778

LXXVII1.-The

Cornpowads of Ethyl Alcohol with Water.

By D. MENDEL~EFF.

DALTON'S
great doctrine respecting the atomic constitution of matter
has not hitherto been applied to the explanation of the phenomena of
dissolntion, and notwithstanding the many admirable investigations
on this subject, the views of chemists respecting the relation between
ordinary cases of combination and the phenomena of dissolution
remain still undefined. However, the part played by solutions in
nature, i n the laboratory, and in the arts, is so important that t h e
fulness of our chemical conceptions seems to suffer from the want of
clearness in the doctrine relating t o them.
In communicating the result of some of my investigations and
hypotheses, I will restrict myself t o the particular case of solutions of
ethylic alcohol in water, chiefly because, among solutions, the mixtures of alcohol and water have been most fully studied, at any rate,
with reference to the dependence of change of specific gravity on the
proportion of alcohol. Practical necessity has led to many accurate
investigations of this subject, and from the time of Gilpin to our own
the mass of accurate information has been steadily increasing, and
permits of a sound judgment being formed. Collating all the information a t our disposal, I have constructed the following Table [I) of
the most trustworthy data :-

TABLE
I.
Percentage
by weight of
alcohol,
21.

Specific gravity in
a vacuum a t 15" C.,
taking water at 4
'
= 10,000, and a t
15' = 9991'6,

Percentage
by weight of
alcohol,

P*

8.

5
10
15
20
25
30
35
40
45
50

9904 '1
9831.2
9768 *4
9707.9
9644'3
9570.2
9484.5
9389.6
9287 ' 8
9179.0

Specific p a r i t y in a
vacuum at 15' C.,
taking water at 4"
= 10,000, and at
15" = 9991.6,
8.

55
60
65

70
75
80
a5
90
95
100

9067.4
8953.8
8838.6
8719.5
8601.4
8479.8
8354.8
8225 '0
8086.9
7936.6

It is interesting to note that, after making some necessary correc-

THE COMPOUNDS OF ETHYL ALCOHOL WITH WATER.

779

tions, the data mentioned by different observers, taking only the most
trustworthy observations, show very small differences. For example,
in the case of a solution of 50 per cent. of alcohol we find the following :-

TABLE11.

................
.............
.................
.............
.............
............
.........
................

Gilpin..
Gay-Lnssac
Fownes
Drinkwater.
Baumhauer
Mendeleeff..
Dupr6 and Page
Squibb.,

1792
1824
1847
1848

1060
1865
1869
1884

9187.0
9182 .0
9180.0
9178.8
9180 .0
9179.7
9178.5
9178 .O

In the above table of specific gravities, the greatest error is within

0.0002, and only in some cases attains 0.0003. No other solution
besides that of alcohol, and none of its other properties, are known
with such a degree of accuracy, and in addition the solutions can be
obtained in all proportions, and therefore the example which I have
taken is a typical one.
Without describing the methods by which I have arrived a t my
views on the nature of solutions (some of the preliminary investigations on this subject have been published by me in the Journal of
the Russian Chemical Society, and in Professor Ostwalds Zeitschrift
jijrphysikaZishe Chemie), I will now state the hypothesis which is in
accordance with them.
Solutions may be regarded as strictly definite, atomic chemical
combinations a t temperatures higher than their dissociation temperature. Definite chemical substances may be either formed or
decomposed a t temperatures which are higher than those a t which
dissociation commences ; the same phenomenon occurs in solutions j
at ordinary temperatures they can be either formed o r decomposed.
In addition, the equilibrium between the quantity of the definite
compound and of its products of dissociation is defined by the laws of
chemical equilibrium, which laws require a relation between equal
volumes and their dependence on the mass of the active component
parts. Therefore, i f the above hypothesis of solution be correct, comparisons must be made of equal volumes ; the specific gravities are
the weights of equal volumes, and moreover we must expect the
specific gravities of solutions to depend on the extent t o which the
active substances are produced ; therefore, the expression for specific
gravity s, as a function of the percentage composition p , must be a
parabola of the second order :n)(100 - p I a),
s = N(p
3 H 3

780

MENDELEEFF : THE COMPOUNDS OF

or t,his may be represented b y the general equations

=C

+ Ap + Bp2.

