Studies on the mechanism of the hydrogen electrode reaction by means of deuterium tracer—III. The stoichiometric number

✍ Scribed by T. Matsushima; M. Enyo

• Publisher: Elsevier Science
• Year: 1974
• Tongue: English
• Weight: 580 KB
• Volume: 19
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(74)80030-7

✦ Synopsis

The stoichiometric number of the hydrogen electrode reaction on Rh, Ni, Pt, Au, Ag, and Ir was determined by means of deuterium tracer at the reversible potential. It is shown that, along with the change of the rate-determining step in the reaction route, H, $2H(a) followed by H(a) + B z$ H+B + e, where B = H,O or OH-, the stoichiometric number? experimentally observed should change by the relation,v = (m + 2)/(m + 1), where m = u,/2v, and u, and v,, are the exchange rates of these steps. The experimental v us m relation observed on these metals qualitatively satisfied this relation. Disagreement which existed were quantitatively explained by taking the isotope effect into account. The isotope effect of the individual steps, which were needed to interpret the disagreements, were found to be of reasonable magnitude. X N X, N 1, this reduces approximately to* i, = 2N,F(Xo -X)/N,At.