Ellingham Diagram

Ellingham Diagram D E P A R T M E NT O F
Metallurgical Engineering
Institute of Technology Banaras Hindu University
 Ellingham diagrams are basically graphical

representation of G0 vs. T relations for the
chemical reactions of chemical and metallurgical
engineering interest.
 H. J. T. Ellingham in 1944, was first to plot the
standard free energy of formation of oxides against
temperature and these later became known as
Ellingham diagram.
 Later on the same plotting was applied for sulphides,
chlorides, fluorides etc.
 Oxide diagrams are mostly used in metallurgy.
Metallurgical Thermodynamics 1
D E P A R T M E NT O F
Features of Ellingham diagram D E P A R T M E NT O F
1) Formation reaction for oxides may be generalized as

2x 2
M + O2 (g) = Mx Oy
y y
Where the values of x and y will depend on the specific
compound. M and Mx Oy are general symbols for metal
and metal oxides, respectively.
Specific examples are
2 Ni + O2 (g) = 2 NiO
4 2
Al + O2 (g) = Al2O3
3 3
Free energy is an extensive property hence value ΔG 0

of a reaction would depend on the no. of moles involved.
In the Ellingham diagram 1 mole of O2constitutes the

basis in the oxide formation reaction.
Thus the values of ΔG 0 are per mole of oxygen.

S tan dard free energy means the reac tan t (metal)
and product are in their s tan dard state or pure
states e.g. at unit activity
2) Since G0 = H0 - T S0

The variation of H0 not being large, it can be
treated as constant over a wide range of
temperatures. S0 however, changes with
temperature particularly when gaseous phases are
involved with the condensed phases.
The plot of G0 against temperature is a straight
line. So the slope of the line is - S0 .
Let us consider the reaction

M(s) + O2 (g) = MO(s)
S0 = S0 (oxide) - S0 (metal) - S0 (oxygen gas)
since S0 (oxide) and S0 (metal) are practically the

same, the entropy change (S0) arises
predominantly due to disappearance of one mole
of oxygen gas and hence it is -ve.
So the slope of the line is positive.
The entropy changes of various such metal oxidation

process are expected to be substantially of the same
value. Therefore, the most of the oxide lines slope
upwards and parallel to each other.
The plot of G0 against temperature is a straight

line as long as there is no phase change (melting,
boiling, phase transformation) in either the reactant
and products. The reason is that when such phase
change takes place, there is a change in entropy and
since the change entropy is the slope of the line,
therefore when such changes takes place, the
straight line will change its slope.
let us consider the melting of reactant. The reaction is

M(l) + O2(g) = MO(s)
S0 = S0 (oxide) - S0 (metal (l)) - S0 (oxygen gas)
Since S0 (metal (l)) > S0 (metal (s))
S0 is more negative than when both were solid.
Hence the slope of the line will be further upwards
from the temperature of melting.
if the reactant boils. We can write
S0 (metal (g)) > S0 (metal (l))
S0 is more negative than when metal oxide was solid
and metal was liquid
Hence the slope of the line will be further upwards
from the boiling point.
llet’s consider the melting of product. The reaction is

M(s) + O2(g) = MO(l)
S0 = S0 (oxide(l)) - S0 (metal (s)) - S0 (oxygen gas)
Since S0 (oxide (l)) > S0 (oxide (s))
S0 is less negative than when both were solid

Hence the line will be bend downward with +ve slope from the
temperature of melting. if the product boils. We can write
S0 (oxide (g)) > S0 (oxide (l))
S0 is less negative than when metal oxide was liquid and metal
was solid
Hence the line will be bend further downward with +ve slope from
the temperature of melting.
3) The intercept of the 0

straight line with the
ordinate at absolute zero ΔG0
gives approximately the

value of H0, since from
ΔH0
the equation
G0 = H0 - T S0
when T = 0, G0 = H0
0 T/K
4) since G0 must have a negative

value for the reaction to take
0
place, it can be seen from this plot
that all metals shown below the
negative areas of G0 are oxidized ΔG0
spontaneously by oxygen while
those above are not e. g. gold
5) When a line touches the positive
regions of G0 this means beyond
that temperature no further
oxidation can take place or the
oxide formed in that region is
unstable or oxides will start 0 T/K
462 K
decomposing when G0 = 0. i. e

