ) – “58.93” is molar mass of cobalt, “1”

is number electron in reaction (1.l) and “2” is number electron in

reaction (1.a).

Joseph Kafumbila Page 67

 Co2+ =Co3+ +e− (1.l)

Co+2 + 2e− = Coo (1.a)

Ma +3 1 58.93
a (Co ) C
CE(Co +3 ) = * * *CE(CC) (4.35)
58.93 2 M(CC)

a
o Current efficiency: CE(Mn +3 ) – “54.94” is molar mass of
manganese, “1” is number electron in reaction (1.n) and “2” is
number electron in reaction (1.a).

Mn2+ =Mn3+ +e− (1.n)

Co+2 + 2e− = Coo (1.a)

Ma
a (Mn+3 ) 1 58.93 C
CE(Mn +3 ) = *2*M *CE(CC) (4.36)
54.94 (CC)

a −
o Current efficiency: CE(MnO − ) – “118.94” is molar mass of MnO4 ,
4
“5” is number electron in reaction (1.o) and “2” is number
electron in reaction (1.a).

Mn+2+4H2 O =MnO− +
4 +8H +5e
−
(1.o)

Co+2 + 2e− = Coo (1.a)

Ma(MnO−) 5 58.93
a C
CE(MnO −) =
4
*2*M *CE(CC) (4.37)
4 118.94 (CC)

 Mass of O2 : M(O2 ) - “4” is number electron in reaction (1.k) and “2” is

number electron in reaction (1.a).

2H2 O = 4H + + O2 + 4e− (1.k)

Co+2 + 2e− = Coo (1.a)

CEa(O ) 31.998 4
M(O2 ) =CEC 2 * 58.93 *2*M(CC) (4.38)
(CC)

 pH of outlet anodic up flow solution:

Quantity of soluble sulfur in inlet anodic up flow solution is equal to

quantity of soluble sulfur in outlet anodic up flow solution

Joseph Kafumbila Page 68

  Over potential: 𝜌𝑎 - the constraint is that the concentration of Mn+3 in
the OAUFS is equal to the saturation concentration of Mn+3.

 The concentration of Mn+3.in the outlet anodic up flow solution is equal

to the saturation concentration in the system A or B.

o Equation (4.39) gives the saturation concentration of Mn+3

C(Mn+3 )
8.314*333.15*2.303*log( )=μ(MnOOH) +3μ(H+) -2μ(H2 O) -μ°(Mn+3 ) (4.39)
γ3

o Molar fraction of MnOOH, γMnO2 and δMnO2 in the

heterogeneous solid solution. The chemical potentials of MnOOH,
γMnO2 and δMnO2 in the solid are given by Equations (4.40),
(4.41), (4.42). Where X(MnOOH), X(γMnO2 ) and X((δMnO2 ) are the
molar fractions of MnOOH, γMnO2 and δMnO2.

μ(MnOOH) =μ°(MnOOH)+8.314*333.15*2.303*log(X(MnOOH) ) (4.40)

μ(γMnO2 ) =μ°(γMnO2) +8.314*333.15*2.303*log(X(γMnO2 )) (4.41)

μ(δMnO2) =μ°(δMnO2 )+8.314*333.15*2.303*log(X(δMnO2 )) (4.42)

o The first constraint is given by Equation (4.43)

1=X(MnOOH)+X(𝛿MnO2 ) +X(𝛾MnO2 ) (4.43)

o The second and third constraints are given by Equations (4.44)

and (4.45) that give the thermodynamic equilibrium of chemical
reactions (1.x) and (1.y)

μ(𝛿MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH)+2*μ(H+) (4.44)

μ(𝛾MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (4.45)

In system A, the value of μ(MnOOH) in Equation (4.39) is given by Equation

(4.40). Where μ°(MnOOH) is the standard chemical potential of MnOOH at 60°C (-
561898.46 j/mole) and X (MnOOH) is molar fraction of MnOOH in the heterogeneous solid
solution (MnOOH, γMnO2 and δMnO2).

In system B, the value of μ(MnOOH) is given by Equation (4.46).

Joseph Kafumbila Page 69

 μ(MnOOH) =μ°(MnOOH) (4.46)

The values of μ(H+) and μ(H2 O) are given by Equations (4.48) and (4.49). Where
μ°(H2 O) is standard chemical potential of water at 60°C (-239725.80 j/mole).

μ(H+) =8.314*333.15*2.303*log(C(H+) *γ1 ) (4.48)

μ(H2 O) =μ°(H2 O) +8.314*333.15*2.303*log(aw ) (4.49)

 Anodic potential: “Ea ”

Ea =E(O2 ) +ρa (4.50)

4.3.9. Top mixed solution

 TMS is the mixture of OCUFS and OAUFS

 Quantity respectively of CoT, MnT, S, CoSO4 , Co+3, MnSO4, Mn+3, and

MnO−4 in TMS is the sum of the quantities in OCUFS and OAUFS.

 Quantity of Co+2 in TMS is quantity of COT minus quantity of CoSO4 in

TMS.

 Quantity of Mn+2 in TMS is quantity of MnT minus the sum of quantities

of Mn+3, and MnO−4 in TMS.

 Mass balances of sulfur and electrical charge neutrality allow having the
concentrations of H + , SO−2 −
4 , HSO4 in TMS.

This step is added to visualize the redox potential of couples (Co+3 /Co+2 ),
(Mn+3 /Mn+2 ), and (MnO− +2
4 /Mn )

4.3.10. Electrode outlet solution

EOS is TMS after sulfate balancing, redox potential balancing and precipitation
of TSS,.
 During the sulfate balancing the free sulfate must be in equilibrium with
soluble Cobalt and Manganese sulfate complexes according to chemical
reactions (4.a), (4.b) and (4.c).

Joseph Kafumbila Page 70

 H + +SO−2 −
4 =HSO4 log(k)=2.395 at 60°C (4.a)

Co2+ +SO−2
4 =CoSO4 log(k)=2.414 at 60°C (4.b)

Mn2+ +SO−2
4 =MnSO4 log(k)=2.417 at 60°C (4.c)

 During the redox potential balancing, the redox potential of couples

(Co+3 /Co+2 ), (Mn+3/Mn+2), and (MnO− +2
4 /Mn ) must be equal.

o Co+3 and Mn+2 react to produce Co+2 and Mn+3 or Co+2 and Mn+3
react to produce Co+3 and Mn+2.

Mn+2+Co+3 =Mn+3+Co+2 (1.ae)

Mn+3+Co+2 =Mn+2+Co+3 (1.af)

o Mn+2 and MnO− 4 react to produce Mn

+3
or Mn+3 disproportionate
into Mn+2 and MnO−4.

4Mn+2+MnO− + +3
4 +8H =5Mn +4H2 O (1.ac)

5Mn+3+4H2 O =4Mn+2 +MnO−

4 +8H
+
(1.ad)

 In Case where there is production of Mn+3, MnOOH can precipitate when

the Mn+3 concentration reaches the saturation concentration. In acid
media, MnOOH reacts with acid to produce δ-MnO2 and γMnO2 .

Mn+3+2H2 O=MnOOH + 3H + (1.w)

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

o Equation (4.51) gives the saturation concentration of Mn+3

C(Mn+3 )
8.314*333.15*2.303*log( )=μ(MnOOH) +3μ(H+) -2μ(H2 O) -μ°(Mn+3 ) (4.51)
γ3

o Molar fraction of MnOOH, γMnO2 and δMnO2 in the

heterogeneous solid solution. The chemical potentials of MnOOH,
γMnO2 and δMnO2 in the solid are given by Equations (4.52),
(4.53), (4.54). Where X(MnOOH), X(γMnO2 ) and X((δMnO2 ) are the
molar fractions of MnOOH, γMnO2 and δMnO2.

Joseph Kafumbila Page 71

 μ(MnOOH) =μ°(MnOOH)+8.314*333.15*2.303*log(X(MnOOH) ) (4.52)

μ(γMnO2 ) =μ°(γMnO2) +8.314*333.15*2.303*log(X(γMnO2 )) (4.53)

μ(δMnO2) =μ°(δMnO2 )+8.314*333.15*2.303*log(X(δMnO2 )) (4.54)

o The first constraint is given by Equation (4.55)

1=X(MnOOH)+X(𝛿MnO2 ) +X(𝛾MnO2 ) (4.55)

o The second and third constraints are given by Equations (4.56)

and (4.57) that give the thermodynamic equilibrium of chemical
reactions (1.x) and (1.y)

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

μ(𝛿MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH)+2*μ(H+) (4.56)

μ(𝛾MnO2) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (4.57)

In system A, the value of μ(MnOOH) in Equation (4.51) is given by Equation

(4.52). Where μ°(MnOOH) is the standard chemical potential of MnOOH at 60°C (-
561898.46 j/mole) and X (MnOOH) is molar fraction of MnOOH in the heterogeneous solid
solution (MnOOH, γMnO2 and δMnO2).

In system B, the value of μ(MnOOH) is given by Equation (4.58).

μ(MnOOH) =μ°(MnOOH) (4.58)

The values of μ(H+) and μ(H2 O) are given by Equations (4.59) and (4.60). Where
μ°(H2 O) is standard chemical potential of water at 60°C (-239725.80 j/mole).

μ(H+) =8.314*333.15*2.303*log(C(H+) *γ1 ) (4.59)

μ(H2 O) =μ°(H2 O) +8.314*333.15*2.303*log(aw ) (4.60)

Joseph Kafumbila Page 72

4.3.11. Outlet solution

 Flow rate: “V(OS) ” is the outlet solution flow rate

V(OS) =VEOS - VDFS (4.61)

 Concentration of Cobalt in OS is 55g/L.

4.4. Mass balance

4.4.1. System A

Tables (4.1), (4.2) and (4.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (4.4) gives current efficiencies of compounds at cathode and anode.

