_If the same current be made to pass through several different
electrolytes, the quantity of each ion produced will be proportional
to its combining weight divided by its valency, and if the current
vary, the quantity of each ion liberated per second will be
proportional to the current._
This is the great law of electro-chemical equivalents. The amount of
hydrogen liberated per second by a current of one ampere is about
.00001038 gramme, or nearly one six-thousandth of a grain. This is the
electro-chemical equivalent of hydrogen. That of any other substance
may be found by Faraday's law.
From Faraday's results it appears that the passage of the same amount
of electricity is required in order to decompose one molecule of any
compound of the same chemical type, but it does not follow that the
same amount of energy is employed in the decomposition. For example,
the combining weights of copper and zinc are nearly equal. Hence it
will require the passage of about the same amount of electricity to
liberate a pound of copper from, say, the copper sulphate as to
liberate a pound of zinc from zinc sulphate; but the work to be done
is much less in the case of the copper. This is made manifest in the
following way:--A battery, which will just decompose the copper salt
slowly, liberating copper, oxygen, and sulphuric acid, will not
decompose the zinc salt at all so as to liberate metallic zinc, but
immediately on sending the current through the electrolyte,
polarization will set in, and the opposing electro-motive force thus
introduced will become equal to that of the battery, and stop the
current before metallic zinc makes its appearance. In the case of the
copper, polarization also sets in, but never attains to equality with
the electro-motive force of the primary battery. In fact, in all cases
of electrolysis, polarization produces an opposing electro-motive
force strictly proportional to the work done in the cell by the
passage of each unit of electricity. If the strength of the battery be
increased, so that it is able to decompose the zinc sulphate, and if
this battery be applied to the copper sulphate solution, the latter
will be _rapidly_ decomposed, and the excess of energy developed by
the battery will be converted into heat in the circuit.
One important point in connection with electrolysis which Faraday
demonstrated is that the decomposition is the result of the passage of
the current, and is not simply due to the attraction of the
electrodes. Thus he showed that potassium iodide could be decomposed
by a stream of electricity coming from a metallic point on the prime
conductor of his electric machine, though the point did not touch the
test-paper on which the iodide was placed.
Public-domain text, read in full here on John Shaqi.
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