INORGANIC CHEMISTRY ELLINGHAM DIAGRAM

 THERMODYNAMICS OF REDUCTION PROCESSES (ELLINGHAM DIAGRAM)

The extraction of metals from their oxides using carbon or other metals, and by thermal decomposition,
involves a number of points which merit detailed discussion.
For a spontaneous reaction, the free energy change G must be negative.
G = H – TS
H is the enthalpy change during the reaction, T is the absolute temperature, and S is the change in
entropy during the reaction. Consider a reaction such as the formation of an oxide:
M + O2  MO
Dioxygen is used up in the course of this reaction. Gases have a more random structure (less ordered)
than liquids or solids. Consequently gases have a higher entropy than liquids or solids. In this reaction
S the entropy or randomness decreases, the hence S is negative. Thus if the temperature is raised
then TS becomes more negative. Since TS is subtracted in the equation, then G becomes less
negative. Thus the free energy changed increases with an increase of temperature.
0
–100
 2Cu2O
–200 4Cu + O2
FeO
2
–300 + O2 C + O2  CO2
2Fe
Gº/kJ mol–1 of O2

–400 CO 2
2 2C +
O2 
–500 +O 2

2CO ZnO 2CO

2
+ O2
–600 2Zn
–700
A
–800
3Al 2O 3
–900 O  2/
l+ 2
4/3A gO
–1000 O  2M
+ 2
2Mg
–1100
–1200

0ºC 400ºC 800ºC 1200ºC 1600ºC 2000ºC

273 K 673 K 1073 K 1473 K 1873 K 2273 K
Temperature
The free energy changes that occur when one gram molecule of a common reactant (in this case
dioxygen) is used may be plotted graphically against temperature for a number of reactions of metals
of their oxides. This graph is shown in figure and is called an Ellingham diagram (for oxides). Similar
diagrams can be produced for one gram molecule of sulphur, giving an Ellingham diagram for sulphides,
and similarly for halides.

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 The Ellingham diagram for oxides shows several important features:
(i) The graph for metal oxide all slope upwards, because the free energy change increases with an
increase of temperature as discussed above.
(ii) The free energy changes all follows a straight line unless the materials metal or vaporize.
(iii) When the temperature is raised, a point will be reached where the graph crosses the G = 0
line. Below this temperature the free energy of formation of the oxide is negative, so the oxide
is stable. Above this temperature the free of formation of the oxide is positive, and the oxide
becomes unstable, and should decompose into the metal and dioxygen.
(iv) Any metal will reduce the oxide of other metals which lie above it in the Ellingham diagram
because the free energy will become more negative by an amount equal to the different between
the two graphs at that particular temperature.
Limitations of Ellingham Diagram
(i) The graph simply indicates whether a reaction is possible or not i.e., the tendency of reduction
with a reducing agent is indicated. This is so because it is based only on the thermodynamic
concepts. It does not say about the kinetics of the reduction process (Cannot answer questions
like how fast it could be ?).
(ii) The interpretation of G is based on K(G = – RT lnK). Thus it is presumed that the
reactants of products are in equilibrium.

1. Bauxite, Al2O3. x H2O Electrolysis of Al2O3 dissolved in For the extraction, a good source of
Aluminium
2. Cryolite, Na3AlF6 molten Na3AlF6 electricity is required.

1. Haematite, Fe2O3 Reduction of the oxide with CO Temperature approaching 2170 K is

Iron
2. Magnetite, Fe3O4 and coke in Blast furnace required.
It is self reduction in a specially
1. Copper pyrites, CuFeS2 designed converter. The reduction
2. Copper glance, Cu2 S Roasting of sulphide takes place easily. Sulphuric acid
Copper
3. Malachite, CuCO3.Cu(OH)2 partially and reduction leaching is also used in
4. Cuprite, Cu2O hydrometallurgy from low grade
ores.
1. Zinc blende or Sphalerite, ZnS
Roasting followed by reduction The metal may be purified by
Zinc 2. Calamine, ZnCO3
with coke fractional distillation.
3. Zincite, ZnO