Table (4.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.180 11.317 11.317 5.659
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.132 1.132 1.132
Co(+2) g/l 27.432 26.682 26.759 26.695 26.695
CoSO4 g/l 85.657 74.521 75.634 75.803 75.803
Co(+3) g/l 3.046*10-12 3.689*10-13 6.366*10-13 5.174*10-13 5.174*10-13
Mn(+2) g/l 2.590 1.934 2.000 1.918 1.918
MnSO4 g/l 3.876 5.684 5.504 5.729 5.729
Mn(+3) g/l 1.866*10-06 3.810*10-07 5.295*10-07 5.295*10-07 5.295*10-07
MnO4(-) g/l 4.831*10-18 1.484*10-24 4.831*10-19 1.459*10-23 1.459*10-23
Ac1 g/l 1.394 2.653 2.444 2.456 2.456
Ac2 g/l 8.255 14.152 13.308 13.308 13.308
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 4.003 4.003 4.003 4.003
pH 2.000 1.722 1.757 1.755 1.755
ORP v 1.081 1.021 1.031 1.031
OVP

Joseph Kafumbila Page 73

 Table (4.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5,047 0,000
Gas
Mass kg/h 0,097 2,138
Liquid
Mass t/h 5,654 5,659
Volume m3/h 4,999 5,000
SG t/m3 1,131 1,132
Co(+2) g/l 26,666 26,695
CoSO4 g/l 73,239 75,803
Co(+3) g/l 3,917*10-45 5,174*10-13
Mn(+2) g/l 1.951 1.918
MnSO4 g/l 5.639 5.729
Mn(+3) g/l 4.083*10-39 5.295*10-07
MnO4(-) g/l 1.139*10-184 1.459*10-23
Ac1 g/l 2.855 2.456
Ac2 g/l 14.993 13.308
CoT g/l 54.497 55.500
MnT g/l 4.004 4.003
pH 1.690 1.755
ORP v -1.093 1.031
OVP v -0.800

Table (4.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.657 11.310 11.310 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.697 26.681 26.681 26.682
CoSO4 g/l 75.806 74.522 74.522 74.521
Co(+3) g/l 7.446*10-13 3.723*10-13 3.723*10-13 3.689*10-13
Mn(+2) g/l 1.918 1.934 1.934 1.934
MnSO4 g/l 5.730 5.684 5.684 5.684
Mn(+3) g/l 7.619*10-07 3.810*10-07 3.810*10-07 3.810*10-07
MnO4(-) g/l 8.980*10-23 4.490*10-23 4.490*10-23 1.484*10-24
Ac1 g/l 2.457 2.653 2.653 2.653
Ac2 g/l 13.311 14.152 14.152 14.152
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 4.003 4.003 4.003 4.003
pH 1.755 0.000 1.722 1.722
ORP v 1.041 1.021
OVP -0.067

Joseph Kafumbila Page 74

 Table (4.4): Current efficiency – System A

Current efficiency (%)

Cathode Anode
Co CC 64.10 O2 100.00
H2 35.90
Co(+3) 1.64*10-11 Co(+3) 7.20*10-12
Mn (+3) 1.80*10 -05 Mn (+3) 7.91*10-06
MnO4(-) 1.15*10-21 MnO4(-) 5.92*10-21

4.4.2. System B

Tables (4.5), (4.6) and (4.7) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido redox potential and OVP is over potential.
Table (4.8) gives current efficiencies of compounds at cathode and anode.

Table (4.5): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.180 11.317 11.317 5.659
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.132 1.132 1.132
Co(+2) g/l 27.432 26.676 26.753 26.689 26.689
CoSO4 g/l 85.657 74.537 75.649 75.817 75.817
Co(+3) g/l 3.046*10-12 4.693*10-09 4.224*10-09 4.160*10-09 4.160*10-09
Mn(+2) g/l 2.590 1.931 1.997 1.915 1.915
MnSO4 g/l 3.876 5.679 5.498 5.724 5.724
Mn(+3) g/l 1.866*10-06 4.841*10-03 4.357*10-03 4.252*10-03 4.252*10-03
MnO4(-) g/l 4.831*10-18 5.037*10-04 4.533*10-04 4.987*10-04 4.987*10-04
Ac1 g/l 1.394 2.647 2.439 2.451 2.451
Ac2 g/l 8.255 14.124 13.283 13.283 13.283
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 4.003 4.003 4.003 4.003
pH 2.000 1.723 1.758 1.756 1.756
ORP v 1.081 1.292 1.289 1.289
OVP

Joseph Kafumbila Page 75

 Table (4.6): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.047 0.000
Gas
Mass kg/h 0.097 2.137
Liquid
Mass t/h 5.654 5.659
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.132
Co(+2) g/l 26.662 26.689
CoSO4 g/l 73.251 75.817
Co(+3) g/l 3.916*10-45 4.160*10-09
Mn(+2) g/l 1.951 1.915
MnSO4 g/l 5.640 5.724
Mn(+3) g/l 4.082*10-39 4.252*10-03
MnO4(-) g/l 1.156*10-184 4.987*10-04
Ac1 g/l 2.849 2.451
Ac2 g/l 14.969 13.283
CoT g/l 54.497 55.500
MnT g/l 4.004 4.003
pH 1.691 1.756
ORP v -1.093 1.289
OVP v -0.800

Table (4.7): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.657 11.310 11.310 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.691 26.676 26.676 26.676
CoSO4 g/l 75.822 74.536 74.537 74.537
Co(+3) g/l 5.805*10-09 2,903*10-09 4,693*10-09 4.693*10-09
Mn(+2) g/l 1.914 1.932 1.931 1.931
MnSO4 g/l 5.721 5.680 5.679 5.679
Mn(+3) g/l 5.929*10-03 2.965*10-03 4.841*10-03 4.841*10-03
MnO4(-) g/l 2.632*10-03 1.316*10-03 5.037*10-04 5.037*10-04
Ac1 g/l 2.451 2.647 2.647 2.647
Ac2 g/l 13.284 14.127 14.124 14.124
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 4.003 4.003 4.003 4.003
pH 1.756 1.723 1.723 1.723
ORP v 1.298 1.292 1.292
OVP 0.191

Joseph Kafumbila Page 76

 Table (4.8): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 63.97 O2 99.78
H2 35.85
Co(+3) 1.32*10-07 Co(+3) 5.21*10-08
Mn (+3) 1.45*10 -01 Mn (+3) 5.70*10-02
MnO4(-) 3.91*10-02 MnO4(-) 1.67*10-01

4.5. Observations
Anodic potentials of systems A and B are respectively 1.041V (-0.067V) at pH
1.755 and 1.298V (0.191V) at pH 1.756. The values in parentheses are the over-
potentials comparatively to oxygen anodic potential. In the system (A) there is not
revolution of oxygen on the anode. In both cases there is not precipitation of Manganese.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . The anodic pH of systems (A) and
(B) is respectively 1.755 and 1.756. In both cases the anodic solutions are in Mn+2
predominance area. The system (B) is close to the boundary. This shows high
concentrations of Mn+3 and MnO− 4 in anodic solution for system (B) comparatively to
system (A).

E=1.515-0.106*pH (4.1)

Joseph Kafumbila Page 77

5. Mass balance of Cobalt electrowinning circuit –
Anode potential at saturation concentration of
Co(III)

5.1. Flow diagram

Figure 4.1

5.2. Problematic
The electrolytic precipitation of Cobalt at the anode is start when Co(III)
reaches the saturation concentration. The saturation concentration is reached with
reaction (1.v).

Co+3 +2H2 O=CoOOH + 3H + (1.v)

5.3. Design criteria

The change comparatively to the design criteria of chapter (4) is given

5.3.1. Outlet anodic up flow solution

 Over potential: 𝜌𝑎 – the constraint is that the concentration of Co+3 in

OAUFS is equal to the saturation concentration of Co+3 according to
reaction (1.v).

o Equation (5.1) gives the saturation concentration of Co+3

C(Co+3 )
8.314*333.15*2.303*log( )=μ(CoOOH) +3μ(H+ ) -2μ(H2 O) -μ°(Co+3 ) (5.1)
γ3

o The value of μ(CoOOH) is given by Equation (5.2). Where μ°(CoOOH)

is the standard chemical potential at 60°C (-376676.89j/mole)

μ(CoOOH) =μ°(CoOOH) (5.2)

Joseph Kafumbila Page 78

  Quantity of Mn in the precipitate: the constraint is that the concentration
of Mn+3.in the outlet anodic up flow solution is equal to the saturation
concentration in the system A and B.

5.4. Mass balance

5.4.1. System A

Tables (5.1), (5.2) and (5.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (5.4) gives current efficiencies of compounds at cathode and anode. Table (5.5)
gives the composition of solids.

Table (5.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.133 11.271 11.271 5.635
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.126 1.127 1.127 1.127
Co(+2) g/l 27.432 28.556 28.447 28.370 28.370
CoSO4 g/l 85.657 69.589 71.193 71.394 71.394
Co(+3) g/l 3.046*10-12 2.520*10-14 3.273*10-13 1.015*10-12 1.015*10-12
Mn(+2) g/l 2.590 0.188 0.428 0.370 0.370
MnSO4 g/l 3.876 0.482 0.822 0.981 0.981
Mn(+3) g/l 1.866*10-06 2.366*10-09 1.887*10-07 1.887*10-07 1.887*10-07
MnO4(-) g/l 4.831*10-18 2.825*10-33 4.831*10-19 1.378*10-24 1.378*10-24
Ac1 g/l 1.394 4.411 3.954 3.974 3.974
Ac2 g/l 8.255 20.754 19.254 19.254 19.254
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 0.364 0.727 0.727 0.727
pH 2.000 1.502 1.549 1.547 1.547
ORP v 1.081 0.942 1.048 1.048
OVP

Joseph Kafumbila Page 79

 Table (5.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.086 5.755
Gas
Mass kg/h 0.176 2.251
Liquid
Mass t/h 5.630 5.635
Volume m3/h 4.999 5.000
SG t/m3 1.126 1.127
Co(+2) g/l 28.350 28.370
CoSO4 g/l 68.788 71.394
Co(+3) g/l 4.262*10-45 1.015*10-12
Mn(+2) g/l 0.377 0.370
MnSO4 g/l 0.963 0.981
Mn(+3) g/l 8.075*10-40 1.887*10-07
MnO4(-) g/l 7.309*10-187 1.378*10-24
Ac1 g/l 4.471 3.974
Ac2 g/l 20.951 19.254
CoT g/l 54.490 55.500
MnT g/l 0.727 0.727
pH 1.496 1.547
ORP v -1.092 1.048
OVP v -0.800

Table (5.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.627 11.257 11.257 1.124
Volume m3/h 4.999 9.998 9.998 0.998
SG t/m3 1.126 1.126 1.126 1.126
Co(+2) g/l 28.761 28.556 28.556 28.556
CoSO4 g/l 70.393 69.590 69.589 69.589
Co(+3) g/l 2.071*10-09 1.035*10-09 2.520*10-14 2.520*10-14
Mn(+2) g/l 2.730*10-06 0.189 0.188 0.188
MnSO4 g/l 7.031*10-06 0.481 0.482 0.482
Mn(+3) g/l 2.800*10-09 1.400*10-09 2.366*10-09 2.366*10-09
MnO4(-) g/l 1.646*10-13 8.229*10-14 2.825*10-33 2.825*10-33
Ac1 g/l 4.352 4.411 4.411 4.411
Ac2 g/l 20.557 20.754 20.754 20.754
CoT g/l 55.510 55.000 55.000 55.000
MnT g/l 5.292*10-06 0.364 0.364 0.364
pH 1.508 1.502 1.502 1.502
ORP v 1.267 0.942 0.942
OVP 0.143

Joseph Kafumbila Page 80

 Table (5.4): Current efficiencies – System A

Current efficiency (%)

Cathode Anode
Co CC 49.67 O2 80.95
H2 50.33
Co(+3) 2.48*10-11 Co(+3) 5.05*10-08
Mn (+3) 4.94*10 -06 Mn (+3) 19.05
MnO4(-) 8.34*10-23 MnO4(-) 9.95*10-12

Table (5.5): Solid compositions – System A

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 8.74*10-06 0.00
δMnO2 0.00 97.88 0.00
γMnO2 0.00 2.12 0.00
Element
Mn 0.00 63.19 0.00

5.4.2. System B

Tables (5.6), (5.7) and (5.8) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (5.9) gives current efficiencies of compounds at cathode and anode. Table (5.10)
gives the composition of solids.

