“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 (\({}^ · P{ }Cl_2 ,(CH_3 )_2 C^· { }OH\), etc.) and yields a low-reactivity free radical (\(CH_2 = C(CH_3 ) C^· { }H_2 ,{ }CH_2 = CH C^· { }HOH\), 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.