The Competition Kinetics of Unbranched Chain Processes of Free-Radical Addition to Double Bonds of Molecules with the Formation of 1:1 Adducts

Silaev, Michael M.

doi:10.1080/00914030008033886

Cited by 17 publications

(106 citation statements)

References 10 publications

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“…The consecutive and parallel reactions involved in this free-radical nonbranched-chain addition process are presented below (Scheme 1). In the case of comparable component concentrations with a nonoverwhelming excess of the saturated component, extra reaction (1b) (k 1b / = 0) is included in the initiation stage [10,11]. In the case of an overwhelming excess of the saturated component reaction (1b) is ignored (k 1b = 0) [8,9,12].…”

Section: Addition To the C=c Bond Of Alkenes And Their Derivativesmentioning

confidence: 99%

“…We will consider kinetic variants for the case of comparable component concentrations with an excess of the saturated component [10,11] and the case of an overwhelming excess of the saturated component over the unsaturated component [8,9,12].…”

Section: Or Hmentioning

confidence: 99%

“…In reaction (4), which is competing with (parallel to) reactions (3) and (3a) (chain propagation through the reactive radical R • ), the resulting low-reactive radical that does not participate in further chain propagation and inhibits the chain process is supposed to be the alkyltetraoxyl 1 : 2 radical adduct 4, 5 RO • 4 , which has the largest weight and size. This radical is possibly stabilized by a weak intramolecular H· · · O hydrogen bond [47] shaping it into a six-membered cyclic structure 6 (seven-membered cyclic structure in the case of aromatic and certain branched acyclic hydrocarbons) [48,49]:…”

Section: Addition Of Hydrocarbon Free Radicalsmentioning

confidence: 99%

“…It covers free radical additions to alkenes [10,11], their derivatives [8,9], formaldehyde (first compound in the aldehyde homological series) [8,9,12], and oxygen [13,14] (which can add an unsaturated radical as well) yielding various 1 : 1 molecular adducts, whose formation rates as a function of the unsaturated compound concentration pass through a maximum (free radical chain additions to the C=N bond have not been studied adequately). In the kinetic description of these nontelomerization chain processes, the reaction between the 1:1 adduct radical and the unsaturated molecule, which is in competition with chain propagation through a reactive free radical ( • PCl 2 , C 2 H 5…”

Section: Introductionmentioning

confidence: 99%

“…This publication presents a comprehensive review of the nonbranched-chain kinetic models developed for particular types of additions of saturated free radicals to double bonds [8][9][10][11][12][13][14]. It covers free radical additions to alkenes [10,11], their derivatives [8,9], formaldehyde (first compound in the aldehyde homological series) [8,9,12], and oxygen [13,14] (which can add an unsaturated radical as well) yielding various 1 : 1 molecular adducts, whose formation rates as a function of the unsaturated compound concentration pass through a maximum (free radical chain additions to the C=N bond have not been studied adequately).…”

Section: Introductionmentioning

confidence: 99%

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Competition Kinetics of the Nonbranched‐Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen

Silaev

2011

International Journal of Chemical Engineering

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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 reactions 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-CH 2 =C(CH 3 )-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 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.In memory of Polina I. Semenova (Musatova)

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Section: Addition To the C=c Bond Of Alkenes And Their Derivativesmentioning

confidence: 99%

Section: Or Hmentioning

confidence: 99%

Section: Addition Of Hydrocarbon Free Radicalsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Competition Kinetics of the Nonbranched‐Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen

Silaev

2011

International Journal of Chemical Engineering

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The Antioxidant Properties of Oxygen

Silaev¹

2013

AJPC

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New reaction scheme is suggested for the initiated nonbranched-chain addition of free radicals to the multiple bond of the molecular oxygen. The scheme includes the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which (tetraoxyl) is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the proposed scheme rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the γ-induced nonbranched-chain processes of the free-radical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing different amounts of oxygen at 296 K. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. The energetics of the key radical-molecule reactions is considered.

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Kinetics of the Free-Radical Nonbranched-Chain Addition

Silaev¹

2017

AJPST

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The aim of this study was the conclusion of simple kinetic equations to describe ab initio initiated nonbranched-chain processes of the saturated free-radical addition to the double bonds of unsaturated molecules in the binary reaction systems of saturated and unsaturated components. In the processes of this kind the formation rate of the molecular addition products (1:1 adducts) as a function of concentration of the unsaturated component has a maximum. Five reaction schemes are suggested for this 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 (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 radical-molecule reactions is considered.

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The Competition Kinetics of Unbranched Chain Processes of Free-Radical Addition to Double Bonds of Molecules with the Formation of 1:1 Adducts

Cited by 17 publications

References 10 publications

Competition Kinetics of the Nonbranched‐Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen

Competition Kinetics of the Nonbranched‐Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen

The Antioxidant Properties of Oxygen

Kinetics of the Free-Radical Nonbranched-Chain Addition

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