Ellingham Diagrams

• Shows free energy of formation of

compounds of a similar type as a function
of temperature
• Shows relative stabilities of the
compounds
• First introduced for oxides
• Referred to as Ellingham diagrams

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• The entropy and enthalpy of formation of a
compound do not change significantly with
temperature unless there is a change of
state
• Standard free energy change for the
formation of a compound is a linear
function of temperature if state is constant

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• For M + O2 = MO2 the free energy change

G  H  TS  H
o
T
o
T
o
T
o
298  TS 0
298

• Values of ΔHo (enthalpy change) and ΔSo (entropy

change) are available in the literature
• It should beo noted that o
S  S products  S reac tan ts
o

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• The slopes of the lines are similar apart
from the lines for oxidation of C and S
• For C + O2 = CO2 there is a small volume
change and the line is horizontal
• For 2C + O2 = 2CO there is an increase in
volume and the slope (-ΔSo) is negative
• For 1/2S2 + O2 = SO2 there is a small
increase in volume
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham diagrams
• An element can reduce the oxide of any
element above it at a particular
temperature
• We can distinguish three groups
1. Upper third: noble and common base
metals (Cu, Pb, Ni, Fe, Sn)
2. Deoxidisers (Si, Mn, Cr, V, Ti)
3. Stable refractory oxides (Al, Zr, Ca, Mg)
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• Where lines cross the relative stabilities of
the oxides change with increasing
temperature
• From a practical point of view the most
important line is for CO (2C + O2 =2CO)
which slopes downwards
• The temperature at which the lines cross
is the temperature above which reduction
of the metal oxide is possible
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• Can superimpose nomographic scales around
the diagram
• For the reaction M + O2 = MO2
 a MO2 
G  G o
 RT ln  
 a M . PO 
 2 

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• If oxygen gas at less than 1 atm is in equilibrium
with a pure metal and its pure oxide, ΔG = 0 and
the activities of the condensed phases are unity,
and
1
G o
  RT ln  RT ln PO2
PO2

So if ΔGo and T are known we can calculate the

equilibrium oxygen partial pressure for the
reaction
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams

• Effect of carbon and hydrogen as reducing

agents can also be assessed
• MO(s) + CO(g) = M(s) + CO2(g) can be
considered as a two-stage reaction
• 2M + O2 = 2MO ΔGo1 ………………(1)
• 2CO + O2 = 2CO2 ΔGo2……………….(2)
• Subtracting 1 from 2
• 2MO +2CO = 2M +2CO2 ΔGo3 = ΔGo2 –ΔGo1…(3)
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• The free energy change for reactions 1
and 2 at a given temperature can by
determined from the Ellingham diagram
and hence the free energy change for the
overall reaction can be determined.
• The equilibrium CO/CO2 ratio can also be
determined

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• From reaction 3
 PCO 2 .a M 2 
G o
  RT ln  2 
3
 PCO 2 .a MO 2 
 
• For pure solids the activity is 1 and so
2
 PCO   PCO 
G 0
 RT ln   2 RT ln 
3
 PCO   PCO 
 2   2 

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• When ΔGo = 0, CO/CO2 = 1 and the line
2CO + O2 = 2CO2 can be extrapolated
back to the point C on the - ΔGo axis at
T = 0oK
• We can construct a second nomograph
around the diagram to give the CO/CO2
ratio at which a pure metal oxide is
reduced by CO
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Ellingham Diagrams
• Standard free energy – temperature
diagrams can also be constructed for other
compounds
• Those of most interest are sulphides and
chlorides.

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces