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.
| Published in | American Journal of Polymer Science and Technology (Volume 3, Issue 3) |
| DOI | 10.11648/j.ajpst.20170303.11 |
| Page(s) | 29-49 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2017. Published by Science Publishing Group |
Low-Reactive Radical, Autoinhibitor, Competing Reaction, Kinetic Equation, Energy
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APA Style
Michael M. Silaev. (2017). Kinetics of the Free-Radical Nonbranched-Chain Addition. American Journal of Polymer Science and Technology, 3(3), 29-49. https://doi.org/10.11648/j.ajpst.20170303.11
ACS Style
Michael M. Silaev. Kinetics of the Free-Radical Nonbranched-Chain Addition. Am. J. Polym. Sci. Technol. 2017, 3(3), 29-49. doi: 10.11648/j.ajpst.20170303.11
AMA Style
Michael M. Silaev. Kinetics of the Free-Radical Nonbranched-Chain Addition. Am J Polym Sci Technol. 2017;3(3):29-49. doi: 10.11648/j.ajpst.20170303.11
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Download@article{10.11648/j.ajpst.20170303.11,
author = {Michael M. Silaev},
title = {Kinetics of the Free-Radical Nonbranched-Chain Addition},
journal = {American Journal of Polymer Science and Technology},
volume = {3},
number = {3},
pages = {29-49},
doi = {10.11648/j.ajpst.20170303.11},
url = {https://doi.org/10.11648/j.ajpst.20170303.11},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpst.20170303.11},
abstract = {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.},
year = {2017}
}
TY - JOUR T1 - Kinetics of the Free-Radical Nonbranched-Chain Addition AU - Michael M. Silaev Y1 - 2017/06/05 PY - 2017 N1 - https://doi.org/10.11648/j.ajpst.20170303.11 DO - 10.11648/j.ajpst.20170303.11 T2 - American Journal of Polymer Science and Technology JF - American Journal of Polymer Science and Technology JO - American Journal of Polymer Science and Technology SP - 29 EP - 49 PB - Science Publishing Group SN - 2575-5986 UR - https://doi.org/10.11648/j.ajpst.20170303.11 AB - 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. VL - 3 IS - 3 ER -
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