, Volume 23, Issue 6, pp 597-605

Temperature dependence of the Tafel slope for oxygen reduction on platinum in concentrated phosphoric acid

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Oxygen reduction on bright platinum in concentrated H3PO4 has been investigated with the rotating disc electrochemical technique at temperatures from 25 to 250° C and oxygen pressures up to 1.77 MPa. Cyclic voltammetry has been employed to study the anodic film formed on platinum in concentrated H3PO4 and the possible electroreduction of H3PO4 on platinum. The apparent transfer coefficient for the oxygen reduction has been found to be approximately proportional to temperature rather than independent of temperature. Such behaviour is difficult to reconcile with accepted theories for the effect of electrode potential on the energy barriers for electrode processes. It is of importance to establish an understanding of this phenomenon. Possible factors which can contribute to the temperature dependence of the transfer coefficient but which would not necessarily result in a direct proportionality to temperature include potential dependent adsorption of solution phase species, restructuring of the solution in the compact layer, proton and electron tunnelling, a shift in rate-determining step, changes in the symmetry of the potential energy barrier, penetration of the electric field into the electrode phase, insufficient correction for ohmic losses, and impurity effects.

This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.