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

Bengtsson, Gösta; Fronaeus, Sture LU and Bengtsson-Kloo, L (2002) In Journal of the Chemical Society. Dalton Transactions p.2548-2552
Abstract
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the Chemical Society. Dalton Transactions
issue
12
pages
2548 - 2552
publisher
Royal Society of Chemistry
external identifiers
  • wos:000176051000025
  • scopus:0036017278
ISSN
1472-7773
DOI
10.1039/b201602h
language
English
LU publication?
yes
id
453bf86a-1058-4801-bbbd-279969d08ea3 (old id 336001)
date added to LUP
2007-08-08 11:40:41
date last changed
2017-11-19 04:05:53
@article{453bf86a-1058-4801-bbbd-279969d08ea3,
  abstract     = {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.},
  author       = {Bengtsson, Gösta and Fronaeus, Sture and Bengtsson-Kloo, L},
  issn         = {1472-7773},
  language     = {eng},
  number       = {12},
  pages        = {2548--2552},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society. Dalton Transactions},
  title        = {The kinetics and mechanism of oxidation of hydroxylamine by iron(III)},
  url          = {http://dx.doi.org/10.1039/b201602h},
  year         = {2002},
}