ON T H E EBULLIOSCOPIC METHOD FOR DETERMINING T H E

EQUILIBRIUM CONSTANT O F ESTERIFICATION

W. SWIETOSLAWSKI
Znstilute of Physical Chemistry, Polytechnic High School, Warsaw, Poland
Received November $6, 1988

A method of determining the so-called equilibrium constant of esterifica-

tion by ebullioscopic measurements has previously been described (1).
I n the present investigation, a new ebullioscopic apparatus was used and
some improvements and simplifications introduced in the technique.
It is clear that the boiling points of two reacting mixtures, the first one
containing say 1 mole of ethyl alcohol and 1 mole of acetic acid, and the
other 1 mole of ethyl acetate and 1 mole of water, differ considerably a t
the beginning of the reaction. The boiling temperatures, however, ap-
proach each other as the mixtures tend towards the equilibrium state. We
may consider that equilibrium is established when the two mixtures boil
at the same temperature. The composition of the two mixtures which
must be identical is determined in order to calculate the equilibrium con-
stant.
Previous experiments, with mixtures of the reacting substances in molar
proportions, showed that it was not easy to get identical values for the
boiling points of the two mixtures undergoing changes in opposite direc-
tions. Jozefowicz obtained a difference of O.l"C., whilst Miss Blaszkowska
succeeded in reducing the difference to 0.04"C. I n the latter case the boil-
ing point of the equilibrium mixture could be extrapolated with an ap-
proximation of 0.010"C. These relatively small differences could be due
either to errors in the ebullioscopic measurements or to the very small
velocity of reaction in the neighborhood of the equilibrium state.
The exact determination of the boiling point of a mixture containing
volatile liquids is complicated by the fact that the volatile parts of the mix-
ture evaporate and accumulate in the dead space of the ebullioscopic ap-
paratus; this may cause differences in the measurements. On the other
hand, the velocity of reaction may decrease to such a degree that the
equilibrium and the equalization of the boiling points of the two mixtures
might perhaps never be reached in practice. In order to investigate the
cause of the phenomenon, the conditions governing ebullioscopic measure-
ments have been improved. A new ebullioscopic apparatus suitable for
investigating mixtures of volatile substances (2) and provided with a stop-
701
7 02 W. SW IETOSLAW SKI

cock in order to determine the correction for the dead space of the appara-
tus has been constructed. The new apparatus is shown in figure 1. The
test tube sealed to the part B is immersed in the boiling liquid. This test
tube is filled with mercury, into which the bulb of the thermometer dips.
The temperature read on the thermometer does not correspond to the true
boiling point on account of the overheating of the liquid, a correction for
which can, however, be introduced without difficulty (3). I n measure-
ments of boiling points it is very important to obtain in both pieces of
ebullioscopic apparatus an equal intensity of boiling. For this purpose
they are provided with drop-counters, f. The intensity of the heating is

FIQ. 1

regulated in such a manner that the number of drops flowing from the
condenser D through the tube F is equal for both mixtures, reacting in
opposite directions.

ESTABLISHMENT OF THE EQUILIBRIUM AND DETERMINATION O F THE

BOILING POINTS

The arrangement of the apparatus is shown in figure 2. The two ebullio-

scopes, A and B, each filled with one of the two mixtures undergoing changes
in opposite directions, are connected by means of stop-cocks 1 and 2 with
a manostat E of 3 to 4 liters capacity. The stop-cock 5 allows us either to
fill the apparatus with nitrogen or to connect it with the atmosphere.
 EQUILIBRIUM CONSTANT O F ESTERIFICATION 703

During the first part of the experiment (lasting several weeks) two other
ebullioscopes, C and D, remain empty and the stop-cocks 3 and 4 are
closed. The experiment is started by filling the whole apparatus with
nitrogen. Then A and B are filled with the two mixtures. The stop-cock 5
is then closed and tho bulbs of both ebullioscopes heated until the liquids
begin to boil. The stop-cocks 1 and 2 are then opened. After having es-
tablished a rate of equal boiling, measurements of the boiling points of
the mixtures sre started. For this purpose only one thermometer with an
arbitrary scale is used, and it is carried over several times from one test
tube to the other in order to eliminate the influence of the pressure changes
in the whole apparatus. After measuring the difference of the boiling
points, At = t A - tg, the stop-cocks 1and 2 are closed and the boiling of the
mixtures maintained for several days. The measurement is repeated by

