Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen
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 inv...
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| Format: | Article |
| Language: | English |
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Wiley
2011-01-01
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| Series: | International Journal of Chemical Engineering |
| Online Access: | http://dx.doi.org/10.1155/2011/830610 |
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| author | M. M. Silaev |
| author_facet | M. M. Silaev |
| author_sort | M. M. Silaev |
| collection | DOAJ |
| description | 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—
CH2=C(CH3)•CH2, CH2=CH•CHOH, H•C=O, 𝑜−CH3C6H4CH2O•4, or HO•4—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. |
| format | Article |
| id | doaj-art-59bc33de295b41a3a62153f56d2b51fc |
| institution | OA Journals |
| issn | 1687-806X 1687-8078 |
| language | English |
| publishDate | 2011-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | International Journal of Chemical Engineering |
| spelling | doaj-art-59bc33de295b41a3a62153f56d2b51fc2025-08-20T02:05:32ZengWileyInternational Journal of Chemical Engineering1687-806X1687-80782011-01-01201110.1155/2011/830610830610Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and OxygenM. M. Silaev0Department of Chemistry, Moscow State University, Vorob'evy Gory, Moscow 119991, RussiaFive 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— CH2=C(CH3)•CH2, CH2=CH•CHOH, H•C=O, 𝑜−CH3C6H4CH2O•4, or HO•4—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.http://dx.doi.org/10.1155/2011/830610 |
| spellingShingle | M. M. Silaev Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen International Journal of Chemical Engineering |
| title | Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen |
| title_full | Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen |
| title_fullStr | Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen |
| title_full_unstemmed | Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen |
| title_short | Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen |
| title_sort | competition kinetics of the nonbranched chain addition of free radicals to olefins formaldehyde and oxygen |
| url | http://dx.doi.org/10.1155/2011/830610 |
| work_keys_str_mv | AT mmsilaev competitionkineticsofthenonbranchedchainadditionoffreeradicalstoolefinsformaldehydeandoxygen |