Ag2O will decompose at 462 K.
6) The stability of an oxide is directly 0

related to its - G0 values; less stable
oxides have a small - G0 and more
stable oxides have a high - G0 value.
ΔG0 -300 kJ
7) An oxide can be reduced by only
those metals below it in Ellingham
diagram; the reverse cannot take
place. For example at 1073 K, Cr2O3
can be reduced by aluminium but Al2O3
cannot reduced by chromium:
1073 K
T/K
8) G0 of an oxide may be greater

0
than another at low temperature but
becomes less than the other at higher
temperature. Thus while the MnO is
reduced by Na below 493 K, the
ΔG0
reverse is true above that temperature.
9)The line of the reaction C + O2 = CO2 C + O2 = CO2
runs nearly horizontally on the chart i.e
493 K
its slope is zero or practically there is
no entropy change for this reaction. T / K
This can be seen from the fact that the initial and final volumes are
practically the same which is the one volume of oxygen gas and one
volume of CO2, respectively; entropy of the solid being negligible.
10) The line for the reaction 0

2 C + O2 = 2CO runs
downwards i.e. it has a
negative slope, this is due ΔG0
to the large increase in
entropy: two volume of
gaseous CO are formed
from one volume of oxygen
gas. In this case G0
become more negative as T/K
the temperature increases.
11) That the line for CO formation 0

runs downward is of great
importance in pyrometallurgy. It
enables almost all the metal –
ΔG0
metal oxide lines meet C – CO
lines at high temperature. This
makes most the oxides unstable
beyond point of intersection.
This is called reversion of
stability. This means that
reduction of most metal oxides
by carbon is possible at high T/K
temperature.
2CO(g) + O2(g) = 2CO2(g); ΔS0 = -ve
C(s) + O2(g) = CO2(g); ΔS0 = 0
2C(s) + O2(g) = 2CO(g); ΔS0 = +ve
12) Carbon monoxide can reduce all oxides above the CO2
lines. For example at 7000C NiO can be reduced by CO
2 CO + O2 = 2 CO2 G0 = - 95 kcal.
2 Ni + O2 = 2 NiO G0 = - 75 kcal.
2CO + 2NiO = 2Ni + 2CO2 G0 = - 20 kcal.
13) All oxides above H2O lines can be reduced by H2 e.g at
7000C
2 H2 + O2 = 2 H2O G0 = - 92 kcal.
2 Co + O2 = 2 CoO G0 = - 75 kcal.
2CoO + 2 H2 = 2Co+ 2 H2O G0 = - 17 kcal.
Nomographic scale on D E P A R T M E NT O F
Ellingham Diagram
The diagram already described can be made more useful by

superimposing grids or nomographic scales around them.
1. PO2 grid : Consider the reaction involving the oxidation of pure
solid metal to pure solid oxide
2 M (s) + O2 (g) = 2 MO (s)
G0 = - R T ln (1 / PO2) = R T ln PO2
Hence knowing G0 and T the corresponding equilibrium PO2
can be calculated for any such reaction.
When G0 = 0, PO2 = 1 atm and the equilibrium PO2 values
radiate from the point ‘O’ on the G0 axis. For the fixed
values of PO2 the G0 is plotted as a function of T
2) CO / CO2 grid: For the reaction

2 CO + O2 = 2 CO2
G0 = - 135000 + 41.57 T cal / mole
G0 = - R T ln K = - R T ln (P2CO2 / P2CO . PO2)
RT ln PO2 = G0 - 2 R T ln (PCO / PCO2)
= - 135000 + 41.57 T - 2 R T ln (PCO / PCO2)
RT ln PO2 can be plotted as a function of
temperature for fixed values of CO / CO2. When
T = 0 , RT ln PO2 = - 135000 cal / mole. The
equilibrium (PCO / PCO2) values radiate from the
point ‘C’ on the G0 axis.
3. H2 / H2O grid: For the reaction