Joseph Kafumbila Page 81

 Table (5.6): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.228
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.159 11.297 11.297 5.648
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.129 1.130 1.130 1.130
Co(+2) g/l 27.432 27.494 27.490 27.427 27.427
CoSO4 g/l 85.657 72.384 73.711 73.877 73.877
Co(+3) g/l 3.046*10-12 2.205*10-08 1.985*10-08 1.826*10-08 1.826*10-08
Mn(+2) g/l 2.590 1.183 1.324 1.244 1.244
MnSO4 g/l 3.876 3.278 3.338 3.527 3.527
Mn(+3) g/l 1.866*10-06 1.352*10-02 1.217*10-02 1.180*10-02 1.180*10-02
MnO4(-) g/l 4.831*10-18 8.893*10-02 8.003*10-02 7.395*10-02 7.395*10-02
Ac1 g/l 1.394 3.379 3.071 3.092 3.092
Ac2 g/l 8.255 17.029 15.897 15.918 15.918
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 2.431 2.588 2.574 2.574
pH 2.000 1.617 1.658 1.656 1.656
ORP v 1.081 1.336 1.331 1.331
OVP

Table (5.7): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.064 2.258
Gas
Mass kg/h 0.138 2.209
Liquid
Mass t/h 5.643 5.648
Volume m3/h 4.999 5.000
SG t/m3 1.129 1.130
Co(+2) g/l 27.377 27.427
CoSO4 g/l 71.360 73.877
Co(+3) g/l 4.061*10-45 1.826*10-08
Mn(+2) g/l 1.288 1.244
MnSO4 g/l 3.533 3.527
Mn(+3) g/l 2.722*10-39 1.180*10-02
MnO4(-) g/l 1.565*10-185 7.395*10-02
Ac1 g/l 3.508 3.092
Ac2 g/l 17.557 15.918
CoT g/l 54.494 55.500
MnT g/l 2.574 2.574
pH 1.601 1.656
ORP v -1.092 1.331
OVP v -0.800

Joseph Kafumbila Page 82

 Table (5.8): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.644 11.287 11.287 1.128
Volume m3/h 4.999 9.999 9.999 0.999
SG t/m3 1.129 1.129 1.129 1.129
Co(+2) g/l 27.618 27.498 27.494 27.494
CoSO4 g/l 73.389 72.375 72.384 72.384
Co(+3) g/l 2.461*10-08 1.230*10-08 2.205*10-08 2.205*10-08
Mn(+2) g/l 1.085 1.187 1.183 1.183
MnSO4 g/l 3.035 3.284 3.278 3.278
Mn(+3) g/l 1.378*10-02 6.888*10-03 1.352*10-02 1.352*10-02
MnO4(-) g/l 1.836*10-01 9.180*10-02 8.893*10-02 8.893*10-02
Ac1 g/l 3.257 3.382 3.379 3.379
Ac2 g/l 16.518 17.038 17.029 17.029
CoT g/l 55.506 55.000 55.000 55.000
MnT g/l 2.289 2.431 2.431 2.431
pH 1.633 1.617 1.617 1.617
ORP v 1.339 1.336 1.336
OVP 0.223

Table (5.9): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 52.84 O2 84.88
H2 42.06
Co(+3) 4.76*10-07 Co(+3) 1.66*10-07
Mn(+3) 3.30*10-01 Mn(+3) 8.04
MnO4 (-) 4.78 MnO4 (-) 7.08

Table (5.10): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 8.28*10-03 7.34*10-03 0.00
δMnO2 97.87 97.87 0.00
γMnO2 2.12 2.12 0.00
Element
Mn 63.19 63.19 0.00

Joseph Kafumbila Page 83

5.5. Observations
Anodic potentials of systems A and B are respectively 1.267V (0.143V) at pH
1.508 and 1.339V (0.223V) at pH 1.633. The values in parentheses are the over-
potentials comparatively to oxygen anodic potential.

In the system A, the anodic potential value does not yet have the anodic
potential value of saturation concentration of Co+3 we reach the anodic potential value
where all Manganese in IAUFS is precipitated. The solid precipitates only on the anode
as anodic sludge. The anodic current efficiency of Mn+3 is 19.05% due to the
precipitation of anodic sludge. The concentration of Manganese in the outlet solution is
0.364g/L. 90.92% of Manganese from inlet solution precipitates as anode sludge.

In the system B, the anodic potential value reaches the anodic potential value of
saturation concentration of Co+3 . The solids precipitate in the bottom as bottom solution
sludge and at the anode as anodic sludge. The anodic current efficiencies of Mn+3 and
MnO− 4 are respectively 8.04% and 7.09%. The cathodic current efficiencies of Mn
+3
and
−
MnO4 are respectively 0.33% and 4.78%. The concentration of Manganese in outlet
solution is 2.431g/L. 3.606% and 35.68% of Manganese from inlet solution precipitate
as bottom sludge and anodic sludge respectively.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . In both cases the anodic solutions
+2
are in Mn predominance area. The system (B) is close to the boundary. This shows
high concentrations of Mn+3 and MnO−
4 in anodic solution for system (B) comparatively
to system (A).

Joseph Kafumbila Page 84

6. Mass balance of Cobalt electrowinning circuit –
Anodic potential at value of Manganese current
efficiency

6.1. Problematic
It has been observed during electrodeposition of Manganese at the anode as
MnO2 in divided cell that (Xiaosan SONG et al, 2021 and Charles E. Abbey, 2019):

 Anodic Manganese current efficiency at the anode increases linearly with

the increase of Manganese concentration in solution up to 30g/L when
the point zero current efficiency for zero Manganese is taken account. In
the zinc plant the behavior has been observed. In the lab-test the
behavior was not observed.
 Temperature does not affect anodic Manganese current efficiency.
 Anodic Manganese current efficiency increases with the increase of acid
concentration up to.
 Current density does not affect anodic Manganese current efficiency.

The chemical reactions of oxidation of water into oxygen and Mn(II) into
Mn(III) are in competition and are shared the same electrical current. Kinetic of water
oxidation depends on the nature of anode surface. This means that the current efficiency
of Manganese (II) increases with the increase of Manganese concentration in a rhythm
imposed of the kinetic of water oxidation into oxygen. The kinetic of water oxidation
into oxygen is high on Manganese dioxide than on lead oxide. The increase in Manganese
concentration increases the quantity of Manganese dioxide on the surface of anode and
in consequence the increase of kinetic of water oxidation into oxygen. At above 30g/L of
Manganese the kinetic of water oxidation into oxygen is high enough to slow down the
kinetic of Manganese oxidation. Below 30g/L of manganese in solution, there is a
current efficiency of Manganese corresponding to Manganese concentration in solution.

At Mintek in South Africa, a cobalt electrowinning test was done using an

electrolyte containing 20g/L of Manganese to demonstrate the possibility of removing
manganese from the system by means of the electrowinning cell sludge.

A standard lab scale undivided electrolysis cell was used in the test. It had an
approximatively capacity of 5.5l and held single cathode and two anodes. The test was
run for 24hours with an initial concentration of Cobalt of 55g/L. After test, the anodic

Joseph Kafumbila Page 85

sludge was collected, dried, weighed and analyzed. The sludge contained 50.1% of
Manganese and 5.45% of Cobalt. The efficiency of manganese oxidation is around
7.5%and only 2% of Manganese in feed solution has been precipitated as MnO2 (Mintek
invention).

In the Cobalt electrowinning cell and at anodic potential below the anodic
potential of Cobalt precipitation, only the oxidation reactions of water into oxygen and
Manganese (II) into Manganese (III) are in competition and are shared the same
electrical current. The assumption is that below 20g/L of Manganese in solution, the
current efficiency of Manganese oxidation increases linearly with Manganese
concentration to 7.5% at 20g/L of Manganese. For 4g/L of Manganese in Inlet solution,
the current efficiency is around 1.5%. The mass balance is done to find the minimum
anodic potential where the anodic potential gives 1.5% of Mn+3 on the anode.

6.2. Flow diagram

The flow diagram is given by Figure (4.1).

6.3. Design criteria

6.3.1. Outlet anodic up flow solution

 Over potential: 𝜌𝑎 – Mn+3 anodic current efficiency is 1.5%

 Quantity of Mn in the precipitate: the constraint is that the concentration
of Mn+3.in the outlet anodic up flow solution is equal to the saturation
concentration in the system A and B.

6.4. Mass balance

6.4.1. System A

Tables (6.1), (6.2) and (6.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (6.4) gives current efficiencies of compounds at cathode and anode. Table (6.5)
gives the composition of solids.

