IJIREM

Kinetics of Nonbranched-Chain Processes of the FreeRadical Addition to Molecules of Alkenes, Formaldehyde, and Oxygen with Competing Reactions of Resulting 1:1 Adduct Radicals with Saturated and Unsaturated Components of the Binary Reaction System

Michael M. Silaev

Five reaction schemes are suggested for the initiated nonbranchedchain addition of free radicals to the multiple bonds of the unsaturated compounds. The proposed schemes include the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the unsaturated component in binary systems consisting of a saturated component (hydrocarbon, alcohol, etc.) and an unsaturated component (alkene, allyl alcohol, formaldehyde, or dioxygen). The unsaturated compound in these systems is both a reactant and an autoinhibitor generating low-reactive free radicals. A similar kinetic description is applicable to the nonbranched-chain process of the free-radical hydrogen oxidation, in which the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant). The energetics of the key radicalmolecule reactions is considered.

Binary System, Unsaturated Compound, Low-Reactive Radical, Autoinhibitor, Competing Reaction, Non-Branched-Chain Addition, Kinetic Equation, Rate, Parameters, Thermochemical Data, Energy

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[Michael M. Silaev (2017) Kinetics of Nonbranched-Chain Processes of the FreeRadical Addition to Molecules of Alkenes, Formaldehyde, and Oxygen with Competing Reactions of Resulting 1:1 Adduct Radicals with Saturated and Unsaturated Components of the Binary Reaction System IJIREM Vol-4 Issue-1 Page No-569-588] (ISSN 2350 - 0557). www.ijirem.org

Michael M. Silaev

Department of Chemistry, Lomonosov Moscow State University, Vorobievy Gory, Moscow 119991, Russia