Page:A Treatise on Electricity and Magnetism - Volume 1.djvu/356

 of soda electrolyses one equivalent of the salt as well as one equivalent of the water, and this would be contrary to the law of electrochemical equivalents.

But if we suppose that the components of sulphate of soda are not SO₃ and NaO but SO₄ and Na,—not sulphuric acid and soda but sulphion and sodium—then the sulphion travels to the anode and is set free, but being unable to exist in a free state it breaks up into sulphuric acid and oxygen, one equivalent of each. At the same time the sodium is set free at the cathode, and there decomposes the water of the solution, forming one equivalent of soda and two of hydrogen.

In the dilute sulphuric acid the gases collected at the electrodes are the constituents of water, namely one volume of oxygen and two volumes of hydrogen. There is also an increase of sulphuric acid at the anode, but its amount is not equal to an equivalent.

It is doubtful whether pure water is an electrolyte or not. The greater the purity of the water, the greater the resistance to electrolytic conduction. The minutest traces of foreign matter are sufficient to produce a great diminution of the electrical resistance of water. The electric resistance of water as determined by different observers has values so different that we cannot consider it as a determined quantity. The purer the water the greater its resistance, and if we could obtain really pure water it is doubtful whether it would conduct at all.

As long as water was considered an electrolyte, and was, indeed, taken as the type of electrolytes, there was a strong reason for maintaining that it is a binary compound, and that two volumes of hydrogen are chemically equivalent to one volume of oxygen. If, however, we admit that water is not an electrolyte, we are free to suppose that equal volumes of oxygen and of hydrogen are chemically equivalent.

The dynamical theory of gases leads us to suppose that in perfect gases equal volumes always contain an equal number of molecules, and that the principal part of the specific heat, that, namely, which depends on the motion of agitation of the molecules among each other, is the same for equal numbers of molecules of all gases. Hence we are led to prefer a chemical system in which equal volumes of oxygen and of hydrogen are regarded as equivalent, and in which water is regarded as a compound of two equivalents of hydrogen and one of oxygen, and therefore probably not capable of direct electrolysis.