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CHMT3050A / CHMT3018A:
Ore dressing and Extractive
Metallurgy
31st August 2023
Mrs. Zama Mthabela
[email protected]
School of Chemical and Metallurgical Engineering 2
8th Lecture

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 Course Content - Part 1
Week 1: Course Brief and Comminution
• Course Rules and expectations.
• Communition, Crushers and Unit operation
• Energy Laws
Week 2: Milling
• Grinding, Screening
• Unit operation
Week 3: Particle Size Analysis
• Particle Characterization
• Methods and equipment
Week 4: Mass Balancing
• Metallurgical efficiency/ accounting

Week 5: Separation:
• Handpicking
• gravity concentration, 4
• magnetic
 Course Content - Part 2
Week 6: Separation and introduction to Solution Chemistry
•
•
Magnetic and Gravity separation examples
Upgrading methods,
This lecture
•
•
Flotation, sedimentation, thickening and filtration,
Solution chemistry.
will cover:
Week 6: Test 1 based on Week 1 – 5 work.

Week 7: Solution Chemistry Continues

• Precipitation,
• Solubility
• Electrochemical Reaction Principles

Week 8: Spring Break (04 – 08 September 2023)

Week 9: Thermodynamics
• Cell Potential,
• Predicting the feasibility of reactions,
• Thermodynamic calculations,
• Chemical Potential, Free Energy.
Week 9: Hydrometallurgy
• leaching,
• Leaching reactions
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• Leaching Reagents
 Course Content - Part 3
Week 10: Hydrometallurgy
• Leaching reactions and reagents
• Different Leaching methods.

Week 11: Solvent Extraction and Coal

• Solvent extraction,
• Ion exchange,
• Coal and technologies associated with coal usage after mining,
• Recap on past topics in preparation for next topic.

Week 12: Pyrometallurgy

• Roasting and calcination of concentrates,
• smelting converting,
• electrowinning/refining,
• industrial metal extraction processes.

Week 12: Occupational Health and Safety Act

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Week 13: Test 2 based on Week 6 - 12 work.
 Assessments Dates

• Exam : TBC
• Tests 1 : 23th August 2023
• Test 2 : 12th October 2023
• Assignment : 12th October 2023
(report writing format)

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 Learning Objectives
• Recap the basic principles of electrochemistry reaction.
• Understand the difference between the Reducing and
Oxidising Agents.
• Evaluate the thermodynamic principles.
• Evaluate the chemical potential energy.
• Understand the Gibbs Free Energy, Enthalpy and
Entropy.
• To learn to predict if the reaction will be spontaneous
from calculation.
• Understand the meaning of the data obtained.

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 Learning Outcomes
By the end of the lecture you should:
• Fully understand electrochemistry reaction principles.
• Know the difference between Reducing and Oxidising
Agents.
• Understand all thermodynamic principles.
• Understanding the meaning of results obtained from
calculations.
• Know how to predict the outcome of a reaction from
calculations.

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 Recommended Textbooks
• William F Smith en Javad Hashemi. Introduction to
Engineering, 5th Edition, McGraw-Hill International Edition
2015.
• Mineral processing technology B A. Wills, 4th, 5th 6th, 7th
or 8th will adequately meet the requirements for the Ore
dressing.
• Brown, L Theodore, Lemay, H Eugene Jr. and Bursten, E
Bruce. Chemistry: the central science.
• Woollacott, L and Eric, R. Minerals and Metal Extraction: an
overview.

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Recap

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 Electrochemical
Reaction Principles
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 Oxidation-Reduction
Reactions
• Redox equilibria:
– Redox reactions involves the transfer of electrons
• OIL (Oxidation is loss)
• RIG (reduction is gain)
• Electrode potential:
– Measures the tendency of a substance to be oxidized or
reduced (Potential energy difference = measured in Volts)
– Measures between two electrodes:
• Electrons flow from high potential (anode) to low potential
(cathode).
• Red Cat / An Ox
• Reaction involving electron transfer can be conducted in
an electrochemical cell.

