Chemical kinetic modeling and shock tube study of methyl propanoate decomposition
Publication in refereed journal


摘要The unimolecular decomposition kinetics of methyl propanoate (MP), including the direct C−O/C−C bond fissions and molecular reaction channels, were studied by using high-level ab initio calculations and Rice–Ramsperger–Kassel–Marcus/master equation (RRKM/ME) theory. Four homolytic bond-fission and ten hydrogen transfer reactions of the MP unimolecular decomposition were identified. The phenomenological rate constants were determined using the RRKM/ME theory over a temperature range of 1000−2000 K and a pressure range of 0.01 atm to the high-pressure limit. At 1 atm, the branching ratios show that the dissociation reactions MP ↔ •CHC([dbnd]O)OCH + CH, MP ↔ CHOC•([dbnd]O) + CH and MP ↔ CHCHC([dbnd]O)O• + CH dominate MP pyrolysis over the temperature range of 1000−1500 K. Our calculated rate constants were adopted in a detailed kinetic model to reproduce the laser-absorption measured CO and CO concentration time-histories during the pyrolysis of 0.2% MP/Ar in a shock tube from 1292−1551 K and at 1.6 atm. The updated mechanism accurately predicted the early-time CO and CO formation over the entire temperature range. In particular, our mechanism well reproduced the CO time-histories from the early-time formation to the final plateau level.
著者Ning H., Wu J., Ma L., Ren W., Davidson D., Hanson R.
期刊名稱Combustion and Flame
出版社Elsevier Inc.
頁次30 - 40
關鍵詞Methyl propanoate decomposition, Shock tube, Ab initio calculations, Chemical kinetics

上次更新時間 2021-04-05 於 00:11