CHAPTER 4

THE CLAUSIUS-CLAPEYRON
EQUATION
4.1 Introduction
The Clausius-Clapeyron equation is of great importance for calculating the
effect of change of pressure (P) on the equilibrium transformation temperature (T) of
a pure substance, and may be represented as
;

Ecuacin 4.1

where H is the heat of transformation and V is the volume change associated with
the transformation. However, care should be taken in selecting the units of the
quantities in Eq.(4.1). If H and V are expressed in cal and cubic centimeter
respectively, then the value of
obtained will be in cal/c.c.y deg. In order to
convert the value of
from this unit to the more convenient unit of atm/deg,
the following factor is used:

1 cal 41.293 cc atm

4.2 Application of Clausius-Clapeyron Equation to Phase Changes
The Clausius-Clapeyron equation is applicable to any phase change-fusion,
vaporization, sublimation, allotropic transformation, etc.
4.2.1 Liquid-Vapour (Vaporization) Equilibria
Applying Eq.(4.1) to a liquid-vapour equilibrium, we have
;

(4.2)

where
is the molar heat of vaporization or latent heat of evaporation,
is
the molar volume of vapour, and
is the molar volume of liquid. Since the
molar volume of vapour is very much larger than the molar volume of liquid,
is
negligible as compared to
, and hence

(4.3)

Assuming that the vapour behaves as an ideal gas, the volume

related to

;
Substituting the value of

, may be

(4.4)

, in Eq. (4.3),

(4.5)

The equation can be rearranged in the most generally used differential form

(4.6)

If we assume as an approximation, however, that other the interval in question

remains constant, then integration of Eq.(4.6) yields
; (4.7a)
or

(4.7b)

where C and C are integration constants.

It is evident from Eq. (4.7b) that if log P for any liquid metal is plotted against
1/T, the plot should be a straight line. The slope (m) of the straight line will be given
by

;
and the intercept of the line with Y-axis will yive the value of constant C. From the
slope of line, the heat of vaporization of liquid may be calculated. However, the heat
of vaporization of a liquid metal calculated in this way will be the mean value over
the temperature interval concerned.
Eq.(4.6) may also be integrated between the limits P1 and P2, corresponding
to temperatures T1, and T2 respectively. Assuming that the temperature range is
small enough so that
is independent of temperature, integration of Eq.(4.6)
yields

or

(4.8)

Eq.(4.8) may be used to calculate the vapour pressure at any temperature if the
vapour pressure at another temperature and the mean heat of vaporization over that
tempera-cure range are known. The following example illustrates the application of
the Clausius-Clapeyron equation to liquid-vapour equilibria.
Example 4. A
The vapour pressure of liquid Titanium at 2227C (2500 K) is 1.503 mm Hg
(200 N/m2). The heat of vaporization at the normal boiling point of Titanium is 104
kcal/mole (435.14 kJ/mol). Calculate its normal boiling point.

Solution:
Let us assume that the normal boiling point of Titanium is T. At this
temperature, the vapour pressure is equal to 1 atm, or 760 mm Hg. Pitting the
appropriate values in Eq.(4.8),

On simplification,
Thus the normal boiling point of Titanium is 3285C
However, a more accurate integration of Eq.(4.6) can be carried out if the
variation of heat of vaporization with temperature is taken into account. Using
Kirchhoff's equation at constant pressure,

Or

(4.9)

where I, is an integration constant. Putting the value of

(4.10)

On integration,

(4.11)

where I2 is another integration constant. If Cp is independent of temperature,

Eq.(4.11) reduces to

(4.12)

4.2.2 Solid-Vapour (Sublimation) Equilibria

On the basis of assumptions similar to those made in liquid-vapour equilibria,
an expression similar to Eq.(4.6) may also be obtained for solid-vapour equilibria.

(4.13)

4.2.3 Solid-Liquid (Fusion) Equilibria

Applying the Clausius-Clapeyron equation to solid-liquid equilibria,

;
0r

(4.14)

where
is the molar heat of fusion
, are the molar volumes of liquid
and solid respectively. Ec.(4.15) may be applied to calculate the change in melting
point of a metal with change of pressure, as illustrated in the following example.
Example 4.B
The molting point of Gallium is 30C (303K) at 1 atm (101,325 N/m). The
densities of solid and liquid Gallium are 5,885 and 6.08 g/cc () respectively. The
heat of fusion of gallium is If.5 cal/g (77.40 x 10 j/kg). Calculate the change in
melting point of Gallium for an increase of pressure of 1 atm (101,325 N/m).
Solution:
Molar volume of liquid gallium

where x denotes the atomic weight of Gallium. Similarly, molar volume of solid
Gallium, V ,.

The value of heat of fusion of Gallium is given in cal/g. In order to find the value in
terms of cal/mole, we must multiply by ;ts atomic weight. Thus:
Molar heat of fusion = 18.5 x cal/mole.
Putting the appropriate values in Eq.(4.14),

In order to change the value in atm/deg, we should use the conversion 1 cal = 41.293
cc-atm. Thus,

Or

Thus, the melting point of gallium will be decreased 2.16 x 10-3 deg.

