Principle of Hydrometallurgy (Thermodynamics and Kinetics of Leaching)

Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana
PRINCIPLES OF HYDROMETALLURGY
METE 351
Credit Hours: 3
Ing. Dr. Mrs. Bennetta Koomson
Material Engineering Department
Faculty of Mechanical and Chemical Eng.
College of Engineering
4/8/2022
T. A. (Mr. Agbanga Godwin) 1
Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana
Learning Objectives
Students should be able to:

• Identify and locate species in a stability and speciation diagrams
• Create a simple Eh–pH diagram
• Determine equilibrium species concentrations in complex systems
• Create a speciation diagram
• Draw
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phase diagrams 2
THERMODYNAMICS AND KINETICS
OF LEACHING
Stability and Speciation Diagrams
Stability diagrams are very important tools for the study of leaching
systems. These diagrams show the areas of stability (predominant
areas) of various metal compounds/species. The lines between the
stability areas of the compounds are known as stability lines (derived
from the equilibrium reaction equations).
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A stability and speciation diagrams can provide a visual
and quantitative representation of species availability.
They are useful in determining the effects of conditions on

the distribution of species
Producing these diagrams requires thermodynamic data

and calculations.
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THERMODYNAMICS AND KINETICS OF
LEACHING
The diagrams can be used to design dissolution
(leaching/reaction) paths without painstaking
experimentations.
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LEACHING
Some of the conditions for metal extraction from metal-
containing materials can be determined using what is called
dissolution/reaction/leaching paths. These diagrams can also be
used for the designs of precipitation systems as well.
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OF LEACHING
Stability diagrams can be drawn from the knowledge of reaction
equations involving the metals and metal compounds. Laborious
manual treatments have been replaced by computer application
drawing these stability diagrams. The steps helpful in preparing
these diagrams include:

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• Writing relative stability equations using system variable
• Get equation for relative stability line
• Plot relative stability line
• Identify the relative stability regions

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Activity
Activity is a measure of the effective concentration
of a species under non-ideal (e.g., concentrated)
conditions.
The activity of pure substances in condensed phase
(solid or liquid ) is normal taken as unity (the
number 1)
Activity depends on temperature, pressure and
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composition of the mixture, among other things.
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Construction of Stability Diagrams
Activity
This determines the real chemical potential for a
real solution rather than an ideal one.
𝑢−𝑢0
𝑎= 𝑒 𝑅𝑇
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Activity
a = Activity
𝑢 = Chemical potential (dependent on standard state)
𝑢0 = The standard chemical potential
R = Gas constant
T = Absolute temperature
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Activity
Because the standard state of solids and liquids in their molar
density at room temperature and pressure, which is equal to
their "concentrations" their activities are one from the
expression above.
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LEACHING
Example one
Using 𝑀2 𝑂/𝑀2+ system
𝑀2 𝑂 + 2𝐻+ = 2𝑀2+ + 𝐻2 𝑂 + 2𝑒 −
[𝑀2+ ]2 [𝑒 − ]2
𝑄= ( Activity of all solids and liquids goes to one)
[𝐻 + ]2
𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝑀2+ − 2𝐿𝑜𝑔 𝐻+ + 2𝐿𝑜𝑔 𝑒 −
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LEACHING
𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝑀2+ + 2𝑝𝐻 − 2𝑝𝐸
𝑝𝐸 ≥ 𝐿𝑜𝑔 𝑀2+ + 𝑝𝐻 − 0.5𝐿𝑜𝑔𝐾
𝐸ℎ
But 𝑝𝐸 =
0.0591
𝐸ℎ = 0.0591𝐿𝑜𝑔 𝑀2+ + 0.0591𝑝𝐻 − 0.5 ∗ 0.0591𝐿𝑜𝑔𝐾
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Example two
Using M(OH)3 /𝑀3+ system
M(OH)3 + 3𝐻+ = 𝑀3+ + 3𝐻2 𝑂
[𝑀3+ ]
[ [𝐻 + ]3
𝐿𝑜𝑔 𝐾 ≥ 𝑀3+ − 3𝐿𝑜𝑔 𝐻 +
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𝐿𝑜𝑔 𝐾 ≥ 𝐿𝑜𝑔 𝑀3+ + 3𝑝𝐻
𝐿𝑜𝑔 𝑀3+ = −3𝑝𝐻 + 𝐿𝑜𝑔𝑄
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Example three
Using Fe(OH)3 /𝐹𝑒 3+ system
Fe(OH)3 + 3𝐻+ = 𝐹𝑒 3+ + 3𝐻2 𝑂
[𝐹𝑒 3+ ]
[𝐻 + ]3
𝐿𝑜𝑔 𝐾 ≥ 𝐹𝑒 3+ − 3𝐿𝑜𝑔 𝐻+
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𝐿𝑜𝑔 𝐾 ≥ 𝐿𝑜𝑔 𝐹𝑒 3+ + 3𝑝𝐻
𝐿𝑜𝑔 𝐹𝑒 3+ = −3𝑝𝐻 + 𝐿𝑜𝑔𝑄
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Example four
Using 𝐶𝑢2 𝑂/𝐶𝑢2+ system
𝐶𝑢2 𝑂 + 2𝐻 + = 2𝐶𝑢2+ + 𝐻2 𝑂 + 2𝑒 −
[𝐶𝑢2+ ]2 [𝑒 − ]2
[𝐻 + ]2
𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝐶𝑢2+ − 2𝐿𝑜𝑔 𝐻 + + 2𝐿𝑜𝑔 𝑒 −
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𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝐶𝑢2+ + 2𝑝𝐻 − 2𝑝𝐸
𝑝𝐸 ≥ 𝐿𝑜𝑔 𝐶𝑢2+ + 𝑝𝐻 − 0.5𝐿𝑜𝑔𝐾

