Heat of Vaporization

The Clausius-Clapeyron
Importance & Calculation
The heat of vaporization
The heat of vaporization of a liquid is a useful
thermodynamic quantity because it allows the calculation
of the vapor pressure of the liquid at any temperature.
Two practical applications of heats of vaporization are
distillations and vapor pressure:
Distillation is one of the most practical methods for
separation and purification of chemical compounds. The
heat of vaporization is the fundamental quantity that
determines the experimental conditions at which an
industrial or laboratory-scale distillation should be run.
The concentration of a gas is given by its vapor
pressure. Knowledge of the heat of vaporization permits
the control of vapor pressure by setting the temperature
of the liquid being vaporized.

Derivation of the Clausius-
Clapeyron Equation
Two phases in equilibrium at constant
pressure and temperature have the same
Gibbs free energy. dG = Vdp - SdT yields
The Clausius Clapeyron Equation is derived from the second law of
thermodynamics. It applies to all types of transitions between
phases, for example, melting, sublimation and solid-solid
transitions between polymorphs.










The Clapeyron equation is valid along any phase co-existence line.
It explains, for example, that the solid-liquid phase co-existence line
for water has a negative slope in a p vs. T phase diagram, since the
change in volume is going from ice to water is negative (ice floats in
water).
h T essure wit ange of pr Rate of ch
dT
dP
ke place changes ta at which emperature absolute t T
eight the same w ated with nge associ volume cha V
ce t of subs iven weigh ion for ag of transit t or heat latent hea H
where:
V T
H
dT
dP
=
=
=
=
A
A
=
tan
When the Clapeyron equation is applied to
liquid/vapor phase co-existence, several
simplifying assumptions can be made.
First, since the volume of a gas is much greater
than the volume of a condensed phase,



Second, the gas is assumed to obey the ideal
gas law


which allows the Clapyron equation to be
simplified as follows:
gas liquid gas
V V V V ~ = A
P
nRT
V
gas
=
Third, H is assumed to be independent of temperature
and pressure, allowing indefinite integration over p and T



Choosing the constant of integration to equal ln p
0
,
where p
0
equals one pressure unit, e.g., 1 Torr if pressure
is measured in Torr, allows the pressure units to cancel
and yields:
2 2
e therefor
T
dT
nR
H
P
dP
nRT
H P
dT
dP A
=
A
=
constant
1
ln +
(

A
=
T nR
H
p
This equation is useful for determining H from a
plot of ln (p/p
0
) vs. 1/T.
If definite integration from p
1
to p
2
and from T
1
to T
2

is performed, the result is
This equation is useful for determining the vapor pressure p
2

at temperature T
2
given H and the vapor pressure at one
temperature (p
1
, T
1
), e.g., the normal boiling point.
( )
|
|
.
|

\
|

A
=
|
|
.
|

\
|
A
=
} }
1 2 1
2
2
1 1
ln
ln
2
1
2
1
T T nR
H
P
P
or
nRT
H
P d
T
T
P
P
The Clausius-Clapeyron equation may also be
treated graphically. Assuming H to be constant
in the range of temperature considered,
integration of this equation may be written:



that is, of the form y = mx + c.
Experimental data for pressures and
temperatures may therefore be plotted as ln P
against the reciprocal of temperature. The slope
of the resulting graph is then (-H/R) from
which the heat change of the phase reaction
may be calculated.
Example
To calculate the pressure under which water boils
at 99C.given that:
Latent heat of water at 100C = 540 x 18
cal/mole
R = 1 .987 cal/mole
P
2
= pressure required at T
2
= 372K



P
2
= 733.6 mm pressure.

|
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|

\
|
=
|
.
|

\
|
373
1
372
1
987 . 1
18 x 540
760
ln
2
P