Ellingam Diagrams

An Ellingham diagram is a graph showing the

temperature dependence of the stability for
compounds.
This analysis is usually used to evaluate the
ease of reduction of metal oxides and
sulphides.
These diagrams were first constructed by
Harold Ellingham in 1944.
 Salient features of Ellingham Diagram
Curves -metallic oxides are basically straight
lines with a positive slope.
The slope is proportional to S, which is fairly
constant with temperature.
The lower the position of a metal's line in the
Ellingham diagram, the greater is the stability
of its oxide
Stability of metallic oxides decreases with
increase in temperature.
 The formation free energy of carbon dioxide
(CO2) is almost independent of temperature,
while that of carbon monoxide (CO) has
negative slope and crosses the CO2 line near
700C.
According to the Boudouard reaction, carbon
monoxide is the dominant oxide of carbon at
higher temperatures (above about 700C), and
the higher the temperature (above 700C) the
more effective a reductant (reducing agent)
carbon is. (2CO=CO2+C)
While the formation enthalpy of CO2 is higher
than that of CO, the formation entropy is
much lower. Consequently, the standard free
energy of formation of CO2 from its
component elements is almost constant and
independent of the temperature, while the
free energy of formation of CO decreases with
temperature.
 A metal whose Gibbs free energy of formation is lower on
the diagram at given T, will reduce an oxidized substance
whose free energy of formation is higher on the diagram.
For ex. Al, can reduce FeO to Fe, Al itself being oxidized to
Al2O3. (This reaction is employed in thermite.)
The aluminium reduces the oxide of another metal, most
commonly iron oxide, because aluminium forms stronger
bonds with oxygen than iron:
Fe2O3 + 2 Al 2 Fe + Al2O3(Metallothermic reduction
reaction)
2Fe2O3 + 3C 4Fe + 3CO2(Carbothermic Reaction)
 The products are aluminium oxide, free elemental iron,[3] and a
large amount of heat. The reactants are commonly powdered and
mixed with a binder to keep the material solid and prevent
separation.
Commonly the reacting composition is five parts iron oxide red
(rust) powder and three parts aluminium powder by weight, ignited
at high temperatures. A strongly exothermic (heat-generating)
reaction occurs that via reduction and oxidation produces a white
hot mass of molten iron and a slag of refractory aluminium oxide.
The molten iron is the actual welding material; the aluminium oxide
is much less dense than the liquid iron and so floats to the top of
the reaction, so the set-up for welding must take into account that
the actual molten metal is at the bottom of the crucible and
covered by floating slag.
 The greater the gap between any two lines, the
greater the effectiveness of the reducing agent
corresponding to the lower line.
The intersection of two lines implies an oxidation-
reduction equilibrium.
At the point of intersection the free energy
change for the reaction is zero, below this T,
it is positive and the metallic oxide is stable in the
presence of the reductant, while above the point
of intersection the Gibbs energy is negative and
the oxide can be reduced.
 Richardson Nomographic scale to
Ellingham Diagram
To avoid calculating the equilibrium partial pressure for
each value of G, Richardson2 added a nomographic
scale to the Ellingham diagram.
The equilibrium partial pressure is found as follows:
A line is drawn from the origin of the graph (T = 0, G =
0) through the point on the Ellingham line of interest,
at the required temperature. The equilibrium partial
pressure is read off at the point where the drawn line
crosses the nomographic scale.
Equilibrium Partial Pressure of Oxygen
The scale on the R.H.S is( Po2)is the
equilibrium partial pressure of O2 that is
equilibrium with the M and MO
Significance:
If the O2 pressure is higher than equilibrium
O2 pressure then Metal will be oxidised.
Use: At any temperature, EQM Partial-
pressure can be found Directly.
 Disadvantages
The analysis is thermodynamic in nature, and
ignores reaction kinetics. Thus, processes that
are predicted to be favourable by the
Ellingham diagram can still be slow.
Meatls and Mo only in Standard states.