[Low-reactive free radicals inhibiting nonbranched chain processes of addition]

The kinetics of inhibition of nonbranched chain processes of addition of reactive free radicals at double bonds O=O, C=O, and C=C of molecules in liquid homogeneous binar systems from saturated and unsaturated components by low-reactive free radicals (o-CH3C6H4CH2O*4, HO*4; HC=O; CH2=C(CH3)CH2, and CH2=CHCHOH) was studied. It was assumed that as the concentration of the unsaturated component (as a source of low-reactive free radicals) increases (after the optimum concentration is attained, which corresponds to the maximum rate of the process) the phenomena of increasing inhibition of these processes may act as the elements of self-regulation of similar processes in nature, which returns them into the stationary state. The energetics of the key radical-molecular gas phase reactions was analyzed. The thermal effects of total dissociation reactions of simple alkylperoxyl (exo effect) and alkoxyl (endo effect) reactive free radicals in the gas phase were compared. The kinetic equations (with one to three parameters being directly determined), obtained by the quasi-steady-state treatment, are presented, which make it possible to describe nonmonotonic (with a maximum) dependencies of the rates of formation of molecular 1:1-adducts on the concentration of the unsaturated component.