CHAPTER 3.

Ellingham Diagram
Masakatsu Hasegawa
Graduate School of Energy Science, Kyoto University

3.3.1. STANDARD GIBBS ENERGY CHANGE OF FORMATION

OF COMPOUNDS


The standard Gibbs energy change of formation of a compound, DGf , is defined as
the Gibbs energy change when one mole of a compound is formed from elements at
1 atmospheric pressure and can be calculated as




DGf ¼ DHf  T DSf
2 3 2 3
ðT ðT
ð3:3:1Þ
¼ 4DH298 þ DCpdT 5  T 4DS298 þ ðDCp=T Þ dT 5

298 298

Ellingham [1] plotted the experimentally determined variation with temperature of

DGf
for oxides and sulfides and found that the relationship approximated to straight line
over the temperature ranges in which no phase transformations occurred. Thus, within


the limits of accuracy of the available thermodynamic data, the variation of DGf could be
formulated as


DGf ¼ A þ BT ð3:3:2Þ


where A and B were constants. Figure 3.3.1 shows the DGf  T relations for oxidation
reactions involving one mole of gaseous oxygen; such a figure is called the Ellingham
diagram. The thermodynamic data used in this figure are cited from the compilation
by Kubaschewski et al. [2]. For example, they gave the following expression for oxidation
of manganese:
2MnðsolidÞ þ O2 ðgasÞ ¼ 2MnOðsolidÞ ð3:3:3Þ


DGf ð3:3Þ=J mol1 ¼ 769,440 þ 145:6T ð3:3:4Þ

Based on DS ¼ [@DG/@T]p, the values of constants A and B in Equation (3.3.2),

respectively, correspond to the enthalpy change, DHf , and the negative of the entropy


change, –DSf . As seen in Figure 3.3.1, the intercepts of all the representative lines at 0 K


are negative; A ¼ DHf < 0. These imply that oxidation reactions are exothermic. On the

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508 Masakatsu Hasegawa

other hand, the standard entropy of a gaseous species is generally greater than that



of a condensed component, e.g., S298(O2) ¼ 205.1 J K–1 mol–1, S298(solid Mn) ¼


32.0 J K–1 mol–1 and S298(solid MnO) ¼ 59.8 J K–1 mol–1 [3]. Thus the values for DSf

for oxidation reactions involving one mole of gaseous oxygen are very close to S




(O2); B ¼ DSf  S (O2). Therefore, all the lines in Figure 3.3.1 are almost parallel to
each other over the temperature ranges in which both of the metals and the oxides



are condensed phases. In approximated formula (3.3.2), the DHf and DSf terms are
assumed to be constant in a specified range. This does not take into account the small

PCO /PCO 1/1010 1/108 1/106 1/105 1/104

2

PH2 /PH2O 1/103

1/1010 1/108 1/106 1/105

PO2 /atm.
1/104 1/102
Temperature (K)
1/103
0 1000 2000 1/10
0 1
O 2
1/10
IrO 2 1/1
O 2= O
Ir + Cu
=4 1/10 10-2
+ O 2 Cu 2O
uO 2 O3 10/1
2C 2u + O 2 = Fe 2
4C =6 O4 2H 2O 2 1/1
Fe 3 CO 2 O2 = 10-4
2C + O2 2 2 2 H2 +
= =
+O O4
+O
2 O2 102/1
2 =2
4F
e3 O+ = 2FeO 10/1
CO F eO 2C 2Fe + O 2
6
C + O2 = CO2 10-6
103/1
102/1
O4
)Fe 3
H (1/2 TiO 2
DG° (kJ⋅(mol O2)-1)

=
-500 )Fe
+ O2 O2
=6
ZnO 103/1 104/1 10-8
(3/2 O5
+ =2
C 2Ti 3 Z n + O2
= 4T
i 3O 5
2
+ O2
6Ti 2
O 3 104/1 105/1 10-10
O
= 2Mn
+ O2 105/1
2Mn SiO 2
O2 = 106/1
Si + 10-12
6
10 /1
107/1
= 2T
i 2O 3 TiO 7 10-14
+ O2 =2 10 /1
iO + O2
4 T 2Ti 108/1
O3
)AI 2 108/1 10-16
-1000 = (2/3
O2
3)A
I+ Mg
O 109/1
(4/ O2
=2 Melting Boiling 109/1
2M
g +
=2
Ca
O
point point 10-18
O2
2C
a + Metal 10 /110 1010/1
Oxide
10-20

