Pyrometallurgy

Course Code: MSE 353

Frank Ofori Agyemang (Ph.D)

Materials Engineering Department
 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 2

 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:

 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 (similar
diagrams can also be drawn for metals reacting with sulfur,
chlorine, etc.)

• 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, CO is better reducing agent than C, and above

980K, C is better reducing agent that CO
 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.