Study of the Mechanism of Homolytic Reactions in Solution by a Combination of Isotopic and Mass-spectrometric Methods

The use of mass spectrometry for the isotopic analysis of the products of homolytic reactions in deuterated solvents has made is possible to find the ratio of all isotopic forms of the substances studied and has opened up new possibilities in the study of the mechanism of homolytic reactions.
The present review examines critically work carried out by this method. These studies have made it possible to investigate the properties and regular features of the behaviour of various kinds of hydrocarbon radical in various solvents; have led to the discovery of reliable criteria for distinguishing free-radical processes from homolytic reactions taking place in the reaction complex without the liberation of radicals; and have made possible a deeper study of the mechanism of a number of types of free-radical reaction – the photolysis of organic halides and their reactions with metals, the thermal decomposition of benzoyl peroxide, diazo-compounds, and azo-compounds, various reactions of organometallic compounds, and processes of hydrocarbon oxidation. The bibliography contains 144 references.