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 The Electrochemical
Series/Activity
• Built up by arranging various redox equilibria in order of their standard
electrode potentials (redox potentials).
– Standard electrode potential for the hydrogen reaction = 0 (reference
electrode).
• Most reactive metals appears at the bottom of the electrochemical series:
⁻ Readily lose electrons,
⁻ Have the most negative E+0 values,
⁻ Best reducing agents.
• Most reactive non-metals appears at the top of the electrochemical
series:
₋ Readily gain electrons,
₋ Have the most positive E+0 values,
₋ Best oxidizing agents.

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The Electrochemical
Series/Activity

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 Cell Potential & Nernst Equation
• Potential difference is called the cell potential (or EMF for electromotive
force, Ecell)
– For a spontaneous reaction, Ecell is positive and ΔG (Gibbs free energy, used to
determine if a reaction occurs spontaneously) is negative. Thus, when ΔG is
negative the reaction is spontaneous.
• Merging electrochemistry with thermodynamics gives Nernst equation:
∆𝐺 = −𝑛𝐹𝐸
∆𝐺° = −nFE°
𝑅𝑇
Nernst Equation: ∴ 𝐸 = 𝐸° − 𝑛𝐹
ln K
Where:
• E = potential for redox rxn
• E°= standard potential for redox rxn
• n = number of electron involved in the electrochemical rxn
• F = Faraday’s constant = 96485 Coulomb/mol of electron/
• R is the molar gas constant 8.3144J/Km0l-1
• T = temperature in Kelvin
• K = Equilibrium constant of dissociation rxn

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 Standard Cell Potential
• Cell potential is different for each voltaic cell;
its value varies with metal ion concentration
and temperature.
• The standard cell potential, E°𝑐𝑒𝑙𝑙 :
E°𝑐𝑒𝑙𝑙 = E°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 - E°𝑎𝑛𝑜𝑑𝑒
• The cell potentials indicates which reaction
takes place at the anode and which one at the
cathode.
– To calculate E°𝑐𝑒𝑙𝑙 , subtract the E°𝑐𝑒𝑙𝑙 of the oxidized
half reaction from the E°𝑐𝑒𝑙𝑙 of the reduction half
reaction.
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 Predicting the feasibility of
a possible redox rxn
• Redox potentials are one way of measuring
how easily a substance loses electrons. They
give a measure of the relative positions of
equilibrium in rxns.
• When ever you link two of these equilibria
together electrons flow from one equilibrium to
the other
– The equilibrium with the more negative (or less
positive) E°value will move to the left
– The equilibrium with the more positive (or less
negative) E° value will move to the right

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 Reducing and Oxidising Agents
• A substance which is capable of being reduced very
easily is a strong oxidizing agent.
• Vice versa: a substance which is capable of being
oxidized very easily is a strong reducing agent.
• Fluorine (F2) is the strongest oxidizing agent (as it is
at the top of the standard cell potential table). It will
oxidize any substance below on the table.

Conclusion: if the standard reduction potential is

higher then a half-cell will undergo reduction.

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Example

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 Example
Calculate the standard cell potential of a voltaic cell that
uses the Ag / Ag+ and Sn / Sn2+ half-cell reactions.
Write the balanced equation for the overall cell reaction
that occurs. Identify the anode and the cathode.

Follow the following steps:

• List the known values.
• Balance the overall redox equation: Ensure that the
number of electrons lost in the oxidation must equal
the number of electrons gained in the reduction.
• Add the equations: E°𝑐𝑒𝑙𝑙 = E°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 - E°𝑎𝑛𝑜𝑑𝑒

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Example Cont.

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Example Cont.

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 Example Cont.
1. Write out the values:

2. Decide which one is anode and cathode:

3. Balance redox equation:

4. Calculate cell potential:

The voltage for the silver ion reduction will not be doubled even though the
reduction half-reaction had to be doubled to balance the overall redox
equation.

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 Example Cont.
Is the reaction spontaneous?
• Yes, the standard cell potential is positive.
• The Tin is oxidized at the anode, while the silver ion is reduced
at the cathode.
• If this question were to extend to calculating the cell potential under
non-standard conditions, then you would apply this formula:
𝑅𝑇
𝐸 = 𝐸° − ln Q
𝑛𝐹
Where:
• Q is the ratio of concentrations (or activities) of the products
divided by the reactants.
𝑅𝑒𝑑
• For the redox reaction: Q =
𝑂𝑥

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Thermodynamics

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 Question?

Is this the type we are about to discuss??

