Thermodynamics

Ellingham diagrams are a particular graphical form of the principle that the thermodynamic
feasibility of a reaction depends on the sign of G, the Gibbs free energy change, which is
equal to H TS, where H is the enthalpy change and S is the entropy change.

Simple Ellingham diagram for high temperature (0C 2500C) oxidation of several metals
and carbon
The Ellingham diagram plots the Gibbs free energy change (G) for each oxidation reaction
as a function of temperature. For comparison of different reactions, all values of G refer to
the reaction of the same quantity of oxygen, chosen as one mole O (
1

2
mol O
2) by some authors
[2]
and one mole O
2 by others.
[3]
The diagram at right refers to 1 mole O, so that for example the line marked Cr
2O
3 shows G for the reaction 2/3 Cr(s) +
1

2
O
2(g)
1

3
Cr
2O
3(s), which is
1

3
of the molar Gibbs energy of formation G
f
(Cr
2O
3, s).
In the temperature ranges commonly used, the metal and the oxide are in a condensed state
(liquid or solid), and oxygen is a gas with a much larger molar entropy. For the oxidation of
each metal, the dominant contribution to the entropy change (S) is the removal of
1

2
mol O
2, so that S is negative and roughly equal for all metals. The slope of the plots dG/dT =
S is therefore positive for all metals, with G always becoming more negative with lower
temperature, and the lines for all the metal oxides are approximately parallel. Since these
reactions are exothermic, they always become feasible at lower temperatures. At a
sufficiently high temperature, the sign of G may invert (becoming positive) and the oxide
can spontaneously reduce to the metal, as shown for Ag and Cu.
For oxidation of carbon, the red line is for the formation of CO: C(s) +
1

2
O
2(g) CO(g) with an increase in the number of moles of gas, leading to a positive S and a
negative slope. The blue line for the formation of CO
2 is approximately horizontal, since the reaction C(s) + O
2(g) CO
2(g) leaves the number of moles of gas unchanged so that S is small.
As with any chemical reaction prediction based on purely thermodynamic grounds, a
spontaneous reaction may be very slow if one or more stages in the reaction pathway have
very high activation energies E
A
.
If two metals are present, two equilibria have to be considered. The oxide with the more
negative G will be formed and the other oxide will be reduced.
Salient features
1. Curves in the Ellingham diagrams for the formation of metallic oxides are basically
straight lines with a positive slope. The slope is proportional to S, which is fairly
constant with temperature.
2. The lower the position of a metal's line in the Ellingham diagram, the greater is the
stability of its oxide. For example, the line for Al (oxidation of aluminium) is found to
be below that for Fe (formation of Fe
2O
3).
3. Stability of metallic oxides decreases with increase in temperature. Highly unstable
oxides like Ag
2O and HgO easily undergo thermal decomposition.
4. The formation free energy of carbon dioxide (CO
2) is almost independent of temperature, while that of carbon monoxide (CO) has
negative slope and crosses the CO
2 line near 700 C. According to the Boudouard reaction, carbon monoxide is the
dominant oxide of carbon at higher temperatures (above about 700 C), and the higher
the temperature (above 700 C) the more effective a reductant (reducing agent) carbon
is.
5. A reduced substance (such as a metal), whose Gibbs free energy of formation is lower
on the diagram at a given temperature, will reduce an oxide whose free energy of
formation is higher on the diagram. For example, metallic aluminium can reduce iron
oxide to metallic iron, the aluminium itself being oxidized to aluminium oxide. (This
reaction is employed in thermite.)
6. The greater the gap between any two lines, the greater the effectiveness of the
reducing agent corresponding to the lower line.
7. The intersection of two lines implies an oxidation-reduction equilibrium. Reduction
using a given reductant is possible at temperatures above the intersection point where
the G line of that reductant is lower on the diagram than that of the metallic oxide to
be reduced. At the point of intersection the free energy change for the reaction is zero,
below this temperature 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.




Reducing agents
In industrial processes, the reduction of metal oxides is often effected by a carbothermic
reaction, using carbon as a reducing agent. Carbon is available cheaply as coal, which can be
rendered to coke. Moreover, when carbon reacts with oxygen it forms the gaseous oxides
carbon monoxide and carbon dioxide, so the thermodynamics of its oxidation is different
from that for metals: its oxidation has a more negative G with higher temperatures (above
700 C). Carbon can thus serve as reducing agent. Using this property, reduction of metals
may be performed as a double redox reaction at relatively low temperature.
Use of Ellingham diagrams
The main application of Ellingham diagrams is in the extractive metallurgy industry, where it
helps to select the best reducing agent for various ores in the extraction process, purification
and grade setting for steel manufacturing. It also helps to guide the purification of metals,
especially the removal of trace elements. The direct reduction process for making iron rests
firmly on the guidance of Ellingham diagrams, which show that hydrogen can alone reduce
iron oxides to the metal.
Reducing agent for haematite
In iron ore smelting, haematite gets reduced at the top of the furnace, where temperature is in
the range 600 700 C. The Ellingham diagram indicates that in this range carbon monoxide
acts as a stronger reducing agent than carbon since the process
2 CO + O
2 2 CO
2
has a more-negative free energy change than the process:
2 C + O
2 2 CO.
In the upper part of the blast furnace, haematite is reduced by CO (produced by oxidation of
coke lower down, at higher temperatures) even in the presence of carbon though this is
mainly because the kinetics for gaseous CO reacting with the ore are better.
Reducing agent for chromic oxide-carbon cannot be used
The Ellingham curve for the reaction 2C(s) + O
2(g) 2CO(g) slopes down and falls below the curves for all the metals. Hence, carbon can
normally act as a reducing agent for all metal oxides at very high temperatures. But
chromium formed at these temperatures reacts with carbon to form its carbide, which gives
undesirable properties to the chromium metal obtained. Hence, for high temperature
reduction of chromic oxide, carbon cannot be used.
Alumino thermic process

Thermite reaction proceeding for a railway welding. Shortly after this, the liquid iron flows
into the mould around the rail gap
The Ellingham curve for aluminium lies below the curves of most metals such chromium,
iron, etc. This fact indicates that aluminium can be used as the reducing agent for oxides of
all these metals. This result is illustrated as follows:
The free energies of formation of chromium(III) oxide and aluminium oxide per mole of
oxygen consumed are -540kJ and -827kJ respectively. The processes are:
(1)
(2)
The second equation minus the first equation gives:


So aluminium oxide is more stable than chromium oxide (at least at normal temperatures, and
in fact all the way up to the decomposition temperatures of the oxides). Since the Gibbs free
energy change is negative, aluminium can reduce chromium oxide.
In pyrometallurgy, Al is used as a reducing agent in the alumino-thermic process or thermite
process to extract Cr and Mn by reduction of their oxides.
References
1. Ellingham, H. J. T. (1944), "Transactions and Communications", J. Soc. Chem. Ind.
(London) 63 (5): 125, doi:10.1002/jctb.5000630501.
2. Atkins, Peter; de Paula, Julio (2006), Physical Chemistry: Thermodynamics And
Kinetics (8th ed.), W.H. Freeman, p. 215, ISBN 0716785676. This reference plots the
diagram upside-down, with G decreasing upwards.
3. Ellingham diagram tutorial and interactive diagram (University of Cambridge)