10-22

10-30 10-28 10-26 10-24

(a)
Figure 3.3.1 Ellingham diagram for some oxides; Richardson nomographic scales are included:
(a) Al, Ca, Cu, Fe, Ir, Mg, Mn, Si, Ti, and Zn.
Ellingham Diagram 509

PCO /PCO 2 1/1010 1/108 1/106 1/105 1/104

PH2 /PH2O 1/103

1/1010 1/108 1/106 1/105

PO2/atm.
1/104 1/102
Temperature /K
1/103
0 1000 2000 1/10
0 1
O 2
dO RuO 2 1/10
= 2P O4 O2 = 1/1
+ O2 o3 Ru +
2Pd 2C
= 1/10 10-2
O2 O2
+ 2Mo =2
CO 2 10/1
oO O2 = iO + O2
6C O2 + = 2N 2CO
O
2Mo O2 = 2H 2 1/1
2P
bO 2Ni +
2H 2
+ O2 10-4
=
+ O2
oO
102/1
2Pb = 2C 10/1
+ O2
2Co C+O2 = CO2
10-6
103/1
102/1
2C
oO 2 + O2 =
H =M
DG° (kJ⋅(mol-O2)-1)

-500 + O2
2CO
103/1 104/1 10-8
Mo
C
r 2O 3
= (2
/3)C 104/1 105/1 10-10
O2
)Cr + O5
(4/3 )Ta 2
(2/5 105/1
O2 = 106/1
) Ta + rO 2 10-12
(4/5 =Z
Zr +O 2
6
10 /1
107/1
7 10-14
eO 2 10 /1
=C
+O 2
108/1
Ce BeO
=2 108/1
-1000 =2
BaO e+
O2 10-16
+ O2 2B
2Ba 109/1
Melting Boiling 109/1
a 2O 3
/3)L point point 10-18
= (2
)La+
O2 Metal 10
10 /1 1010/1
(4/3 Oxide
10-20

10-22

10-30 10-28 10-26 10-24

(b)
Figure 3.3.1, cont'd (b) Ba, Be, Ce, Co, Cr, La, Mo, Ni, Pb, Pd, Ru, Ta, and Zr.

Cp changes, DCp, in Equation (3.3.1). Thus, it should be pointed out here that the lin-
earity of Ellingham plots is a slight approximation.
The open and solid circles in Figure 3.3.1 identify the melting and boiling points of
the metals, while the open triangles represent the melting points of the oxides. As seen in


Figure 3.3.1, the slopes of the lines representing DGf –T relations change at temperatures
in which the phase transformations of reactants or products occur. Consider the fusion of
manganese:
510 Masakatsu Hasegawa

MnðsolidÞ ¼ MnðliquidÞ ð3:3:5Þ

The thermal data on manganese, i.e., heat capacity, Cp, heat of fusion, DHF, and
melting temperature, TM, have been reported as follows [3] (see Table 3.1.A7 of
Chapter 3.1):

CpðsolidMnÞ=J K1 mol1 ¼ 46:44 ð3:3:6Þ

1 1
CpðliquidMnÞ=J k mol ¼ 46:02 ð3:3:7Þ
DHF
=J mol1 ¼ 14,600 ð3:3:8Þ
TM =K ¼ 1517 ð3:3:9Þ
Figure 3.3.2 indicates that, at a given temperature below the melting point 1517 K,


the enthalpy change from solid Mn to liquid Mn, DHF(T), is not equal strictly to the heat


of fusion, DHF, and can be calculated by extrapolating the heat capacity of liquid Mn:


DHF ðT Þ ¼ H
ðliquid MnÞ  H
ðsolid MnÞ
ðT

ð3:3:10Þ
¼ DHF þ fCpðliquid MnÞ  Cpðsolid MnÞgdT
1517

Equation (3.3.10) is also available at temperature over the melting point when Cp
(solid Mn) is extrapolated. From the thermal data, the integration term in Equa-
tion (3.3.10) at 1600 K can be calculated as
ð
1600

fCpðliquid MnÞ  Cpðsolid MnÞdT g ¼ ð46:02  46:44Þ  ð1600  1517Þ

ð3:3:11Þ
1517
¼ 34:86 J mol1

70

Mn(liquid)

60
DHF°= 14.6 kJ⋅mol-1
H (kJ⋅mol-1)

DHF°(T)

50

Mn(solid) 1517K
40
1400 1500 1600
T (K)
Figure 3.3.2 Standard enthalpy change of the fusion of manganese.
Ellingham Diagram 511

Comparing Equations (3.3.8) and (3.3.11), it can be concluded that the integration


term is negligible. Thus DHF(T) can be considered to be independent of temperature and



equal to DHF. In analogy with the enthalpy change, the entropy change, DSF(T), can be
given as




