Page:A Treatise on Electricity and Magnetism - Volume 1.djvu/359

263.] force, and can therefore be measured according to the very same principles used in the measurement of electromotive forces.

Chemical affinity being therefore, in certain cases, reduced to the form of a measurable quantity, the whole theory of chemical processes, of the rate at which they go on, of the displacement of one substance by another, &c., becomes much more intelligible than when chemical affinity was regarded as a quality sui generis, and irreducible to numerical measurement.

When the volume of the products of electrolysis is greater than that of the electrolyte, work is done during the electrolysis in overcoming the pressure. If the volume of an electrochemical equivalent of the electrolyte is increased by a volume v when electrolysed under a pressure p, then the work done during the passage of a unit of electricity in overcoming pressure is vp, and the electromotive force required for electrolysis must include a part equal to vp, which is spent in performing this mechanical work.

If the products of electrolysis are gases which, like oxygen and hydrogen, are much rarer than the electrolyte, and fulfil Boyle's law very exactly, vp will be very nearly constant for the same temperature, and the electromotive force required for electrolysis will not depend in any sensible degree on the pressure. Hence it has been found impossible to check the electrolytic decomposition of dilute sulphuric acid by confining the decomposed gases in a small space.

When the products of electrolysis are liquid or solid the quantity vp will increase as the pressure increases, so that if v is positive an increase of pressure will increase the electromotive force required for electrolysis.

In the same way, any other kind of work done during electrolysis will have an effect on the value of the electromotive force, as, for instance, if a vertical current passes between two zinc electrodes in a solution of sulphate of zinc a greater electromotive force will be required when the current in the solution flows upwards than when it flows downwards, for, in the first case, it carries zinc from the lower to the upper electrode, and in the second from the upper to the lower. The electromotive force required for this purpose is less than the millionth part of that of a Daniell's cell per foot.