Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

Handle URI:
http://hdl.handle.net/10754/625322
Title:
Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate
Authors:
Wu, Junjun; Khaled, Fathi; Ning, Hongbo; Ma, Liuhao; Farooq, Aamir ( 0000-0001-5296-2197 ) ; Ren, Wei
Abstract:
We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.
KAUST Department:
Clean Combustion Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Wu J, Khaled F, Ning H, Ma L, Farooq A, et al. (2017) Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate. The Journal of Physical Chemistry A. Available: http://dx.doi.org/10.1021/acs.jpca.7b06119.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry A
Issue Date:
3-Aug-2017
DOI:
10.1021/acs.jpca.7b06119
Type:
Article
ISSN:
1089-5639; 1520-5215
Sponsors:
The authors are very grateful to Dr. Lidong Zhang at University of Science and Technology of China and Dr. Peng Zhang at Hong Kong Polytechnic University for the discussion on rate constant calculations. We are also thankful for Shenzhen Supercomputing Center for providing computational facilities. This work is supported by National Natural Science Foundation of China (11502222) and Research Grants Council of the Hong Kong SAR, China (14234116). Shock tube experiments were carried out at King Abdullah University of Science and Technology (KAUST) and this work was funded by Competitive Center Funding (CCF) program at KAUST.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b06119
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorWu, Junjunen
dc.contributor.authorKhaled, Fathien
dc.contributor.authorNing, Hongboen
dc.contributor.authorMa, Liuhaoen
dc.contributor.authorFarooq, Aamiren
dc.contributor.authorRen, Weien
dc.date.accessioned2017-08-10T11:43:34Z-
dc.date.available2017-08-10T11:43:34Z-
dc.date.issued2017-08-03en
dc.identifier.citationWu J, Khaled F, Ning H, Ma L, Farooq A, et al. (2017) Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate. The Journal of Physical Chemistry A. Available: http://dx.doi.org/10.1021/acs.jpca.7b06119.en
dc.identifier.issn1089-5639en
dc.identifier.issn1520-5215en
dc.identifier.doi10.1021/acs.jpca.7b06119en
dc.identifier.urihttp://hdl.handle.net/10754/625322-
dc.description.abstractWe report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.en
dc.description.sponsorshipThe authors are very grateful to Dr. Lidong Zhang at University of Science and Technology of China and Dr. Peng Zhang at Hong Kong Polytechnic University for the discussion on rate constant calculations. We are also thankful for Shenzhen Supercomputing Center for providing computational facilities. This work is supported by National Natural Science Foundation of China (11502222) and Research Grants Council of the Hong Kong SAR, China (14234116). Shock tube experiments were carried out at King Abdullah University of Science and Technology (KAUST) and this work was funded by Competitive Center Funding (CCF) program at KAUST.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b06119en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b06119.en
dc.titleTheoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formateen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Aen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Mechanical and Automation Engineering, The Chinese University of Hong Kong, New Territories, Hong Kongen
dc.contributor.institutionShenzhen Research Institute, The Chinese University of Hong Kong, New Territories, Hong Kongen
kaust.authorKhaled, Fathien
kaust.authorFarooq, Aamiren
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.