Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling

Mariam El Rachidi, Sébastien Thion, Casimir Togbé, Guillaume Dayma, Marco Mehl, Philippe Dagaut, William J. Pitz, Judit Zádor, Mani Sarathy

Research output: Contribution to journalArticlepeer-review

35 Scopus citations


This study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O/N mixture was maintained at 0.7s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850-1000K for ϕ = 2.0 and ϕ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl+O, as well as the C-C and C-H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C-C/C-H scission branching ratio of the cyclopentyl radical decomposition.
Original languageEnglish (US)
Pages (from-to)469-477
Number of pages9
JournalProceedings of the Combustion Institute
Issue number1
StatePublished - Jun 23 2016

Bibliographical note

KAUST Repository Item: Exported on 2023-09-13
Acknowledgements: This work was funded by King Abdullah University of Science and Technology (KAUST) and Saudi Aramco under the FUELCOM program. It was also supported by competitive research funding from KAUST. JZ was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration, under contract DE-AC04-94AL85000. 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.

ASJC Scopus subject areas

  • Mechanical Engineering
  • Chemical Engineering(all)
  • Physical and Theoretical Chemistry


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