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

Mariam J. Al Rashidi*, Marco Mehl, William J. Pitz, Samah Mohamed, S. Mani Sarathy

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

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 ∼900 K. 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 + O2 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.

Original languageEnglish (US)
Pages (from-to)358-371
Number of pages14
JournalCombustion and Flame
Volume183
DOIs
StatePublished - 2017

Bibliographical note

Funding Information:
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 Copyright:
© 2017 The Combustion Institute

Keywords

  • Computational kinetics
  • Cyclopentane
  • Detailed mechanism
  • Pressure-dependent rate constants

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Fuel Technology
  • Energy Engineering and Power Technology
  • General Physics and Astronomy

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