Or
𝐸ℎ
But 𝑝𝐸 =
0.059
𝐸ℎ = 0.059𝐿𝑜𝑔 𝐶𝑢2+ + 0.0591𝑝𝐻 − 0.0591 0.5𝐿𝑜𝑔𝑄
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OF LEACHING
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OF LEACHING
Multi-Species system: Constrained equilibrium
Example five
Using 𝐶𝑢 − 𝐻2 𝑂 system ( 𝐶𝑢𝑂, 𝐶𝑢2 𝑂, 𝐶𝑢 )
𝐶𝑢 → 𝐶𝑢2+ + 2𝑒 − 𝐿𝑜𝑔𝐾 = −11.5 (1)
Cu𝑂 + 2𝐻 + → 𝐶𝑢2+ + 𝐻2 𝑂 𝐿𝑜𝑔𝐾 = 7.3 (2)
𝐶𝑢2 𝑂 + 2𝐻 + → 2𝐶𝑢2+ + 2𝑒 − + 2𝐻2 𝑂 𝐿𝑜𝑔𝑘 − 7.0
(3)
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OF LEACHING
We need to find the relative stability of the following pairs
1) 𝐶𝑢𝑂 − 𝐶𝑢2 𝑂
2) 𝐶𝑢 − 𝐶𝑢𝑂
3) 𝐶𝑢𝑂 − 𝐶𝑢2 𝑂
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OF LEACHING
Solution
(1) Multiple equation (2) by 2
reverse equation (3)
2𝐶𝑢𝑂 + 4𝐻+ = 2𝐶𝑢2+ + 2𝐻2 𝑂 𝐿𝑜𝑔𝐾 = 14.6
2𝐶𝑢2+ + 2𝑒 − + 2𝐻2 𝑂 = 𝐶𝑢2 𝑂 + 2𝐻+ 𝐿𝑜𝑔𝐾 = 7
Resulting
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OF LEACHING
2𝐶𝑢𝑜 + 2𝐻 + + 2𝑒 − → 𝐶𝑢2 𝑂 𝐿𝑜𝑔𝐾 = 21.6
𝐿𝑜𝑔𝐾 ≥ −2𝐿𝑜𝑔 𝐻 + − 2𝐿𝑜𝑔 𝑒 −
𝐿𝑜𝑔𝐾 ≥ 2𝑝𝐻 + 2𝑝𝐸
21.6 ≥ 2𝑝𝐻 + 2𝑝𝐸
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10.8 ≥ 𝑝𝐻 + 𝑝𝐸
PE ≤ −𝑝𝐻 + 10.8
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(2) Using equation (1) and reverse equation (2)
𝐶𝑢 → 𝐶𝑢2+ + 2𝑒 − 𝐿𝑜𝑔𝐾 = −11.5
𝐶𝑢2+ + 𝐻2 𝑂 → Cu𝑂 + 2𝐻 + 𝐿𝑜𝑔𝐾 = −7.3
Resulting
Cu + 𝐻2 𝑂 → 𝐶𝑢𝑂 + 2𝐻 + + 2𝑒 − 𝐿𝑜𝑔𝐾 = −18.8
𝐿𝑜𝑔𝐾 ≥ −2𝑝𝐻 − 2𝑝𝐸

