Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System

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Michael M. Silaev
Michael M. Silaev
1 Lomonosov Moscow State University

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Kinetics of  Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in  which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System Banner
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Five reaction schemes are suggested for the initiated nonbranched-chain 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 (olefin, allyl alcohol, formaldehyde, or dioxygen).

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No external funding was declared for this work.

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The authors declare no conflict of interest.

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Michael M. Silaev. 2013. \u201cKinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System\u201d. Global Journal of Science Frontier Research - B: Chemistry GJSFR-B Volume 13 (GJSFR Volume 13 Issue B6): .

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GJSFR Volume 13 Issue B6
Pg. 31- 53
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Crossref Journal DOI 10.17406/GJSFR

Print ISSN 0975-5896

e-ISSN 2249-4626

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v1.2

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September 21, 2013

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English

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Five reaction schemes are suggested for the initiated nonbranched-chain 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 (olefin, allyl alcohol, formaldehyde, or dioxygen).

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Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System

Michael M. Silaev
Michael M. Silaev Lomonosov Moscow State University

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