2 H2 + O2 = 2 H2O
G0 = - 118000 + 26.57 T cal / mole
RT ln PO2 = G0 - 2 R T ln (PH2 / PH2O)
= -118000 + 26.57 T - 2 R T ln (PH2 /
PH2O)
RT ln PO2 can be plotted as a function of
temperature for fixed values of H2 / H2O. When T
= 0 , RT ln PO2 = - 118000 cal / mole. The
equilibrium (PH2 / PH2O) values radiate from the point
‘H’ on the GMetallurgical
0 axis.Thermodynamics
23
Use of Nomographic Scale Institute of Technology Banaras Hindu University
O 0
Equilibrium
pCO /pCO2
ΔG0 Equilibrium
pH2/pH2O
H
Equilibrium
C pO2
T
0 K 0oC Temperature →
pO2
pCO / pCO2
pH2/ pH2O
Use of Nomographic Scale
Disadvantages of D E P A R T M E NT O F
Ellingham diagram Institute of Technology Banaras Hindu University
1) The diagram is applicable only for the substances present

in their standard states. But practically activity may not
be unity.
2) Compound whose formation lines are represented in the
diagram are assumed to be stoichiometric only which often
is not true.
3) The information regarding rate of the reaction can not be
obtained.
4) The diagram do not show the condition under which the
reaction tend to occur.
5) Where oxide formation lines in the diagram are close
together accurate measurement and subsequent calculation
is difficult.
6) The possibility of formation of intermetallic compound
between reactants and products is ignored
Problems
i. At what temps will carbon reduce a) SnO2(s) b) Cr2O3

(s) and c) SiO2(s)?
ii. Steam blown through hot coke gives rise to the fuel gas
mixture called water gas (CO+H2): C + H2O = CO + H2.
calculate the temperature the coke must be maintained
for the reaction to be feasible?
iii. At what temperature the Ag2O just begin to decompose
at one atmospheric pressure?
iv. In what temperature range can hydrogen be used to
reduce SnO2 to Sn?
v. Deduce the standard free energy change for the
reduction of Al2O3 by Mg at 1000 0C?
vi. Explain the reasons for the change in slope of the
following lines:
Problems
2Mg + O2 = 2 MgO at 1100 0C.

2Pb + O2 = 2 PbO at 1470 0C
4 Li + O2 = 2 Li2O at 1300 0C
VII. Estimate the standard free energy change for the following reaction at
1200 K.
a) reduction of copper (I) oxide with hydrogen and b) reduction copper oxide
(I) with carbon?
VIII. At what temperature is the reaction:
4/3 Cr + O2 = 2/3 Cr2O3 at equilibrium when PO2 is 10-14 atm.
VII. Calculate the equilibrium oxygen pressure between Al2O3 and Al at 1000 K.
Could a vacuum of 10-10 mm Hg prevent the oxidation of aluminum?
VIII. Suppose CaO is placed in a vacuume in which the partial pressure of oxygen
is 10-5 mm Hg at 1000 K. Will CaO be reduced?
IX. Which is the suitable material for the steam pipe Ni or Al?
X. What is the equilibrium CO / CO2 ratio at 1000K for the following reaction:
MnO + CO = Mn + CO2?
XI. At what temperature is the reaction PbO + H2 = Pb + H2O at equilibrium
when the H2 / H2O ratio is 1/104?
Ellingham Diagrams for Metallurgical Engineering
Non-Standard State Condition Institute of Technology Banaras Hindu University
• The pattern of lines on the standard Ellingham diagram is well

established since the reactants and products are assumed to
be in their standard states i. e. at unit activities.
• What will happen if the activities are less than one i. e. the
reactants and products individually or both are under non-
standard state condition?
• The free energy change for the reaction M + O2 = MO2 is

 a MO 2 
G  G  R T ln 
0

 a M . pO2 
• If all the reactants and products are in the standard state
then RT ln terms becomes zero and G = G0
• If M is not in standard state, but MO2 is in standard state

then
 1 
G  G 0  R T ln  
 a M . pO2 
 1 
• The values of the product  
depends only on
 M O2 
a . p
temperature because it is nothing but equilibrium constant.
• At given temperature if the activity of M decreases the PO2
will have to increase.
• By the same logic if the reactant activity is one but that of
product decreases then PO2 value would have to decrease to
maintain the equilibrium constant same for a fixed
temperature
O Reactant
M(s) + O2 (g) = MO2 (s) activity
decreases
If M is not in standard state,
but MO2 is in standard state ΔG Reactant
then
activity
 1  increases
G  G  R T ln 
0

 a M . pO2 
The values of the product
depends only on temperature
because it is nothing but T/K
equilibrium constant.
p O2
At given temperature if the activity of M decreases the PO2 will have

to increase.
By the same logic if the O product

reactant activity is one but activity
increases
that of product decreases
then PO2 value would have
ΔG
product
to decrease to maintain
activity
decreases
the equilibrium constant
same for a fixed temperature
a MO 2
ΔG = ΔG + R T ln
0
T/K
p O2 pO2
 If the activity of the