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 ELLINGHAM'S DIAGRAMS ASSIGNMENT-1 INORGANIC CHEMISTRY

Paragraph for Questions 1 and 4

Ellingham diagram is a graph showing the variation of the standard free energy of formation (Gº) of metal
oxides with temperature. The diagram also shows lines for formation of CO and CO2.
Ag2O
+250 CuO

0
CO 2
CO
ZnO
FeO
Gº\kJ

CCO2

–500

SiO2
CCO
Al2O3
TiO2 MgO
CaO
–1000

500 1000 1500 2000 2500

Temperature/ºC

Using the Ellingham diagram given above answer the following.

1. The equation of lines in the diagram is given by
(A) G = H – TS (B) G = H + TS
(C) Gº = Hº – TSº (D) Gº = Hº + TSº
2. The statement that is true for the line C  CO2 is
(A) The standard entropy change of the above reaction is positive
(B) The standard entropy change of the above reaction is negative
(C) The standard entropy change of the above reaction is almost zero.
(D) None of these
3. The statement that is true for the line CO  CO2 is
(A) the standard entropy change of the above reaction is positive
(B) the standard entropy change of the above reaction is negative
(C) the standard entropy change of the above reaction is zero.
(D) None of these
4. The preferred temperature for Mg to be used as a reducing agent for SiO2 is
(A) below 2200ºC
(B) above 2500ºC
(C) not possible at any temperature
(D) None of these

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 Paragraph for Q.5 to Q.7
Ellingham diagram reveals that the curves involving the formation of MgO, ZnO and CO can be given as
above. On the basis of these curves answer the following questions :-

2C +
-200 O2 
2 CO
-400
-600
gO
2M
-800 O2
g+
2M
-1000

500 1000 1500 T(°C)

5. Gº vs T plot in Ellingham diagram slopes downward for the reaction -
(A) 2Mg + O2 
 2MgO (B) 2Zn + O2 
 2ZnO
(C) 2CO + O2   2CO2 (D) 2C + O2   2CO
6. At what temperature , Zn and carbon have equal affinity for oxygen -
(A) 500ºC (B) 1000ºC (C) 1200ºC (D) 1500ºC
7. At this temperature Gº of this reaction is : ZnO + C 
 Zn + CO
(A) Positive (B) Zero (C) Negative (D) Cannot be predicted
Paragraph for Q.8 to Q.10
The Ellingham diagram represent the formation of oxides of several metals together with oxides of
C (i.e. CO and CO2). The diagram given below is not to scale yet it can help in making a lot of predictions.
FeO
Fe
0
O2
O 2
C
+½
CO
ºC
710 CCO2
Gº in kJ mol—1

Cr 2O
3

Cr
SiO 2
i
TiO
2
C
T
Si CO
50 0ºC
1
ZrO 2
Al 2O 3 Zr
Al 1105ºC

gO
MgM 649ºC

Temperature in ºC
8. Which is the chief reducing agent if the carbon reduction of iron oxides is carried out below 710ºC?
(A) CO (B) C
(C) Either C or CO (D) Cannot be predicted on the basis of give information

