When the potential gradient is one volt (10^8 C.G.S. units) per
centimetre this becomes
u + v = 1.036 × 10^-7 × k/m.
Thus by measuring the value of k/m, which is known as the equivalent
conductivity of the solution, we can find u + v, the velocity of the
ions relative to each other. For instance, the equivalent conductivity
of a solution of potassium chloride containing one-tenth of a
gram-equivalent per litre is 1119 × 10^-13 C.G.S. units at 18° C.
Therefore
u + v = 1.036 × 10^7 × 1119 × 10^-13
= 1.159 × 10^-3 = 0.001159 cm. per sec.
In order to obtain the absolute velocities u and v, we must find some
other relation between them. Let us resolve u into ½(u + v) in one
direction, say to the right, and ½(u - v) to the left. Similarly v can
be resolved into ½(v+u) to the left and ½(v-u) to the right. On
pairing these velocities we have a combined movement of the ions to
the right, with a speed of ½(u - v) and a drift right and left, past
each other, each ion travelling with a speed of ½(u + v), constituting
the electrolytic separation. If u is greater than v, the combined
movement involves a concentration of salt at the cathode, and a
corresponding dilution at the anode, and _vice versa_. The rate at
which salt is electrolysed, and thus removed from the solution at each
electrode, is ½(u + v). Thus the total loss of salt at the cathode is
½(u + v) - ½(u - v) or v, and at the anode, ½(v + u) - ½(v - u), or u.
Therefore, as is explained in the article ELECTROLYSIS, by measuring
the dilution of the liquid round the electrodes when a current passed,
W. Hittorf (_Pogg. Ann._, 1853-1859, 89, p. 177; 98, p. 1; 103, p. 1;
106, pp. 337 and 513) was able to deduce the ratio of the two
velocities, for simple salts when no complex ions are present, and
many further experiments have been made on the subject (see _Das
Leitvermögen der Elektrolyte_).
By combining the results thus obtained with the sum of the velocities,
as determined from the conductivities, Kohlrausch calculated the
absolute velocities of different ions under stated conditions. Thus,
in the case of the solution of potassium chloride considered above,
Hittorf's experiments show us that the ratio of the velocity of the
anion to that of the cation in this solution is .51 : .49. The
absolute velocity of the potassium ion under unit potential gradient
is therefore 0.000567 cm. per sec., and that of the chlorine ion
0.000592 cm. per sec. Similar calculations can be made for solutions
of other concentrations, and of different substances.
Table IX. shows Kohlrausch's values for the ionic velocities of three
chlorides of alkali metals at 18° C, calculated for a potential gradient
of 1 volt per cm.; the numbers are in terms of a unit equal to 10^-6 cm.
per sec.:--
TABLE IX.
Public-domain text, read in full here on John Shaqi.
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