Oxygen electrode reaction. Part 1.—Nature of the inhibition process

Abstract

Standard electrochemical techniques were used to investigate the interaction of oxygen with both smooth and platinized platinum in aqueous solution. The formation of oxide films on the metal surface follows Elovich kinetics and this is explained in terms of increasing inhibition of the chemisorption of oxygen molecules at the interface by electrostatically-adsorbed water molecules. This type of effect, which is well known from the behaviour of organic compounds in double layer studies, is used to account for the failure of the conventional oxygen electrode to attain its reversible potential value. The theory also accounts for literature reports of departures from simple Nernstian and Tafel behaviour of this electrode system.