DSF ðT Þ ¼ S ðliquid MnÞ  S ðsolid MnÞ
ðT


¼ DSF þ ½fCpðliquid MnÞ  Cpðsolid MnÞg=T dT ð3:3:12Þ
1517



 DSF ¼ DHF =TM

Based on the considerations above, the standard free energy change of Reac-


tion (3.3.5), DGF(T), is expressed as






DGF ðT Þ=J mol1 ¼ DHF ðT Þ  T DSF ðT Þ  DHF  T DHF =TM
ð3:3:13Þ
¼ 14,600  9:6T
Combining Equations (3.3.4) and (3.3.13), we obtain
2MnðliquidÞ þ O2 ðgasÞ ¼ 2MnOðsolidÞ ð3:3:14Þ




1
DGf ð3:14Þ=J mol ¼ DGf ð3:3Þ  2DGF ðT Þ ¼ 798,640 þ 164:8T ð3:3:15Þ
The slope of Mn(liquid) – MnO(solid) line in Equation (3.3.15) is greater than that of
Mn(solid) – MnO(solid) line in Equation (3.3.4). As seen in Figure 3.3.1, the slopes
increase slightly at the melting points of the metals and increase drastically at the boiling
points of the metals because the entropy change of vaporization is generally much greater
than that of fusion. Based on the analogical consideration, it can be understood that the


DGf –T plot has a smaller slope at higher temperature owing to the opposite effect of
fusion of the oxides.

3.3.2. EQUILIBRIUM OXYGEN PARTIAL PRESSURE

Consider the equilibrium among a metal M, its oxide MxOy and gaseous oxygen of
partial pressure PO2.
ð2x=yÞM þ O2 ðgasÞ ¼ ð2=yÞMx Oy ð3:3:16Þ
When both of M and MxOy are in their standard states, the equilibrium constant, K,
corresponding to this reaction can be expressed as
K ¼ 1=PO2 ð3:3:17Þ
Strictly equilibrium constants should be expressed in terms of fugacity instead of
partial pressure for gaseous species, but the difference between fugacity and partial
512 Masakatsu Hasegawa

pressure is not significant at high temperature and low pressure. The equilibrium oxygen
partial pressure of Reaction (3.3.16) at a given temperature can be fixed as


DGf ¼ RT ln K ¼ RT ln PO2 ð3:3:18Þ

If, at any temperature, the actual partial pressure of oxygen is greater than the
calculated value from Equation (3.3.18), spontaneous oxidation of metal M occurs,
while oxide MxOy decomposes to metal M and gaseous oxygen at the oxygen partial
pressure less than the equilibrium value. In other words, an element is unstable and its


oxide is stable at higher oxygen potentials than its DGf –T line on the Ellingham diagram.


Therefore, the larger negative value for DGf an oxide has, the more stable it is. It can be
visualized clearly in Figure 3.3.1 that aluminum has a stronger affinity for oxygen than
iron and can reduce iron monoxide because Al–Al2O3 line lies lower than Fe–FeO line.
Richardson and Jeffes [4] improved the Ellingham diagram by adding a nomographic
scale, which is designed so that the equilibrium oxygen partial pressure between metal
and its oxide can be read off directly at a given temperature. As mentioned above, the
equilibrium oxygen partial pressure can be calculated from Equation (3.3.18). The


left-hand side of this equation, DGf , has been already illustrated for the selected oxides
on the diagram, while, based on the right-hand side, the PO2 scale is constructed.
Namely, a particular PO2 scale corresponds to a line which passes through point O,
i.e., RT ln PO2 ¼ 0 at 0 K, and has a slope of R ln PO2. Figure 3.3.3b shows how to read
off the value for the equilibrium oxygen partial pressure between pure liquid Mn and
pure solid MnO at 1750 K. The procedure consists of drawing the line which passes
through point O and point a representing the value for Mn(liquid) – MnO(solid) line
at 1750 K, and extending the line until it intersects the PO2 scale; we can obtain
PO2 ¼ 6  1016 atm.

3.3.3. EQUILIBRIUM CO/CO2 RATIO AND THE

BOUDOUARD REACTION
Consider the equilibrium among gaseous species of CO, CO2, and O2.

