History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
seven tenths being resolved into independent ions of chlorine
(chloridion) and sodium (sodion): NaCl⇄[Na·] + Cl´, each moving freely
in all directions, like gaseous molecules. On passing the current,
electrodes placed in the solution exert a directive action on the free
ions, these alone being concerned in determining the conductivity, the
un-ionised molecules or the solvent itself exercising no influence.
Methods of determining the migration velocity of the ions have been
worked out by Hittorf, Kohlrausch, Lodge, and others.
[Illustration: SVANTE AUGUST ARRHENIUS.]
The theory of ionisation affords a satisfactory explanation of many
chemical phenomena. It accounts for the characteristic properties of
acids, and explains why different acids have varying “strengths” and
why a “weak” acid has the same “strength” as the “strong” acid at
high equivalent dilutions: in each case the acid is nearly completely
ionised—in other words, the “strength” of an acid depends on the
concentration of its hydrogen ions. So, too, the “strength” of a base
is related to the number of its hydroxyl ions. Aqueous ammonia is
relatively a “weak” base—its solution contains few hydroxyl ions. On
the other hand, caustic potash is a “strong” base—its solution, on
moderate dilution, is almost completely ionised: KOH = K· + OH´, the
positive ion being represented by one or more dots, and the negative
ion by one or more dashes. The theory accounts, too, for many phenomena
in analytical chemistry—such as why magnesia is precipitated by ammonia
only in the absence of ammonium chloride, and why sulphuretted hydrogen
throws down zinc sulphide in the absence of hydrochloric acid. It
also serves to explain many thermo-chemical facts observed by Hess,
Thomsen, and others, such as the fact that the heat of neutralisation
of the “strong” acids and bases is independent of their nature, and has
the uniform value of 13,700 calories, in agreement with the value, as
calculated by Van ’t Hoff, for the reaction H· + OH´ = H2O, deduced
from Kohlrausch’s measurements of the conductivity of water at varying
temperatures.
Certain phenomena relative to the effect of concentration (mass action)
in determining chemical change—many of which have been studied by
Ostwald and his pupils, as, for example, why two dilute solutions can
be mixed together without thermal disturbance; numerous hydrolytic
actions; the alkalinity and acidity of salts on solution; the behaviour
of the “indicators” in analysis; such phenomena as the precipitability
of common salt in aqueous solution by hydrogen chloride; the influence
of an excess of a precipitant; the varying behaviour of reagents; the
varying colour of salt solutions; the reason why water is formed in so
many reactions; why a potential difference occurs at the surface of
two electrolytic solutions, etc.—phenomena for the most part otherwise
unintelligible, are all capable of explanation by means of it.
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