Page:A Treatise on Electricity and Magnetism - Volume 1.djvu/368

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326
ELECTROLYTIC POLARIZATION.
[272

means. These are of two kinds. In the batteries of Grove and Bunsen the negative plate is immersed in a fluid rich in oxygen, and the hydrogen, instead of forming a coating on the plate, combines with this substance. In Grove's battery the plate is of platinum immersed in strong nitric acid. In Bunsen's first battery it is of carbon in the same acid. Chromic acid is also used for the same purpose, and has the advantage of being free from the acid fumes produced by the reduction of nitric acid.

A different mode of getting rid of the hydrogen is by using copper as the negative metal, and covering the surface with a coat of oxide. This, however, rapidly disappears when it is used as the negative electrode. To renew it Joule has proposed to make the copper plates in the form of disks, half immersed in the liquid, and to rotate them slowly, so that the air may act on the parts exposed to it in turn.

The other method is by using as the liquid an electrolyte, the cation of which is a metal highly negative to zinc.

In Daniell's battery a copper plate is immersed in a saturated solution of sulphate of copper. When the current flows through the solution from the zinc to the copper no hydrogen appears on the copper plate, but copper is deposited on it. When the solution is saturated, and the current is not too strong, the copper appears to act as a true cation, the anion SO4 travelling towards the zinc.

When these conditions are not fulfilled hydrogen is evolved at the cathode, but immediately acts on the solution, throwing down copper, and uniting with SO4 to form oil of vitriol. When this is the case, the sulphate of copper next the copper plate is replaced by oil of vitriol, the liquid becomes colourless, and polarization by hydrogen gas again takes place. The copper deposited in this way is of a looser and more friable structure than that deposited by true electrolysis.

To ensure that the liquid in contact with the copper shall be saturated with sulphate of copper, crystals of this substance must be placed in the liquid close to the copper, so that when the solution is made weak by the deposition of the copper, more of the crystals may be dissolved.

We have seen that it is necessary that the liquid next the copper should be saturated with sulphate of copper. It is still more necessary that the liquid in which the zinc is immersed should be free from sulphate of copper. If any of this salt makes its way to the surface of the zinc it is reduced, and copper is deposited