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Thermodynamics

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 Predicting The Feasibility
of Reaction
• Thermodynamics:
– Provides quantitative answers regarding stability and
reaction viability.
– Thermodynamic calculations determine whether the
addition of a specific amount of compound will
dissolve or precipitate. This information will tell you:
• If leaching of specific mineral will be favourable under a
specific condition.
• Voltage needed for recovery of a desired metal under specific
conditions.
• If balanced chemical reactions are likely to occur.
• The concentration of individual species when reaction are at
equilibrium.

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 Thermodynamics Calculations
• Thermodynamic calculations of solubility are useful
tools to understand the fundamentals of
hydrometallurgy.
• The thermodynamics characteristics of the reaction
system will indicate the maximum possible extent to
which the value-bearing mineral can be converted to a
soluble species, as well as the solubility of that specie
in the aqueous solution.
• The degree to which such a transfer can be achieved is
determined by the rate at which the reaction proceed.

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 Important Principles
• Two types of reactions that occur in aqueous solution
• Ion exchange reactions
• Redox reactions
• Thermodynamics: feasibility criteria
• Kinetics and rate of process: how long it takes to
complete the process.
• Heat transfer: for improving the thermal efficiency of
the process.
• Electrochemistry: to estimate, over-potential, current
efficiency.
• Hydrometallurgy: Eh-pH diagram, rate estimation of
leaching process.
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 Types of Hydrometallurgy
Reactions
• Classification of these chemical reactions
depends on the type of species reacting with
the metal
– Precipitation
– Hydrolysis
– Electrochemical
– Conversion
– Complexation
– Solvation
– Ionic disassociation

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 Chemical Potential
• Energy that can be absorbed or released.
• For pure solids and pure liquids the chemical
potential is the molar free energy G that is a
function of temperature and pressure only.
G = µ = µ(T,P)
• The chemical potential of a component at 1 atm is
known as µ° (standard state), so:
µ = µ°(T)
• This is a thermodynamic function expressing the
ability of an uncharged atom or molecule in a
chemical system to perform physical work.

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 Chemical Potential
• The below chemical potential equations are
used when dealing with ideal gases and
solutions. Do not confuse the two.
• Chemical potentials in an ideal gas mixture:
µi(g) = µi(g)° + RT lnPi
Pi = partial pressure of component i.
• Chemical potentials in ideal solutions:
µi(sol) = µi(sol)° + RT lnXi
Xi = mole fraction of component i in solution

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 Chemical Potential: Summary
The chemical potential (𝞵) is a measure of how
much the Gibbs free enthalpy (free energy) of a
system changes if you:
❑ add or remove the number of particles
of a particle species
❑ keep the number of the other particles at
constant temperature and pressure.

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 Gibbs Free Energy
The Gibbs free energy of a system is defined as the enthalpy of
the system minus the product of the temperature times the
entropy of the system:
G = H - TS
∆G = ∆H - T∆S
If the data are collected under standard-state conditions, the
result is the standard-state free energy of reaction (∆Go)

∆G° = ∆H° - T∆S°

∆G is the difference in the energy between reactants and products.

∆G is unaffected by external factors that change the kinetics of the
reaction.
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 Reaction Prediction Guidelines
Change in the Enthalpy of the reaction:
∆ H > 0 then the reaction is: Endothermic - absorbs heat. More energy is
needed to break bonds in the reactants.
∆ H < 0 then the reaction is: Exothermic - releases heat. The total energy
of the products is less than the total energy of the reactants.

Change in the Entropy of the reaction:

∆ S > 0 the reaction is product-favoured.
∆ S < 0 the reaction is reactant-favoured.

Change in the Gibbs Free Energy of the reaction:

∆ G > 0 it is: Endergonic - NON-SPONTANEOUS
∆ G < 0 it is: Exergonic - SPONTANEOUS

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 Gibbs Free Energy
• The relationship between the free energy of reaction at any
moment in time (∆G) and the standard-state free energy of
reaction (∆G° ) is described by the below equation:

∆G = ∆G° + RT ln Q
Where:
• ∆G° is the Gibbs energy change for a system under standard
conditions (1 atm, 298K).
• R is the ideal gas constant
• T is the temperature in kelvins.
• Q is the ratio of concentrations (or activities) of the products
divided by the reactants.

