Petroleum Chemistry, Vol.43, No.4, 258-272, 2003
Competition kinetics of nonbranched chain processes of free radical addition to the C=C, C=O, and O=O double bonds of molecules
Eight rate equations with one to three parameters to be directly determined were derived by the quasi-steady-state treatment using five schemes including reactions that compete with chain propagation reactions through a reactive radical. The schemes involve three or four types of free radicals, of which one inhibits the chain process. These equations describe nonmonotonic (with maximum) dependences of the formation rate for the products of addition of saturated free radicals to the double bond of molecules (1 : 1 adducts) on the concentration of an unsaturated compound in nonbranched chain processes in liquid homogeneous binary systems consisting of saturated (hydrocarbon, alcohol, etc.) and unsaturated (olefin, formaldehyde, or dioxygen) components. A similar kinetic description was applied to the nonbranched radical chain process of hydrogen oxidation.