In the electrooxidation of various organic substances on a smooth platinum electrode, the reaction order with respect to the oxidizable substance is usually fractional, while at higher volume concentrations, the rate is independent of the concentration, which is due to the adsorption of the oxidizable substances on a uniformly inhomogeneous electrode surface.
In the electrooxidation of alcohols and aldehydes within the entire range of pH, the rate of the oxidation process at constant potentials (with respect to the hydrogen electrode in the same solution) practically does not vary with variation of the pH. The dependence of the rate of oxidation of carboxylic acids on the pH < 5 is explained by dissociation of the acid and oxidation of the anions.
An investigation of the influence of the concentration of a neutral salt on the rate of electrooxidation of methanol and formic acid indicates that variation of the ϕ1-potential does not influence these processes.
The kinetic equations of the oxidation of alcohols and carboxylic acids were analyzed, with a consideration of the change in the state of the electrode surface and in the adsorption of the oxidizable substance with the potential.
The most probable is the mechanism according to which the slow step is the oxidation by OH radicals of a particle adsorbed on the uniformly inhomogeneous surface of the platinum electrode.
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We should like to thank A. N. Frumkin for his valuable consideration of the results of the work.
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Khazova, O.A., Vasil'ev, Y.B. & Bagotskii, V.S. Electrooxidation of organic substances on a platinum electrode Communication 2. Kinetics of the oxidation of alcohols, aldehydes, and carboxylic acids, considering the inhomogeneity of the surface of the platinum electrode. Russ Chem Bull 14, 1743–1751 (1965). https://doi.org/10.1007/BF00850152
- Formic Acid
- Carboxylic Acid
- Electrode Surface