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FREE RADICALS BY MASS SPECTROMETRY: XV. THE: MERCURY-PHOTOSENSITIZED DECOMPOSITION OF FORMIC ACID, ACETIC ACID, AND METHYL FORMATE

1959; NRC Research Press; Volume: 37; Issue: 2 Linguagem: Inglês

10.1139/v59-052

1480-3291

P. Kebarle, F. P. Lossing,

Analytical Chemistry and Chromatography

The Hg( 3 P 1 ) photosensitized decomposition of formic acid proceeds by two intramolecular rearrangement reactions, leading respectively to H 2 O and CO, and to H 2 and CO 2 . No free radicals are produced. The decomposition reactions of methyl formate and of acetic acid proceed predominantly by the formation of free radicals, but intramolecular rearrangements also occur to a significant extent. For both these latter compounds the evidence suggests the occurrence of two modes of dissociation into free radicals:[Formula: see text]No evidence for the alternative mode of dissociation[Formula: see text]was found.