430 Introduction to the Thermodynamics of Materials, Sixth Edition

12.5 THE EFFECT OF PHASE TRANSFORMATIONS

In the previous section, it was stated that the variation of Δ G °  with temperature
can be approximated by a straight line only over ranges of temperature in which no
change of phase of a reactant or product occurs. However, the enthalpy of a high-
temperature phase (e.g., the liquid phase) exceeds that of a low-temperature phase
(e.g., the solid phase) by the latent enthalpy of the phase change. Similarly, the entropy
of the higher-temperature phase exceeds that of the lower-temperature phase. Thus, a
change in the slope of the Δ G ° line (an elbow ) occurs on an Ellingham line at the tem-
perature of a phase change in either a reactant phase or product phase of the reaction.
Consider the reaction

A ( s ) + O2( g ) = AO2( s )

for which Δ H °  is the standard enthalpy change and Δ S °  is the standard entropy
change. At T m ,A , the melting temperature of A, the change of phase

A ( s ) → A (l )

occurs, for which the standard enthalpy change (the enthalpy of melting) is ∆H m,A


and the corresponding change in entropy is ∆Sm,A . Thus, for the reaction


A (l ) + O2( g ) = AO2( s )

the standard enthalpy change is ∆H  − ∆H m ,A and the standard entropy change is

∆S  − ∆Sm ,A . Since ∆H m,A 
and ∆Sm,A

are positive quantities (melting is an endo-
thermic process), then Δ H   –  Δ H m  ,A  is a larger negative quantity than is Δ H °  and
°
  °

Δ S °  –  ∆Sm,A

is a larger negative quantity than is Δ S ° . Consequently, the Ellingham
line for the oxidation of liquid A to form solid AO2  has a greater slope than the cor-
responding line for the oxidation of solid A, and the line contains an elbow upward 
at T m ,A . This is shown in Figure 12.9a. The line does not contain a discontinuity,
since, at T m ,A , GA ( s ) = GA (l ) .
If the melting temperature of the oxide, Tm,AO2, is lower than the melting tem-
perature of the metal, then, at Tm,AO2 , the change of phase

AO2( s ) → AO2(l )

occurs, for which the standard enthalpy and entropy changes are, respectively,
∆H m,AO

2
and ∆Sm,AO

2 . Thus, for the reaction

A ( s ) + O2( g ) = AO2(l )

the standard enthalpy change is ∆H  + ∆H m ,AO2 and the standard entropy change
is ∆S  + ∆Sm ,AO2 , both of which are less than the corresponding quantities Δ H °  and
Reactions Involving Pure Condensed Phases and a Gaseous Phase 431

0K 0K

O (s)
DG° =A DG°
+O
2
AO (I)
O2 =
A (I) A (s) +
= AO (s)
A (s) + O 2
O (s)
DH°m,AO2 =A
DH°m,A +O
2
A (s)

Tm,A T Tm,AO T
2
(a) (b)

Figure  12.9  (a) The effect of melting of the metal on the Ellingham line for the oxidation of
the metal. (b) The effect of melting of the metal oxide on the Ellingham line for
the oxidation of the metal.

Δ S ° . In this case, the Ellingham line for oxidation of the solid metal to produce the
liquid oxide has a lower slope than the line for oxidation of the solid metal to the
solid oxide, and thus, as shown in Figure 12.9b, the Ellingham line has an elbow
downward  at Tm,AO2 . In brief, if Tm,A < Tm,AO2 , the Ellingham line is as shown in
Figure 12.10a, and, if Tm,A > Tm,AO2 , the line is as shown in Figure 12.10b.

12.5.1 Example of the Oxidation of Copper

Copper is a metal which melts at a lower temperature than its lowest oxide Cu2 O.
The standard Gibbs free energy change for the oxidation of solid copper to form
solid cuprous oxide in the range of temperature 298 K to T m ,Cu  is

∆G° = –338, 900 – 14.2T ln T + 247T (i)

J

DG° DG°

Tm,A Tm,AO2 T Tm,AO2 Tm,A T

(a) (b)

Figure  12.10  Illustration of the effects of phase changes of the reactants and products of a
reaction on the Ellingham line for the reaction.
432 Introduction to the Thermodynamics of Materials, Sixth Edition

and for the oxidation of liquid copper to form solid cuprous oxide in the range of
temperature T m ,Cu  to 1503 K,

∆G° = – 390, 800 – 14.2T ln T + 285.3T J (ii)

These two lines, which are drawn in Figure 12.11, intersect at 1356 K, which is the
melting temperature of copper. ∆G(l ) − ∆G(ii ) gives

∆G = 51, 900 − 38.3T J

for the phase change

4Cu( s ) = 4Cu(l )

or, for the melting of 1 mole of Cu,

∆Gm,

Cu = 12, 970 − 9.58T J

from which

∆H m,

Cu = 12, 970 J

–120
(s)
2O
u
2C
=

–130
2
O
+
(I)
u
4C

–140
DG°, kJ/mole O2

)
–150 O (s
Cu
2
=
O2
)
+
–160 u (s
4C 1356 K

–170

–180
1100 1200 1300 1400 1500
Temperature, K

Figure  12.11  The Ellingham line for the oxidation of copper.

Reactions Involving Pure Condensed Phases and a Gaseous Phase 433

and

∆Sm,

Cu = 9.58 J/K

Thus, at T m ,Cu , the slope of the Ellingham line for the oxidation of Cu increases by
9.58 J/K.

12.5.2 EXAMPLE OF THE CHLORINATION OF IRON

Since FeCl2  boils at a lower temperature than the melting temperature of Fe, the
Ellingham diagram for the chlorination of Fe shows elbows downward at the melting
temperature of FeCl2  and at the boiling temperature of FeCl2 . For

Fe( s ) + Cl 2( g ) = FeCl 2( s )

∆G° = –346, 300 – 12.68T ln T + 212.9T J (iii)

in the range 298 K to Tm,FeCl2. For

Fe( s ) + C12( g ) = FeC12(l )

∆G° = – 286, 400 + 63.68T J (iv)

in the range Tm,FeCl2 to Tb,FeCl2 . For

Fe( s ) + Cl 2( g ) = FeCl2( g )

∆G° = –105, 600 + 41.87 ln T – 375.1T J (v)

in the range Tb,Cl2 to T m ,Fe . Lines (iii), (iv), and (v) are shown in Figure 12.12, which
shows that

Tm,FeCl2 = 969 K and Tb,FeCl2 = 1298 K

For FeCl2( s )  →  FeCl2( l ) , ∆G(iv) − ∆G(iii) gives

∆Gm,

FeCl2 = 59, 900 + 12.68T ln T − 149.0T J

Thus,

∆H m ,FeCl2 = −T 2 
(
 ∂ ∆Gm ,FeCl2 T  )
 = 59, 900 − 12.68T J
 ∂T 
 