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Technical presentation

The Ellingham Diagram

Bapin Kumar Rout

Research and Development, Steelmaking and Casting Research Group

Before we start: Thermodynamic terminologies


Gibbs Free Energy ( G ): Energy of the system available to do work

G= H-T*. S
Enthalpy term

Entropy term

H: Measure of the actual energy that is liberated when the reaction occurs
S: Measure of the change in the possibilities for disorder in the products
compared to the reactants

Spontaneity of the Reaction ( G<0)

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Free Energy and Equilibrium


Standard state free energy ( G0=):

Under non-standard conditions, we need to use G instead of G.

1. If G is negative, the forward


reaction is spontaneous.
2. If G is 0, the system is at
equilibrium.
3. If G is positive, the reaction is
spontaneous in the reverse
direction.
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The Ellingham Diagram


Ellingham1 plotted experimentally determined standard free energy of formation
(G0) of various oxides (and sulfides) using one mole of oxygen with temperature

Ellingham Found that, the standard enthalpy and entropy of formation of a compound
dont change significantly with temperature as long as there is no change of state

Thus, G0-T relationship is approximated to straight lines:

Y= mx+C

Intercept

Slope

1Ellingham H. J. T., Reducibility of Oxides and sulfides in Metallurgical Processes , J Soc Chem Ind (London) 63 125 (1944)

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The Ellingham Diagram

Oxide stable

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Metal stable

The Ellingham Diagram

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The Ellingham Diagrams

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The Ellingham Diagrams

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Two intersecting lines


T<TE A and BO2 are most stable
T>TE B and AO are most stable
At T=TE A,B,AO,BO2 are in equilibrium

A as a reducing agent to reduce BO2 to form B and AO- T> TE


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The Ellingham Diagrams

Research and Development, Steelmaking and Casting Research Group

The Ellingham Diagram

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The Ellingham Diagrams

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The Ellingham Diagrams

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Additional scales on Ellingham diagram

Y=-mX

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Reading pO2 from Ellingham diagram

In to avoid calculating the equilibrium


partial pressure for each value of G,
Richardson2 added a nomographic scale
to the Ellingham diagram

For a metal oxidation reaction ,


2M (s) + O2 (g) = 2MO (s)
The equilibrium constant has the form
K=1/pO2
G= RT ln(pO2)

2 F.D. Richardson

and J.H.E. Jeffes, "The Thermodynamics of Substances of Interest in Iron and Steel Making from 0C to 2400C: I-Oxides," J. Iron
and Steel Inst. (1948), 160 261.

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Reading pO2 from Ellingham diagram


1. Identify a point corresponding to
a selected temperature on the
line for: Fe + O FeO, above M
2. Using this point, and the point O
in the top left corner, draw a line
across the diagram
3. Read the partial pressure of
O2 from the right hand axis

At any oxygen pressure higher than


~10-8.5, the iron will be oxidised at the
temperature of 1600C

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Other gas mixtures


The oxygen required to cause oxidation in the gas phase need
not to come from oxygen gas. Consider the following reaction:
2CO (g) + O2 (g) = 2CO2 (g)
For this reaction,

We see that pO2 is equivalent to a ratio: pco/ pco2


Similarly for the reaction 2H2+O2=2H2O pO2 is equivalent to a
ratio: pH2O/ pH2
Thus two nomographic scale may be added to the diagram, with
a new origin, C and H respectively for pco/ pco2 and pH2O/ pH2
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CO-CO2 gas mixture as reducing agent (374)


MO2+2CO=M+2CO2
At T>Ts CO-CO2 mixture is reducing
w.r.t MO2 at pCO/pCO2=1
At T<Ts CO-CO2 mixture is oxidising
w.r.t MO2 at pCO/pCO2=1

If CO-CO2 mixture to be made reducing at T<Ts the pCO/pCO2(>1) must be increasing


At T=Tu pCO/pCO2 should be increased from 1to 10 to maintain reaction equillibrium

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Limitation

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Limitation

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References
1. D.R. Gaskell, "Introduction to the Thermodynamics of Materials
2. http://www.doitpoms.ac.uk/tlplib/ellingham_diagrams/

Thank you

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Questions?

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