Review Article. Competition kinetics of the nonbranched-chain addition of free radicals to olefins, formaldehyde, and oxygen

Silaev, M.M.

Автор: Silaev M.M.
Журнал: International Journal of Chemical Engineering
Том: 2011
Год издания: 2011
Издательство: Hindawi Publishing Corporation
Местоположение издательства: United States
Первая страница: 1
Последняя страница: 19
DOI: 10.1155/2011/830610
Аннотация: Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of alkenes, formaldehyde, and oxygen. The schemes include the reaction competing with chain propagation through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them – СН2=С(СН3)ĊН2, СН2=СНĊНОН, НĊ=O, o-СН3С6Н4СН2О4, or НО4 – is low-reactive and inhibits the chain process. Based on the suggested schemes, nine 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 (hydrocarbon, alcohol, etc.) and an unsaturated component (olefin, 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 nonbranched-chain free-radical hydrogen oxidation. The energetics of the key radical-molecule reactions is considered.
Добавил в систему: Силаев Михаил Михайлович

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Review Article. Competition kinetics of the nonbranched-chain addition of free radicals to olefins, formaldehyde, and oxygenстатья

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