2COðgasÞ þ O2 ðgasÞ ¼ 2CO2 ðgasÞ ð3:3:19Þ

 
DGf ð3:19Þ=J mol1 ¼ RT ln PCO2 2 =PCO 2 PO2
¼ 564,830 þ 173:7T ½2 ð3:3:20Þ

According to the Gibbs Phase Rule, when one gas phase exists in a two-component
system (C and O), there are three degrees of freedom, which give the number of
independent intensive variables in the system under consideration. A paricular variable,
PO2, however, can be fixed by giving the two intensive properties, i.e., temperature and
PCO/PCO2 ratio, as shown in Equation (3.3.21):
Ellingham Diagram 513

Temperature (K)
0 1000 2000

1
PCO/(PCO+PCO2)

Ptotal= 1 atm.

PCO/PCO2
0.5 0.1 atm.
0.01 atm.

PO2/atm.
1/102
0
(a)
1/10
O
0
1
1/1

CO 2 10-2
=2 10/1
+ O2
2CO
2C
+O 102/1 10-4
2 =2
CO b

C + O2 = CO2 103/1 10-6

a
DG° (kJ⋅(mol-O2)-1)

-500 104/1
10-8
C
O 105/1
= 2Mn P
+ O2 tota 10-10
2Mn l =1
atm
.01 0.1 . 106/1
2MnO; a MnO = 0 atm
2M n + O2 = . 10-12
0.0 10 /17
1a
tm
. 10-14
8
10 /1
-1000 10-16
Melting Boiling 109/1
point point
Metal 10-18
1010/1
Oxide

10-20

0 1000 1750 2000

(b) Temperature (K) 10-22
-30 -28 -26 -24
10 10 10 10
Figure 3.3.3 (a) The variation with temperature of PCO/[PCO þ PCO2] in the CO þ CO2 þ O2 gaseous
phase in equilibrium with solid carbon at Ptotal ¼ 0.01, 0.1, and 1 atm. (b) Procedures to read off the
equilibrium values for oxygen partial pressure and CO/CO2 ratio by using the Richardson
nomographic scales.
514 Masakatsu Hasegawa

 
RT ln PO2 ¼ 564,830 þ 173:7T  2RT ln½PCO=PCO2  Jmol1 ð3:3:21Þ

By using this equation, for instance, the equilibrium PO2 in the gas phase at 1750 K
and PCO/PCO2 ¼ 10/1 can be calculated to be 1.6  1010 atm.
Equation (3.3.21) also indicates the relation between the scale of PO2 (the left-hand
side) and that of PCO/PCO2 ratio (the right-hand side) in Figure 3.3.1; the latter can be


constructed as follows. The DGf –T line for Reaction (3.3.19) is extrapolated to lower
and higher temperatures until it intersects the ordinate at T ¼ 0 K and the scale of
PCO/PCO2 ratio; these intersects are marked C and 1/1, respectively. A particular scale
of PCO/PCO2 ratio corresponds to a line which passes through point C and has a slope
of {173.7  2R ln [PCO/PCO2]}. Figure 3.3.3b shows how to read off the equilibrium
PO2 at 1750 K and PCO/PCO2 ¼ 10/1. Point b represents the value at 1750 K on the
line connecting point C and a scale of PCO/PCO2 ratio ¼ 10/1. Then, by drawing
the line which passes through point O and point b, and extending the line until it inter-
sects the PO2 scale, we can obtain PO2 ¼ 1.6  1010 atm.
Gaseous species of CO and CO2 are formed by oxidation of pure solid carbon, which
represented by the following reactions, respectively:

2CðsolidÞ þ O2 ðgasÞ ¼ 2COðgasÞ ð3:3:22Þ

DGf ð3:3:22Þ=Jmol1 ¼ RT ln Kð3:3:22Þ
ð3:3:23Þ
¼ RT ln ½PCO2 =PO2  ¼ 223,430  175:3T ½2
CðsolidÞ þ O2 ðgasÞ ¼ CO2 ðgasÞ ð3:3:24Þ

1
DGf ð3:3:24Þ=Jmol ¼ RT ln K ð3:3:24Þ
ð3:3:25Þ
¼ RT ln ½PCO2 =PO2  ¼ 39,4130  0:8T ½2

It is noted here that Equation (3.3.20) is given by combining Equations (3.3.23) and


(3.3.25). Figure 3.3.1 shows the DGf –T plots for Reactions (3.3.22) and (3.3.24) and
indicates that, at low temperatures, CO2 formation predominates, whereas at higher
temperatures, CO formation predominates. Now, consider the equilibrium of the system
consisting of solid carbon and gaseous phase consisting of CO, CO2, and O2. According
to the Phase Rule, there are two degrees of freedom in this system. This means that
the equilibrium partial pressures are to be fixed by giving two intensive properties,
e.g., temperature and total pressure, Ptotal, defined as

