New Kinetic Models of Free-Radical Nonbranched-Chain Addition to C=C, C=O, and O=O Molecular Bonds

Abstract

A free radical may be low-reactive if its unpaired p-electron may be delocalized, e.g., over conjugated bonds as in the case of allyl radical CH2=CHĊH2 or along a double bond from carbon to the more electron-affine oxygen as in the case of formyl radical HĊ=O. Note that the activity of a free radical is also connected to the reaction heat in which it participates. In nonbranched-chain processes of reactive free radical (addend) addition to double bonds of molecules, the formation of rather low-reactive free radicals in reactions, which are parallel to or competing with propagation via a reactive radicals, lead to chain termination, because these low-reactive radicals do not participate in further chain propagation and because they decay when colliding with each other or with chain-carrier reactive radicals thus resulting in inefficient expenditure of the latter and process inhibition.