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

Junjun Wu, Fethi KHALED, Hongbo Ning, Liuhao Ma, Aamir Farooq, Wei Ren

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17 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)6304-6313
Number of pages10
JournalThe Journal of Physical Chemistry A
Volume121
Issue number33
DOIs
StatePublished - Aug 14 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.

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