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Issue 12, 1985
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Kinetics and mechanism of electron-transfer reactions of bismuth(V) in aqueous acidic perchlorate–fluoride media. Part 1. Oxidation of hypophosphorous acid

Abstract

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 BiV and H3PO2. The reaction is first order in the concentration of each of BiV, H3PO2, and H+. It is catalysed by BiIII through complex formation with the reactive species HBiF6. The rate law (i) holds where Kp is the protonation –d[BiV]//dt=(Kpk′+KpKk[BiIII])//1 +K[BiIII])[BiV][H3PO2][H+](i) constant of [BiF6] and K the complex formation constant between BiV and BiIII. The values of Kpk and K were found to be 0.125 ± 0.015 dm6 mol–2 s–1 and 45 ± 6 dm3 mol–1 respectively at 35° 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 H2PO2 respectively. Bismuth(V) does not absorb in the u.v. region but Bi III does, the wavelength depending on the source of BiIII and the medium.

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Article information


J. Chem. Soc., Dalton Trans., 1985, 2571-2574
Article type
Paper

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

K. M. Inani, P. D. Sharma and Y. K. Gupta, J. Chem. Soc., Dalton Trans., 1985, 2571
DOI: 10.1039/DT9850002571

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