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.
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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.
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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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Baradyn, M., Ratkiewicz, A. Kinetics of the hydrogen abstraction alkane + O2 → alkyl + HO2 reaction class: an application of the reaction class transition state theory. Struct Chem 31, 731–746 (2020). https://doi.org/10.1007/s11224-019-01459-x
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DOI: https://doi.org/10.1007/s11224-019-01459-x