EXPERIMENT 1

DETERMINATION OF VAPOUR PRESSURE AND ENTHALPY OF

VAPORISATION

Introduction
The Clausius-Clapeyron equation in Physical Chemistry courses is introduced as a means of
describing the variation of the vapour pressure with temperature and for determining the
enthalpy of vaporisation:

dlnP ΔH vap
o

= (1)
dT RT 2

If Hvap is independent of temperature then integration will give

ΔH ovap
lnP = − + const (2)
RT

This experiment demonstrates how one can determine the vapour pressure of water in the
range 50oC to 80oC using the simplest of laboratory equipment i.e. a tall beaker, a measuring
cylinder, and a thermometer as shown below in Figure 1.

Figure 1.: Diagram of Apparatus

A sample of air is trapped in an inverted 10 mL measuring cylinder immersed in a beaker of
water. The water is heated to about 80oC, and the trapped gas becomes saturated with water
vapour rapidly at this temperature. The temperature of the water bath and the volume of the
gas in the measuring cylinder are recorded. The bath is then cooled and the readings of
temperature and gas volume are taken at intervals of 5oC or less. The number of moles of
water in the gas phase changes with temperature, but the amount of air is constant.

With knowledge of the number of moles of air in the gas sample, the partial pressure of air
can be calculated at each temperature, and the vapour pressure of the water can be obtained
by determining the difference from the barometric pressure. The number of moles of air in
the mixture can be found from the measurements of volume, temperature, and pressure at the
temperature near 0oC, where the water content of the gas is less than 1% and is neglected.
The enthalpy of vaporisation is calculated through the Clausius-Clapeyron equation from a
plot of the logarithm of the vapour pressure versus 1/T (Equation (2)).
Note:
There is a small systematic error resulting from the use of inverted measuring cylinders
because the meniscus at the water interface is reversed. It has been estimated, by introducing
known volumes of air into a completely filled inverted cylinder, that the error involved with
the use of 10 mL measuring cylinders is 0.2 mL. Then this value is subtracted as a correction
to each volume reading.

Procedure
1. Fill a 10 mL measuring cylinder with tap water up to the 9 mL mark or as needed.
Cover the top with a finger and quickly invert and lower the cylinder into a tall beaker
that has been filled with tap water. An air sample of 2 to 3 mL should be trapped within
the cylinder.

2. Add more water if necessary to the beaker to ensure that the trapped air is surrounded
by water. Then heat the beaker and water on a hot plate until the volume of trapped air
has expanded just beyond the scale on the measuring cylinder.

3. Remove the beaker from the hot plate and allow the water to cool. When the gas begins
to contract and the volume can again be read, read and record the volume to the closest
 0.1 mL and the temperature of the water to the nearest 0.1oC. Stir the water bath
frequently to avoid thermal gradients.

4. Carefully take the water bath to a tray on the bench top. As the water cools, make
additional measurements at approximately 4oC intervals down to 50oC. Ice may be
added to speed the cooling; any overflow from the bath will be trapped in the tray
below the beaker.

5. After the temperature has reached 50oC, cool the water rapidly to less than 5oC by
adding ice. Record the gas volume and the water temperature.

6. Obtain a reading of the atmospheric pressure. Record all your data in the data sheet
provided.

Analysis of Data
1. Correct all volume readings by subtracting 0.2 mL to compensate for the inverted
meniscus. Using the measured values for the volume and temperature from Step 5 and
the atmospheric pressure, calculate the number of moles of the trapped air. Assume that
the vapour pressure of the water is negligible compared to atmospheric pressure at that
low temperature:
Patmospheric x Vcorr. (at  5 o C)
n air = (3)
RT

2. For each temperature, calculate the partial pressure of air in the gas mixture as follows:

n air RT
Pair = (4)
Vcorr.

where Pair = pressure of air (Pa),

nair = number of moles of air (mol),
Vcorr. = volume (m3), corrected for the inverted meniscus,
R = universal gas constant (8.314 JK-1 mol-1),
T = temperature (K).

3. Calculate the vapour pressure of water at each temperature i.e.

PH 2O = Patm − Pair (5)

 where Patm is the atmospheric pressure. (An optional, small correction may be made by
correcting for the effect of the difference in water levels in beaker and measuring
cylinder).
4. Plot ln PH 2O versus 1/T and draw the best straight line through the points. Determine the

slope, and using the Clausius-Clapeyron equation, calculate Hvap.

5. Find the value of the vapour pressure at 65oC using the graph.

6. Discuss the accuracy of the results (from 4. and 5. above).

7. Discuss experimental errors which (could) have influenced your results, and how they
could be avoided (if possible).
DATA SHEET EXPERIMENT 1

Determination of vapour pressure and enthalpy of vaporisation

Surname:________________________ Initial(s):________ Student No::______________

Date:_________________

Partner(s) name(s):__________________________________________________________

___________________________________________________________________________

Atmospheric pressure:_____________ mmHg = ______________ Pa

Temp. Temp. Volume Corrected Pair (Pa) PH2O (Pa) ln PH2O

1/T (K-1)
(oC) (K) (mL) volume (mL) (note 1) (note 2)

Note 1: Pair = nRT / Vcorrected where n = Patmospheric x Vcorrected at T < 5oC / RT

Note 2: PH2O = Patmospheric - Pair