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The kinetics and mechanism of oxidation of hydroxylamine by iron(III)

Author

  • Gösta Bengtsson
  • Sture Fronaeus
  • L Bengtsson-Kloo

Summary, in English

The kinetics of oxidation of hydroxylamine by iron() have been studied spectrophotometrically. The effects of pH, reactant and product concentrations led to two experimental rate expressions. The results obtained are consistent with a mechanism dependent on the relative iron(III)-to-hydroxylamine concentrations; an excess of iron() gives a stoichiometry of 2 : 1 for the total reaction and N2O as the oxidation product, whereas at equal amounts or excess of hydroxylamine the stoichiometry reduces to 1 : 1 with N-2 as the main product. In the latter case the rate expression d[ Fe(III)]/dt = k[Fe(III)](2) [NH2OH](2) /[Fe(III)](2) [H+](4) is obtained. The consistent mechanism identifies two pre-equilibria and the reaction of two different nitrogen-containing intermediates as the rate-determining step depending on the reactant ratios. The proposed mechanism does also involve the metal hydroxide complex Fe(OH)(2+), in agreement with previous results.

Publishing year

2002

Language

English

Pages

2548-2552

Publication/Series

Journal of the Chemical Society. Dalton Transactions

Issue

12

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Inorganic Chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1472-7773