On the high-temperature unimolecular decomposition of ethyl levulinate

Handle URI:
http://hdl.handle.net/10754/622324
Title:
On the high-temperature unimolecular decomposition of ethyl levulinate
Authors:
Alabbad, Mohammed; Giri, Binod; Szőri, Milán; Farooq, Aamir ( 0000-0001-5296-2197 )
Abstract:
The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.
KAUST Department:
Clean Combustion Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
AlAbbad M, Giri BR, Szőri M, Farooq A (2016) On the high-temperature unimolecular decomposition of ethyl levulinate. Proceedings of the Combustion Institute. Available: http://dx.doi.org/10.1016/j.proci.2016.06.034.
Publisher:
Elsevier BV
Journal:
Proceedings of the Combustion Institute
Issue Date:
20-Sep-2016
DOI:
10.1016/j.proci.2016.06.034
Type:
Article
ISSN:
1540-7489
Sponsors:
Research reported in this publication was funded by King Abdullah University of Science and Technology (KAUST), and by the scientific fund of Faculty of Education at University of Szeged (CS-009/2015). Experimental work was carried out at the Chemical Kinetics and Laser Sensors Laboratory at KAUST. Milán Szőri was a Magyary Zoltán fellow in the framework of TÁMOP 4.2.4.A/2-11-1-2012-0001 (A2-MZPD-12-0139) and currently a János Bolyai Research Scholar of the Hungarian Academy of Sciences(BO/00113/15/7).
Additional Links:
http://www.sciencedirect.com/science/article/pii/S154074891630092X
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorAlabbad, Mohammeden
dc.contributor.authorGiri, Binoden
dc.contributor.authorSzőri, Milánen
dc.contributor.authorFarooq, Aamiren
dc.date.accessioned2017-01-02T09:08:26Z-
dc.date.available2017-01-02T09:08:26Z-
dc.date.issued2016-09-20en
dc.identifier.citationAlAbbad M, Giri BR, Szőri M, Farooq A (2016) On the high-temperature unimolecular decomposition of ethyl levulinate. Proceedings of the Combustion Institute. Available: http://dx.doi.org/10.1016/j.proci.2016.06.034.en
dc.identifier.issn1540-7489en
dc.identifier.doi10.1016/j.proci.2016.06.034en
dc.identifier.urihttp://hdl.handle.net/10754/622324-
dc.description.abstractThe pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.en
dc.description.sponsorshipResearch reported in this publication was funded by King Abdullah University of Science and Technology (KAUST), and by the scientific fund of Faculty of Education at University of Szeged (CS-009/2015). Experimental work was carried out at the Chemical Kinetics and Laser Sensors Laboratory at KAUST. Milán Szőri was a Magyary Zoltán fellow in the framework of TÁMOP 4.2.4.A/2-11-1-2012-0001 (A2-MZPD-12-0139) and currently a János Bolyai Research Scholar of the Hungarian Academy of Sciences(BO/00113/15/7).en
dc.publisherElsevier BVen
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S154074891630092Xen
dc.subjectAb initioen
dc.subjectEthyl levulinateen
dc.subjectEthyleneen
dc.subjectSix-center eliminationen
dc.subjectUnimolecular dissociationen
dc.titleOn the high-temperature unimolecular decomposition of ethyl levulinateen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalProceedings of the Combustion Instituteen
dc.contributor.institutionDepartment of Chemical Informatics, Faculty of Education, University of Szeged, Boldogasszony sgt. 6, H6725 Szeged, Hungaryen
kaust.authorAlabbad, Mohammeden
kaust.authorGiri, Binoden
kaust.authorFarooq, Aamiren
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