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Ellingham Diagram: Gibbs Free Energy Vs Temperature Diagrams For M-MO Systems

The Ellingham diagram graphs the standard free energy of formation (ΔG°) of metal oxides against temperature. It allows assessment of: 1. The relative thermal stabilities of oxides based on their position - lower lines indicate more stable oxides. 2. Possible reduction reactions and temperatures - intersections identify equilibrium temperatures for carbon to reduce a metal oxide. 3. Selection of appropriate reducing agents using free energy changes - the more negative ΔG° indicates a thermodynamically favored reduction.

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Pransh Khubchandani
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580 views25 pages

Ellingham Diagram: Gibbs Free Energy Vs Temperature Diagrams For M-MO Systems

The Ellingham diagram graphs the standard free energy of formation (ΔG°) of metal oxides against temperature. It allows assessment of: 1. The relative thermal stabilities of oxides based on their position - lower lines indicate more stable oxides. 2. Possible reduction reactions and temperatures - intersections identify equilibrium temperatures for carbon to reduce a metal oxide. 3. Selection of appropriate reducing agents using free energy changes - the more negative ΔG° indicates a thermodynamically favored reduction.

Uploaded by

Pransh Khubchandani
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Ellingham Diagram

Gibbs Free Energy vs


Temperature Diagrams for
M-MO Systems
Metal Extraction
Which one to choose
as a reducing agent ?
What is my reduction
temperature ?

Metallurgical Coke Calcium

Aluminum
Steel Making -Basic Oxygen Furnace

What is the possible


reaction ?
[Fe] + [O] = (FeO)
[C] + [O] = {CO}
Thermal Stability of Materials
Synthesis of Advanced Materials and Devices
oxidation reaction between 1 mole of a metal (M) with 1
mole of oxygen gas to produce 1 mole of the metal oxide,

M(s) + O2(g) = MO2 (s) with K = 1 / pO2


H.J.T. Ellingham
+ ive

ΔG° = – RT lnK = – RT ln (1/ pO2) = RT ln pO2


If K > 1
ΔGO

then ln K is positive, ΔGo is negative and the forward reaction is favorable.


if K = 1
0 then ln K is zero, ΔGo is zero and the reaction is at equilibrium.
ΔGo(T) = A + BT (slope intercept form)
by neglecting ln T, T2 and 1/T
- ive

ΔG° = ΔH° – TΔS°


‘A’ term corresponds to ΔH & B term corr. to ΔS
For oxidation reactions, slope is positive
T0
0k Temperature, T
General Oxidation Reaction
22. 4 Ag + O2 = 2Ag2O
21. 4Cu + O2 = 2Cu2O
20. 4 Fe3O4 + O2 = 2 Fe2O3
19. 2 Pb + O2 = 2 PbO
18. 2 Ni + O2 = 2 NiO
17. 2H2 + O2 = 2 H2O
16. 2CO + O2 = 2 CO2
15. 2 Fe + O2 = FeO2
14. 6 FeO + O2 = 2 Fe3O4
13. 2/3 Fe + O2 = 1/2 Fe3O4
12. 2Zn + O2 = 2 ZnO
ΔGO

11. 4/3 Cr + O2 = 2/3 Cr2O3


10. 4 Na + O2 = 2 Na2O
S 9. 2Mn + O2 = 2 MnO
B 8. 4/3 V + O2 = 2/3 V2O3
7. Si + O2 = SiO2
M
6. Ti + O2 = TiO2
5. U + O2 = UO2
4. 4/3 Al + O2 = 2/3 Al2O3
Temperature, T 3. 4 Li + O2 = 2 Li2O
24. C + O2 = CO2 2. 2Mg + O2 = 2 MgO
23. 2 C + O2 = 2 CO 1. 2Ca + O2 = 2 CaO
Features of Ellingham Diagram
 As per standard relation for free energy change of a
reaction : .

