Student’s Guide and Code of Conduct

Any student who is absent from lectures, laboratory practicals, tutorials, workshops etc in
one particular course without permission for a total of three (3) cumulative lecture
periods or more in any semester shall be deemed not to have satisfied the requirements for
the course, in terms of attendance for the semester, and he/she shall not be allowed to write
the End-of-Semester Examinations for the course.
A candidate shall compulsorily be deferred (Df) to come and repeat the course at the next
available opportunity. The candidate must not be awarded zero percent (0%).

Rule for the course

All Phones should be on silence and in your bags or pockets. If a student is seen using
phone in the course of the lecture, the phone will be seized and confiscated at the exams
office
Pyrometallurgy

Course Code: MSE 353

Frank Ofori Agyemang (Ph.D)

Materials Engineering Department
Course Objectives
• Provide fundamental understanding of aspects of
chemistry and material science relevant to extraction
of metals

• Provide methodologies for producing and refining of

metals (esp. iron to steel)

• Select appropriate steelmaking process

• Understand the processing of other non-ferrous metals

such as Al, Cu, Li etc.
3
Course Outcomes
• Use Ellingham diagram in the extraction of metals

• Gain general knowledge of the various methods

available for the production of ferrous materials

• Design a system, component, or process to meet the

desired needs

• Identify, formulate and solve engineering problems

• Understand principles underlying processing-

structure-properties-performance

4
Prerequisites
• Knowledge of thermodynamics of materials (phase
diagrams, Gibbs free energy, physical chemistry)

• Principles of material and energy balance across

process units

5
Attendance is your job – come to class!
 Our regularly scheduled time (Mondays 8:00-10:00
am at PB201) and Wednesdays (at NEB=GF)
Assignments
Don’t copy from others; don’t plagiarize – its just the
right thing to do!!
Tutorials – by (Esther Doku)

6
Forms of Assessment (Tentative)

Quizzes/Assignment 15
Mid-Sem Exam 15
Final Exam 70
Total 100

7
 Course Outline
1. Binary Solution (Review)
2. Fundamental principles of pyrometallurgy (Ellingham
diagram)
3. Introduction to Pyrometallurgy
• Drying, Calcination, Roasting
• Fuel

4. Recovery of iron from ore

5. The refining of iron to steel

6. Pyrometallurgy of other metals – Alumimium, Copper 8

Recommended Books
1. Bailey, F. W. J. (2011), Fundamentals of Engineering Metallurgy and
Materials, 5th Edition, Cassell.
2. Callister, W. D., Rethwisch, D. G. (2018), Materials Science and
Engineering, An Introduction, 10th Edition, Wiley & Sons
3. Hwang, Jiann-Yang., (2016), 7th International Symposium on High-
Temperature Metallurgical Processing, Wiley.
4. Phillip J. Mackey, Eric J. Grimsey, Rodney T. Jones, Geoffrey A. Brooks.,
(2016), Celebrating the Megascale: Proceedings of the Extraction and
Processing Division Symposium on Pyrometallurgy in Honor of David G.C.
Robertson, Springer International Publishing
5. S. K. Dutta and Y. B. Chokshi, (2020) Basic Concepts of iron and Steel
making, Springer Nature.
 Course Outline
1. Binary Solution (Review)
2. Fundamental principles of pyrometallurgy
(Ellingham diagram)
3. Introduction to Pyrometallurgy
• Drying, Calcination, Roasting
• Fuel

4. Recovery of iron from ore

5. The refining of iron to steel

6. Pyrometallurgy of other metals – Alumimium, Copper 10

 QUIZ ONE
• Differentiate between Oxidation reaction and Reduction Reaction

• State the equation of Gibbs free energy

• State the First and Second Law of Thermodynamics

 Ellingham Diagram
• Plot of free energy change as a function of temperature
is called Ellingham Diagram

• The Gibbs free energy (ΔG) is a measure of the

thermodynamic driving force that makes a reaction
occur.

• - ΔG => reaction can proceed spontaneously without

external inputs, while a + ΔG => non-spontaneous.

