THE CLAUSIUS-CLAPEYRON EQUATION

Skills to develop

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.

The Clausius-Clapeyron Equation

The vaporization curves of most liquids have similar shape. The vapor pressure steadily
increases 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, ∆Hvap, and temperature T are related,

𝑃 = 𝐴𝑒 ∆𝐻𝑣𝑎𝑝/𝑅𝑇
where R (= 8.3145 J mol-1 K-1) and A are the gas constant and unknown constant. This is known
as the Clausius- Clapeyron equation. If P1 and P2 are the pressures at two temperatures T1 and
T2, the equation has the form:

𝑃1 ∆𝐻𝑣𝑎𝑝 1 1
ln ( ) = ( − )
𝑃2 𝑅 𝑇2 𝑇2
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.

Contributors: DELA CRUZ, REDEN JAY A.

PESCADOR, MAJETH C.
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 and 383 K respectively.

Solution:

Using the Clausius-Clapeyron equation, we have:

40700 1 1
(−(8.3145)(363−373)
𝐏𝟏 = 1.0
= 𝟎. 𝟔𝟗𝟕 𝐚𝐭𝐦

40700 1 1
(−(8.3145)(383−373)
𝐏𝟐 = 1.0
= 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 ∆Hsub. Use a piece of paper and derive the Clausius-Clapeyron
equation so that you can get the form:

𝑃1 1 1
∆𝑯𝒔𝒖𝒃 = 𝑅 ln ( )( − )
𝑃2 268 273

2.965 1 1
= 8.3145 ln ( )( − )
4.560 268 273

= 𝟓𝟐𝟑𝟕𝟎 𝐉 𝐦𝐨𝐥−𝟏

Note that the heat of sublimation is the sum of heat of melting and the heat of vaporization.

Contributors: DELA CRUZ, REDEN JAY A.

PESCADOR, MAJETH C.
Example 3

The vapor pressure of a substance is 21 torr at 27OC. Calculate the vapor pressure at 310 K if
enthalpy of vaporization is 24 KJ/mol.

Solution:

∆Hvap 1 1
𝐏𝟐 = P1𝑒 − R
( − )
T2 T1
24000 1 1
= 21𝑒 −8.3145(310−300)
= 𝟐𝟖. 𝟔 𝐭𝐨𝐫𝐫

*Notice that as the temperature rises, the pressure also rises.

Example 4

The vapor pressure of a substance is 30 torr at 250 K. At what temperature will the substance
have a vapor pressure of 150 torr? The enthalpy of vaporization is 45 KJ/mol.

1 8.3145 ln150/30
𝐓𝟐 = [ − ]
250K 45000
= 𝟐𝟕𝟎 𝐊

Useful Formulas to Remember

∆Hvap 1 1
( − )
𝐏𝟐 = P1e R T2 T1

∆Hvap 1 1
(T1−T2)
𝐏𝟏 = P2e R
∆𝐇𝐯𝐚𝐩 should always 𝐢𝐧 𝐉/𝐦𝐨𝐥
P2
R ln(P1)
∆𝐇𝐯𝐚𝐩 = 𝐽
1 1 𝑅 = 8.3145
T2−T1 𝑚𝑜𝑙. 𝐾
P2 −1
1 R ln( )
𝐓𝟐 = [T1 − P1
]
∆Hvap

Contributors: DELA CRUZ, REDEN JAY A.

PESCADOR, MAJETH C.
NAME: DATE:
Favorite Anime Character (plus 5): (NO KOREAN DRAMA, “OTTOKE?”)

Clausius-Clapeyron Equation Problems

Write your answers on the space provided in each item. Use separate sheet for your solutions.
(Strictly no parasitism.)

01. A substance has a heat of vaporization of 16.69 kJ/mole. At 254.3 K it has a vapor
pressure of 92.44 mm Hg. Calculate its vapor pressure at 275.7 K.

Final Answer:

02. At 50.14 K a substance has a vapor pressure of 258.9 torr. Calculate its heat of
vaporization in kJ/mol it if has a vapor pressure of 161.2 torr at 277.5 K.

Final Answer:

03. A substance has a vapor pressure of 0.2020 atm at 261.5 K. If its heat of vaporization
is 20.94 kJ/mol, calculate its vapor pressure at 240.9 K.

Final Answer:

04. At 213.1 K a substance has a vapor pressure of 45.77 mmHg. At 243.7 K it has a
vapor pressure of 193.1 mm Hg. Calculate its heat of vaporization in kJ/mol.

Final Answer:

05. What is the vapor pressure of a substance at 308.1 K if it has a vapor pressure of 73.15
torr at 286.6. Its heat of vaporization is 25.44 kJ/mol.

Final Answer:

06. A substance has a vapor pressure of 77.86 mm Hg at 318.3 K and a vapor pressure of
161.3 mmHg at 340. 7 K. Calculate its heat of vaporization in kJ/mol.

Final Answer:

Contributors: DELA CRUZ, REDEN JAY A.

PESCADOR, MAJETH C.