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Formylmethyl and formylmethylperoxyl radicals and their chlorinated derivatives. Formation and reactions in irradiated aqueous solutions

Journal Article · · Journal of Physical Chemistry
DOI:https://doi.org/10.1021/jp961628s· OSTI ID:405312
; ; ;  [1]
  1. National Inst. of Standards and Technology, Gaithersburg, MD (United States)

The formylmethyl radical, {sup .}CH{sub 2}CHO, is known to act as an oxidant. For comparison, the chlorinated analogues, {sup .}CCl{sub 2}CHO and {sup .}CCl{sub 2}CClO, were produced in irradiated aqueous solutions and their oxidation reactions studied. The {sup .}CCl{sub 2}CHO radical is an oxidizing species, which reacts with ascorbate, ABTS{sup 2-} [2,2`-azinobis(3-ethylbenzothiazoline-6-sulfonate ion)], and phenolate ions somewhat more slowly than {sup .}CH{sub 2}CHO. In contrast, {sup .}CCl{sub 2}CClO reacts with the same compounds much more rapidly than {sup .}CH{sub 2}CHO. All three formylmethyl radicals react with O{sub 2} to yield peroxyl radicals. The peroxyl radicals derived from the chlorinated formylmethyl are stronger oxidants than their parent species, but the peroxyl radical derived from the unchlorinated formylmethyl is a weaker oxidant than its parent species. Peroxyl radicals were also produced by the reaction of e{sub aq}{sup -} with CCl{sub 3}CH{sub 2}OH and with chloral hydrate in aerated solutions. These radicals, {sup .}OOCCl{sub 2}CH{sub 2}OH and {sup .}OOCCl{sub 2}CH(OH){sub 2}, are highly reactive oxidants. 31 refs., 2 figs., 3 tabs.

OSTI ID:
405312
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 39 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English

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