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Kinetics of the hydrogen abstraction alkane + O2 → alkyl + HO2 reaction class: an application of the reaction class transition state theory

  • Maciej Baradyn
  • Artur RatkiewiczEmail author
Original Research
  • 24 Downloads

Abstract

In this work, the kinetics of reaction class of hydrogen abstraction from saturated hydrocarbons by O2 molecules has been studied. The high-pressure reaction rate constants were determined using reaction class transition state theory/structure-activity relationship (RC-TST/SAR) methodology, augmented by linear energy relationship (LER) and/or barrier height grouping (BHG) approximations for evaluation of the reaction barrier heights. The parameters needed have been derived from DFT calculations at M06-2X/aug-cc-pVTZ level for a training set of 23 reactions, involving hydrogen abstraction by O2 molecule at primary, secondary, and tertiary carbon sites. The reference reaction rate constant C2H6 + O2 → C2H5 + HO2 was obtained by extrapolation of the simplest reaction within the title family CH4 + O2 → CH3 + HO2. Kinetic parameters of the later one, calculated from canonical variational transition state theory (CVT), were taken from literature. The influence of low-frequency internal rotations has been investigated in details. The error analysis shows that the average systematic error of RC-TST/SAR-derived rate constants at low temperatures is within 25% compared to the explicit RC-TST results and diminishes at higher temperatures. This suggests that the proposed methodology can be effectively implemented in the automated mechanism generation codes to create the fuel combustion mechanisms.

Keywords

H abstraction by O2 Thermal rate constants On-the-fly kinetics Combustion Reaction class transition state theory 

Notes

Acknowledgments

The authors would like to thank the Computational Center of the University of Bialystok (Grant GO-008) for providing access to the supercomputer resources and the GAUSSIAN 09 program.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict(s) of interest.

Supplementary material

11224_2019_1459_MOESM1_ESM.pdf (5.2 mb)
ESM 1 Tables: List of processes selected to the representative (training) set for the title reaction class. The optimized geometries and frequencies of all species calculated at M06-2X/aug-cc-pVTZ level of theory for representative set. Numerical data (RC-TST/SAR-LER rate constants) for Figs. 7 and 10(a–-b). Figures: Optimized geometries of all species calculated at M06-2X/aug-cc-pVTZ level of theory for representative set. The hindrance potential and HO/HR values for selected processes. Relative absolute deviations as functions of the temperature between rate constants obtained with explicit RC-TST formulation. (PDF 3754 kb)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of ChemistryUniversity of BialystokBialystokPoland

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