The Electrolysis of Alkali Salts.
It has been observed by Arrhenius that when an alkali salt is being electrolyzed in aqueous solution, mercury forming the cathode, some time elapses before the hydrogen makes its appearance. This suggests that hydrogen is not the primary result of the electrolysis, but is due, perhaps, to the secondary action of the water of the solution upon the alkali amalgam, produced in the first instance by the discharge of the positive iron, i. e., the alkali metal. The interval of time which elapses from the turning on of the current to the first appearances of the hydrogen increases very slowly as the strength of the current diminishes, and when the current is maintained constant 1-20 ampere, increases as the concentration increases, and as the temperature decreases. For equivalent solutions of electrolytes, having the same positive iron, this time is practically constant. Theory indicates that the electromotive force required for electrolysis increases at the outset with the amount of electrolytic products already separated. But when secondary reactions take place, preventing the continuous accumulations of these products if the electrolysis goes slowly, the electromotive force required for electrolysis is determined almost solely by these secondary reactions. Evidently if the result of the secondary actions is the same as it is in the case of alkali salts, the electromotive force required for the decomposition will be practically for the same also. Recent experiments have shown that this is approximately the case. If they are confirmed, there will be no necessity for assuming the primary decomposition of the water.
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