• The equation for Gibbs free energy is:

Ellingham Diagram for metal oxides
Ellingham Diagram for metal sulfides
 Construction of Ellingham Diagram

• ΔG versus T plot can be drawn as a series of straight

lines

• The slope of the line changes when any of the materials

involved melt or vaporize

• ΔG is negative for most metal oxides

 Construction of Ellingham Diagram
• Ellingham diagram shows metals reacting to form oxides, sulfides
chlorides etc. It was originally constructed for oxides.

• Thermodynamic data can be found quickly without the need for

repetitive calculations.

• For oxides; the oxygen partial pressure is taken as 1 atmosphere, and

all of the reactions are normalized to consume one mole of O2.

• The majority of the lines slope upwards.

• gas + condensed phase = condensed phase => ΔS ↓
• A notable exception to this is the oxidation of solid carbon.
 C + O2 = CO2 (solid + 1 mol gas = 1 mol gas)
• Little ΔS and line is nearly horizontal
 2C + O2 = 2CO (solid + 1 mol gas = 2 mol gas)
• ΔS ↑ and line slopes sharply downward
Ellingham Diagrams
 Uses of Ellingham Diagram
1. Predict which reducing agents can reduce which oxides
and at which temperatures

2. Determine the partial pressure of oxygen that is in

equilibrium with a metal oxide at a given temperature

3. Determine the ratio of carbon monoxide to carbon

dioxide that will be able to reduce the oxide to metal at a
given temperature
 Ease of Reduction
• Reactions closer to the top are the most noble metals (eg.
Au and Pt) and their oxides are unstable and are easily
reduced

• A given metal can reduce the oxides of all metals whose

lines lie above theirs on the diagram.
• 2Mg + O2 = 2MgO line lies below the Ti + O2 = TiO2
line, and so Mg can reduce TiO2 to Ti
• 2C + O2 = 2CO line is downward-sloping, it cuts
across many of the other metals.
Equilibrium Partial Pressure of Oxygen

• The “PO2” scale is used to determine what partial pressure

of oxygen will be in equilibrium with the metal and metal
oxide at a given temperature.

• If the oxygen partial pressure is higher than the

equilibrium value, the metal will be oxidized, and if it is
lower than the equilibrium value then the oxide will be
reduced.
How to read PO2
• Find the point where the oxidation line of interest
crosses that temperature.

• Line up the straightedge with both that point, and with

the point labelled “0”.

• With the straightedge running through these two points,

read off the oxygen partial pressure (in atmospheres).
Ratio CO/CO2 Needed for Reduction
• With carbon as reducing agent, there is a minimum ratio of CO to
CO2 that will be able to reduce a given oxide.

• The harder the oxide is to reduce, the greater the proportion of CO

needed in the gases.

• To determine the CO/CO2 ratio to reduce a metal oxide at a

particular temperature, use the same procedure as for determining
the equilibrium pressure of oxygen
 Use of Ellingham Diagram
• Order of reactivity:
• The most reactive elements (i.e. the ones with the most stable
oxides) are at the bottom of the diagram.
• Ag2O – CuO – FeO – TiO2 – Al2O3 – CaO

Increasing stability of oxides

• The lines for carbon reactions intersect at 980K.
• Below 980K, CO disproportionates:
2CO(g) = C(s) + CO2(g)
• Above 980K
C(s) + CO2(g) = 2CO(g)

• So below 980K, C is better reducing agent than CO, and above

980K, CO is better reducing agent than C
 Boudouard Reaction
• Consider the following reaction
CO2 + C → 2CO
• Determine the partial pressures of gaseous species at equilibrium.
Examine the effect of pressure on the equilibrium.
 Ellingham Diagram
1. Can carbon be used to reduce zinc oxide to zinc at
a) 1000 K and b) 1500 K?
The reaction we require is: 2C + 2ZnO2 = 2Zn + 2CO
2. What is the best reducing agent at all temperatures up to 2000oC?
3. Write the chemical equations corresponding to the lines ending with
Al2O3 and ZnO. Show how they can be combined to give a
spontaneous reaction between one of these metals and the oxide of the
other.
4. Why is gold not found in nature as its oxide?
5. Will Al powder react with Cr2O3? If so at what temperature? Write
balance equation.
 Ellingham Diagram
Q. Can carbon be used to reduce zinc oxide to zinc at
a) 1000 K and b) 1500 K?
The reaction we require is: 2C + 2ZnO2 = 2Zn + 2CO

