Kinetics and mechanisms of electron-transfer reactions of bismuth(V) in aqueous acidic perchlorate-fluoride media. Part 1. Oxidation of hypophosphorous acid

Article abstract of DOI:10.1039/DT9850002571

Solutions of bismuth(V) from NaBiO3 have been obtained in 1.0 mol dm^-3 HClO4 and 1.5 mol dm^-3 HF with a view to studying the redox system involving Bi^V and H3PO2.The reaction is first order in the concentration of each of Bi^V, H3PO2, and H⁺.It is catalysed by Bi^III through complex formation with the reactive species HBiF6.The rate law (i) holds where K_p is the protonation constant of ^- and K the complex formation constant between Bi^V and Bi^III.The values of K_pk and K were found to be 0.125+/-0.015 dm⁶ mol^-2 s^-1 and 45+/-6 dm³ mol^-1 respectively at 35 deg C and I = 2.0 mol dm^-3, k' and k are the second-order rate constants for the reaction between HBiF6 and H3PO2, and the complex and H3PO2 respectively.Bismuth(V) does not absorb in the u.v. region but Bi^III does, the wavelength depending on the source of Bi^III and the medium.

Full text of DOI:10.1039/DT9850002571

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