𝑝𝐸 ≥ −𝑝𝐻 + 9.4
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(3) Multiply equation (1) by 2 and reverse equation (3)
2𝐶𝑢 = 2𝐶𝑢2+ + 4𝑒 − 𝐿𝑜𝑔𝐾 = −23
2𝐶𝑢2+ + 2𝑒 − + 2𝐻2 𝑂 = 𝐶𝑢2 𝑂 + 2𝐻 + 𝐿𝑜𝑔𝐾 = 7
Resulting
2𝐶𝑢 + 2𝐻2 𝑂 = 𝐶𝑢2 𝑂 + 2𝑒 − + 2𝐻 + 𝐿𝑜𝑔𝐾 = −16
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OF LEACHING
𝐿𝑜𝑔𝑄 = 2𝐿𝑜𝑔 𝐻 + + 2𝐿𝑜𝑔[𝑒 − ]
𝐿𝑜𝑔𝐾 ≥ −2𝑝𝐻 − 2𝑝𝐸
𝑝𝐸 ≥ 8 − 𝑝𝐻
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Resultant phases
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Resultant phases
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Make a phase stability diagram for copper in water
𝑂𝑛𝑙𝑦 𝐶𝑢+ , 𝐶𝑢2+ ,𝐶𝑢, 𝐶𝑢𝑂, 𝐶𝑢𝑂2 ions are considered
Cu+ + 𝑒 − ↔ 𝐶𝑢 3.41 ∆𝐺𝑟𝑜 = −49.98 kJ/mol
Cu𝟐+ + e− ↔ 𝐶𝑢+ (3.42) ∆𝐺𝑟𝑜 = −15.36 kJ/mol
CuO + 2H + ↔ 𝐶𝑢2+ + H2 O (3.43) ∆𝐺𝑟𝑜 = −42.06 kJ/mol
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Cu2 O + 2H + ↔ 2Cu+ + H2 O (3.44) ∆𝐺𝑟𝑜 = 8.85 kJ/mol
2CuO + 2H + + 2e− ↔ Cu2 O + H2 O (3.45) ∆𝐺𝑟𝑜 = −124.05 kJ/mol
2Cu2+ + H2 O + 2e− ↔ Cu2 O + 2H + (3.46) ∆𝐺𝑟𝑜 = −39.93 kJ/mol
Cu2 O + 2H + + 2e− ↔ 2Cu + H2 O 3.47 ∆𝐺𝑟𝑜 = −91.11 kJ/mol
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𝐶𝑢𝑂 + 2𝐻 + + 2𝑒 − ↔ 𝐶𝑢 + 𝐻2 𝑂 3.48 ∆𝐺𝑟𝑜 = −107.58 kJ/mol

[Taken 𝑎𝐶𝑢+ = 1 × 10−5 , a𝐶𝑢2+ = 1 × 10−3 ]
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OF LEACHING
Calculate equations for equilibrium lines.
Using the general expression

2.303RT aProduct
E = E° − Log[ ]
nF aRectant
Using the reaction for copper above for equation (3.41)

2.303RT aCu
E = E° − Log[ + ]
nF a𝐶𝑢
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From research the E ° valve for this reaction
𝐸 𝑜 value is 0.520 V
2.303RT aCu
E = 0.520 − Log[ + ]
nF a𝐶𝑢
2.303RT
E = 0.520 + Log[𝑎𝐶𝑢+ ]
nF
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𝑎𝐶𝑢 + = 1 × 10−5
n=1
2.303RT
E = 0.520 + Log[1 × 10−5 ]
nF
E = 0.224 V
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° 2.303RT a𝐶𝑢2+
E = E + Log[ ]
nF a𝐶𝑢+
From research the E ° valve for this reaction
E ° value is 0.153V
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2.303RT a𝐶𝑢2+
E = 0.153 + Log[ + ]
nF a𝐶𝑢
a𝐶𝑢2+ = 1 × 10−3
n=1
E = 0.271 V
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OF LEACHING
Equation 3.43 is not a half-cell reaction. Therefore, the