Joseph Kafumbila Page 86

 Table (6.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.787 26.853 26.789 26.789
CoSO4 g/l 85.657 74.246 75.387 75.556 75.556
Co(+3) g/l 3.046*10-12 4.092*10-13 6.729*10-13 5.615*10-13 5.615*10-13
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.348 5.200 5.424 5.424
Mn(+3) g/l 1.866*10-06 3.990*10-07 5.457*10-07 5.457*10-07 5.457*10-07
MnO4(-) g/l 4.831*10-18 1.783*10-24 4.831*10-19 1.606*10-23 1.606*10-23
Ac1 g/l 1.394 2.743 2.522 2.535 2.535
Ac2 g/l 8.255 14.528 13.646 13.646 13.646
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.780 3.802 3.802 3.802
pH 2.000 1.707 1.743 1.741 1.741
ORP v 1.081 1.024 1.033 1.033
OVP

Table (6.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.050 0.353
Gas
Mass kg/h 0.100 2.134
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.760 26.789
CoSO4 g/l 72.991 75.556
Co(+3) g/l 3.936*10-45 5.615*10-13
Mn(+2) g/l 1.860 1.828
MnSO4 g/l 5.337 5.424
Mn(+3) g/l 3.896*10-39 5.457*10-07
MnO4(-) g/l 8.729*10-185 1.606*10-23
Ac1 g/l 2.938 2.535
Ac2 g/l 15.330 13.646
CoT g/l 54.497 55.500
MnT g/l 3.803 3.802
pH 1.678 1.741
ORP v -1.093 1.033
OVP v -0.800

Joseph Kafumbila Page 87

 Table (6.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.812 26.786 26.787 26.787
CoSO4 g/l 75.504 74.247 74.246 74.246
Co(+3) g/l 8.308*10-13 4.154*10-13 4.092*10-13 4.092*10-13
Mn(+2) g/l 1.808 1.834 1.834 1.834
MnSO4 g/l 5.357 5.347 5.348 5.348
Mn(+3) g/l 7.980*10-07 3.990*10-07 3.990*10-07 3.990*10-07
MnO4(-) g/l 1.059*10-22 5.296*10-23 1.783*10-24 1.783*10-24
Ac1 g/l 2.554 2.743 2.743 2.743
Ac2 g/l 13.727 14.528 14.528 14.528
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.758 3.780 3.780 3.780
pH 1.738 1.707 1.707 1.707
ORP v 1.044 1.024 1.024
OVP -0.065

Table (6.4): Current efficiencies – System A

Current efficiency (%)

Cathode Anode
Co CC 63.29 O2 98.50
H2 36.71
Co(+3) 1.76*10-11 Co(+3) 8.44*10-12
Mn(+3) 1.83*10-05 Mn(+3) 1.50
MnO4 (-) 1.25*10 -21 MnO4 (-) 6.97*10-21

Table (6.5): Solid compositions – System A

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.87 0.00
γMnO2 0.00 2.12 0.00
Element
Mn 0.00 63.19 0.00

Joseph Kafumbila Page 88

6.4.2. System B

Tables (6.6), (6.7) and (6.8) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (6.9) gives current efficiencies of compounds at cathode and anode. Table (6.10)
gives the composition of solids.

Table (6.6): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.781 26.848 26.784 26.784
CoSO4 g/l 85.657 74.260 75.400 75.569 75.569
Co(+3) g/l 3.046*10-12 5.901*10-09 5.311*10-09 5.173*10-09 5.173*10-09
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.350 5.203 5.427 5.427
Mn(+3) g/l 1.866*10-06 5.756*10-03 5.181*10-03 5.030*10-03 5.030*10-03
MnO4(-) g/l 4.831*10-18 1.127*10-03 1.014*10-03 1.079*10-03 1.079*10-03
Ac1 g/l 1.394 2.738 2.519 2.531 2.531
Ac2 g/l 8.255 14.511 13.631 13.631 13.631
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.787 3.809 3.809 3.809
pH 2.000 1.708 1.744 1.742 1.742
ORP v 1.081 1.299 1.295 1.295
OVP

Joseph Kafumbila Page 89

 Table (6.7): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.049 0.341
Gas
Mass kg/h 0.100 2.136
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.757 26.784
CoSO4 g/l 73.000 75.569
Co(+3) g/l 3.935*10-45 5.173*10-09
Mn(+2) g/l 1.863 1.828
MnSO4 g/l 5.347 5.427
Mn(+3) g/l 3.902*10-39 5.030*10-03
MnO4(-) g/l 8.811*10-185 1.079*10-03
Ac1 g/l 2.935 2.531
Ac2 g/l 15.318 13.631
CoT g/l 54.497 55.500
MnT g/l 3.809 3.809
pH 1.678 1.742
ORP v -1.093 1.295
OVP v -0.800

Table (6.8): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.807 26.782 26.781 26.781
CoSO4 g/l 75.517 74.258 74.260 74.260
Co(+3) g/l 6.939*10-09 3.469*10-09 5.901*10-09 5.901*10-09
Mn(+2) g/l 1.807 1.835 1.834 1.834
MnSO4 g/l 5.357 5.352 5.350 5.350
Mn(+3) g/l 6.664*10-03 3.332*10-03 5.756*10-03 5.756*10-03
MnO4(-) g/l 4.352*10-03 2.176*10-03 1.127*10-03 1.127*10-03
Ac1 g/l 2.550 2.739 2.738 2.738
Ac2 g/l 13.710 14.514 14.511 14.511
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.766 3.787 3.787 3.787
pH 1.739 1.708 1.708 1.708
ORP v 1.303 1.299 1.299
OVP 0.194

Joseph Kafumbila Page 90

 Table (6.9): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 63.07 O2 98.25
H2 36.68
Co(+3) 1.62*10-07 Co(+3) 5.51*10-08
Mn (+3) 1.68*10 -01 Mn (+3) 1.50
MnO4(-) 8.35*10-02 MnO4(-) 0.25

Table (6.10): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.87 0.00
γMnO2 0.00 2.12 0.00
Element
Mn 0.00 63.19 0.00

6.5. Observations
The minimum values of anodic potential in the cases A and B are respectively
1.044V (OVP=-0.065V) at pH 1.738 and 1.303V (OVP=0.194V) at pH 1.739. In both
cases the value of minimum potential is less than the value of potential of cobalt
saturation concentration. In system (A) there is not revolution of oxygen on the anode.

In the system A, the solid precipitates only on the anode as anodic sludge. The
concentration of Manganese in the outlet solution is 3.78g/L. 5.58% of Manganese from
inlet solution precipitates as anode sludge.

In the system B, the solids precipitate only at the anode as anodic sludge. The
anodic current efficiency of MnO−4 is 0.25%. The cathodic current efficiencies of Mn
+3

and MnO− 4 are respectively 0.17% and 0.08%. The concentration of Manganese in outlet
solution is 3.787g/L. 5.39% of Manganese from inlet solution precipitates as anodic
sludge.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . In both cases the anodic solutions
+2
are in Mn predominance area. The system (B) is close to the boundary. This shows
high concentrations of Mn+3 and MnO−
4 in anodic solution for system (B) comparatively
to system (A).

Joseph Kafumbila Page 91

7. Mass balance of Cobalt electrowinning circuit –
Anode potential of solution in front of anode
surface and Anode potential of metallic anode at
Cobalt saturation concentration

7.1. Problematic
The kinetic of Manganese oxidation into Manganese (III) is fixed by the kinetic
of water oxidation into oxygen. In consequence the chemical composition of soluble
species in front of anode is out of balance thermodynamically. Therefore two anodic
potentials are defined: The first anodic potential is potential of metallic anode and the
second potential is potential of solution in front of anode surface. The difference
between the two potential is that the value of first anodic potential is given by external
power. The second anodic potential is given by the chemical composition soluble species
in solution in front of the anode.

The external power is fixed to reach the anodic potential of chemical reaction
(1.m). The accumulation of Mn(II) in solution in front of the anode prevents the increase
of Co(III) in solution to cause precipitation of CoOOH on the anode. Therefore there is
direct oxidation of Co(II) into CoOOH.

Co2+ +2H2 O=CoOOH+3H + +e− (1.m)

7.2. Flow diagram

The flow diagram is given by Figure (4.1).

7.3. Design criteria

7.3.1. Outlet anodic up flow solution

 Over potential of anodic potential of metallic anode at Cobalt

precipitation: 𝜌1𝑎 – Equation (7.1) gives the value of anodic potential

96485*E=μ°(CoOOH) +3μ(H+) -μ(Co+2 ) -2μ(H2 O) (7.1)

Joseph Kafumbila Page 92

  Over potential of anodic potential of solution in front of anode: 𝜌2𝑎 –
Mn+3 anodic current efficiency is 1.5%.

 Quantity of Mn in the precipitate: the constraint is that the concentration

of Mn+3.in the outlet anodic up flow solution is equal to the saturation
concentration in the system A and B.

7.4. Mass balance

7.4.1. System A

Tables (7.1), (7.2) and (7.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (7.4) gives current efficiencies of compounds at cathode and anode. Table (7.5)
gives the composition of solids.

Table (7.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.787 26.853 26.789 26.789
CoSO4 g/l 85.657 74.246 75.387 75.556 75.556
Co(+3) g/l 3.046*10-12 4.092*10-13 6.729*10-13 5.615*10-13 5.615*10-13
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.348 5.200 5.424 5.424
Mn(+3) g/l 1.866*10-06 3.990*10-07 5.457*10-07 5.457*10-07 5.457*10-07
MnO4(-) g/l 4.831*10-18 1.783*10-24 4.831*10-19 1.606*10-23 1.606*10-23
Ac1 g/l 1.394 2.743 2.522 2.535 2.535
Ac2 g/l 8.255 14.528 13.646 13.646 13.646
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.780 3.802 3.802 3.802
pH 2.000 1.707 1.743 1.741 1.741
ORP v 1.081 1.024 1.033 1.033
OVP

Joseph Kafumbila Page 93

 Table (7.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.050 0.353
Gas
Mass kg/h 0.100 2.134
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.760 26.789
CoSO4 g/l 72.991 75.556
Co(+3) g/l 3.936*10-45 5.615*10-13
Mn(+2) g/l 1.860 1.828
MnSO4 g/l 5.337 5.424
Mn(+3) g/l 3.896*10-39 5.457*10-07
MnO4(-) g/l 8.729*10-185 1.606*10-23
Ac1 g/l 2.938 2.535
Ac2 g/l 15.330 13.646
CoT g/l 54.497 55.500
MnT g/l 3.803 3.802
pH 1.678 1.741
ORP v -1.093 1.033
OVP v -0.800

Table (7.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.812 26.786 26.787 26.787
CoSO4 g/l 75.504 74.247 74.246 74.246
Co(+3) g/l 8.308*10-13 4.154*10-13 4.092*10-13 4.092*10-13
Mn(+2) g/l 1.808 1.834 1.834 1.834
MnSO4 g/l 5.357 5.347 5.348 5.348
Mn(+3) g/l 7.980*10-07 3.990*10-07 3.990*10-07 3.990*10-07
MnO4(-) g/l 1.059*10-22 5.296*10-23 1.783*10-24 1.783*10-24
Ac1 g/l 2.554 2.743 2.743 2.743
Ac2 g/l 13.727 14.528 14.528 14.528
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.758 3.780 3.780 3.780
pH 1.738 1.707 1.707 1.707
ORP (1) v 1.319 (0.210) 1.024 1.024
ORP (2) 1.044 (-0.065)

Joseph Kafumbila Page 94

 Table (7.4): Current efficiencies – System A

Current efficiency (%)

Cathode Anode
Co CC 63.29 O2 98.50
H2 36.71
Co(+3) 1.76*10-11 Co(+3) 8.44*10-12
Mn (+3) 1.83*10 -05 Mn (+3) 1.50
MnO4(-) 1.25*10-21 MnO4(-) 6.97*10-21

Table (7.5): Solid compositions – System A

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.87 0.00
γMnO2 0.00 2.12 0.00
Element
Mn 0.00 63.19 0.00

7.4.2. System B

Tables (7.6), (7.7) and (7.8) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (7.9) gives current efficiencies of compounds at cathode and anode. Table (7.10)
gives the composition of solids.

