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364 rate-controlling step in place of diffusion The higher the rotation rate of the electrode, the sooner the transition occurs between the transport-controlled process and the surface-controlled process The current increase at 16 V corresponds to platinum 'surface oxide' formation The electrocatalytic oxidation of lower aliphatic compounds such as alcohols, aldehydes, hydrocarbons and formic and oxalic acid at platinumgroup electrodes has a number of typical features The chemisorption process usually involves the dissociation of several hydrogen atoms from the original molecule and a so-far not completely identified intermediate (often termed 'reduced carbon dioxide' for the reactions of methanol, formaldehyde and formic acid) remains adsorbed on the electrode At electrode potentials higher than 035 V (versus a hydrogen electrode located in the same solution and saturated with hydrogen at standard pressure) all the hydrogen atoms formed during chemisorption are oxidized anodically.



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The adsorbed intermediate can be oxidized at potentials higher than +04 V; the larger the coverage by the adsorbed intermediate, the higher the threshold potential of the anodic oxidation This phenomenon can be explained by the 'pair mechanism' of the anodic process, proposed by S Gilman Water molecules in the vicinity of the adsorbed intermediate are highly polarized, facilitating their oxidation The OH radicals formed then immediately attack this intermediate in a surface reaction At a constant potential, the rate of this process decreases because the number of sites available for oxidation of water gradually diminishes However, if a pulse of increasing positive potential is applied to the electrode, then the oxidation of water resulting in OH radical formation is accelerated by increasing the potential and the rate of the overall electrode process is enhanced, as shown for methanol in Fig 545.

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Clearly, the rate of the process at low potentials decreases with increasing concentration of methanol owing to the retarding effect of electrode coverage with the intermediate In contrast, at higher potentials, the rate of the process increases with increasing concentration (the oxidation of water is so fast that the overall rate increases with increasing surface coverage) So far, several examples have been given of the inhibition of electrocatalytic processes This retardation is a result of occupation of the catalytically more active sites by electroinactive components of the electrolyte, preventing interaction of the electroactive substances with these sites The electrode process can also be inhibited by the formation of oxide layers on the surface and by the adsorption of less active intermediates and also of the products of the electrode process.

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