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 9. At ~ 1100ºC, which of the following reactions is thermodynamically most favourable ?
(A) TiO2 + C  Ti + CO2 (B) CO2 + C  2CO
(C) Al2O3 + 3C  2Al + 3CO (D) Cr2O3 + 3C  2Cr + 3CO
10. Which of following statements is incorrect ?
(A) Si cannot reduce MgO at all
(B) Al can reduce MgO at above 1500ºC
(C) Al can reduce Cr2O3 as well as TiO2
(D) Al cannot reduce ZrO2 but Mg can reduce ZrO2 at 1000ºC
11. Statement-1 : Al cannot reduce MgO below 1500ºC while Al can reduce MgO above 1500ºC.
Statement-2 : Mg is a liquid at less than 1500ºC and gas at above 1500ºC.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
12. Choose CORRECT statement based on Ellingham diagram :
(A) Reduction of metal oxides takes place at room temperature only
(B) A particular metal oxide can be reduced by many reducing agents but temperature for reduction is
same for all reductants
(C) Suitable reducing agent for metal oxide reduction is predicted on the basis of enthalpy change of
reaction
(D) None of these
13. If Ellingham graph for an element E(s) runs parallel to the temperature axis upto some fixed temperature 'T'
from it's starting point then select CORRECT statement :
(A) Element will have melting point and boiling point both before temperature 'T'
(B) Gº value for the reaction E(s) + O2(g)  EO2(g) will be zero upto temperature 'T'
(C) S value for the reaction E(s) + O2(g)  EO2(g) will be  0 upto temperature 'T'
(D) Both (B) and (C) are correct
14. Which of the following statement about Ellingham diagram is CORRECT :
(A) On increasing temperature, stability of metal oxides increases
(B) Reduction of metal oxide is easier if the metal formed is in liquid state than solid state at the temperature
of reduction
(C) Reduction of metal oxide is easier if the metal formed is in solid state than liquid state at the temperature
of reduction
(D) All above statements are correct

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 PARAGRAPH
Ellingham diagram is the key to find suitable reducing agent for the reduction of metal oxide.
Consider the following graph

(3)

Gº / kJ mol of O2 (2)

—1

(1)

T1
Temperature (ºC)

15. Select correct statements based on the above graph :

(A) For reaction (2) Gº increases with increase in temperature
(B) For reaction (3) Gº increases with increase in temperature
(C) For reaction (1) Gº increases with increase in temperature
(D) All are correct
16. Choose incorrect statement out of following :
(A) At temperature 'T1', Gº values for reaction (1), (2) and (3) are non-zero
(B) For reaction (1), S is negative
(C) For reaction (3), S is positive
(D) For reaction (3), S is negative
17. Match the column
Column-I Column-II
Element Property based on Ellingham diagram
(A) Mg (P) Highest value of |Gº| amongst the column -I element's oxide formation
(B) Al (Q) Lowest value of |Gº| amongst the column -I element's oxide formation
(C) Fe (R) Can reduce atleast one metal oxide of given elements
(D) Hg (S) Best reducing agent among these
(T) It's metal oxide has lowest thermal stability among oxides of
the column -I metals

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 18. Column-I Column-II
Reaction Property based on Ellingham diagram given
on page no. 1
(P) C(s) + O2(g)  CO2(g) (1) S  0
1
(Q) Ca(s) + O (g)  CaO(s) (2) S is negative
2 2

3
(R) 2Al(s) + O (g)  Al2O3(s) (3) S is positive
2 2

1
(S) C(s) + O (g)  CO(g) (4) Most feasible reaction at low temperature
2 2
Code :
(P) (Q) (R) (S)
(A) 1 2 2, 4 3
(B) 1 2, 4 2 3
(C) 1 2, 3 3 4
(D) 3 2 1 3, 4
19. In Ellingham diagram Fe2O3 can be reduced by how many of the following elements.
Ca, Mg, Ag, Hg, Al
20. Find the number of unstable oxides below temperature 200ºC out of following oxides.
CaO, MgO, Al2O3, Fe2O3

21. It is the plot of DG° vs T for Pb ® PbO

1535°C

888°C
DG°
1749°C
327°C

T°C
Find the sum of values of boiling point of Pb and melting point of PbO in K.