Joseph Kafumbila Page 95

 Table (7.6): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.781 26.848 26.784 26.784
CoSO4 g/l 85.657 74.260 75.400 75.569 75.569
Co(+3) g/l 3.046*10-12 5.901*10-09 5.311*10-09 5.173*10-09 5.173*10-09
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.350 5.203 5.427 5.427
Mn(+3) g/l 1.866*10-06 5.756*10-03 5.181*10-03 5.030*10-03 5.030*10-03
MnO4(-) g/l 4.831*10-18 1.127*10-03 1.014*10-03 1.079*10-03 1.079*10-03
Ac1 g/l 1.394 2.738 2.519 2.531 2.531
Ac2 g/l 8.255 14.511 13.631 13.631 13.631
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.787 3.809 3.809 3.809
pH 2.000 1.708 1.744 1.742 1.742
ORP v 1.081 1.299 1.295 1.295
OVP

Table (7.7): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.049 0.341
Gas
Mass kg/h 0.100 2.136
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.757 26.784
CoSO4 g/l 73.000 75.569
Co(+3) g/l 3.935*10-45 5.173*10-09
Mn(+2) g/l 1.863 1.828
MnSO4 g/l 5.347 5.427
Mn(+3) g/l 3.902*10-39 5.030*10-03
MnO4(-) g/l 8.811*10-185 1.079*10-03
Ac1 g/l 2.935 2.531
Ac2 g/l 15.318 13.631
CoT g/l 54.497 55.500
MnT g/l 3.809 3.809
pH 1.678 1.742
ORP v -1.093 1.295
OVP v -0.800

Joseph Kafumbila Page 96

 Table (7.8): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.807 26.782 26.781 26.781
CoSO4 g/l 75.517 74.258 74.260 74.260
Co(+3) g/l 6.939*10-09 3.469*10-09 5.901*10-09 5.901*10-09
Mn(+2) g/l 1.807 1.835 1.834 1.834
MnSO4 g/l 5.357 5.352 5.350 5.350
Mn(+3) g/l 6.664*10-03 3.332*10-03 5.756*10-03 5.756*10-03
MnO4(-) g/l 4.352*10-03 2.176*10-03 1.127*10-03 1.127*10-03
Ac1 g/l 2.550 2.739 2.738 2.738
Ac2 g/l 13.710 14.514 14.511 14.511
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.766 3.787 3.787 3.787
pH 1.739 1.708 1.708 1.708
ORP (1) v 1.319 (0.210) 1.299 1.299
ORP (2) 1.303 (0.194)

Table (7.9): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 63.07 O2 98.25
H2 36.68
Co(+3) 1.62*10-07 Co(+3) 5.51*10-08
Mn(+3) 1.68*10-01 Mn(+3) 1.50
MnO4 (-) 8.35*10 -02 MnO4 (-) 0.25

Table (7.10): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.87 0.00
γMnO2 0.00 2.12 0.00
Element
Mn 0.00 63.19 0.00

Joseph Kafumbila Page 97

7.5. Observations
The values of first and second anodic potentials for system A are respectively
1.319 V (0.210V) and 1.044V (-0.065V) at pH 1.738. The values of first and second
anodic potentials for system B are respectively 1.319 V (0.210V) and 1.303V (0.194V) at
pH 1.739. In both cases the over potential of metallic anode are high than zero.
Therefore oxygen can be released to the anode. In the system (B), the second anodic
potential is close to the first anodic potential.

In the system A, the solid precipitates only on the anode as anodic sludge. The
concentration of Manganese in the outlet solution is 3.78g/L. 5.58% of Manganese from
inlet solution precipitates as anode sludge.

In the system B, the solids precipitate only at the anode as anodic sludge. The
anodic current efficiency of MnO−4 is 0.25%. The cathodic current efficiencies of Mn
+3

and MnO− 4 are respectively 0.17% and 0.08%. The concentration of Manganese in outlet
solution is 3.787g/L. 5.39% of Manganese from inlet solution precipitates as anodic
sludge.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . In both cases the anodic solutions
+2
are in Mn predominance area. The system (B) is close to the boundary. This shows
high concentrations of Mn+3 and MnO−
4 in anodic solution for system (B) comparatively
to system (A).

Joseph Kafumbila Page 98

8. Mass balance of Cobalt electrowinning circuit –
Anode potential of solution in front of anode
surface, Anode potential of metallic anode and
Cobalt adsorption onto Manganese solid surface

8.1. Problematic
Cobalt is adsorbed on the surface of Manganese solid and is reacted with
manganese solid to give CoOOH according to reaction (1.ab) for 𝛿MnO2 which is main
compound of solid solution.

𝛿MnO2 +2Co+2+2H2 O=Mn+2+2CoOOH+2H + (1.ab)

8.2. Flow diagram

The flow diagram is given by Figure (4.1).

8.3. Design criteria

8.3.1. Outlet anodic up flow solution

CoOOH, MnOOH, 𝛿MnO2 and 𝛾MnO2 form a heterogeneous solid solution. The
chemical potentials of solids in the homogeneous solid solutions are given by Equations
(8.1), (8.2), (8.3) and (8.4). Equations (8.5), (8.6), (8.7) and (8.8) give the chemical
potential of Co+2 , Mn+2, H + and H2 O.

μ(CoOOH) =μ°(CoOOH) +RTlog(X(CoOOH) ) (8.1)

μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (8.2)

μ(𝛿MnO2 ) =μ°(𝛿MnO2 )+RTlog(X(𝛿MnO2 ) ) (8.3)

μ( 𝛾MnO2 ) =μ°( 𝛾MnO2 ) +RTlog(X( 𝛾MnO2 ) ) (8.4)

μ(Co+2 ) =μ°(Co+2 ) +RTlog(C(Co+2 )*γ(Co+2 ) ) (8.5)

Joseph Kafumbila Page 99

 μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (8.6)

μ(H+) =RTlog(C(H+ ) *γ(H+) ) (8.7)

μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (8.8)

Equation (8.9) gives the sum of molar fractions in heterogeneous solid solution.

1=X(MnOOH)+X(CoOOH)+X(𝛿MnO2 ) +X( 𝛾MnO2 ) (8.9)

Equations (8.10), (8.11) and (8.12) give the thermodynamic condition for
heterogeneous solid solution.

μ(𝛿MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (8.10)

μ(𝛾MnO2 ) +μ(Mn+2 ) +2μ(H2 O) =2μ(MnOOH) +2*μ(H+) (8.11)

μ(MnOOH) +μ(Co+2 ) =μ(CoOOH) +μ(Mn+2 ) (8.12)

8.4. Mass balance

8.4.1. System A

Tables (8.1), (8.2) and (8.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (8.4) gives current efficiencies of compounds at cathode and anode. Table (8.5)
gives the composition of solids.

Joseph Kafumbila Page 100

 Table (8.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.787 26.853 26.789 26.789
CoSO4 g/l 85.657 74.246 75.387 75.556 75.556
Co(+3) g/l 3.046*10-12 4.092*10-13 6.729*10-13 5.615*10-13 5.615*10-13
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.348 5.200 5.424 5.424
Mn(+3) g/l 1.866*10-06 3.990*10-07 5.457*10-07 5.457*10-07 5.457*10-07
MnO4(-) g/l 4.831*10-18 1.783*10-24 4.831*10-19 1.606*10-23 1.606*10-23
Ac1 g/l 1.394 2.743 2.522 2.535 2.535
Ac2 g/l 8.255 14.528 13.646 13.646 13.646
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.780 3.802 3.802 3.802
pH 2.000 1.707 1.743 1.741 1.741
ORP v 1.081 1.024 1.033 1.033
OVP

Table (8.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.049 0.353
Gas
Mass kg/h 0.100 2.134
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.760 26.789
CoSO4 g/l 72.991 75.556
Co(+3) g/l 3.936*10-45 5.615*10-13
Mn(+2) g/l 1.860 1.828
MnSO4 g/l 5.337 5.424
Mn(+3) g/l 3.896*10-39 5.457*10-07
MnO4(-) g/l 8.730*10-185 1.606*10-23
Ac1 g/l 2.938 2.535
Ac2 g/l 15.330 13.646
CoT g/l 54.497 55.500
MnT g/l 3.803 3.802
pH 1.678 1.741
ORP v -1.093 1.033
OVP v -0.800

Joseph Kafumbila Page 101

 Table (8.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.812 26.786 26.787 26.787
CoSO4 g/l 75.504 74.247 74.246 74.246
Co(+3) g/l 8.307*10-13 4.154*10-13 4.092*10-13 4.092*10-13
Mn(+2) g/l 1.808 1.834 1.834 1.834
MnSO4 g/l 5.357 5.347 5.348 5.348
Mn(+3) g/l 7.979*10-07 3.990*10-07 3.990*10-07 3.990*10-07
MnO4(-) g/l 1.059*10-22 5.295*10-23 1.783*10-24 1.783*10-24
Ac1 g/l 2.554 2.743 2.743 2.743
Ac2 g/l 13.727 14.528 14.528 14.528
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.758 3.780 3.780 3.780
pH 1.738 1.707 1.707 1.707
ORP1 v 1.319 (0.210)
ORP2 v 1.044 (-0.065) 1.024 1.024

Table (8.4): Current efficiencies – System A

Current efficiency (%)

Cathode Anode
Co CC 63.29 O2 98.50
H2 36.71
Co(+3) 1.76*10-11 Co(+3) 1.04*10-04
Mn(+3) 1.83*10-05 Mn(+3) 1.50
MnO4 (-) 1.25*10 -21 MnO4 (-) 6.97*10-21

Table (8.5): Solid compositions – System A

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.86 0.00
γMnO2 0.00 2.12 0.00
CoOOH 0.00 2.60*10-05 0.00
Element
Mn 0.00 63.19 0.00
Co 0.00 4.71*10-03 0.00

Joseph Kafumbila Page 102

8.4.2. System B

Tables (8.6), (8.7) and (8.8) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (8.9) gives current efficiencies of compounds at cathode and anode. Table (8.10)
gives the composition of solids.

