The reaction of 2V3++ Br2+ 2H2O → 2VO2++ 2Br–+ 4H+ obeys the rate expression –d[VIII]/dt=k′[VIII][Br2][H+]–1 with k′= 4·57 ± 0·44 s–1, Ea= 63·6 ± 2·9 kJ mol–1 and ΔS‡=–38·1 ± 7J mol–1 K–1 at 25 °C and ionic strength, µ= 2·0M. V3+ Therefore reacts with Br2 at a negligible rate compared with that of VOH2+. Added chloride ion enhances the rate of the reaction while bromide decreases it.
A. Adegite and M. H. Ford-Smith, J. Chem. Soc., Dalton Trans., 1972, 2113 DOI: 10.1039/DT9720002113
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