Abstract
The electrolytic reduction of O 2 on Cu was studied in dilute H 2SO 4 at 25°C by steady-state and transient electrochemical techniques. A distinctive hump (i.e. a current maximum) is observed in the steady-state potentiostatic polarization curve approximately 50 mV negative to the open-circuit corrosion potential. Results of transient studies, of varying the solution agitation, and varying the concentrations of oxygen, sulphuric acid, and sulphate ions indicate that the hump is due to cathodic film formation which inhibits the rate of oxygen reduction. The inhibiting film appears to be composed of intermediates from the O 2 reduction process and also may contain adsorbed sulphate ions. The film is removed under corrosion conditions by rapid dissolution of the substrate copper. Extrapolation of the cathodic Tafel curve to the corrosion potential yields corrosion rates lower than those measured because of the cathodic passivation.
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