Fia. 2

opening each time the stop-cocks 1 and 2. When, for example, the forma-
tion of ethyl acetate is investigated, it is possible to fill the ebullioscopes
with mixtures which are quite near to the equilibrium state, for instance,
which differ in their boiling points by not more than O.30O0C., or even
0.0GO"C. The realization of practically identical boiling points for both
liquids, within 0.001"-0.003"C., requires four to nine weeks. In some
cases, when impurities were probably present or when the one-sided evapo-
ration produced a little difference in the composition of the two liquids, we
noted a greater difference. As is shown in the table, At did not, however,
exceed 0.010"C.
DETERMINATION OF T H E COMPOSITION CORRESPONDING TO T H E
EQUILIBRIUM STATE '

In the previous work the composition of the liquid in a state of equilib-

rium was determined by considering the function :
t = f (K')
704 W. SWIETOSLAWSKI

where t is the boiling point of the mixture a t the pressure of 1 atmosphere

and
I ,

K' = %!
I ,

c1c2

cl', cz', c1', cql being the concentrations of the acid, alcohol, water, and ester
respectively. On plotting the values of K' against t a curve is obtained
which allows us to find the equilibrium constant K = x4,
when the boil-
ClCZ
ing point, tc, of the equilibrium mixture is known, or may be determined by
extrapolation. In the present investigation the method of determining
the constant K or the concentrations, cl, c2, c3, c4, corresponding to the
equilibrium state, has been considerably improved and simplified. It
consists in the following operations. When the equalization of the boiling
points of the two mixtures is reached, a mixture M is prepared, which is
very near to the equilibrium state, but still contains a small excess of water
and ester. This mixture is introduced into the third ebullioscope C.
Subsequently a corresponding mixture of acid and alcohol, N, is prepared
and introduced into a bath at 0°C. Then the bulbs of the three ebullio-
scopes, A, B, and C, are heated and the boiling points tA, t B and tc deter-
mined by means of the same thermometer. The liquids boil under some
unknown pressure p'. Let the boiling temperatures be unequal, say
tA > tB > tb. As mentioned above, the difference, t A - tg, is small and
does not exceed 0.010"C. Now the stop-cock 3 is closed, the bulb of the
apparatus C cooled and a small quantity of the liquid N, containing alcohol
and acid, is introduced. The measurements are repeated by reading again
the temperatures in A, B, and C. After repeating this procedure several
times, a mixture is finally obtained which has a boiling temerature tc
fulfilling the condition: tA > tc > tB. In order to obtain a complete series
of data, it is necessary once more to add the same quantity of the mixture
N containing acid and alcohol, and to find that the boiling point of the
liquid in C is now higher than that of two others, say t a > tA > tg. With
.all these data the composition of the equilibrium mixture may be obtained
without any difficulty.
When the boiling point of the mixture in equilibrium is known, a fourth
ebullioscope, D, filled with water is used. After opening the stop-cocks 3
and 4 the boiling temperatures tc and tD are measured under the pressure
.existing in the system. Then a manometer filled with water is connected
..through the stop-cock 5 and a series of determinations of the boiling points
of water (tD) and of the li4uid (tc) a t different pressures is carried out, in
dt
order to determine the value of - for this liquid and obtain from it by
dP
calculation the boiling point at 760 mm. of mercury.
 EQUILIBRIUM CONSTANT OF ESTERIFICATION 705

Up to the present, we have carried out several investigations only on the

reaction that takes place in the formation of ethyl acetate. It is quite
clear, however, that the same method may be applied in many other cases.

EXPERIMENTAL DATA

Three series of experiments were ma.de in order to test the application of

the method described. The reacting substances were carefully purified
by methods described in previous papers and the mixtures weighed out by
means of the apparatus previously described (4).
TABLE 1
EXPERIMENTAL VALUES I I1 I11
1. Proportion of alcohol and acid.. . . . 1: 1 3:1 1:3
2. Initial temperature difference A h . . . 0.061"C. 0.233"C. 0.605"C.
3. Time in days.. . .: . . . . . . . . . . . . . . . . . 25 42 44
4. Final temperature difference, A t . . , o.ooooc. 0.002"c. 0.008"C.
5. Number of drops, n. . . . . . . . . . . . . . . 120 108 109
6. Correction for the dead space.. . . . . -0.018"C. -0.014°C. -0.048"C.
7. Correction for overheating.. . . . . . . -0.033"C. -0.034"C. -0.034"C.
8. Boiling point corresponding to the
equilibrium state. . . . . . . . . . . . . . . . 76.25"C. 73.66"C. 90.78"C.
9. Equilibrium constant, K . . . . . . . . . . 3.82 2.47 4.74

