Abstract
Gold or platinum electrodes are withdrawn from various electrolyte solutions, at a constant potential, into a water-saturated nitrogen gas phase (“emersion” under potentiostatic control). The Volta potential difference between a vibrating SnO 2 surface (Kelvin's vibrating capacitor method) and either the emersed electrode or the surface of a solution of known redox potential is evaluated and subsequently used to determine the difference, if any, between the absolute electrode potential of the metal electrode in the immersed and emersed state. It is shown that, upon emersion of a metal electrode, the absolute electrode potential decreases by up to 0.32 V, and further, that the magnitude of this decrease is reduced for electrolytes containing specifically adsorbing anions. This change is attributed to the reorientation of the water molecules at the solution/gas interphase.
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