In 1876, Kohlrausch compared the conductivity of the chlorides, bromides,
and iodides of potassium, sodium, and ammonium respectively. He found that
altering the cation did not affect the _differences_ of conductivity
between the three salts, thus showing that these differences of
conductivity were dependent on the nature of the anion only, and not on the
particular base with which it was combined. The difference of conductivity
between an iodide and a bromide, for example, is the same whether
potassium, sodium, or ammonium salts are compared. A similar experiment has
been made with a series of cations combined with various anions. The
difference of conductivity of the salts in the series is the same whichever
anion is used, _i.e._ the difference of conductivity between potassium
chloride and sodium chloride is the same as that between {31} potassium
bromide and sodium bromide. Hence we may conclude that the conductivity of
any salt is an ionic property.
Kohlrausch's law may be expressed by the formula c = d(u + v), where c is
the conductivity of the salt, d the degree of dissociation, _i.e._ the
fraction of the electrolyte broken up into ions, and u and v the velocity
of the anions and cations respectively. When all the molecules of the
electrolyte are dissociated, d = 1, and the formula becomes c_{[infinity]}
= u + v.
As we have already seen, a salt is formed by the union of a metal M with an
acid radical R. Potassium sulphate, K_2SO_4, consists of the metal K_2 and
the acid radical SO_4. Ammonium chloride, NH_4Cl, consists of the basic
radical NH_4 and the acid radical Cl. The various acids may be considered
as salts of the metal hydrogen. Thus sulphuric acid, H_2SO_4, is the
sulphate of hydrogen. Bases may be considered as salts with the hydroxyl
group, OH, replacing the acid radical. Thus potash, KOH, is the hydroxyl of
potassium. The various electrolytic combinations may be represented by the
following symbols:--
Salts = MR.
Acids = HR.
Bases = MOH.
The various chemical reactions of an electrolyte are all ionic reactions,
the chemical activity of an electrolytic solution being proportional to its
electric conductivity, _i.e._ the degree of dissociation of its ions. The
acidity of an electrolytic solution is due to the presence of the
dissociated ion H^+, and its strength is determined by the concentration of
these free hydrogen ions. Hence the greater the degree of dissociation the
stronger the acid.
The basic character of a solution is determined by the presence of the
hydroxyl radical OH^-. The greater the concentration of the hydroxyl ions,
_i.e._ the greater the dissociation, the stronger is the base.
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