Kinetic investigation of the oxidation of bromide ions by cobalt(III). Part 2.—The influence of pyridine and hydrocarbon on the reaction in acetic acid solvent
- 1 January 1986
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 82 (5) , 1405-1411
- https://doi.org/10.1039/f19868201405
Abstract
The kinetics of cobalt(III) acetate reduction in acetic acid have been studied under nitrogen at 60–93 °C in the presence of bromide, p-xylene and pyridine. At high p-xylene concentration the initial rate of reaction obeys the rate law [graphic omitted] =kc [CoIII]2[HBr]2//[CoII][Py]2 with kc= 0.057 s–1 at 80 °C and an apparent activation enthalpy of 59.8 ± 5.0 kJ mol–1. The value of the apparent reaction order with respect to hydrocarbon tends to one at low concentrations. The overall stoichiometry of reduced CoIII and oxidized Br– ions, ΔCoIII/ΔBr–, is close to two. The mechanism of reaction involves attack of hydrocarbon by bromine species coordinated to cobalt.Keywords
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