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DOI: 10.1039/A805675G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 651-656

Kinetics and thermodynamics of the reaction of aliphatic N-bromamines with bromide ion in acid media, and the pKa of N-bromamines[hair space]†

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Juan M. Antelo, Florencio Arce, Juan Crugeiras, Edward T. Gray and Patricia Yebra

Abstract

The kinetics of the oxidation of bromide ions by aliphatic N-bromamines in aqueous acid media were studied using a pH jump technique. The reaction is first order in both bromide ion and total bromamine concentrations, and takes place only through the protonated N-bromamine. For two of the N-bromamines studied (N-Br-dimethylamine and N-Br-diethylamine), hydrolysis competed with the reaction with bromide ions, whereas in all the other cases hydrolysis was too slow to be detected. The pKa values obtained from the kobsvs. [H+] data at 25 °C are 2.88 for N-Br-dimethylamine, 3.24 for N-Br-diethylamine, 3.33 for N-Br-piperidine (all at I = 0.1 M), 2.26 for N-Br-iso-butylamine and 2.92 for N-Br-sec-butylamine (both at I = 0.5 M).

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