Experimental and Detailed Kinetic Modeling Study of Cyclopentanone Oxidation in a Jet-Stirred Reactor at 1 and 10 atm

Cyclopentanone oxidation was studied in a jet-stirred reactor at 1 and 10 atm and over the temperature range of 730–1280 K for fuel-lean (φ = 0.5), stoichiometric, and fuel-rich (φ = 2) mixtures. A total of 16 reaction intermediates and products were identified and quantified using online Fourier transform infrared spectrometry and offline gas chromatography. A kinetic submodel was developed, supported by theoretical calculations for the rate constants of hydrogen abstraction reactions by H atoms and OH and CH₃ radicals at the MP2/aug-cc-pVDZ level of theory. The resulting model consisting of 343 species involved in 2065 reactions was used to simulate the present experiments and showed good agreement with the data. The main oxygenated intermediates are aldehydes, and cyclopentenone was also found to be an important species for cyclopentanone oxidation. The rate of production analyses showed that cyclopentanone is mainly consumed by a sequence of reactions producing CO and the but-1-en-4-yl radical. Unimolecular reactions reported in the literature were found to have a very low contribution to the fuel consumption in our experimental conditions. It was finally highlighted that some of the discrepancies observed between the simulation and experiments arise from the chemistry of cyclopentenone that would need to be more detailed