_Solutions which conduct Electricity._--The laws of solution which we have
studied in the previous chapter apply only to those solutions, chiefly of
organic origin, which do not conduct electricity. Solutions of electrolytes
such as the ordinary salts, acids, and bases, which are ionized on
solution, give values for the various constants of solution which do not
accord with those required by theory. If, for instance, we take a
gramme-molecule of an electrolyte such as chloride of sodium, and dissolve
it in a litre of water, we find that the lowering of the freezing point is
nearly double the theoretical value of 1.85deg. The same holds good for the
osmotic pressure, and for all the constants which are proportional to the
molecular concentration of the solute. The solution behaves, in each case,
as if it contained more than one gramme-molecule of sodium chloride per
litre. It behaves, in fact, as if it contained i times the number of
molecules of solute originally introduced into it. If n be the original
number of molecules, then it will apparently contain n' = in molecules.
This law is universal for all electrolytic solutions; the theoretical value
for their concentration, osmotic pressure, and all the proportional
physical constants must be multiplied by this quantity, i = n'/n, which is
the ratio of the apparent number of the molecules present to the number
originally introduced.
A similar dissociation of the molecule is observed in the case of many
gases. The vapour of chloride of ammonium, for instance, is decomposed by
heat, and it may be shown experimentally that the increase of pressure on
heating above {25} that which theory demands, is due to an increase in the
number of the gaseous molecules present. Some of the vapour particles are
dissociated into two or more fragments, each of which plays the part of a
single molecule.
Arrhenius, in 1885, advanced the hypothesis that the apparent increase in
the number of molecules of an electrolytic solution was also due to
dissociation. This interpretation at once threw a flood of light on a
number of phenomena hitherto obscure.
_Coefficient of Dissociation._--We have seen that in order to obtain values
which accord with experiment we have to multiply the number of
gramme-molecules of the solute by the coefficient i, which is called the
Coefficient of Dissociation.
This coefficient of dissociation, i, may be found by observing the lowering
of the freezing point of a normal solution, and dividing it by 1.85. i =
t/1.85.
The coefficient of dissociation varies with the degree of concentration of
the solution, rising to a maximum when the solution is sufficiently
diluted.
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