ELLINGHAM DIAGRAMS

What are Ellingham diagrams?

They are a series of representations commonly used in metallurgy, representing energy.

free of a reaction (ΔGdepending on the temperature (T). For a spontaneous reaction, the
The change in Gibbs energy, ∆ G, must be negative. The free energy of formation is
negative for the majority of oxides, and then in the diagram a ∆G=0 is written in the
upper part of the diagram, and the values of ∆G shown are all negative numbers.

This analysis is generally used to assess the ease of reduction of oxides and sulfides.
in metals. This taking into account that ∆H and ∆S are essentially constant with the
temperature unless a phase change occurs, the graph of free energy versus the
temperature can be plotted as a series of lines, where ∆S is the slope and ∆H is the
intercept with the Y axis. That is, if we have to:
ΔG=Δ H−T Δ S
ΔG

Figure 1.
And the diagram is representedΔG vs Tthen it can be said that:

ΔG= y
Δ H=n
T =x
ΔS=m
Taking this into account and reorganizing, we have to:
y=−xm
Thus we obtain the equation of a line, where we have the slope and the y-intercept.
origin, which is why it is reiterated that generally this type of equations generates lines. The
the slope of the line changes when any of the materials are mixed, melted or
vaporize.

ΔG

Figure 2.
However, several aspects need to be clarified; generally, the Ellingham diagram is one that
where we combine an element X with oxygen to form an oxide:
1
nX+ O 2 → m X O
2
To explain the behavior of the slopes of the lines in the Ellingham diagrams
we will proceed to study carbon in 3 cases:
C(s )+O 2 (g) CO 2(g) First Case

In this case, we are starting from reactants where there is 1 mole of gas and 1 mole is produced.
of gas, this means that the change in entropy will be very close to or practically 0
( ΔS≈0¿, therefore in the equationΔG=Δ H−TΔS, the termTΔSit will be practically 0
¿), therefore, the Gibbs free energy(ΔG¿ It will not vary with the temperature and this
it will finally give us a constant function.

ΔG

T
Figure 3. Graph ofΔG=Δ H−TΔS, whenΔS≈0

2C O( g) +O 2() → 2 C O 2(g) Second case

We start with 3 moles of gas in the reactants and obtain 2 moles in the product.
from gas, so we are moving from a state of more disorder to a state of less
disorder since there is less entropy, that is, the variation of entropy will be negative.
ΔS< 0, then in the equationΔG=Δ H−TΔS, TΔSit will be <0, then the equation remains
ΔG=Δ H− (−T Δ S → ) ΔG=ΔH+TΔSIn conclusion, the Gibbs free energy goes
increase depending on the temperature increase.
ΔG

T
Figure 4. Graph ofΔG=Δ H−TΔS, whenΔS<0

2 C (s) +O 2( g) → 2 C O( g) Third case

In this case, we have 1 mole of gas in the reactants and 2 moles of gas in the products.
taking this into account, disorder increases, therefore, entropy variation increases, it is
to say thatΔS> 0then in the equationΔG=Δ H−TΔSthe termΔS>0, then
we can assert that as the temperature increases, the function will decrease, that is, the higher
lower temperature free energy of Gibbs.
ΔG

T
Figure 5. Graph ofΔG=Δ H−TΔS, whenΔS>0

An Ellingham diagram typically consists of graphs of changes in Gibbs energy.

with the temperature for the formation of oxides [Figure 6], except for the three cases
previously explained about carbon.
1
M (s )+ O 2 (g) → M O ()where M is the metal, and 0 is the oxygen
2
Most of the lines with positive slope are because the metal and the oxide are present.
as condensed phases (solid or liquid). Then in the different reactions, it
a gas reacts with a condensed phase to form another condensed phase, which reduces the
entropy. To explain what has been said, we have to:
Figure 6. Oxide formation graph ΔG°( Kcal) vsT(° C )
1 1
M+
From the equation (s ) O→M
2 (g) O (s )there are moles of gas in the reactants and 0 moles of gas
2 2
in the products which makes thatΔS<0 and in turnΔGbe less negative so that the
The slope of the line for oxidized metals will always be increasing.

When the temperature rises, a point will be reached where the graph crosses the line.
Δ G=0". Below this temperature, the free energy of formation of the oxide is negative.
so the oxide is stable. Above this temperature, the free energy of formation
The oxide is positive, the oxide becomes unstable and will decompose into metal and dioxygen.
Any metal will reduce the oxide of another metal that is above it in a
Ellingham diagram. For example: Al reduces FeO, CrO, and NiO in the thermite reaction, but the
Alno reduces MgO at a temperature below 1500 °C, [see in figure 6].

Ellingham diagrams

Richardson added another scale to the diagrams, where it is stated that at any temperature the
the variation of standard free energy is given by:
ΔG°=−RTlnPO 2

But
G=G°+ RTlnP
ThereforeΔG°it can be seen as the decrease in free energy of one mole of oxygen (g)
when its pressure decreases from 1 atm to P O2 ATM at temperature T.