Ptotal ¼ PCO þ PCO2 þ PO2 ð3:3:26Þ

Equations (3.3.23), (3.3.25), and (3.3.26) involve three unknown quantities, PCO,
PCO2, and PO2. Hence, values for PCO, PCO2, and PO2 can be obtained by solving
these three equations simultaneously for a given temperature, T, and total pressure, Ptotal:
Ellingham Diagram 515

hn o i2
PO2 ¼ K ð3:3:22Þ1=2 þ ðK ð3:3:22Þ þ 4Ptotal ðK ð3:3:24Þ þ 1ÞÞ1=2 =2ðK ð3:3:24Þ þ 1Þ
ð3:3:27Þ
PCO ¼ K ð3:3:22Þ1=2 PO2 1=2 ð3:3:28Þ
PCO2 ¼ K ð3:3:24ÞPO2 ð3:3:29Þ

The results are illustrated in Figure 3.3.3a as relations between PCO/[PCO þ PCO2]
and temperature at Ptotal ¼ 0.01, 0.1, and 1 atm. The proportion of CO increases at
higher temperature and lower total pressure. These behaviors can be explained easily
by applying Le Chatelier’s principle, which states that “when subjected to an external
influence, the state of a system at equilibrium shifts in the direction which tends to nullify
the effect of the external influence,” to the Boudouard reaction expressed in Equa-
tion (3.3.30), since this reaction is endothermic and the volume change is positive.

CO2 ðgasÞ þ CðsolidÞ ¼ 2COðgasÞ ð3:3:30Þ

1
DG ð3:3:30Þ=J mol ¼ DGf ð3:3:22Þ  DGf ð3:3:24Þ ¼ 170,700  174:5T ð3:3:31Þ

The Boudouard curves shown in Figure 3.3.3a can be also illustrated on the
Ellingham diagram. The broken curves in Figure 3.3.3b, which represent the Boudouard
reaction, are obtained by plotting Equation (3.3.27) as the RT ln PO2–T relations. It is
noteworthy that, at Ptotal ¼ 0.01 atm., solid carbon is stable and then the scale of PCO/
PCO2 ratio is unavailable within the corresponding hatched area in Figure 3.3.3b.
By using the scale added to the Ellingham diagram, the PCO/PCO2 ratio can be read
off directly which is in equilibrium with any metal þ oxide systems. Figure 3.3.3b shows
the procedure to obtain equilibrium ratio for the following reaction at 1750 K:

2MnðliquidÞ þ 2CO2 ðgasÞ ¼ 2MnOðsolidÞ þ 2COðgasÞ ð3:3:32Þ

The procedure consists of drawing the line which passes through point C and point a
representing the value for Mn(liquid)  MnO(solid) line at 1750 K, and extending the
line until it intersects the scale of PCO/PCO2 ratio; we can obtain PCO/
PCO2 ¼ 5  103. The scale of PH2/PH2O ratio in Figure 3.3.1 is used in exactly the same
manner as that of PCO/PCO2 ratio, except that the point H on the ordinate at T ¼ 0 K is
used instead of point C.

3.3.4. INFLUENCE OF ACTIVITY OF CONDENSED PHASES

ON GIBBS ENERGY CHANGE
It should be noted that the Ellingham diagram (Figure 3.3.1) gives the Gibbs energy
changes when the reactants and products are in their standard states. Now consider the
516 Masakatsu Hasegawa

oxidation reaction of pure solid manganese when the MnO activity is 0.01. The Gibbs
free energy change for this reaction can be expressed as
2MnðsolidÞ þ O2 ðgasÞ ¼ 2MnOðsolid, aMnO ¼ 0:01Þ ð3:3:33Þ
DGf ð3:3:33Þ=J mol1 ¼ DGf
ð3:3:3Þ þ 2RT ln aMnO
¼ 769,440 þ 145:6T þ 2  8:314  T  lnð0:01Þ ð3:3:34Þ
¼ 769,440 þ 69:0T
The Gibbs energy change of Reaction (3.3.33) is also illustrated in Figure 3.3.3b.

REFERENCES
[1] H.J.T. Ellingham, J. Soc. Chem. Ind. 63 (1944) 125.
[2] O. Kubaschewski, C.B. Alcock, Metallurgical Thermochemistry, fifth ed., Pergamon Press, Oxford,
1979, p. 378.
[3] O. Kubaschewski, C.B. Alcock, P.J. Spencer, Materials Thermochemistry, sixth ed., Pergamon Press,
Oxford, 1993, p. 258.
[4] F.D. Richardson, J.H.E. Jeffes, J. Iron Steel Inst. 160 (1948) 261.