Free Radicals by Mass Spectrometry: Xv. The: Mercury-Photosensitized Decomposition of Formic Acid, Acetic Acid, and Methyl Formate

The Hg(3P1) photosensitized decomposition of formic acid proceeds by two intramolecular rearrangement reactions, leading respectively to H2O and CO, and to H2 and CO2. 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.