Liquid-Vapor Equilibrium

Edmund C. Shearer
Fort Hays Kansos State College
Hoys, Kansas 67601
at Constant Temperature
A n experiment in physical chemistry

Liquid-vapor equilibrium is usually demonstrated in the

physical chemistry laboratory by constructing a boiling
point-composition diagram a t constant pressure.l.2 How-
ever, procedures for determining liquid-vapor equilibria a t TO
constant temperature are found in few sources of experi- VACUUM
ments. There is a need for experiments a t constant tem-
perature.
Since most physical chemistry texts introduce the study
of binary liquid systems when Raoult's law is presented;
vapor pressure-composition diagrams would be just as in-
teresting and possibly more informative in demonstrating
the principles of liquid-vapor equilibria than boiling
point-composition measurements.
One such apparatus has been described by Tobey3 but Figure 1. Apparatus for determining liquid-vapor equilibria at constant
it suffers from the disadvantages of being a complicated temwrature.
special-purpose apparatus for liquid systems having boil-
ing points above 100°C. The experiment described below

involves less complex equipment and can be applied to a
wider range of liquid systems.
Apparatus
The apparatus represented in Figure 1 is a portion of a
portable vacuum system equipped with a mercury
manometer, a sample vessel, and a gas sampling loop for
direct injection of gases into a gas chromatograph. The
sample vessel was constructed from a 250-ml round bot-
tom boiling flask by attaching a male 24/40 ground glass
joint for insertion into the vacuum line. A 10130 ground
glass joint for receiving a standard taperware thermometer
is attached so that the thermometer bulb lies near the
bottom of the flask. Several sample vessels may be con-
nected to the manifold in this manner making i t possible
to determine several points in a run.
The gas sampling loop has a volume of 21.02 ml in the
u m e r chamber and 2.71 ml in the lower and is o ~ e r a t e d
with pressure stopcocks having a 120" bore. ~ons&ucted
in this manner, three different volumes may be chosen for
gas analysis.
Experimental Procedure
After a pair of liquids has been chosen for study, samples of the
pure liquids are introduced into the gas chromatograph to optim-
ize chromatographic conditions and to determine the retention
times of liquids. Mixtures of the two liquids are prepared in ap-
proximate volume percent in 10%increments.
The vapor pressure of each pure liquid and each mixture is
measured by introducing into the sample vessel a volume suffi-
cient to cover the thermometer bulb. A magnetic stirring bar is
resented at the 104th Meeting of the Kansas Academy of
Science, April 14, 1972.
'Daniels, Farrington, Williams, J. W., Bender, Paul, Alberty,
R. A., Cornwell, C. D., and Hamiman, John E., "Experimental
Physical Chemistry," 7th ed., McGraw-Hill Book Co., New York,
1970, p. 61.
Shoemaker, David P., and Garland, Carl W., "Experiments in
Physical Chemistry," 2nd ed., McGraw-Hill Book Co., New York,
1967, p. 166.
Tobey, Stephen W., J. CHEM. EDUC., 39,258 (1962).
446 /Journal of Chemical Education
=h
o LIQUID
LOO
A VAPOR
MOLE% CHLOROFORM
Figure 2. Phase diagram of the acatone-chloroform system at 22'C.
placed in the vessel to provide agitation. The vessel is slowly
opened to vacuum to remove all traces of air from the system.
When the air has been removed, the vacuum is closed and the
liquid is permitted to vaporize and expand into the apparatus.
The vaporization is allowed to continue until the temperature
rises to a predetermined value. The temperature is just below
mom temperature to prevent condensation in other areas of the
system. Achieving the specified temperature is aided by immers-
ing the sample vessel in a water bath.
When equilibrium is achieved, the vapor pressure is recorded
and the gas sampling loop is filled with vapor. The vapor is in-
jected into the gas chromatograph by diverting the helium flow
from the bypass through the upper and lower chambers of the
LOOD.
The sample vessel 1s removed from rhe vsruum system and the
liquid i s onnlymd by gar chromatopaphy ualng ronvenrional liq.
uid mjrrtion techriiquei. The rime required for the erprriment is
approximately 20 min/solution.
Results
Phase diagrams for the acetone-chloroform system a t
22°C and the acetone-diethyl ether system a t 23.5-C have
been constructed from data collected by this method. The
diagrams are presented in Figures 2 and 3, respectively.