Nernst Equation is not used. Thus, the G. free energy
equation is use.
General expression
𝑎𝐻2 𝑂 𝑎𝐶𝑢2+
∆𝐺𝑟0 = −2.303RTLog[ ]
𝑎𝐶𝑢𝑂𝑎2 𝐻 +
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∆G −42,060
= = −𝐿𝑜𝑔𝑎𝐶𝑢2+ − 2𝑝𝐻
2.303𝑅𝑇 2.303(8.314)(298)
𝑎𝐶𝑢2+ = 1 × 10−3
pH = 5.19.
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8,850
= −2LogaCu+ − 2pH
2.303(8.314)(298)
𝑎𝐶𝑢 + = 1 × 10−5
pH = 4.22
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2.303RT aCu2 𝑂aH2 O
E = E° − Log[ 2 2 + ]
n𝐹 a CuOa H
−∆𝐺 −(−124,050𝐽/𝑚𝑜𝑙)
E° = =
𝑛𝐹 2(96,485𝐽/(𝐶 𝑚𝑜𝑙))(𝐽/(𝐶𝑉)
E ° = 0.643 V
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2.303RT (1)(1)
E = E° − Log[ 2 + ]
n𝐹 (1) 𝑎𝐻
2∗2.303∗8.314∗298
E = E° + Log(a𝐻 + )
2 96,485
𝐸 = 0.643 − 0.0591pH
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2.303RT aCu2 𝑂 a𝐻 +
E = E° − Log[ 2 2+ ]
n𝐹 a 𝐶𝑢 𝑎𝐻2 𝑂
−∆𝐺 −(−39,930𝐽/𝑚𝑜𝑙)
E° = =
𝑛𝐹 2(96,485𝐽/(𝐶 𝑚𝑜𝑙))(𝐽/(𝐶𝑉)
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E ° = 0.207 V
𝐸 = 0.207 + 0.0591pH + 0.0591Loga𝐶𝑢2+
𝐸 = 0.0296 + 0.0591pH
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2.303RT 𝑎𝑐 𝐶 𝑎𝑑 𝐻2 𝑂
E = E° − Log[ b ℎ + ]
n𝐹 a C𝑎 𝐻
−∆𝐺 −(−91,110 𝐽/𝑚𝑜𝑙)

E° = =
𝑛𝐹 2(96,485𝐽/(𝐶 𝑚𝑜𝑙))(𝐽/(𝐶𝑉)
E ° = 0.472 V
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2.303∗8.314∗298 𝑎2 𝐶𝑢 𝑎1 𝐻2 𝑂
E = 0.472 V − Log[ 2 + ]
2(96,485) a𝐶𝑢2 𝑂𝑎 𝐻
E = 0.472 − 0.0591pH
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2.303RT 𝑎𝐶𝑢 𝑎𝑑 𝑎𝐻2 𝑂

E = E° − Log[ ]
n𝐹 aCuO𝑎2 𝐻 +
−∆𝐺 −(−107,580𝐽/𝑚𝑜𝑙)
E° = =
𝑛𝐹 2(96,485𝐽/(𝐶 𝑚𝑜𝑙))(𝐽/(𝐶𝑉)
E ° = 0.558 V
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2.303∗8.314∗298 𝑎2 𝐶𝑢 𝑎1 𝐻2 𝑂
E = 0.558 − Log[ ]
2(96,485) aCuO𝑎2 𝐻 +
E = 0.558 − 0.0591pH
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Plot the equilibrium lines with equation labels
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General steps in extracting stability phase diagram from equilibrium line plots for
copper water system
𝐶𝑢2+ would not exist below the 𝐶𝑢2+ /𝐶𝑢 + equilibrium line. Therefore, the portion
of the 𝐶𝑢2+ /𝐶𝑢𝑂 line that is below the 𝐶𝑢2+ /𝐶𝑢 + line should be erased.
𝐶𝑢/𝐶𝑢𝑂 line which is between the line for 𝐶𝑢/𝐶𝑢2 𝑂 and 𝐶𝑢2 𝑂/𝐶𝑢𝑂 and cannot
exist between those lines because all the 𝐶𝑢 would have converted to 𝐶𝑢2 𝑂 and all
the 𝐶𝑢𝑂 would have converted to 𝐶𝑢2 𝑂 before the line is reached by the species.
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𝐶𝑢 would not exist above the line for 𝐶𝑢+ formation, making
the 𝐶𝑢/𝐶𝑢𝑂 line invalid throughout the diagram
The 𝐶𝑢/𝐶𝑢+ line which would not be valid after crossing to

the right of the 𝐶𝑢+ /𝐶𝑢2 𝑂 line because the 𝐶𝑢+ would be
converted to 𝐶𝑢2 𝑂 after crossing that line. Thus, the
𝐶𝑢/𝐶𝑢+ would be erased to the right of the 𝐶𝑢 + /𝐶𝑢2 𝑂 line.
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Noncomplex metal ions tend to be stable on the acidic
side with the lowest oxidation states at lower potentials
and lower ion activities.
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OF LEACHING
The resultant diagram is presented below
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Principle of Hydrometallurgy (Thermodynamics and Kinetics of Leaching)

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Principle of Hydrometallurgy (Thermodynamics and Kinetics of Leaching)

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Kwame Nkrumah University of

Science & Technology, Kumasi, Ghana

Ing. Dr. Mrs. Bennetta Koomson

Material Engineering Department

Faculty of Mechanical and Chemical Eng.

