Kinetics and Nature of Mechanochemical Reactions

Certain general characteristics of the kinetics, mechanism, and nature of the primary step in chemical reactions initiated by mechanical action in various low- and high-molecular-weight substances have been examined. The formal kinetics of mechanochemical reactions occurring in constant and variable mechanical fields have been analysed in Section II. In constant fields the rate of the process is determined by the rate of the primary chemical stage and in variable fields the rate-limiting stage may be the supply and absorption of elastic energy. Section III deals with the mechanisms of the conversion of elastic into chemical energy. The chemical changes in a substance are associated either with the elastic deformation of the electron shells of the reacting species or with the generation of non-equilibrium vibrationally excited states in the process of dissipation of elastic energy as heat. Under certain conditions, local short-lived regions of intense absorption of elastic energy may play a major role. Data concerning the nature of the primary active species in mechanochemical reactions – free radicals in various charged states – are discussed in the last section.
The bibliography includes 153 references.