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Kinetics and mechanism of the oxidation of nitrous acid by bromine in aqueous sulfuric acid

✍ Scribed by Ivan Valent; Igor Schreiber; Miloš Marek

Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
98 KB
Volume
32
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics and mechanism of the reaction between nitrous acid and bromine are studied in dilute sulfuric acid medium, using both the stopped-flow method and conventional spectrophotometry. The partial reaction order with respect to Br 2 moderately differs from 1, showing a saturation at a higher concentration of bromine. The second order of the reaction towards nitrous acid has been observed. Hydrogen and bromide ions significantly suppress the rate of reaction. Despite the apparent simplicity, the mechanism is rather complex, with two reaction pathways proposed. The first one is represented by the reaction of bromine with the intermediate dinitrogen trioxide. A direct nucleophilic attack of ion Ϫ NO 2 towards the bromine molecule is suggested as the second pathway. The proposed mechanism accounts for the observed behavior; in almost all cases a satisfactory quantitative agreement with the experiments is obtained.

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