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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.
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 '
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
EXPERIMENTAL DATA
TABLE 2
Changes in tA - t, with time
3 moles alcohol and 1 mole acetic acid
I
~
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
_--
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 - -
SUMMARY