Clausius - Clapeyron relation: Application

Clausius–Clapeyron relation, named after Rudolf Clausius and Benoît Paul Émile Clapeyron describes
a discontinuous phase transition between two phases of matter of a single constituent, dP/dT =
L/T*Δv = Δs/Δv, [L/T=s]

L is the specific latent heat, T is the temperature delta v is the specific volume change of the phase
transition, and delta s is the specific entropy change of the phase transition. This equation
calculates most of thermodynamic properties at phase transition boundary. It is a very good tool to
read phase diagrams.

This is a typical Pressure-Temperature, phase diagram of water, P is in Y axis and T is in X axis. The
Clausius–Clapeyron relation can be used to find the relationship between pressure and temperature
along phase boundaries. The slope of the tangents to this curve at different points gives value of
dP/dT for all those points. You get L, T, delta v and delta s at phase transition.

Example:

Case 1: dP/dT is known

Question: Between 99.5 and 100.5 degc, dP/dT for water 2.717 cm Hg / deg. The corresponding
specific volume of water vapor and liquid water are 1674 cc and 1 cc respectively. Find latent heat
for vaporization of water at 100 degc
Answer: Clausius-Clapeyron equation, dP/dT = L/T*Δv

dP/dT = 2.717*13.59*981 dynes per sq cm / deg., Δv at phase transition point is 1673 cc, T = [100+273] = 373K.

dP/dT = L/T*Δv can be written as dP/dT = L /T [vvapor-vLiquid]. Substituting these values, gives latent heat = 540
calories/g. Experimental value is 539 calories/g.

It is thus possible to calculate latent heat of vaporization at series of temperatures

provided the vapor pressure-temperature curve has been established experimentally.
The results become less accurate as critical point is approached because [v vapor-vLiquid]
becomes almost zero at critical point. If on the other side the latent heat is known, you
can calculate dp/dT. Why dP/dT is important? The reverse dT/dP represents influence
of pressure on boiling point. dT/dP for water is 0.37 deg/cm Hg. Water will boil at about
100.37 degc at 77 cm and at 99.63 degc at 75 cm Hg.

Case 2: dP/dT is not known

Since at phase transition point, vapor and liquid are in equilibrium, vapor-pressure-
temperature and boiling point- pressure curves are identical. Clausius – Clapeyron
equation can be further written as, ln (P2 / P1) = (ΔH / R) (1/T1 - 1/T2) , ΔH is latent
heat for vaporization in J/mol, P1 and P2 are vapor pressures at T1 and T2
temperatures. P1 and P2 should be in same units, T is in kelvin, R is gas constant in J
mol¯1 K¯1.

Question: Determine ΔHvap for a compound that has a measured vapor pressure of
24.3 torr at 273 K and 135 torr at 325 K
Answer: Clausius – Clapeyron equation: ln (P2 / P1) = (ΔH / R) (1/T1 - 1/T2)

P1 = 24.3 torr T1 = 273 K

P2 = 135 torr T2 = 325 K
ln (135/24.3) = (x / 8.31447) (1/273 - 1/325)

1.7148 = (x / 8.31447) (0.00058608)

1.7148 = 0.000070489x

x = 24327 J/mol = 24.3 kJ/mol