Add time:08/28/2019         Source:sciencedirect.com

This work reports thermal decomposition of cyclopentanone behind reflected shock waves over 1150 – 1590 K and 750 – 1800 Torr. Carbon monoxide is one of the main reaction products and its formation was monitored using a quantum cascade laser operating near 4.56 µm. Our results show that cyclopentanone undergoes decomposition, under the present experimental conditions, via reaction channels that produce CO almost exclusively. A recent ab initio study by Zaras et al. revealed that cyclopentanone decomposes to produce CO and ethylene by two channels: ring-opening to form a di-radical which subsequently decomposes, and concerted elimination to produce CO and C2H4 directly; their predicted rate constants are much slower than literature experimental data. To resolve the rate constant discrepancy and to determine whether keto-enol tautomerism plays a significant role, we performed master equation simulations which produced results in good agreement both with the previous ab initio study and with the experimental data obtained in the present work.

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