Table (8.6): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.177 11.315 11.315 5.657
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.131 1.131 1.131 1.131
Co(+2) g/l 27.432 26.781 26.848 26.784 26.784
CoSO4 g/l 85.657 74.260 75.400 75.569 75.569
Co(+3) g/l 3.046*10-12 5.901*10-09 5.311*10-09 5.173*10-09 5.173*10-09
Mn(+2) g/l 2.590 1.834 1.909 1.828 1.828
MnSO4 g/l 3.876 5.350 5.203 5.427 5.427
Mn(+3) g/l 1.866*10-06 5.756*10-03 5.180*10-03 5.029*10-03 5.029*10-03
MnO4(-) g/l 4.831*10-18 1.127*10-03 1.014*10-03 1.079*10-03 1.079*10-03
Ac1 g/l 1.394 2.738 2.519 2.531 2.531
Ac2 g/l 8.255 14.511 13.631 13.631 13.631
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.787 3.809 3.809 3.809
pH 2.000 1.708 1.744 1.742 1.742
ORP v 1.081 1.299 1.295 1.295
OVP

Joseph Kafumbila Page 103

 Table (8.7): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 5.049 0.341
Gas
Mass kg/h 0.100 2.136
Liquid
Mass t/h 5.652 5.657
Volume m3/h 4.999 5.000
SG t/m3 1.131 1.131
Co(+2) g/l 26.757 26.784
CoSO4 g/l 73.000 75.569
Co(+3) g/l 3.935*10-45 5.173*10-09
Mn(+2) g/l 1.863 1.828
MnSO4 g/l 5.347 5.427
Mn(+3) g/l 3.902*10-39 5.029*10-03
MnO4(-) g/l 8.811*10-185 1.079*10-03
Ac1 g/l 2.935 2.531
Ac2 g/l 15.318 13.631
CoT g/l 54.497 55.500
MnT g/l 3.809 3.809
pH 1.678 1.742
ORP v -1.093 1.295
OVP v -0.800

Table (8.8): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.655 11.307 11.307 1.130
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.131 1.131 1.131 1.131
Co(+2) g/l 26.807 26.782 26.781 26.781
CoSO4 g/l 75.517 74.258 74.260 74.260
Co(+3) g/l 6.939*10-09 3.469*10-09 5.901*10-09 5.901*10-09
Mn(+2) g/l 1.807 1.835 1.834 1.834
MnSO4 g/l 5.357 5.352 5.350 5.350
Mn(+3) g/l 6.663*10-03 3.332*10-03 5.756*10-03 5.756*10-03
MnO4(-) g/l 4.352*10-03 2.176*10-03 1.127*10-03 1.127*10-03
Ac1 g/l 2.550 2.739 2.738 2.738
Ac2 g/l 13.710 14.514 14.511 14.511
CoT g/l 55.503 55.000 55.000 55.000
MnT g/l 3.766 3.787 3.787 3.787
pH 1.739 1.708 1.708 1.708
ORP1 v 1.319 (0.210)
ORP2 v 1.303 (0.194) 1.299 1.299

Joseph Kafumbila Page 104

 Table (8.9): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 63.07 O2 98.25
H2 36.68
Co(+3) 1.62*10-07 Co(+3) 1.01*10-04
Mn (+3) 1.68*10 -01 Mn (+3) 1.50
MnO4(-) 8.35*10-02 MnO4(-) 0.25

Table (8.10): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 1.21*10-02 0.00
δMnO2 0.00 97.86 0.00
γMnO2 0.00 2.12 0.00
CoOOH 0.00 7.36*10-03 0.00
Element
Mn 0.00 63.19 0.00
Co 0.00 4.72*10-03 0.00

8.5. Observations
The values of first and second anodic potentials for system A are respectively
1.319 V (0.210V) and 1.044V (-0.065V) at pH 1.738. The values of first and second
anodic potentials for system B are respectively 1.319 V (0.210V) and 1.303V (0.194V) at
pH 1.739. In both cases the over potential of metallic anode are high than zero.
Therefore oxygen can be released to the anode. In the system (B), the second anodic
potential is close to the first anodic potential.

In the system A, the solid precipitates only on the anode as anodic sludge. The
concentration of Manganese in the outlet solution is 3.78g/L. 5.58% of Manganese from
inlet solution precipitates as anode sludge. The anodic sludge contains 63.19% and
4.71*10−3% of Manganese and Cobalt respectively.

In the system B, the solids precipitate only at the anode as anodic sludge. The
anodic current efficiency of MnO−4 is 0.25%. The cathodic current efficiencies of Mn
+3

and MnO− 4 are respectively 0.17% and 0.08%. The concentration of Manganese in outlet
solution is 3.79g/L. 5.39% of Manganese from inlet solution precipitates as anodic

Joseph Kafumbila Page 105

sludge. The anodic sludge contains 63.19% and 4.72*10−3 % of Manganese and Cobalt
respectively.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . In both cases the anodic solutions
+2
are in Mn predominance area. The system (B) is close to the boundary. This shows
high concentrations of Mn+3 and MnO−
4 in anodic solution for system (B) comparatively
to system (A).

Joseph Kafumbila Page 106

9. Mass balance of Cobalt electrowinning circuit –
Anode potential of solution in front of anode
surface, Anode potential of metallic anode,
Cobalt adsorption into Manganese solid and
electrodeposition of CoOOH on the anode

9.1. Problematic
Because of high concentration of Cobalt in solution, the anode is quickly covered
by Cobalt oxide. Oxygen revolution takes place on cobalt oxide. The kinetics of oxidation
of water into oxygen and Cobalt (II) into Cobalt (III) reach the steady state. The
electrodeposition of CoOOH on the anode follows the chemical reaction (1.m). In second
time the Manganese oxidation into Manganese (III) enters in competition and shared
electrical current with water oxidation into oxygen and Cobalt (II) oxidation into Cobalt
(III).

Co2+ +2H2 O=CoOOH+3H + +e− (1.m)

9.2. Flow diagram

The flow diagram is given by Figure (4.1).

9.3. Design criteria

The mass of CoOOH electro-posited on anode corresponds to the conditions of
Mintek invention lab test:

 Cobalt concentration: 55g/L

 Manganese concentration: 20g/L.
 Anodic sludge composition : 50.1% of Cobalt and 5.45% of Manganese
 Anodic Mn(III) current efficiency: 7.5%.
 Quantity of Manganese in the sludge: 2% of quantity of manganese in the
intel solution

Joseph Kafumbila Page 107

9.4. Mass balance

9.4.1. System A

Tables (9.1), (9.2) and (9.3) give the mass balance for system (A) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (9.4) gives current efficiencies of compounds at cathode and anode. Table (9.5)
gives the composition of solids.

Table (9.1): Mass balance – System A

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.153 10.347 11.500 11.500 5.750
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.153 1.150 1.150 1.150 1.150
Co(+2) g/l 24.525 21.759 22.038 21.769 21.769
CoSO4 g/l 80.152 80.336 80.318 81.026 81.026
Co(+3) g/l 2.833*10-12 2.906*10-16 2.836*10-13 3.580*10-16 3.580*10-16
Mn(+2) g/l 12.855 8.124 8.596 8.101 8.101
MnSO4 g/l 19.637 31.559 30.367 31.728 31.728
Mn(+3) g/l 9.398*10-06 1.546*10-09 9.412*10-07 1.898*10-09 1.898*10-09
MnO4(-) g/l 2.277*10-17 2.111*10-29 2.277*10-18 1.164*10-26 1.164*10-26
Ac1 g/l 1.378 0.157 0.080 0.081 0.081
Ac2 g/l 8.598 1.102 0.574 0.574 0.574
CoT g/l 55.000 52.287 52.558 52.558 52.558
MnT g/l 20.000 19.611 19.650 19.650 19.650
pH 2.000 2.941 3.234 3.227 3.227
ORP v 1.081 0.820 0.826 0.826
OVP

Joseph Kafumbila Page 108

 Table (9.2): Mass balance – System A

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 2.699 0.798
Gas
Mass kg/h 0.006 0.712
Liquid
Mass t/h 5.747 5.750
Volume m3/h 5.000 5.000
SG t/m3 1.150 1.150
Co(+2) g/l 21.722 21.769
CoSO4 g/l 79.738 81.026
Co(+3) g/l 3.030*10-45 3.580*10-16
Mn(+2) g/l 8.168 8.101
MnSO4 g/l 31.548 31.728
Mn(+3) g/l 1.623*10-38 1.898*10-09
MnO4(-) g/l 2.494*10-175 1.164*10-26
Ac1 g/l 0.211 0.081
Ac2 g/l 1.473 0.574
CoT g/l 52.022 52.558
MnT g/l 19.651 19.650
pH 2.813 3.227
ORP v -1.096 0.826
OVP v -0.800

Table (9.3): Mass balance – System A

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.748 11.496 11.496 1.149
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.150 1.150 1.150 1.150
Co(+2) g/l 21.797 21.759 21.759 21.759
CoSO4 g/l 80.935 80.336 80.336 80.336
Co(+3) g/l 5.854*10-16 2.927*10-16 2.906*10-16 2.906*10-16
Mn(+2) g/l 8.080 8.124 8.124 8.124
MnSO4 g/l 31.568 31.558 31.559 31.559
Mn(+3) g/l 3.091*10-09 1.546*10-09 1.546*10-09 1.546*10-09
MnO4(-) g/l 1.910*10-26 9.549*10-27 2.111*10-29 2.111*10-29
Ac1 g/l 0.104 0.157 0.157 0.157
Ac2 g/l 0.731 1.102 1.102 1.102
CoT g/l 52.552 52.287 52.287 52.287
MnT g/l 19.571 19.611 19.611 19.611
pH 3.121 2.941 2.941 2.941
ORP1 v 1.051 (0.034)
ORP2 v 0.840 (-0.178) 0.820 0.820

Joseph Kafumbila Page 109

 Table (9.4): Current efficiencies – System A

Current efficiency (%)

Cathode Anode
Co CC 94.36 O2 91.74
H2 5.64
Co(+3) 3.13*10-14 Co(+3) 7.61*10-01
Mn (+3) 1.78*10 -07 Mn (+3) 7.50
MnO4(-) 2.52*10-24 MnO4(-) 1.62*10-24

Table (9.5): Solid compositions – System A

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 0.48 0.00
δMnO2 0.00 77.13 0.00
γMnO2 0.00 1.67 0.00
CoOOH adsorbed 0.00 5.34*10-02 0.00
CoOOH electro-deposited 0.00 8.45 0.00
H2O 0.00 12.21 0.00
Element
Mn 0.00 50.10 0.00
Co 0.00 5.45 0.00

9.4.2. System B

Tables (9.6), (9.7) and (9.8) give the mass balance for system (B) using Realistic
Simulation Program based on thermodynamic equilibrium of species in solution (J.
Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over potential.
Table (9.9) gives current efficiencies of compounds at cathode and anode. Table (9.10)
gives the composition of solids.

