EXPERIMENT on a TERNARY

SYSTEM of LIQUIDS
ARTHUR A. VERNON AND BERTRAM BROWN
Rhode Island State College, Kinpton, Rhode Island

A N INTERESTING experiment in a laboratory

course in physical chemistry can be done to il-
lustrate equilibrium in a three-component system
by determining the amount of one liquid necessary to
make two immiscible liquids become miscible. Experi-
ments of this kind are described by Davison and van
Kloosterl in which the amount of acetic acid necessary
to make benzene-water mixtures miscible is determined
and by Daniels, Mathews, and William~,~ using the
system water-chloroform-acetic acid. The endpoints
in these systems are rather difficult to determine, since
the solutions must be made to change from clear to
cloudy or cloudy to clear. The change is particularly
difficultto determine in the benzene-water-aceticsystem
when the percentage of acetic acid is high.
It has been the experience in this laboratory that the
system nitrobenzene, water and acetic acid is very well
adapted for a three-component experiment. The end-
point for this system is easy to detect since the nitro-
benzene is colored and heavier than water. When the
container is gently rotated, the small droplets of nitro-
benzine, which are present as the equilibrium point is
approached, are gathered in the bottom of the flask
and can be watched as they disappear. As it bas been
worked out, the experiment consists in determining the
amount of acetic acid necessary to make the following
mixtures become miscible:
by watching for the disappearance of the nitrobenzene
droplets which collect in the center on the bottom of the
flask. It is important that mixtures be thoroughly
shaken to make sure all the CsHsNOe has been made
miscible.
The amounts of acetic acid necessary a t equilibrium
have been determined in this way and the results are
given in Table 1. The error involved in these readings
is different for each mixture as given in the table because
of the cumulative effect of the error of each reading.
The greatest error of any one reading was k 0 . 2 cc.,
and the greatest cumulative error was in the case of the
mixture containing 10 cc. of nitrobenzene and seventy
cc. of water. For this mixture i t was d 2 . 5 cc. of acetic
acid. Thus, the worst error of individual measure-
ments was 1.3 per cent. and the worst cumulative error
was 1.52 per cent.
TABLE 1
C&LNOI Hz0 C&COOH
cc Vor. % rr. Vd. % CL Vol. %

These results are plotted on the triangular diagram

The initial mixture of nitrobenzene and water is Cff3coon

placed in an Erlenmeyer flask and acetic acid added
from a buret while the Erlenmeyerflask is rotated gently.
At first the mixture is opaque, while a t the equilibrium
point the solution quickly becomes clear. Enough
A
water is added to give the nitrobenzene-water propor-
tions of the second mixture and the process repeated.
In this way each series of mixtures is tested. As the
amount of acetic acid increases, the change a t the end-
point is less sharp, but i t can be determined accurately
-
1 DAVIWN. A. W. AND VAN KWOSTEK.H. S., "Laboratory
manual of physical chemistry," 2nd ed., John Wiley and Sons,
NewYork City, 1931, p. 104.
DANIELS,F., MATEIEWS J. H., AND WILLIAMS.J. W.,"Exper- as shown in Figure 1. It should be noted that the
mental physical chemistry," 2nd ed., 1929, McGraw-Hill Book
Co.,New York City, p. 106. mixtures as outlined give three overlapping points.
This is valuable in determining how well the curve may sult in a greater error in percentage when the measure-
be drawn a t the peak and gives a measure of the skill ment was made.
of the experimenter. The last point which is of interest if the experiment
The value of the experiment is to a large extent de- is to be used in a laboratory group is the variation with
pendent upon the ease with which students can duplicate temperature of the acetic acid needed to produce misci-
the results. In order to determine this, the experiment bility. Experiments showed an increase in temperature
was given to a group of fifteen seniors majoring in from 25'C. to 35°C. gave equilibrium values of acetic
chemistry and to a group of fourteen pre-medical senior acid two per cent. higher. This change with tempera-
students. Of course, the former were more experienced ture is small enough to make i t a good experiment for
in chemical technic, and thus a comparison between comparison among a group of students who are work-
experienced and inexperienced students could be made. ing in conditions of varying temperature.
It was found that the experiment could be performed On the basis of the information given, i t is felt that
equally well by either type of student. The individual the experiment described is very satisfactory for use in
sets of data gave smooth curves when plotted, but there experimental physical chemistry.
was a maximum variation in the cc. of acetic acid a t
the equilibrium points of about ten per cent. The SUMMARY
cumulative variations were, however, only about this 1. An experiment illustrating equilibrium in a
large and the iinal per cent. of acetic acid varied by a three-component system is described.
little more than five per cent. These variations were 2. The correct values of each component present a t
probably due to errors which occurred in measuring equilibrium is given and tests cited to show that i t is
out the nitrobenzene. A small error here would re- satisfactory for students to perform in the laboratory.