Page:A Treatise on Electricity and Magnetism - Volume 1.djvu/355

From Wikisource
Jump to navigation Jump to search
This page has been proofread, but needs to be validated.
261.]
SECONDARY PRODUCTS OF ELECTROLYSIS.
313

electrolyte and as an anion in another, and also of entering into compound bodies which are not electrolytes, then we must suppose that it receives a positive charge of electricity when it acts as a cation, a negative charge when it acts as an anion, and that it is without charge when it is not in an electrolyte.

Iodine, for instance, acts as an anion in the iodides of the metals and in hydriodic acid, but is said to act as a cation in the bromide of iodine.

This theory of molecular charges may serve as a method by which we may remember a good many facts about electrolysis. It is extremely improbable that when we come to understand the true nature of electrolysis we shall retain in any form the theory of molecular charges, for then we shall have obtained a secure basis on which to form a true theory of electric currents, and so become independent of these provisional theories.

261.] One of the most important steps in our knowledge of electrolysis has been the recognition of the secondary chemical processes which arise from the evolution of the ions at the electrodes.

In many cases the substances which are found at the electrodes are not the actual ions of the electrolysis, but the products of the action of these ions on the electrolyte.

Thus, when a solution of sulphate of soda is electrolysed by a current which also passes through dilute sulphuric acid, equal quantities of oxygen are given off at the anodes, and equal quantities of hydrogen at the cathodes, both in the sulphate of soda and in the dilute acid.

But if the electrolysis is conducted in suitable vessels, such as U-shaped tubes or vessels with a porous diaphragm, so that the substance surrounding each electrode can be examined separately, it is found that at the anode of the sulphate of soda there is an equivalent of sulphuric acid as well as an equivalent of oxygen, and at the cathode there is an equivalent of soda as well as two equivalents of hydrogen.

It would at first sight seem as if, according to the old theory of the constitution of salts, the sulphate of soda were electrolysed into its constituents sulphuric acid and soda, while the water of the solution is electrolysed at the same time into oxygen and hydrogen. But this explanation would involve the admission that the same current which passing through dilute sulphuric acid electrolyses one equivalent of water, when it passes through solution of sulphate