If there is no dissociation, _i.e._ if a = 0, then n' = n, and i = 1. If
all the molecules are dissociated, a = 1, and i = k.
_Faraday's Law._--Faraday found that the quantity of electricity required
to liberate one gramme-molecule of any radical is 96.537 coulombs for each
valency of the radical.
_Electrochemical Equivalent._--The electrochemical equivalent of a radical
is the weight liberated by one coulomb of electricity. It is equal to the
molecular weight of the ion, divided by 96.537 times its valency.
_Electrolytic Conductivity._--The conductivity of an electrolyte is the
inverse of its resistance. C = 1/R.
For a given difference of potential the conductivity of an electrolyte is
proportional to the number of ions in unit volume, the electrical charge on
each ion, and the velocity of the ions.
_The specific conductivity_ [Delta] of an electrolyte is the conductivity
of a cube of the solution, each face of which is one square centimetre in
area. The _molecular conductivity_ of an electrolyte is the conductivity of
a solution containing one gramme-molecule of the substance placed between
two parallel conducting plates, one centimetre apart. The molecular
conductivity is independent of the volume occupied by the gramme-molecule
of the solute, depending only on the degree of dissociation. The molecular
conductivity U is equal to the product of V, the volume of the molecule, by
[Delta], its specific conductivity. U = V[Delta]. Whence [Delta] = U / V,
_i.e._ the specific {29} conductivity equals the molecular conductivity
divided by the volume.
The conductivity of an electrolyte is proportional to the number of ions in
a volume of the solution containing one gramme-molecule. Let M_{[infinity]}
be the conductivity for complete dissociation and M_v the molecular
conductivity at the volume V. Then
M_v / M_{[infinity]} = n"k / nk = n" / n = a,
the degree of dissociation. This is Ostwald's law, which says that the
degree of dissociation is equal to the ratio of conductivity when the
gramme-molecule occupies a volume V, to its conductivity when the solution
is so dilute that dissociation is complete. Hence the degree of
dissociation may also be determined by comparing the electrical
conductivities of two solutions of different degrees of concentration.
| -- -- -- | -- -- -- |
| SO_4 SO_4 SO_4 | SO_4 SO_4 SO_4 |
| | |
| ++ ++ ++ | ++ ++ ++ |
| Cu Cu Cu | Cu Cu Cu |
| | |
+----------------------------+--------------------------------+
FIG. 1.--Before the passage of the current.
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