Between two definite compounds which exist in solutions, we must

dS

expect that the differential coefficient - will be a rectilinear function

4J

ofp:

This consequence can, in the first place, be verified by experiment,

and secondly gives the means of ascertaining what are the definite
combinations existing in the solution.
Applying this method to the solution of H1O and C2H60,
three
definite combinations are found to exist, namely-

C,H,O
CzH60
3CZH60

+ 12H20 = 17.56 per cent. alcohol.

-+ 3H30 = 46.00 ,,
+ HZO = 88.46 ,,
$9

9,

The rectilinear character of the differential coefficient

strated by the annexed diagram

:-

dS

dP

is demon-

- 10
- 20

- 20

- 30

- 30

The parabolas expressing the specific gravities a t 15" C. are calculated by the formula-

0,19581,2(9,36,1
9991.6
I. s = 9991.6 - 17.9913
11. s = 9868.4 - 4 . 0 9 7 5 ~- 0'1958p22(9265,6
111. S = 10166.6 - 1 7 . 5 4 5 ~ - 0 . 0 4 4 3 ~.8267.4 '
IV. s = 9074.9 + 8'192p - 0.1958p2{7936.1
TVith change of temperature, the constants of the parabola change,

ETHYL ALCOHOL WITH WATER.

781

but for temperatures between -30" and +40", a t which accurate

observations exist, the applicability of the parabolic expression is as
exact as it is at 15", and for that temperature an example is given in
line 111, which is t h e longest traced. The difference between the
calculated and t h e observed results in no case exceeds the allowable
errors of experiment, as the following table shows :-

TABLE
111.
Percentage
of
alcohol.

Value by
experiment.
Specific gravity.

Value by
calculation.
Specific gravity.

50
55
60
65

9179 '0
9067'4
8953 'a
8838.6
8719.5
8601 '4
a479 ' 8
836 1. .8

9178.4
9067.3
8954.1
8838.6

70
75
80
85

8721 .O
8601 *1
8479 .o
8354.7

The hypothesis respecting the rectilinear character of the differential coefficient

ds

dP

has been proved to be correct, not only for solutions

of a hundred different salts, but also for solutioiis of H,SO,, of NH,,

of HCl, and otber similar substances, and up to this time I have not
met with a single solution which is an exception.
As the principle of my hypothesis lies in the idea of dissociation of
definite compounds which exist in solutions, I intend t o investigate
minutely solutions at low temperatures, and I expect to obtain
definite compounds in the solid state, and to explain the relation of
the solid compounds which were obtained by me in 1868, and afterwards by Guthrie, who called them cryohydrates; indeed I have
already made some experiments in that direction with the assistance
of Mr. Teeshenko. Thus we have obtained the definite compound
C,H,O + 12H,O in the solid state at -17" C., and the definite compound C,H,O
3H,O in the crystalline form, a t a temperature
which is attained by the mixture of solid carbonic anhydride and
ether.
The fundamental propositions of my investigations, that is to
say, firstly, the rectilinear character of the differential coefficient
d
2.
and, secondly, the existence in solutions of definite comhinadl3 '
tions, I am developing in a special paper, in which I attempt, as far
as possible, to distinguish clearly that portion of the theory which

782

L I N G : ISOMERIC CHANGE I N THE

does not admit of question from the hypothesis which still requires
verification and amplification.
I do not consider that my investigations are finally completed, and
I only venture to lay them before a scientific society as footsteps
along the road leading to the elucidation of the theory of dissolution
in the light of Daltons teaching, and with the help of modern views
respecting dissociation and the dynamic equilibrium of molecules,
which I may be allowed to term association.