l4 The Clausius-Upadi
l4 The Clausius-Upadi
l4 The Clausius-Upadi
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:
(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)
;
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)
(4.7b)
;
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)
(4.10)
On integration,
(4.11)
(4.12)
(4.13)
;
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.
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.