Joseph Kafumbila Page 110

 Table (9.6): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.153 10.347 11.500 11.500 5.750
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.153 1.150 1.150 1.150 1.150
Co(+2) g/l 24.525 21.759 22.038 21.769 21.769
CoSO4 g/l 80.152 80.335 80.317 81.025 81.025
Co(+3) g/l 2.833*10-12 1.340*10-15 2.845*10-13 3.585*10-16 3.585*10-16
Mn(+2) g/l 12.855 8.124 8.596 8.101 8.101
MnSO4 g/l 19.637 31.559 30.366 31.728 31.728
Mn(+3) g/l 9.398*10-06 7.124*10-09 9.462*10-07 1.900*10-09 1.900*10-09
MnO4(-) g/l 2.277*10-17 4.380*10-26 2.277*10-18 1.165*10-26 1.165*10-26
Ac1 g/l 1.378 0.157 0.080 0.081 0.081
Ac2 g/l 8.598 1.102 0.574 0.574 0.574
CoT g/l 55.000 52.287 52.558 52.558 52.558
MnT g/l 20.000 19.611 19.650 19.650 19.650
pH 2.000 2.941 3.234 3.227 3.227
ORP v 1.081 0.864 0.826 0.826
OVP

Table (9.7): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 2.699 0.798
Gas
Mass kg/h 0.006 0.712
Liquid
Mass t/h 5.747 5.750
Volume m3/h 5.000 5.000
SG t/m3 1.150 1.150
Co(+2) g/l 21.722 21.769
CoSO4 g/l 79.737 81.025
Co(+3) g/l 3.030*10-45 3.585*10-16
Mn(+2) g/l 8.168 8.101
MnSO4 g/l 31.548 31.728
Mn(+3) g/l 1.623*10-38 1.900*10-09
MnO4(-) g/l 2.489*10-175 1.165*10-26
Ac1 g/l 0.212 0.081
Ac2 g/l 1.473 0.574
CoT g/l 52.022 52.558
MnT g/l 19.651 19.650
pH 2.812 3.227
ORP v -1.096 0.826
OVP v -0.800

Joseph Kafumbila Page 111

 Table (9.8): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.748 11.496 11.496 1.149
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.150 1.150 1.150 1.150
Co(+2) g/l 21.797 21.759 21.759 21.759
CoSO4 g/l 80.934 80.336 80.335 80.335
Co(+3) g/l 9.765*10-14 4.882*10-14 1.340*10-15 1.340*10-15
Mn(+2) g/l 8.080 8.124 8.124 8.124
MnSO4 g/l 31.568 31.558 31.559 31.559
Mn(+3) g/l 5.156*10-07 2.578*10-07 7.124*10-09 7.124*10-09
MnO4(-) g/l 2.456*10-15 1.228*10-15 4.380*10-26 4.380*10-26
Ac1 g/l 0.104 0.157 0.157 0.157
Ac2 g/l 0.732 1.102 1.102 1.102
CoT g/l 52.552 52.287 52.287 52.287
MnT g/l 19.571 19.611 19.611 19.611
pH 3.121 2.941 2.941 2.941
ORP1 v 1.051 (0.034)
ORP2 v 0.987 (-0.031) 0.864 0.864

Table (9.9): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 94.36 O2 91.74
H2 5.64
Co(+3) 3.13*10-14 Co(+3) 7.61*10-01
Mn(+3) 1.78*10-07 Mn(+3) 7.50
MnO4 (-) 2.52*10 -24 MnO4 (-) 5.32*10-13

Table (9.10): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH 0.00 0.48 0.00
δMnO2 0.00 77.13 0.00
γMnO2 0.00 1.67 0.00
CoOOH adsorbed 0.00 5.34*10-02 0.00
CoOOH electro-deposited 0.00 8.45 0.00
H2O 0.00 12.21 0.00
Element
Mn 0.00 50.10 0.00
Co 0.00 5.45 0.00

Joseph Kafumbila Page 112

9.5. Observations
The values of first and second anodic potentials for system A are respectively
1.051 V (0.034V) and 0.840V (-0.178V) at pH 3.121. The values of first and second
anodic potentials for system B are respectively 1.051 V (0.034V) and 0.987V (-0.031V)
at pH 3.121. In both cases the over potential of metallic anode are high than zero.
Therefore oxygen can be released to the anode. In the system (B), the second anodic
potential is close to the first anodic potential. The increase of pH is due to the increase of
Manganese in the solution.

In the system A, the solid precipitates only on the anode as anodic sludge. The
concentrations of Cobalt and Manganese in the outlet solution are 52.29g/L and
19.61g/L. Current efficiencies of Cobalt are 94.36% and 0.761% at respectively cathode
and anode. Anodic sludge contains 12.21% of water to reach 50.1% of Manganese.

In the system B, the solids precipitate only at the anode as anodic sludge. The
conditions of bottom and top sludge have been reached but the quantities of sludge are
negligible. The concentrations of Cobalt and Manganese in outlet solution are 52.29g/L
and 19.61g/L. Current efficiencies of Cobalt are 94.36% and 0.761% at respectively
cathode and anode. Anodic sludge contains 12.21% of water to reach 50.1% of
Manganese.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO− 4 . In both cases the anodic solutions
+2
are in Mn predominance area. The system (B) is close to the boundary. This shows
high concentrations of Mn+3 and MnO−
4 in anodic solution for system (B) comparatively
to system (A).

Joseph Kafumbila Page 113

10. Mass balance of Cobalt electrowinning circuit –
Anode potential of solution in front of anode
surface, Anode potential of metallic anode,
Cobalt adsorption into Manganese solid,
electrodeposition of CoOOH on the anode and
Oxidation of Manganese by CoOOH

10.1. Problematic
Because of high concentration of Cobalt in solution, the anode is quickly covered
by Cobalt oxide. Oxygen revolution takes place on cobalt oxide. The kinetics of oxidation
of water into oxygen and Cobalt (II) into Cobalt (III) reach the steady state. The
electrodeposition of CoOOH on the anode follows the chemical reaction (1.m). In second
time the Manganese oxidation into Manganese (III) enters in competition and shared
electrical current with water oxidation into oxygen and Cobalt (II) oxidation into Cobalt
(III).

Co2+ +2H2 O=CoOOH+3H + +e− (1.m)

In the same time Manganese (II) reacts with CoOOH according to reaction
(1.ac).

CoOOH +Mn+2=MnOOH +Co+2 (1.ac)

10.2. Flow diagram

The flow diagram is given by Figure (4.1).

10.3. Design criteria

The mass of CoOOH electro-posited on anode corresponds to the conditions of
Mintek invention lab test:

 Cobalt concentration: 55g/L

Joseph Kafumbila Page 114

  Manganese concentration: 20g/L.
 Anodic sludge composition : 50.1% of Cobalt and 5.45% of Manganese
 Anodic Mn(III) current efficiency: 7.5%.
 Quantity of Manganese in the sludge: 2% of quantity of manganese in the
intel solution

For reaction (1.ac) only the system (B) works. CoOOH and MnOOH form a
heterogeneous solid solution. The chemical potentials of solids in the homogeneous
solid solutions are given by Equations (10.1) and (10.2). Equations (10.3) and (10.4)
give the chemical potential of Co+2 and Mn+2 .

μ(CoOOH) =μ°(CoOOH) +RTlog(X(CoOOH) ) (10.1)

μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (10.2)

μ(Co+2 ) =μ°(Co+2 ) +RTlog(C(Co+2 )*γ(Co+2 ) ) (10.3)

μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (10.4)

Equation (10.5) gives the sum of molar fractions in heterogeneous solid

solution.

1=X(MnOOH) +X(CoOOH) (10.5)

Equation (10.6) gives the thermodynamic condition for heterogeneous solid

solution.

μ(CoOOH) +μ(Mn+2 ) =μ(MnOOH) +μ(Co+2 ) (10.6)

In acid media, MnOOH reacts with acid to produce δ-MnO2 and γMnO2 .

2MnOOH+2H + =Mn+2+𝛾MnO2 +2H2 O (1.x)

2MnOOH+2H + =Mn+2+ δ-MnO2 +2H2 O (1y)

Joseph Kafumbila Page 115

10.4. Mass balance

10.4.1. System B

Tables (10.1), (10.2) and (10.3) give the mass balance for system (B) using
Realistic Simulation Program based on thermodynamic equilibrium of species in
solution (J. Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over
potential. Table (10.4) gives current efficiencies of compounds at cathode and anode.
Table (10.5) gives the composition of solids.

Table (10.1): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.153 10.347 11.500 11.500 5.750
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.153 1.150 1.150 1.150 1.150
Co(+2) g/l 24.525 21.759 22.038 21.769 21.769
CoSO4 g/l 80.152 80.335 80.317 81.025 81.025
Co(+3) g/l 2.833*10-12 1.340*10-15 2.845*10-13 3.585*10-16 3.585*10-16
Mn(+2) g/l 12.855 8.124 8.596 8.101 8.101
MnSO4 g/l 19.637 31.559 30.366 31.728 31.728
Mn(+3) g/l 9.398*10-06 7.124*10-09 9.462*10-07 1.900*10-09 1.900*10-09
MnO4(-) g/l 2.277*10-17 4.380*10-26 2.277*10-18 1.165*10-26 1.165*10-26
Ac1 g/l 1.378 0.157 0.080 0.081 0.081
Ac2 g/l 8.598 1.102 0.574 0.574 0.574
CoT g/l 55.000 52.287 52.558 52.558 52.558
MnT g/l 20.000 19.611 19.650 19.650 19.650
pH 2.000 2.941 3.234 3.227 3.227
ORP v 1.081 0.864 0.826 0.826
OVP

Joseph Kafumbila Page 116

 Table (10.2): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 2.699 0.798
Gas
Mass kg/h 0.006 0.712
Liquid
Mass t/h 5.747 5.750
Volume m3/h 5.000 5.000
SG t/m3 1.150 1.150
Co(+2) g/l 21.722 21.769
CoSO4 g/l 79.737 81.025
Co(+3) g/l 3.030*10-45 3.585*10-16
Mn(+2) g/l 8.168 8.101
MnSO4 g/l 31.548 31.728
Mn(+3) g/l 1.623*10-38 1.900*10-09
MnO4(-) g/l 2.488*10-175 1.165*10-26
Ac1 g/l 0.212 0.081
Ac2 g/l 1.473 0.574
CoT g/l 52.022 52.558
MnT g/l 19.651 19.650
pH 2.812 3.227
ORP v -1.096 0.826
OVP v -0.800

