Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

Abstract
Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

Citation
Al Rashidi MJ, Mehl M, Pitz WJ, Mohamed S, Sarathy SM (2017) Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics. Combustion and Flame 183: 358–371. Available: http://dx.doi.org/10.1016/j.combustflame.2017.05.018.

Acknowledgements
The authors would like to acknowledge Dr. Judit Zador for her valuable support and feedback. This work was performed by the Clean Combustion Research Center with funding from King Abdullah University of Science and Technology (KAUST) and Saudi Aramco under the FUELCOM program. Research reported in this publication was also supported by competitive research funding from KAUST. The work at LLNL was supported by the U.S. Department of Energy, Vehicle Technologies Office, program managers Gurpreet Singh and Leo Breton and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratories under contract DE-AC52-07NA27344.

Publisher
Elsevier BV

Journal
Combustion and Flame

DOI
10.1016/j.combustflame.2017.05.018

Additional Links
http://www.sciencedirect.com/science/article/pii/S0010218017301931

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