For a decrease in pressure of one mole of an ideal gasΔGit is a linear function of the
the temperature and the slope of the line is RlnP, thereforeΔGit will become more negative with the
temperature if P<1 and more positive
if P>1. All the lines will start from
ΔG=0yT=0
[Figure 7].
 Figure 7.
Diagram

ΔG°=−RTlnPO 2
Figure 8. Ellinghman diagram when ΔG°=RTln P O2 vs T for some oxides

Applications of the diagram

There are three main uses of Ellingham Diagrams:

1. To determine the ease of reducing a given metallic oxide to metal, in metallurgy, the
Ellingham diagrams are used to predict the equilibrium temperature between a metal,
its oxide and oxygen, and, by extension, the reactions of a metal with sulfur, nitrogen, and
other non-metallic elements.

2. To determine the partial pressure of oxygen that is in equilibrium with a metal oxide at
a given temperature. When the values ofΔG°F for oxides, the diagram of
Ellingham offers a simple and useful way to estimate the partial pressure of oxygen in equilibrium.
as a function of temperature. Therefore, it can be used to predict temperatures
the temperatures at which a metal is stable and the temperatures at which it will oxidize spontaneously. For
temperatures at which the free energy of formation of the oxide is positive, it is favored the
reverse reaction and the oxide will spontaneously decompose into the metal.

3. To determine the range between carbon monoxide and carbon dioxide that it will be able to
to reduce the oxide to metal at a given temperature.

Ellingham diagrams can be very useful in solving problems of

thermal treatment related to the use of protective atmospheres, especially for
determine whether a particular atmosphere is oxidizing or reducing to the metal or alloy
in question. However, using it without understanding can lead to incorrect conclusions.
It is important to understand that the diagram relates to the condition of equilibrium and not
Take into account the kinetics. It is also assumed that there are sufficient oxidizing species.
gifts for the reaction to continue. Some industrial examples illustrate how these
properties can affect the interpretation of the results.

General exercise on Ellingham diagrams:

Can metallic copper be obtained by oxidizing cuprous sulfide, Cu?2Is it at 1200°C? Having in
count figure 8 and approximate values forΔG°

Additional data:
o
Cu2S + O2Cu2O + S2, ΔG(T ) = 0 kJ.

In the diagram we can verify that theΔG° for:

Considering that 1 Kcal = 4.18 KJ

33 kcal
Formation of Cu2O, ΔGº≈−
f =−137.94 kJ/mole2
molO2
60kJ
Formation of the OS2, ΔGº≈−
f =−250.8 kJ/molO2
mole2
1 1
2 S+ O⇔Cu
- See you, 2 O+
2 S 2 ΔGº=0 kJ
2 2

(A) 4Cu+O2⇔2Cu 2O ΔG
º( 1200°C)=−137.94 kJ/molO2
1
(B) S +O SO ΔG
º( 1200°C)=−250.8 kJ/mole2
2 2 2 2
1 1
(C) See you2S +O Cu O+ S2 ΔGº=0kJ
2 2 2 2
Multiplying A*-1 and then adding -A+B+C results in:
1
(D) O 2 ⇔4Cu+SO2
See you2S + See you2O+
2
Equation for obtaining blister copper from a copper matte mixture
copper sulfide-oxides in molten state
To findΔG-A+B+C

ΔG
°(D)=− ΔGº(1200° C)( A)+ΔG º(1200°C)(B)+Δ G º (1200°C)( C)
kJ
ΔG
º( D)=−112.86
molSO2
The P(SO2in the gas is 0.12 atmospheres (12% SO)2)
The P(O2In the gas it is 0.12 atmospheres (excess air) (12%)

o
To calculate the pressure of O2keep in mind that ΔG (T ) it can be expressed as:

Julios ΔGº(T)=− RTlnK=− (1,987)(4,184)TlnK=− 19,14TlogK

[ P( products) a ]
Then ΔG=ΔG º+ RTln b
[ P (reactives) ]

0.12
ΔG ( D )=−112860 Julios+ 19,14Tlog
√0.12
ΔG ( D )=−112860 Joules+ 19,14 ( 1473 ) log0.35Joules
ΔG=−
(D
125714.18
) Joules=−125,714 KJ
It can finally be concluded that the process is thermodynamically favorable.

REFERENCES:

1. Ellingham, HJT; J. Soc. Chem. Ind. (London) 1944, 63, 125.

DeHof, RT;Thermodynamics in Materials Science, McGraw-Hill: New York, 1993.

3. Lupis, CHP; Chemical thermodynamics of materials, North Holland and Elsevier: New
York, 1983.
4. Ponga, PJ van der; Inorganic chemistry of materials, Plenum Press: New York, 1998.

5. McGlashan, ML; Chemical Thermodynamics, Academic Press: London, 1979.

6. Chase Jr., MW; Davies, CA; Downey Jr., JR; Frurip, DJ; McDonald, RA; Syverud, AN; Tabs
JANAF thermochemical,3rded., J. Phys. Chem. Ref. Date 1985, 14, suppl. 1.

7. DeVoe, H.; Thermodynamics and Chemistry, Prentice Hall: Upper Saddle River (New Jersey),
2001.

8. Denbigh, K.; The Principles of Chemical Equilibrium,4thed, Cambridge University Press:

Cambridge, 1981.

9. Nexgurukul, (February 8). Academic area of metallurgy.

htInvalid URL format. Please provide text for translation.

10. [Link]. htps://[Link]/site/portfolio54037/diagrams-of-

ellingham