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Kinetic Equations of Free-Radical Nonbranched-Chain Processes of Addition to Alkenes, Formaldehyde and Oxygenстатья
- Автор: Silaev Michael M.
- Журнал: Archives of Organic and Inorganic Chemical Sciences
- Том: 2
- Номер: 5
- Год издания: 2018
- Первая страница: 256
- Последняя страница: 275
- DOI: 10.32474/AOICS.2018.02.000150
- Аннотация: The aim of this study was to devise simple kinetic equations to describe ab initio initiated nonbranched-chain processes of addition of saturated free-radical to double bonds of unsaturated molecules in binary reaction systems of saturated and unsaturated components. In these processes the formation rate of the molecular addition products (1:1 adducts) as a function of concentration of the unsaturated component reaches a limiting value. Five reaction schemes are suggested for the addition processes. 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 are deduced using quasi-steady-state treatment. These equations provide good fits for the non-monotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the unsaturated component in the binary systems. 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 autoinhibitor (or an antioxidant). The energetics of the key radical-molecule reactions are considered. Keywords: Low-reactive radical; Autoinhibitor; Competing reaction; Non branched-chain Addition; Thermochemical Data.
- Добавил в систему: Силаев Михаил Михайлович
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Полный текст | Simple kinetic equations to describe ab initio initiated nonbranched-chain processes of addition of saturated free-radical to double bonds of unsaturated molecules in binary reaction systems of saturated and unsaturated components are obtained. | M.M._Silaev_Kinetic_Eqs_of...Processes_of_Addition..._Arc.O… | 1,1 МБ | 31 мая 2019 [SilaevMM] |