Students should be able to:

systems. These diagrams show the areas of stability (predominant

areas) of various metal compounds/species. The lines between the

stability areas of the compounds are known as stability lines (derived

from the equilibrium reaction equations).

They are useful in determining the effects of conditions on

Producing these diagrams requires thermodynamic data

The diagrams can be used to design dissolution

(leaching/reaction) paths without painstaking

Some of the conditions for metal extraction from metal-

containing materials can be determined using what is called

dissolution/reaction/leaching paths. These diagrams can also be

used for the designs of precipitation systems as well.

Stability diagrams can be drawn from the knowledge of reaction

equations involving the metals and metal compounds. Laborious

manual treatments have been replaced by computer application

drawing these stability diagrams. The steps helpful in preparing

these diagrams include:

• Writing relative stability equations using system variable

• Get equation for relative stability line

• Plot relative stability line

• Identify the relative stability regions

This determines the real chemical potential for a

real solution rather than an ideal one.

Because the standard state of solids and liquids in their molar

density at room temperature and pressure, which is equal to

their "concentrations" their activities are one from the

Using 𝑀2 𝑂/𝑀2+ system

𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝑀2+ − 2𝐿𝑜𝑔 𝐻+ + 2𝐿𝑜𝑔 𝑒 −

𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝑀2+ + 2𝑝𝐻 − 2𝑝𝐸

𝑝𝐸 ≥ 𝐿𝑜𝑔 𝑀2+ + 𝑝𝐻 − 0.5𝐿𝑜𝑔𝐾

𝐸ℎ = 0.0591𝐿𝑜𝑔 𝑀2+ + 0.0591𝑝𝐻 − 0.5 ∗ 0.0591𝐿𝑜𝑔𝐾

Using M(OH)3 /𝑀3+ system

M(OH)3 + 3𝐻+ = 𝑀3+ + 3𝐻2 𝑂

𝐿𝑜𝑔 𝐾 ≥ 𝑀3+ − 3𝐿𝑜𝑔 𝐻 +

Construction of Stability Diagrams

𝐿𝑜𝑔 𝐾 ≥ 𝐿𝑜𝑔 𝑀3+ + 3𝑝𝐻

𝐿𝑜𝑔 𝑀3+ = −3𝑝𝐻 + 𝐿𝑜𝑔𝑄

Using Fe(OH)3 /𝐹𝑒 3+ system

Fe(OH)3 + 3𝐻+ = 𝐹𝑒 3+ + 3𝐻2 𝑂

Construction of Stability Diagrams

𝐿𝑜𝑔 𝐾 ≥ 𝐿𝑜𝑔 𝐹𝑒 3+ + 3𝑝𝐻

𝐿𝑜𝑔 𝐹𝑒 3+ = −3𝑝𝐻 + 𝐿𝑜𝑔𝑄

Using 𝐶𝑢2 𝑂/𝐶𝑢2+ system

𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝐶𝑢2+ − 2𝐿𝑜𝑔 𝐻 + + 2𝐿𝑜𝑔 𝑒 −

𝐿𝑜𝑔 𝐾 ≥ 2𝐿𝑜𝑔 𝐶𝑢2+ + 2𝑝𝐻 − 2𝑝𝐸

𝑝𝐸 ≥ 𝐿𝑜𝑔 𝐶𝑢2+ + 𝑝𝐻 − 0.5𝐿𝑜𝑔𝐾

Construction of Stability Diagrams

We need to find the relative stability of the following pairs

2𝐶𝑢𝑜 + 2𝐻 + + 2𝑒 − → 𝐶𝑢2 𝑂 𝐿𝑜𝑔𝐾 = 21.6

𝐿𝑜𝑔𝐾 ≥ −2𝐿𝑜𝑔 𝐻 + − 2𝐿𝑜𝑔 𝑒 −

𝐿𝑜𝑔𝐾 ≥ 2𝑝𝐻 + 2𝑝𝐸

21.6 ≥ 2𝑝𝐻 + 2𝑝𝐸