The Clausius-Clapeyron Equation

Applications
Areas in which Clausius-Clapeyron
applies
1. Apply the Clausius-Clapeyron equation to
estimate the vapor pressure at any
temperature.
2. Estimate the heat of phase transition
from the vapor pressures measured at
two temperatures.
Approximation to simplify the equation
1. The change in volume that accompanies
evaporation or sublimation is assumed to be equal
to the volume of the vapor produced. This is a
good assumption at moderate or low pressures. For
example, water is about 1000 times more dense
than its vapor around room temperature and
pressure, so the volume change for complete
evaporation of water equals the volume of vapor
produced to about three significant figures.
2. The enthalpy of vaporization (or sublimation) is
assumed to be constant over the temperature
range of interest. This is never really true, but
changes in these H's are very small at low and
moderate pressures. As one approaches the critical
point, this assumption will fail completely.
3.The vapor is assumed to be an ideal gas.
Again, this is a good assumption at
moderate pressures for most substances.
4.The external pressure doesn't affect the
vapor pressure. There is a slight
dependence on external pressure.

The vaporization curves of most liquids have similar
shape. The vapour pressure steadily increase as the
temperature increases. A good approach is to find a
mathematical model for the pressure increase as a
function of temperature. Experiments showed that the
pressure P, enthalpy of vaporization, , and
temperature T are related,


If P
1
and P
2
are the pressures at two temperatures T
1

and T
2
, the equation has the form:

The Clausius-Clapeyron equation allows us to estimate
the vapor pressure at another temperature, if the
vapor pressure is known at some temperature, and if the
enthalpy of vaporization is known.
( )
|
|
.
|

\
|

A
=
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.
|

\
|
A
=
} }
1 2 2
1
2
1 1
ln
ln
2
1
2
1
T T nR
H
P
P
or
nRT
H
P d
T
T
P
P
H
t cons A and K J mol . where R (
nRT
H
A P
- -
tan 3145 8 exp
1 1
=
|
.
|

\
|
A
=
Gas Constant in Various Units
Example 1
The vapor pressure of water is 1.0 atm at 373 K, and the
enthalpy of vaporization is 40.7 kJ mol-1. Estimate the
vapor pressure at temperature 363 K and 383 K
respectively.
Solution
Using the Clausius-Clapeyron equation, we have:
P at 363 = 1.0 exp (- (40700/8.3145)(1/363 - 1/373)
= 0.697 atm
P at 383 = 1.0 exp (- (40700/8.3145)(1/383 - 1/373)
= 1.409 atm


Note that the increase in vapor pressure from 363 K to
373 K is 0.303 atm, but the increase from 373 to 383 K is
0.409 atm. The increase in vapor pressure is not a linear
process.

The Clausius-Clapeyron equation applies to any
phase transition. The following example shows its
application in estimating the heat of sublimation.
Example 2
The vapor pressures of ice at 268 and 273 are 2.965 and
4.560 torr respectively. Estimate the heat of sublimation
of ice.
Solution
The enthalpy of sublimation is H
sub
. Use a piece of paper
and derive the Clausius-Clapeyron equation so that you
can get the form:

H
sub
= R ln (P268 / P273) (1/268 - 1/273)

= 8.3145*ln(2.965/4.560) / (1/268 - 1/273)

= 52370 J mol-1
Note that the heat of sublimation is the sum of heat
of melting and the heat of vaporization.


Examples to solve
Example 1: Water has a vapor pressure
of 24 mmHg at 25
o
C and a heat of
vaporization of 40.7 kJ/mol. What is the
vapor pressure of water at 67
o
C?
AnswerP
2
= 182 mmHg
Example 2: An unknown liquid has a
vapor pressure of 88mmHg at 45
o
C and
39 mmHg at 25
o
C. What is its heat of
vaporization? AnswerH
vap
= 32.0 kJ
The heat of vaporization for water is 40.7 kJ mol-1.
Calculate vapor pressure at 300 K.
P T/ K
P
2
300
760 373
expect U to know
R = 8.314 J mol
-1
P
2
- AH
vap
1 1
ln ----- = ---------- ( ---- - ---- )
P
1
R T
2
T
1

P
2
-40700 J mol
-1
1 1
ln ------- = ------------------- ( ---- - ----- ) = - 3.914
760 8.31 J mol
-1
300 373
P
2
/ 760 = e
-3.914
= 0.020
P
2
= 0.020*760 mmHg = 15.2 mmHg
when P
1
=800, b.p.=?
Practice Problems
Use a calculator to evaluate the vapor pressure of water at 272,
273, and 360 K. (Use data from lecture material)
AH / R = 41000/8.3142=4931
P at 272 K = 748 Pa; P at 273 K = 799 Pa, P at 360K = 62846 Pa
P at 373 = 101.3 k Pa
Use a spreadsheet to plot the vapor pressure of ice for temperature
between 253 and 275 K.
AH/R = 47000/8.3142 = 5653;
Facts about H
2
O;
m.p. = 272 K
b.p. = 373 K
H
sub
= H
f
+ H
v
T P /Pa
250 91
253 119
255 141
273 610
274 658
Solve by graph
The dissociation pressure of calcium carbonate at
various temperatures are tabulated below.
Calculate the mean heat of the reaction.

Temperature
o
C

650 700 750 800
Pressure mm 8.2 25.3 68.0 168.0
Slope should be around (-818)
Answer 37,700 cal per mole
What are the heat of vaporization (in kJ mol
-1
)
and the normal boiling point of a liquid that
has a vapor pressure of 254 mm Hg at 25
o
C
and a vapor pressure of 648 mm Hg at 45
o
C ?
(R = 8.314 J mol
-1
K
-1
)
HOME WORK ONE WEEK
Assignment
1) The vapour pressure of dichloromethane at 24.1 oC is 53.3 kPa
and its enthalpy of vaporization is 28.7 kJ mol-1. Estimate the
temperature at which its vapour pressure is 70.0 kPa.
Ans= 304 K @ 31oC

2) The vapour pressure of a liquid in the temperature range 200K to
260K was found to fit the expression ln P = (16.255-2501.8)/T.
Calculate the enthalpy of vaporization of the liquid.
Ans= 20.7 kJ mol-1

T (oC) P (kPa)
0 1.92
20 6.38
40 17.7
50 27.7
70 62.3
80 89.3
90 124.9
100 170.9
3) The vapour pressure, P, of nitric acid varies with temperature as
follows:














What are (a) the enthalpy of vaporization of nitric acid and (b) the
normal boiling point?
Ans = a) Tb = 357 K b) H = 38 kJ mol-1