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Autooxidation of diethyl hydroxylamine
Author(s) -
Cáceres T.,
Lissi E. A.,
Sanhueza E.
Publication year - 1978
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550101107
Subject(s) - chemistry , hydroxylamine , autoxidation , radical , dissociation (chemistry) , photochemistry , chlorobenzene , peroxide , hydrogen peroxide , solvent , gas phase , stoichiometry , bond dissociation energy , organic chemistry , catalysis
The autooxidation of diethyl hydroxylamine (DEHA) has been studied both in solution and in the gas phase between 0° and 60°C. The results obtained are interpreted in terms of a nonchain free radical mechanism in which reaction (1)is the rate‐determining step. This reaction is followed by the reaction of HO 2 radicals with DEHA to give hydrogen peroxide. The initial stoichiometry is given by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2DEHA + O}_{\rm 2} \to {\rm 2nitrone + 2H}_{\rm 2} {\rm O} $$\end{document}which implies that the hydrogen peroxide reacts with DEHA to give water and diethyl nitroxide radicals. The activation energy of reaction (1) is 16.5 ± 2 kcal/mol, leading to a dissociation energy of 69.5 ± 2 kcal for the OH bond in DEHA. The oxidation of DEHA in the gas phase is nearly ten times slower than that observed in chlorobenzene solution under similar experimental conditions. This result is related to the stabilization of the free radicals produced by the solvent.