A theoretical and shock tube kinetic study on hydrogen abstraction from phenyl formate

Hongbo Ning, Dapeng Liu, Junjun Wu, Liuhao Ma, Wei Ren, Aamir Farooq

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

The hydrogen abstraction reactions of phenyl formate (PF) by different radicals (H/O(3P)/OH/HO2) were theoretically investigated. We calculated the reaction energetics for PF + H/O/OH using the composite method ROCBS-QB3//M06-2X/cc-pVTZ and that for PF + HO2 at the M06-2X/cc-pVTZ level of theory. The high-pressure limit rate constants were calculated using the transition state theory in conjunction with the 1-D hindered rotor approximation and tunneling correction. Three-parameter Arrhenius expressions of rate constants were provided over the temperature range of 500-2000 K. To validate the theoretical calculations, the overall rate constants of PF + OH → Products were measured in shock tube experiments at 968-1128 K and 1.16-1.25 atm using OH laser absorption. The predicted overall rate constants agree well with the shock tube data (within 15%) over the entire experimental conditions. Rate constant analysis indicates that the H-abstraction at the formic acid site dominates the PF consumption, whereas the contribution of H-abstractions at the aromatic ring increases with temperature. Additionally, comparisons of site-specific H-abstractions from PF with methyl formate, ethyl formate, benzene, and toluene were performed to understand the effects of the aromatic ring and side-chain substituent on H-abstraction rate constants.
Original languageEnglish (US)
Pages (from-to)21280-21285
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number33
DOIs
StatePublished - 2018

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work is supported by the National Natural Science Foundation of China (51776179) and the Research Grants Council of the Hong Kong SAR, China (14234116). Shock tube experiments were carried out at KAUST and this work was funded by the Competitive Center Funding (CCF) program at KAUST. We are also thankful to Shenzhen Supercomputing Center for providing computational facilities.

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