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 Gibbs Free Energy
The Gibbs free energy gives the following information:
• Reaction is spontaneous or not.
• Measures the amount of energy to do work at constant temperature
and pressure.
∆G° < 0
• Spontaneous, favourable, free energy decreases
∆G° > 0
• Non-spontaneous, unfavourable, free energy increases

IMPORTANT: TAKE NOTE

o Sign of ∆G°: direction at which the rxn has to shift to come to
equilibrium.
o Magnitude of ∆G°: how far the standard state is from equilibrium.

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 Gibbs Free Energy Example
What does the value of ∆G° tell us about the following reaction?

N2(g) + 3 H2(g) <---> 2 NH3(g) ∆G° = -32.96 kJ

It is spontaneous right?

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 Example Cont.
What does the value of ∆G° tell us about the following reaction?
N2(g) + 3 H2(g) <---> 2 NH3(g) ∆G° = -32.96 kJ
If the following information is given:
(kJ/mol) (J/mol.K)

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 Example Cont.
What does the value of ∆G° tell us about the following reaction?
N2(g) + 3 H2(g) <---> 2 NH3(g) ∆G° = -32.96 kJ
(kJ/mol) (J/mol.K)

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 Example Cont.
N2(g) + 3 H2(g) <---> 2 NH3(g) ∆G° = -32.96 kJ
(kJ/mol) (J/mol.K)

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 Example

∆G = ∆Go + RT ln Q
𝑆𝑂3 2
𝑄=
𝑆𝑂2 2 ∗ [02]

0.950 2
=
0.100 2∗[0.200]

= 451.25mol

∆G = ∆Go + RT ln Q
∆G = −142kJ/mol + (8.31J/molK)*(1455K) ln (451.25)mol
= - 68.1kJ/mol 44
 Equilibrium Constant
• Is used to determine the amount of each species present at the
equilibrium point of reaction.
• It is an important application in leaching, precipitation, carbon based
and solvent extraction processes.
• It is expressed in two ways:
Kc and Kp
• Significance of Kc
Kc > 1
✓ Favours reaction to the right; more products than reactants; reaction is complete
Kc < 1
✓ Favours reaction to the left; more reactants than products
Kc = 1
✓ the amounts of products and reactants will be about the same; no reaction
occurring
• Activities/concentration of liquids and solids are often but not always
assumed to be 1.
• All [concentrations] are molar (M or mol/L).
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 Relationship Between Free
Energy and Equilibrium
• To describe the system in terms of non-standard state free energy of rxns.
• Magnitude of ∆G° describes how far the standard state is from equilibrium:
– The smaller the value of ∆G° , the closer the standard state is to Kc
– Larger the value of ∆G°, further the rxn has to go to reach Kc

• Under standard conditions Q = 1

∆G = ∆Go + RT ln Q
∆G = ∆Go + RT ln (1)
∴ ∆G = ∆G°
• At equilibrium Q = K
∴ ∆G = 0
∆G = ∆Go + RT ln Q

∆G° = -RT ln K

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 Reaction Free Energy Influenced
by Reaction Conditions
• The Free Energy reaction is influenced by the
following conditions:
– Temperature
– Pressure
– Concentration
• Standard conditions have been established (for
convenience) and are needed to make uniform free
energy comparisons. The standard conditions are:
– Temperature = 25 ℃ (298 K)
– Pressure = 1 atm
– Ion concentration = 1 (not always the case)

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 Free Energy and
Non-Standard Activities
• Important and common non-standard condition
encountered in hydrometallurgy involves the
activity/concentration of species.
∆G° = -RT ln K
The equilibrium plays an important role in hydrometallurgical
processes. It helps provide the following type of information:
– Helps in determining the final configuration of a given
system.
– Provides valuable practical information (eg. How much
concentration to add to form product).
– Provides the concentration of individual species.

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 Gibbs Standard-State
Free Energy
Values of ∆G ° and K for Common Reactions at 25°C:

At equilibrium condition: ∆G° = -RT ln K

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 Announcements
• Ensure to go through Lecture 7 & 8.
• Tutorial questions will be issued with these two lectures.
• The next tutorial session will be on the 14th September 2023.
• Ensure to go over all the work during your Spring break.
• Please note that there will be no lecture or tutorial session next
week as we will be having the:

❑ MID-TERM BREAK 04th – 08th September 2023

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