A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes
The concerted elimination reaction class of peroxyl-hydroperoxyl alkyl radicals (•OOQOOH) plays a crucial role in the low-temperature combustion of normal-alkyl cyclohexanes. The generation of the relatively unreactive HO<sub>2</sub> radicals in this reaction is one of the factors leadin...
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/18/6612 |
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| author | Xiaoxia Yao Jilong Zhang Yifei Zhu |
| author_facet | Xiaoxia Yao Jilong Zhang Yifei Zhu |
| author_sort | Xiaoxia Yao |
| collection | DOAJ |
| description | The concerted elimination reaction class of peroxyl-hydroperoxyl alkyl radicals (•OOQOOH) plays a crucial role in the low-temperature combustion of normal-alkyl cyclohexanes. The generation of the relatively unreactive HO<sub>2</sub> radicals in this reaction is one of the factors leading to the negative temperature coefficient (NTC) behavior, which hinders the low-temperature oxidation of normal-alkyl cyclohexanes. In this study, 44 reactions are selected and divided into 4 different subclasses according to the nature of the carbon atom where the H atom is eliminated and the reaction center position. Utilizing the CBS-QB3 method, we compute the energy barriers for the concerted elimination reactions of peroxyl-hydroperoxyl alkyl radicals. Following this, we assess both the high-pressure limit and pressure-dependent rate constants for all reactions by applying TST and RRKM/ME theory. These calculations allow for the development of rate rules, which come to fruition through an averaging process involving the rate constants of representative reactions within each subclass. Our work provides accurate rate constants and rate rules for this reaction class, which can aid in constructing more accurate combustion mechanisms for normal-alkyl cyclohexanes. |
| first_indexed | 2024-03-10T22:23:56Z |
| format | Article |
| id | doaj.art-2c9eb45798cf49db8c689aa2fca04033 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T22:23:56Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-2c9eb45798cf49db8c689aa2fca040332023-11-19T12:09:55ZengMDPI AGMolecules1420-30492023-09-012818661210.3390/molecules28186612A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl CyclohexanesXiaoxia Yao0Jilong Zhang1Yifei Zhu2National Key Lab of Aerospace Power System and Plasma Technology, Air Force Engineering University, Xi’an 710038, ChinaInstitute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, ChinaSchool of Electrical Engineering, Xi’an Jiaotong University, Xi’an 710049, ChinaThe concerted elimination reaction class of peroxyl-hydroperoxyl alkyl radicals (•OOQOOH) plays a crucial role in the low-temperature combustion of normal-alkyl cyclohexanes. The generation of the relatively unreactive HO<sub>2</sub> radicals in this reaction is one of the factors leading to the negative temperature coefficient (NTC) behavior, which hinders the low-temperature oxidation of normal-alkyl cyclohexanes. In this study, 44 reactions are selected and divided into 4 different subclasses according to the nature of the carbon atom where the H atom is eliminated and the reaction center position. Utilizing the CBS-QB3 method, we compute the energy barriers for the concerted elimination reactions of peroxyl-hydroperoxyl alkyl radicals. Following this, we assess both the high-pressure limit and pressure-dependent rate constants for all reactions by applying TST and RRKM/ME theory. These calculations allow for the development of rate rules, which come to fruition through an averaging process involving the rate constants of representative reactions within each subclass. Our work provides accurate rate constants and rate rules for this reaction class, which can aid in constructing more accurate combustion mechanisms for normal-alkyl cyclohexanes.https://www.mdpi.com/1420-3049/28/18/6612peroxyl-hydroperoxyl alkyl radicalsconcerted elimination reactionkinetic parametersreaction rate rules |
| spellingShingle | Xiaoxia Yao Jilong Zhang Yifei Zhu A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes Molecules peroxyl-hydroperoxyl alkyl radicals concerted elimination reaction kinetic parameters reaction rate rules |
| title | A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes |
| title_full | A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes |
| title_fullStr | A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes |
| title_full_unstemmed | A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes |
| title_short | A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes |
| title_sort | theoretical kinetic study on concerted elimination reaction class of peroxyl hydroperoxyl alkyl radicals •ooqooh in normal alkyl cyclohexanes |
| topic | peroxyl-hydroperoxyl alkyl radicals concerted elimination reaction kinetic parameters reaction rate rules |
| url | https://www.mdpi.com/1420-3049/28/18/6612 |
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