Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics

Handle URI:
http://hdl.handle.net/10754/621735
Title:
Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics
Authors:
Bian, Huiting; Wang, Zhandong ( 0000-0003-1535-2319 ) ; Sun, Jinhua; Zhang, Feng
Abstract:
With the "strain-free" cyclic structure, cyclohexane and alkyl cyclohexanes (and their radicals) have various conformers (e.g. chair, boat, and twist etc.) by pseudorotation of the alkyl ring. Noting that different conformers will undergo different types of H-migration reactions, the mechanism of conformational change may impact the distribution of cyclohexyl and the branched cyclohexyl radical isomers during cyclohexane and alkyl cyclohexanes combustion. Consequently, it will influence the formation of subsequent decomposition products. In this work, the conformational inversion-topomerization mechanism and H-migration reactions for six ethylcyclohexyl radical isomers were systematically studied by ab initio calculations and the transition state theory. The updated sub-mechanism of these conformational changes is incorporated into an ethylcyclohexane pyrolysis model. By comparing the simulated results of the "complete" model including the sub-mechanism of conformational changes and the simplified model ignoring these processes, the effect of inversion-topomerization mechanism on the relative concentrations of various ethylcyclohexyl radicals and the formation of subsequent decomposition products were revealed. © 2016.
KAUST Department:
Clean Combustion Research Center
Citation:
Bian H, Wang Z, Sun J, Zhang F (2016) Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics. Proceedings of the Combustion Institute. Available: http://dx.doi.org/10.1016/j.proci.2016.07.049.
Publisher:
Elsevier BV
Journal:
Proceedings of the Combustion Institute
Issue Date:
26-Jul-2016
DOI:
10.1016/j.proci.2016.07.049
Type:
Article
ISSN:
1540-7489
Sponsors:
National Natural Science Foundation of China[21303174, 51376174, 51376170]
Appears in Collections:
Articles; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorBian, Huitingen
dc.contributor.authorWang, Zhandongen
dc.contributor.authorSun, Jinhuaen
dc.contributor.authorZhang, Fengen
dc.date.accessioned2016-11-03T13:23:51Z-
dc.date.available2016-11-03T13:23:51Z-
dc.date.issued2016-07-26en
dc.identifier.citationBian H, Wang Z, Sun J, Zhang F (2016) Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics. Proceedings of the Combustion Institute. Available: http://dx.doi.org/10.1016/j.proci.2016.07.049.en
dc.identifier.issn1540-7489en
dc.identifier.doi10.1016/j.proci.2016.07.049en
dc.identifier.urihttp://hdl.handle.net/10754/621735-
dc.description.abstractWith the "strain-free" cyclic structure, cyclohexane and alkyl cyclohexanes (and their radicals) have various conformers (e.g. chair, boat, and twist etc.) by pseudorotation of the alkyl ring. Noting that different conformers will undergo different types of H-migration reactions, the mechanism of conformational change may impact the distribution of cyclohexyl and the branched cyclohexyl radical isomers during cyclohexane and alkyl cyclohexanes combustion. Consequently, it will influence the formation of subsequent decomposition products. In this work, the conformational inversion-topomerization mechanism and H-migration reactions for six ethylcyclohexyl radical isomers were systematically studied by ab initio calculations and the transition state theory. The updated sub-mechanism of these conformational changes is incorporated into an ethylcyclohexane pyrolysis model. By comparing the simulated results of the "complete" model including the sub-mechanism of conformational changes and the simplified model ignoring these processes, the effect of inversion-topomerization mechanism on the relative concentrations of various ethylcyclohexyl radicals and the formation of subsequent decomposition products were revealed. © 2016.en
dc.description.sponsorshipNational Natural Science Foundation of China[21303174, 51376174, 51376170]en
dc.publisherElsevier BVen
dc.subjectAb initio calculationen
dc.titleConformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kineticsen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.identifier.journalProceedings of the Combustion Instituteen
dc.contributor.institutionState Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026, PR Chinaen
dc.contributor.institutionNational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026, PR Chinaen
kaust.authorWang, Zhandongen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.