VAPOR PRESSURE OF PURE SUBSTANCES

Measurement of Vapor pressure in One-Coordinate System

Theory
The phase rule predicts the number of degrees of freedom in a heterogeneous system
consisting of p phases and m components:
F = m-p+2
(1)
For this experiment, m is one and p is equal with two (liquid and vapor phase are
coexisting) so F is one too. This means that one of the variables of the system (T and P),
anyone, must be specified before the remaining one can be found.
The correlation between temperature and vapor pressure is given by Clausius-Clapeyron
equation:
dP / dT =VH / V V
(2)
VH is the molar heat of vaporization and VV is the difference between the molar
volume of the vapors and the molar volume of the liquid.
There are 2 approximations before the integration:
V 1 0 so V V V V
V V R T / P ( by ideal gas eq.)
Eq.(2) becomes:
dP/P= (VH/RT2 )T
For a small range of temperature, VH may be considered constant (usually the value
corresponding to the normal boiling point-VH-is taken); by integration eq.(3) becomes:
lnP= -A / T + B
(4),
where A=VH0/R, B=ct.

Method
The measurement of the vapor pressure is done by the Ramsey-Young method. The
boiling point is measured for different pressures of the medium (the boiling point is, by
definition, the temperature which corresponds to a vapor pressure equal with the pressure
of the medium).

Laboratory Equipment
The Laboratory equipment consists of: one boiling flask with round bottom, center neck
and side neck, or the investigated liquid; the side neck is used for a thermometer and the
center one for a corrugated tube condenser; a mercury gage; a vacuum pump; an oil bath
or a water one for the flask.
The picture below shows the experimental setup in our lab.

Procedure
First introduce water in the tube condenser and heat the bath. Then open the stopcock of
the pump and evacuate the air from the equipment as much as possible. The temperature
of the boiling flask will grow till the boiling point is reached and then the vapor pressure
of the liquid is equal to the air pressure in the equipment. This one should be measured by
the mercury gage. After that, open a little the stopcock. Now, the temperature in the
boiling flask is less than the boiling point at this new air pressure, so that the temperature
will increase till the new boiling point is reached. This procedure is repeated 8-9 times.