_Arrhenius' Theory of Electrolysis._--In 1885, Arrhenius brought forward
his theory of the transport of electricity by an electrolyte. According to
this hypothesis, the electric current is carried by the ions, the positive
charges by the cations, and the negative charges by the anions. In virtue
of the attraction between charges of different sign, and repulsion between
charges of like sign, the cations are repelled by the positive charge on
the anode, and attracted by the negative charge on the cathode. Similarly
the anions are repelled by the cathode and attracted by the anode. {27}
An electrolytic solution contains three varieties of particles, positive
ions or cations, negative ions or anions, and undissociated neutral
molecules. The molecular concentration of such a solution, with the
corresponding constants, depends on the total number of these particles,
_i.e._ the sum of the ions and the undissociated neutral molecules. We may
indicate an ion by placing above it the sign of its electrical charge, one
sign for each valency. Thus Na^+ and Cl^- indicate the two ions of a salt
solution; Cu^{++} and SO_4^{--} the two ions of a solution of sulphate of
copper. A point is sometimes substituted for the + sign, and a comma for
the - sign. Thus Na^. and Cl^,; Cu^{..} and SO_4^{,,}.
My friend Dr. Lewis Jones has given a very vivid picture of the processes
which go on in an electrolytic solution when an electric current is
passing. He compares an electrolytic cell to a ballroom, in which are
gyrating a number of dancing couples, representing the neutral molecules,
and a number of isolated ladies and gentlemen representing the anions and
cations respectively. If we suppose a mirror at one end of the ballroom and
a buffet at the other, the ladies will gradually accumulate around the
mirror, and the gentlemen around the buffet. Moreover, the dancing couples
will gradually be dissociated in order to follow this movement.
_Degree of Dissociation._--The degree of dissociation is the fraction of
the molecules in the solution which have undergone dissociation. Let n be
the total number of molecules of the solute, and n" the number of
dissociated molecules. Then n" / n = a will represent the degree of
dissociation. Let k be the number of ions into which each molecule is
split. Then a = n"k / nk, _i.e._ the degree of dissociation is the ratio of
the number of ions actually present in a solution to the number which would
be present if all the molecules of the solute were dissociated.
Let n' be the total number of particles present in a solution {28}
containing n molecules, each of which is composed of k ions. Then if a is
the degree of dissociation,
n' = n - an + ank,
n' = n[1 + a (k - 1)],
n' / n = 1 + a (k - 1) = i.
We thus obtain i the coefficient of dissociation, in terms of the degree of
dissociation a and the number of ions in each molecule k.
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