The graph shows that at 1000 K, we have the following approx. ΔG

values”
1. 2C + O2 = 2CO ΔG = -400 kJmol-
2. 2Zn + O2 = 2ZnO ΔG = -550 kJmol-
Reversing reaction 2 gives:
3. 2ZnO = 2Zn + O2 ΔG = +550 kJmol-
Adding 1 & 3 we get:
4. 2ZnO + 2C = 2Zn + 2COΔG = +150 kJmol-

Reaction is not feasible

 Ellingham Diagram
The graph shows that at 1500 K, we have the following approx. ΔG
values”
1. 2C + O2 = 2CO ΔG = -500 kJmol-
2. 2Zn + O2 = 2ZnO ΔG = -250 kJmol-
Reversing reaction 2 gives:
3. 2ZnO = 2Zn + O2 ΔG = +250 kJmol-
Adding 1 & 3 we get:
4. 2ZnO + 2C = 2Zn + 2COΔG = -250 kJmol-

Reaction is feasible at 1500 K

• At the point on the graph where the two lines cross, ΔG = 0.

• Thus reaction above is feasible at temperatures above 1200 K
 Questions on Ellingham Diagram
• What is the best reducing agent at all temperatures up to 2000oC?
• Ca metal; the lowest line
• Write the chemical equations corresponding to the lines ending
with Al2O3 and ZnO. Show how they can be combined to give a
spontaneous reaction between one of these metals and the oxide of
the other.
• 4/3Al(s) + O2(g) = 2/3Al2O3(s)
• 2Zn(s) + O2(g) = 2ZnO
• Al line is lower than Zn line at all temperatures. Hence Al is better reducing
agent and ends up with oxygen in competition with Zn:-
• 4/3Al(s) + 2ZnO = 2/3Al2O3(s) + 2Zn(s) or 2Al(s) + 3ZnO = Al2O3 +
3Zn(s)
• Will Al powder react with Cr2O3? If so at what temperature? Write
balance equation.
• Yes, at all temperatures
• 2Al(s) + Cr2O3(s) = 2Cr(s) + Al2O3(s)
• This reaction is often used to make small quantities of many metals
 (a) 2CO + O2→2CO2
(a) 2Zn(s) + O2 → 2ZnO

-400 (b) C + O2→ CO2

-500

-600 (a) 2CO(g) + O2(g)→2CO2(g)

(b) C(s)+ O2(g)→ CO2(g)
∆Gᶿ KJ/mol
(c) 2Zn(s) + O2(g) →2ZnO(s)

Temperature ( K)

Qu. Why is Zn not extracted from ZnO through reduction using CO?
 1623K

Qu. Suggest a condition underwhich Mg can reduce Al2O3 & Al can

reduce MgO?
 Questions on Ellingham Diagram
• At about what temperature is it possible to reduce MgO with C?
Write a balanced equation including the physical states of all
species
• At about 1700oC, well above the boiling point of Mg
• MgO(s) + C(s) = Mg(g) + CO(g)
• What is the reaction between C and steam at (a) 100oC and (b)
1000oC
• At 100oC; C(s) + 2H2O(g) = 2H2(g) + CO2(g)
• At 1000oC; C(s) + H2O(g) = H2(g) + CO(g)
• Both reactions are endothermic. At 100oC it will be too slow to be useful.
At high temperatures, reaction is used to produce inflammable mixture of
gases know as “water gas”
• Which is the best oxidizing agent at 1500oC, MgO or Al2O3?
• MgO, the higher line at this temperature
• Why is gold not found in nature as its oxide?
• Since it is above the zero line, ΔGformation (Au2O3)is positive and the
compound is thermodynamically unstable
 Questions on Ellingham Diagram
• Why does the line Zn/ZnO increase its slope sharply at about
900oC?
• The boiling point of Zn is about 900oC. Below this temperature the reaction
is; 2Zn(l) + O2(g) = 2ZnO(s)
• Above this temperature the react is; 2Zn(g) + O2(g) = 2ZnO(s)
• Above 900oC there are 3 moles of gas at the left side of the reaction rather
than only 1. ΔS is approximately tripled and since gas is being lost it will
be negative. The line is ΔG against T. the slope is – ΔS so if ΔS gets more
negative the slope will become more positive