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Abstract
The current flowing between two unattackable electrodes under the influence of a P.D. less than the decomposition voltage of the electrolyte has been investigated and found to be extremely complex.
Curves have been constructed showing the variation of current with time, when the applied E.M.F. is changed by steps of ±o·1 volt. These curves are not appreciably affected by change of shape of electrolysis vessel or distance between the electrodes, or by change of electrode from smooth Pt to smooth Au, but they are greatly altered (a) by change of mechanical condition of the electrode surface, (b) by ageing the electrodes by using them in these experiments for long periods, and (c) by using an electrolyte from which a metal instead of a gas tends to deposit on one electrode.
Shaking an electrode or stirring the surrounding electrolyte during the application of an E.M.F. increases the current flowing if a gas tends to deposit on that electrode, but not if a metal tends to deposit. Increases up to 800% have been observed with freshly platinized electrodes and less than 20% with aged smooth electrodes.
The current passed is recoverable when used (a) in generating gas at one or both electrodes at low pressures, thus forming high-capacity condensers, (b) in charging these condensers, and (c) in generating more gas to replace that lost by diffusion into the electrolyte in the molecular state, and into the electrodes in the atomic state.
A considerable proportion of the total residual current, usually over 80%, is irrecoverable, and only a very small fraction of the irrecoverable part can reasonably be accounted for by the normal processes of diffusion, etc.
It follows therefore that at least 75% of the observed residual current is carried by some process which does not conform with Faraday's laws.
It is suggested that under the influence of a very high potential gradient across an attenuated gas-film covering the electrodes, electrons may be extracted or deposited with production of current not associated with the transport of ions through the electrolyte.