TABLE 2
Changes in tA - t, with time
3 moles alcohol and 1 mole acetic acid
I
~

CHANQES IN tA - 1, TIME CHANGES IN t, - 1,

TIME
-
&us days
0 0.340 43 0.023
2 0.320 54 0.009,
5 0.290 64 0.003
14 0.182 65 0.002
24 0.087 66 0.001

I n table 1 the following data are given: (1) the proportion of ethyl
alcohol and acetic akid in the "initial" mixture; (2) the initial temperature
difference, AtO; (3) the time of duration of measurements, in days; (4)the
final temperature difference, At, when the equilibrium state was taken as
"established"; (5) the number of drops, n, flowing through the drop-
counter per minute; ( 6 ) the correction for the dead space of the ebullio-
scope; (7) the correction for the overheating of the liquid; (8) the boiling
point of the liquid in equilibrium a t 1 atmosphere (compared with the boil-
ing point of water as the standard substance); (9) the equilibrium con-
706 W. SWIETOSLAWSKI

stant IC. The experiments were made by Sobolewski (column I), Kwie-
cinska (column 11),and Bochenk (column 111).
Table 2 illustrates the changes in the difference t A - tB with time. It is
a repetition of experiment I1 and was carried out by Dobry-Szapiro.
It seems that this difference, after several transports of the thermometer
from one apparatus to the other, may be established with an accuracy of
O.O0lo - 0.002"C. It is very probable that this accuracy is greater than
that in the determination of the boiling point of the reacting liquid in the
pure state. The method thus allows of more accuracy than the method of
preparation of the pure liquid substances, and the figures in table 4 should

TABLE 3
_--

ALCOHOL ACID ESTER WATER At

I
degree8 C.
0,9242 0.0404 0.4018 0.4018 4.321 0.202
0.9233 0.0389 0.4033 0.4033 4.529 0.091
0.9225 0.0381 0.4041 0,4041 4.646 0.027
0.9221 0.0377 0.4045 0.4045 4.707 0.010
0.9218 0.0374 0,4048 0.4048 4,753 0.003

TABLE 4
Values 01 K obtained by S w l e t d a w s k i and by others
K
~~-
~
MOLE ALCOHOL
M O L E ACID Ebullioscopic
method 1 Pornanski
I
1: 1 3.82 3.79 3.76 3.70
3: 1 2.47 2.45 - -
1:3 4.74 4.72 - -

be considered to apply to the substances used in our experiments. In two

experiments where different samples of reacting substances were used, the
mixture when in the equilibrium state gave a difference between the boiling
points equal to O.O17OC., whereas the differences t A - t B observed for the
two mixtures in one experiment did not exceed 0.002°C. Table 3 gives an
example of the method for determining the composition of the equilibrium
mixture, C, and its boiling point.
The calculation of K can be performed with great accuracy. In table
4 we have given for K only two decimals because we consider that the
methods of purification of the reacting substances are not sufficiently
trustworthy to guarantee the third decimal. I n table 4 is given a com-
parison of the data obtained by us and by other authors (5).
 EQUILIBRIUM CONSTANT OF ESTERIFICATION 707

SUMMARY

The ebullioscopic method for determining the composition of equilibrium

mixtures seems to be very accurate and is applicable in all cases where the
boiling temperature of the equilibrium solution differs considerably from
the boiling points of the initial mixtures of reacting substances. The
preparation of the equilibrium mixtures] when the equilibrium has been
established, may be performed with a high degree of accuracy. I n the
case of the formation of ethyl acetate the ebullioscopic method is even more
trustworthy than the methods of purification of the reacting substances.
The values for the equilibrium constant of esterification in the liquid phase
have been found for mixtures whose initial composition was 1 mole ethyl
alcohol: 1 mole acid, 3 moles alcohol: 1 mole acid, and 1 mole alcohol:
3 moles acid. The boiling points of the corresponding equilibrium mix-
tures were found to be: 76.25"C., 73.66"C., and 9O.7S0C., respectively.
REFERENCES
(1) SWIETOSLAWSKI, W., BLASZKOWSKA, MISS Z., AND JOSEFOWICZ: Bull. acad. sci.
Polonaise 1929, 149.
(2) SWIETOSLAWSKI,WL: Anales SOC. espafi. fis. quim. 27,439 (1929).
(3) SWIETOSLAWSKI, W.:Bull. acad. sci. Polonaise 1929,464-5.
(4) BLASKOWSKA, Z.:Ind. Eng. Chem., Anal. Ed. 1, 170 (1929).
(5)POZNANSKI, S.: Rocaniki Chem. 8, 387 (1928).