ΔG° = ΔH° – TΔS°

 Thus ΔH°,the standard enthalpy or standard heat


of formation of oxide, can be obtain from the
intercept of the line; and the standard entropy of
formation of oxide, can be obtained from the
slope of the line.
In all cases: 2 M(s) + O2(g) = 2MO (s)

Entropy change (ΔS) = (ΔS) Product - (ΔS) Reactant

= (ΔS) Solid - (ΔS) Gas = - ive

Therefore ΔG° = ΔH° – T (-ΔS°) = + ive

Positive slope  Slopes are upward direction


In case of: 2 C(s) + O2(g) = 2CO (g)

Entropy change (ΔS) = (ΔS) Product - (ΔS) Reactant

= (ΔS) gas,2m - (ΔS) Gas, 1m = + ive

Therefore ΔG° = ΔH° – T (+ΔS°) = - ive

Negative slope  Slope in downward direction


In case of: C(s) + O2(g) = CO2 (g)

Entropy change (ΔS) = (ΔS) Product - (ΔS) Reactant

= (ΔS) gas,1 m - (ΔS) Gas, 1 m ≈ 0

Therefore ΔG° = ΔH° – T (+ΔS°) = ΔH°

Slope zero  Horizontal line with T axis


The lines are straight lines with kinks . The kinks corresponds
to the phase changes either in metal or its oxide due to

 Melting
 Boiling
 Sublimation
 Transition

At melting/boiling/sublimation/transition the entropy will


change hence the slope of the line also changes. The slope of
the line is much sharper for boiling or sublimation compare to
melting.
Reduction of Metal oxide by Carbon
Unlike other cases , in case of 2C + O2 = 2 CO the slope
decreases as entropy increases. i.e ΔG0 of CO is more negative
than the metal oxide above the T of intersection.

This means CO is more stable than MO


Thus Carbon will reduce MO above the intersection temp.

The temperature at which a line of any M-MO intersects with


C-CO line, indicates the equilibrium temperature of reduction
of MO by C at 1 atm pr.

Example: Temperature of Reduction by C for : MnO --> 1400C ;


Al2O3 = 2000 C
Two intersecting lines
Stability Regime of CO and CO2
As shown in the Ellingham diagram the lines C-CO2 and C-CO
cross each other at 723 C .

This indicates CO2 is more stable than CO and above 723 C CO


is more stable.

Thus , reduction of any MO below 723 C produces CO2 and


above 723 C produces CO

Example :
2PbO + C = 2 Pb + CO2 at 100C
ZnO + C = Zn + CO at 1200 C
Selection of Appropriate Reducing Agent for any MO
It is not necessary that two curves M- MO should intersect each other for
reduction.

The metal oxide lying at the bottom of the Ellingham diagram is more stable
than the one lying above it. (Since ΔG is more negative)

Example : Reduction of Cr2O3 by Al or Pb at 1200 C


4/3 Cr + O2 = 2/3 Cr2O3 ΔG = -120 kcal/mol.
4/3 Al + O2 = 2/3 Al2O3 ΔG = -190 kcal/mol.
2 Pb + O2 = 2PbO ΔG = -40 kcal/mol.

Case I : 2/3 Cr2O3 = 4/3 Cr + O2


4/3 Al + O2 = 2/3 Al2O3
-------------------------------------------------
by adding 2/3 Cr2O3 + 4/3 Al = 4/3 Cr + 2/3 Al2O3
ΔG = + 120 – 190 = - 70 kcal/mol. Feasible

Case II : 2/3 Cr2O3 = 4/3 Cr + O2


2 Pb + O2 = 2 PbO
-------------------------------------------------
by adding 2/3 Cr2O3 + 2 Pb = 4/3 Cr + 2 PbO
ΔG = + 120 – 40 = + 80 kcal/mol. Not Feasible
Comparative Stability of Oxides
If the line of M-MO, which is in lower position than the other
MO is more stable. Stability of oxide increases with lowering
the position of oxide.

Al2O3 is more stable than Cr2O3 and PbO.


Additional Scales on Ellingham Diagram
Reading Equilibrium Partial
Pressure from Ellingham Diagram
PO2
PCO/ pCO2
PH2O/ pH2
M(s) + H CO(g)
O22(g) ==MM(s)
MO (s)
2
+
(s)+H2O
CO2 (g)
(g)
ΔG 0
ΔG0= = –– RT
RT ln
ln (P
(1/H2O
pO2
CO2 / )p=CO ) ln pO2
H2RT
= RT ln (PH2 CO// ppH2O
CO2)
Assessment Relative
Stabilities of Compounds

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