reactant decreases the
standard free energy –
temperature plot
rotates anti-clockwise
and If product activity
decreases it shall
rotate in clockwise
direction from the pivot
G0 = H0 on the free
energy axis.
Specific Non-Standard D E P A R T M E NT O F
State Reactions Institute of Technology Banaras Hindu University
 It can be best illustrated by

the reduction MgO by silicon.
2 MgO(s)+Si(s) = 2 Mg(g) +SiO2(s)
G01473 = + 272 kJ
 So there appears to be very
little chance of using silicon as a
reducing agent to produce
magnesium from magnesia.
 The above reaction is obtained
by the intersection of following
two lines:
2Mg (g)+O2(g) =
2MgO(s)
Si(s) + O2(g) =
SiO2 (s)
State Reactions
 From the van’t Hoff isotherm, the actual free energy change
of the this reaction is given by
 p 2
Mg . a SiO 2


G  G  R T ln 2
0 
 a MgO . a Si 
 
 If pMg and aSiO2 can be lowered sufficiently, G can be made

negative even though G0 is positive.
 PMg is lowered by working at a pressure of 10 – 3 atm.
 aSiO2 is lowered by adding sufficient CaO to form
orthosilicate (2 CaO. SiO2). A basic slag would give aSiO2 <
0.001.
State Reactions
The other typical example is reduction of silica by high

manganese ferro-manganese.
The silicon line is well below the manganese line and
therefore the reduction of solid silica by manganese under
standard condition does not arise.
However, if the silicon is dissolved in iron the activity of
silicon is reduced drastically and hence silicon line shall
rotate upwards.
Concurrently as the MnO activity is reduced because of its
combination with silica as manganese silicate the Mn line shall
rotate downwards.
The net result is that two lines intersect at reasonably low
temperature like 1000K and reduction is possible.
Mn(Fe-Mn) + SiO2(sand mould) = Si(Fe-Mn)+ MnO(slag)
State Reactions

Ellingham Diagram

Загружено:

Сведения о документе

Исходное описание:

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Ellingham Diagram

Загружено:

Авторское право:

Доступные форматы

Ellingham Diagram D E P A R T M E NT O F

 Ellingham diagrams are basically graphical

1) Formation reaction for oxides may be generalized as

Free energy is an extensive property hence value ΔG 0

In the Ellingham diagram 1 mole of O2constitutes the

Thus the values of ΔG 0 are per mole of oxygen.

2) Since G0 = H0 - T S0

Let us consider the reaction

since S0 (oxide) and S0 (metal) are practically the

The entropy changes of various such metal oxidation

The plot of G0 against temperature is a straight

let us consider the melting of reactant. The reaction is

llet’s consider the melting of product. The reaction is

Since S0 (oxide (l)) > S0 (oxide (s))

S0 is less negative than when both were solid

3) The intercept of the 0

gives approximately the

4) since G0 must have a negative

decomposing when G0 = 0. i. e

6) The stability of an oxide is directly 0

8) G0 of an oxide may be greater

10) The line for the reaction 0

11) That the line for CO formation 0

2CO(g) + O2(g) = 2CO2(g); ΔS0 = -ve

C(s) + O2(g) = CO2(g); ΔS0 = 0

2C(s) + O2(g) = 2CO(g); ΔS0 = +ve

The diagram already described can be made more useful by

2) CO / CO2 grid: For the reaction

3. H2 / H2O grid: For the reaction

1) The diagram is applicable only for the substances present

i. At what temps will carbon reduce a) SnO2(s) b) Cr2O3

2Mg + O2 = 2 MgO at 1100 0C.

Non-Standard State Condition Institute of Technology Banaras Hindu University

• The pattern of lines on the standard Ellingham diagram is well

• The free energy change for the reaction M + O2 = MO2 is

Non-Standard State Condition Institute of Technology Banaras Hindu University

• If M is not in standard state, but MO2 is in standard state

Non-Standard State Condition Institute of Technology Banaras Hindu University

At given temperature if the activity of M decreases the PO2 will have

Non-Standard State Condition Institute of Technology Banaras Hindu University

By the same logic if the O product

Non-Standard State Condition Institute of Technology Banaras Hindu University

 If the activity of the

 It can be best illustrated by

 If pMg and aSiO2 can be lowered sufficiently, G can be made

The other typical example is reduction of silica by high

Вам также может понравиться