4.2.4 Solid-Solid Equilibria

The rate of change of transition temperature at which two crystalline forms
of a solid are in equilibrium with pressure is given an equation similar to that
discussed, earlier. If a is the stable form above the transition temperature, and g is
the stable form below the transition temperature T, then according to Eq.(4.1)

Or

where Htr,. is the molar heat of transition, V and V are the molar volumes of the
indicated forms, all measured at temperature T.
4.3 Trouton's Rule
Trouton's rule states that the ratio of latent heat of evaporation to the
tsmperature of normal boiling Tb, is constant for all liquids, and is approximately 21
cal/deg/mole, i.e.

The rule is only an approximate one, and is not followed by all liquid metals.
However, this rule may be used to derive an approximate value for latent heat of
evaporation
Example 4.C
The normal boiling point of zinc is 907C (1180 K), Calculate its vapour
pressure at 800C (1073 K), assuming that zinc follows Trouton's rule.
Solution:
According to Eq.(4.7b), the vapour pressure of liquid zinc may be expressed as
Since zinc follows Trouton's rule, the molar heat of vaporization is given by
Substituting the value of Hv n Eq.(4c.1),
The value of C can be obtained by putting boundary conditions. The vapour pressure
at the normal boiling point 907C (1180 K) is 1 atm, and hence we have
Substituting the value of C in Eq.(4.c.2),

where P is in atm.
From Eq.(4.c.3), the vapour pressure of liquid at 800C (1072 K) is given as
P = 0.3483 atm = 226644..77 m
mm
mHHgg
Thus, the vapour pressure of zinc at 800C is 264.7 mm Hg.
G.S. Upadhyaya and R. K. Dube, Problems in Metallurgical Thermodynamics and
Kinetics, Pergamon Press, United Kingdom, 1982, 77-89.
QD171V63, M-34110, 1982

EXERCISES
4.1 Calculate the mean heat of vaporization of Palladium from the following vapour
pressure data:
TC
V.P. mmHg

1314
-7
7.516x10

1351
-6
1.614x10

1668
-5
5.625x10

TK
2
V.P. N/m

1587
-7
1.002x10

1624
-6
215x10

1841
-5
750x10

4.2 The vapour pressures of liquid Thorium Tetraiod de at 800c (1073 K) and 825C
(1098 K) are 468 mm Hg (62,395 N/m2) and 660mm Hg (87,993 N/m2) respectively.
Calculate its mean heat of vaporization.
4,3 The heat of evaporation of Copper at its normal boiling point is 74.5 kcal/mole
(311.71 kJ/mol). The vapour pressure of Copper at 1500C (1773K) is 0.256 mm Hg
(34 N/m2). Calculate the boiling point of Copper
4.4 The vapour pressure of liquid zinc as a function of temperature is given as
Calculate the heat of vaporization of zinc at its boiling point 907C (1180K).
4.5 The densities of liquid and solid Bismuth are 10.0 g/c.c.(10 x103kg/m3) and 9.673
g/c.c. (9.673 x 103 kg/m3) respectively at the normal melting point 270C (543K).
The heat of fusion is 2.633 kcal/mole (11.02 kJ/mol)
Calculate the melting point of Bismuth under a pressure of 100 atm (101,325 x102
N/m2 ). Atomic weight of Bismuth is 209
4.6 The melting point of Cadmium at 1 atm (101325 N/m2) is 321C (594K) and i.s
heat of fusion is 13,66 cal/g (57.15x103 J/kg). The volume change on the melting of
Cadmium is +0.0064 c.c./g (+0.0064 x.l0-3 m2/kg). Calculate the melting point of
Cadmium:
(a) at 2 atm pressure, and
(b) in vacuo
4.7 Mercury melts at -38.87C (234.13K) at 1 atm (101,325 N/m2) pressure. The
densities of liquid and solid mercury are 13.69 g/c.c. (13.69 x 103 kg/m3) and 14.19
g/c.c. (14.19 x 103 kg/m3) respectively at the normal melting point. The heat of fusion
of mercury is 2,33 cal/g (9.75 x 103 J/kg). Calculate the change in melting point of
mercury per atmosphere change in pressure.

4.8 The vapour pressure, P, (measured in mm Hg) of liquid Arsenic, is given by

and that of solid arsenic by
Calculate the temperature at which the two forms of arsenic will have the same
vapour pressure.
4.9 The densities of ice and liquid water at I atm (101,325 N/m2) and 0C (273K) are
0.917 g/c.c. (0.917 x 103 kg/m3) and 0.9998 g/c.c. iO.9998x103 J/kg) respectively. The
heat of fusion of water is 80 cal/g (334.72x103 J/kg). Calculate the melting point of
ice at 0.5 atm (50662.5 N/m2) and 101 atm (102338x102 N/m2).
4.10

The heat of the reaction

Sn (grey) Sn (white)
Is 500 cal/mole (2,092 j/mol) at the transition temperature of 13C (286K). The
atomic weight of tin is 118.7 and the densities of grey and white tin are 5.75 g/c.c.
(5,75 x 103 kg/m3) and 7.23 g/c.c. (7.23x103 kg/m3) respectively. Calculate the
change in the transition temperature if the pressure on the grey tin phase is
increased by 100 atm (101325x102 N/m2).
4.11 Liquid mercury boils at 357C (630 K) at 1 atm (101,325 N/m2). Calculate its
approximate vapour pressure at 100C (373K), assuming that it follows Trouton's
rule.