FREE RADICALS BY MASS SPECTROMETRY: XII. PRIMARY STEPS IN THE MERCURY PHOTOSENSITIZED DECOMPOSITIONS OF ACETONE AND ACETALDEHYDE

Abstract

The primary step in the mercury (Hg³P₁) photosensitized decomposition of acetone at 55 °C. results in the formation of methyl and acetyl radicals. At least 25% of the acetyl radicals are sufficiently long-lived to suffer collision with a second excited mercury atom, the products being ketene and a hydrogen atom. The primary step in the decomposition of acetaldehyde is at least 95% to form methyl and formyl radicals. The methane found was shown by tracer experiments to be the product of a secondary reaction, probably that between methyl and formyl radicals. Other secondary reactions are discussed.