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 ELLINGHAM'S DIAGRAMS ASSIGNMENT-1 INORGANIC CHEMISTRY

1. Ans. (C)
2. Ans. (C)
3. Ans. (B)
4. Ans. (A)
5. Ans. (D)
6. Ans. (B)
7. Ans. (B)
8. Ans. (A)
9. Ans. (B)
10. Ans. (A)
11. Ans. (C)
12. Ans. (D)
13. Ans. (C)
14. Ans. (B)
15. Ans. (C)
16. Ans. (D)
17. Ans. (A)  P, R, S ; (B)  R ; (C)  R ; (D)  Q, T
18. Ans. (A)  P ; (B)  Q, S ; (C)  Q ; (D)  R
19. Ans. (3)
20. Ans. (0)
21. Ans. (3183.00)

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 ELLINGHAM'S DIAGRAMS ASSIGNMENT-2 INORGANIC CHEMISTRY
0
–100
–200 2C +
O2 
–300 2C O
G(kJ/mol)
–400
–500
–600
–700
gO
–800 2M
–900 
g +O 2
Q.1 –1000 2M
–1100
–1200

T1 T2 T3
Temperature
Incorrect statements about the plot is / are:
(A) T1 and T2 are melting point & boiling point of Mg respectively.
(B) T1 and T2 are melting point & boiling point of MgO respectively.
(C) Reduction of MgO by coke is possible above T3
(D) Mg can be extracted from gaseous products by rapid cooling.

Comprehension
Comprehension (Q.2 to Q.4)
Questions given below are based on the given diagram for extractive metallurgy.
0
O
 2Zn
–200 2C+O  +O 2
2CO
2Zn
2

–400
G°,kJ

–600 b.p.
m.p.
–800
–1000
0
500 1000 1500 2000
Temperature, °C 
The points noted by arrows are the melting and boiling points of the metals zinc and magnesium. G° as
a function of temperature for some reactions of extractive metallurgy.
Q.2 At what approximate temperature, zinc and carbon have equal affinity for oxygen?
(A) 1000°C (B) 1500°C (C) 500°C (D) 1200°C
Q.3 At this temperature G° of the reaction is :
ZnO + C  Zn + CO
(A) – ve (B) +ve (C) zero (D) nothing can be said

Q.4 To make the following reduction process spontaneous, temperature should be :

ZnO + C  Zn + CO
(A) < 1000°C (B) > 1100°C (C) < 500°C (D) > 500°C but < 1000°C

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 Paragraph for question nos. 5 to 7
+ve

G°
XO 2
X
–ve YO 2
Y
ZO 2
Z

T1 T2 T3 T4
T
Q.5 Temperature T1 and T3 represents
(A) Melting point and Boiling point of Z (B) Melting point and Boiling point of ZO2
(C) Melting point of Z and ZO2 (D) Boiling point of Z and ZO2

Q.6 At T2 temperature, which of the following reaction is most fessible.

(A) Z + XO2  X + ZO2 (B) Z + YO2  Y + ZO2
(C) X + YO2  Y + XO2 (D) X + ZO2  Z + XO2
Q.7 At T4 temperature, the G for the reaction Y + ZO2  Z + YO2 is
(A) G = (+) (B) G = (–) (C) G = 0 (D) Can not be predicted
Paragraph for question nos. 8 to 10
Most metals are obtained from minerals. A mineral is obtained by mining and is a naturally occuring
substance with a range of chemical composition.
Q.8 Which of the following metal sulphide is reduced by self reduction
(A) Cu2S (B) PbS (C) HgS (D) All are reduced by self reduction

CO CO2
0
Fe O
–500 CCO2

C
CO
Q.9 –1000 MgO

500 1000 1500 1900 2000

Temperature(°C) 

Using the Ellingham diagram, show the temperature at which MgO can be reduced to metal by carbon.
(A) below 1500°C (B) below 1120°C (C) above 1900°C (D) below 1600°C

Q.10 Which of the following method is based upon realtive melting point of ore and impurty.
(A) Bessemerisation (B) Amalgamation (C) Liquation (D) Distillation

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 ELLINGHAM'S DIAGRAMS ASSIGNMENT-2 INORGANIC CHEMISTRY

1. B 2. A 3. C 4. B

5. A 6. A 7. C 8. D

9. C 10. C

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