Electroactive Species produced by Electrolysis at Mercury Cathodes in Aqueous Solution

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THERE is evidence that in electrolysis of aqueous solutions at mercury cathodes the accumulation of atomic hydrogen dissolved in mercury as an amalgam, as suggested by Heyrovsky1 and Ilkovic2. Müller3 re-investigated hydronium ion discharge at dropping mercury electrodes, and attributed long term changes in volume to a slow step in the overall reaction either elimination of hydrogen from an amalgam, or decomposition of aqueous hydrogen molecule ions. The present work confirms that hysteresis is associated with the metal phase. We also present evidence for the occurrence of electrochemical desorption at mercury containing dissolved hydrogen atoms.

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