Simulation of the nonbranched-chain addition of saturated free radicals to alkenes and their derivatives yielding 1: 1 adducts

A reaction scheme is suggested for the initiated addition process. The scheme includes the reaction between the free 1: 1 adduct radical and the unsaturated reactant, which is in competition with chain propagation through a reactive free radical (({}^ cdot P{mathbf{ }}Cl_2 ,(CH_3 )_2 mathop Climits^cdot {mathbf{ }}OH), etc.) and yields a low-reactivity free radical ((CH_2 = C(CH_3 )mathop Climits^cdot {mathbf{ }}H_2 ,{mathbf{ }}CH_2 = CHmathop Climits^cdot {mathbf{ }}HOH), etc.) inhibiting the nonbranched-chain process. Simple rate equations containing one to three parameters to be determined directly are set up using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular addition products (1: 1 adducts) on the concentration of the unsaturated component in liquid homogeneous binary systems consisting of a saturated component (PCl₃, 2-propanol, etc.) and an unsaturated component (methylpropene, 2-propen-1-ol, etc.). The unsaturated compound in these systems is both a reactant and an autoinhibitor generating low-reactivity free radicals.