Table (10.3): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.748 11.496 11.496 1.149
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.150 1.150 1.150 1.150
Co(+2) g/l 21.797 21.759 21.759 21.759
CoSO4 g/l 80.934 80.336 80.335 80.335
Co(+3) g/l 9.765*10-14 4.883*10-14 1.340*10-15 1.340*10-15
Mn(+2) g/l 8.080 8.124 8.124 8.124
MnSO4 g/l 31.568 31.558 31.559 31.559
Mn(+3) g/l 5.157*10-07 2.578*10-07 7.124*10-09 7.124*10-09
MnO4(-) g/l 2.457*10-15 1.228*10-15 4.380*10-26 4.380*10-26
Ac1 g/l 0.104 0.157 0.157 0.157
Ac2 g/l 0.732 1.102 1.102 1.102
CoT g/l 52.552 52.287 52.287 52.287
MnT g/l 19.571 19.611 19.611 19.611
pH 3.121 2.941 2.941 2.941
ORP1 v 1.051 (0.034)
ORP2 v 0.987 (-0.031) 0.864 0.864

Joseph Kafumbila Page 117

 Table (10.4): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 94.36 O2 91.74
H2 5.64
Co(+3) 3.13*10-14 Co(+3) 7.61*10-01
Mn (+3) 1.78*10 -07 Mn (+3) 7.50
MnO4(-) 2.52*10-24 MnO4(-) 5.32*10-13

Table (10.5): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH electro-deposited 0.00 2.10E-02 0.00
δMnO2 electro-deposited 0.00 3.37 0.00
γMnO2 electro-deposited 0.00 7.30E-02 0.00
CoOOH adsorbed 0.00 2.33E-03 0.00
CoOOH electro-deposited 0.00 8.50 0.00
MnOOH oxidized by CoOOH 0.00 0.46 0.00
δMnO2 oxidized by CoOOH 0.00 73.76 0.00
γMnO2 oxidized by CoOOH 0.00 1.60 0.00
H2O 0.00 12.21 0.00
Element
Mn 0.00 50.10 0.00
Co 0.00 5.45 0.00

10.5. Observations
The values of first and second anodic potentials for system B are respectively
1.051 V (0.034V) and 0.987V (-0.031V) at pH 3.121. The over potential of metallic anode
are high than zero. Therefore oxygen can be released to the anode. The second anodic
potential is close to the first anodic potential. The increase of pH is due to the increase of
Manganese in the solution.

The solids precipitate only at the anode as anodic sludge. The conditions of
bottom and top sludge have been reached but the quantities of sludge are negligible. The
concentrations of Cobalt and Manganese in outlet solution are 52.29g/L and 19.61g/L.
Current efficiencies of Cobalt are 94.36% and 0.761% at respectively cathode and anode.
Anodic sludge contains 12.21% of water to reach 50.1% of Manganese. The quantity of
Manganese coming from oxidation reaction (1.ac) is 95.63% of quantity of Manganese in
anodic sludge. This means that in 7.5% of Mn(III) anodic current efficiency, 7.17% is

Joseph Kafumbila Page 118

Co(III) anodic current efficiency. Therefore the anodic current efficiencies are 7.93%
and 91.74% respectively for Cobalt and oxygen.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO−
4 . The anodic solutions are in Mn
+2

predominance area.

Joseph Kafumbila Page 119

11. Mass balance of Cobalt electrowinning circuit –
Anode potential of solution in front of anode
surface, Anode potential of metallic anode,
Cobalt adsorption into Manganese solid and
electrodeposition of CoOOH on the anode with a
known oxygen anodic current efficiency

11.1. Problematic
The oxygen anodic current efficiency is 92%, the quantity of Manganese
oxidized by CoOOH according to reaction (1.ac) is 95% of Manganese in anodic sludge
and the anodic sludge contains 21.21% of water in the structure. The inlet solution
contains 60g/L and 4g/L of Cobalt and Manganese respectively.

11.2. Flow diagram

The flow diagram is given by Figure (4.1).

11.3. Design criteria

Chapter 8.0

11.4. Mass balance

11.4.1. System B

Tables (11.1), (11.2) and (11.3) give the mass balance for system (B) using
Realistic Simulation Program based on thermodynamic equilibrium of species in
solution (J. Kafumbila (1), 2023). Where ORP is oxido-redox potential and OVP is over
potential. Table (11.4) gives current efficiencies of compounds at cathode and anode.
Table (11.5) gives the composition of solids.

Joseph Kafumbila Page 120

 Table (11.1): Mass balance – System B

1 2 3 4 5 6
IS DFS BMS BSS EIS ICUFS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 1.137 10.170 11.308 11.308 5.654
Volume m3/h 1.000 9.000 10.000 10.000 5.000
SG t/m3 1.137 1.130 1.131 1.131 1.131
Co(+2) g/l 27.432 26.985 27.032 26.967 26.967
CoSO4 g/l 85.657 73.723 74.917 75.087 75.087
Co(+3) g/l 3.046*10-12 8.998*10-09 8.098*10-09 7.757*10-09 7.757*10-09
Mn(+2) g/l 2.590 1.646 1.740 1.660 1.660
MnSO4 g/l 3.876 4.731 4.645 4.864 4.864
Mn(+3) g/l 1.866*10-06 7.816*10-03 7.035*10-03 6.804*10-03 6.804*10-03
MnO4(-) g/l 4.831*10-18 4.852*10-03 4.367*10-03 4.467*10-03 4.467*10-03
Ac1 g/l 1.394 2.919 2.675 2.689 2.689
Ac2 g/l 8.255 15.255 14.301 14.301 14.301
CoT g/l 60.000 55.000 55.500 55.500 55.500
MnT g/l 4.000 3.378 3.440 3.440 3.440
pH 2.000 1.680 1.718 1.716 1.716
ORP v 1.081 1.311 1.306 1.306
OVP

Table (11.2): Mass balance – System B

7 8 9 10 11 12
CC H2 OCUFS IAUFS AS O2
Solid
Mass kg/h 4.632 1.879
Gas
Mass kg/h 0.098 1.883
Liquid
Mass t/h 5.649 5.654
Volume m3/h 4.999 5.000
SG t/m3 1.130 1.131
Co(+2) g/l 26.943 26.967
CoSO4 g/l 72.728 75.087
Co(+3) g/l 3.973*10-45 7.757*10-09
Mn(+2) g/l 1.691 1.660
MnSO4 g/l 4.804 4.864
Mn(+3) g/l 3.553*10-39 6.804*10-03
MnO4(-) g/l 5.747*10-185 4.467*10-03
Ac1 g/l 3.066 2.689
Ac2 g/l 15.848 14.301
CoT g/l 54.580 55.500
MnT g/l 3.440 3.440
pH 1.659 1.716
ORP v -1.093 1.306
OVP v -0.800

Joseph Kafumbila Page 121

 Table (11.3): Mass balance – System B

13 14 15 16 17
OAUFS TMS EOS TSS OS
Solid
Mass kg/h 0.000
Gas
Mass kg/h
Liquid
Mass t/h 5.650 11.299 11.299 1.129
Volume m3/h 5.000 9.999 9.999 0.999
SG t/m3 1.130 1.130 1.130 1.130
Co(+2) g/l 27.031 26.987 26.985 26.985
CoSO4 g/l 74.710 73.719 73.723 73.723
Co(+3) g/l 1.017*10-08 5.084*10-09 8.998*10-09 8.998*10-09
Mn(+2) g/l 1.603 1.647 1.646 1.646
MnSO4 g/l 4.663 4.733 4.731 4.731
Mn(+3) g/l 8.592*10-03 4.296*10-03 7.816*10-03 7.816*10-03
MnO4(-) g/l 1.275*10-02 6.377*10-03 4.852*10-03 4.852*10-03
Ac1 g/l 2.778 2.921 2.919 2.919
Ac2 g/l 14.672 15.260 15.255 15.255
CoT g/l 55.420 55.000 55.000 55.000
MnT g/l 3.315 3.378 3.378 3.378
pH 1.702 1.680 1.680 1.680
ORP1 v 1.326 (0.215)
ORP2 v 1.314 (0.203) 1.311 1.311

Table (11.4): Current efficiencies – System B

Current efficiency (%)

Cathode Anode
Co CC 61.44 O2 92.00
H2 37.95
Co(+3) 2.57*10-07 Co(+3) 2.80
Mn(+3) 2.42*10-01 Mn(+3) 4.52
MnO4 (-) 3.67*10 -01 MnO4 (-) 0.68

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 Table (11.5): Solid compositions – System B

Composition (%)
BSS AS TSS
Mineralogy
MnOOH electro-deposited 0.00 2.75*10-04 0.00
δMnO2 electro-deposited 0.00 2.58 0.00
γMnO2 electro-deposited 0.00 5.59*10-02 0.00
CoOOH adsorbed 0.00 1.91*10-04 0.00
CoOOH electro-deposited 0.00 35.08 0.00
MnOOH oxidized by CoOOH 0.00 5.23*10-03
δMnO2 oxidized by CoOOH 0.00 49.00
γMnO2 oxidized by CoOOH 0.00 1.06
H2O 0.00 12.21 0.00
Element
Mn 0.00 33.31 0.00
Co 0.00 22.49 0.00

11.5. Observations
The values of first and second anodic potentials for system B are respectively
1.326 V (0.215V) and 1.314V (0.203V) at pH 1.702. The over potential of metallic anode
are high than zero. Therefore oxygen can be released to the anode. The second anodic
potential is close to the first anodic potential. The increase of pH is due to the increase of
Manganese in the solution.

The solids precipitate only at the anode as anodic sludge. The concentration of
Manganese in outlet solution is 3.378g/L. 15.65% of Manganese in inlet solution is
precipitated as anodic sludge. Cathodic current efficiencies of Mn(III) and permanganate
are 0.242% and 0.367% respectively. Anodic current efficiencies of Co(III), Mn(III) and
permanganate are 2.80%, 4.52% and 0.68% respectively. Anodic sludge contains
33.31% and 22.49% of Manganese and Cobalt respectively. Cobalt grade in anodic
sludge is close to the maximum value at 4g/L of Manganese in the inlet solution.
Comparatively to Mintek results, the grade of Cobalt in the anodic sludge increases with
the decrease of Manganese concentration in the inlet solution.

On the Eh-pH diagrams of systems (A) and (B), Equation (4.1) gives the
boundary of predominance areas of Mn+2 and MnO−
4 . The anodic solutions are in Mn
+2

predominance area.

Joseph Kafumbila Page 123

12. References

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https://www.researchgate.net/publication/370631988_Modeling_and_desi
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