A quantum chemical and kinetics modeling study on the autoignition mechanism of diethyl ether

A detailed chemical kinetics model has been developed to elucidate the auto-ignition behavior of diethyl ether (DEE) under conditions relevant for internal combustion engines. The present model is composed of a C-0-C-4 base module from literature and a DEE module. For the low-temperature oxidation mechanism, the reactions of ROO and QOOH radicals were studied previously with a quantum-chemical and transition state theory approach by Sakai et al. (2015). In the present study, the potential energy surfaces for the unimolec-ular reactions of OOQOOH isomers and 1-and 2-ethoxyethyl radicals were determined with a CBSQB3 composite method. In the presence of an OOH group, the reaction barrier of the hydrogen shift from the beta site (terminal carbon atom) decreases as it does in alkane oxidation but there is no effect on the hydrogen shift from the alpha site (next to the ether oxygen atom). Therefore, the reaction barriers of OOQOOH isomers have the same trend as the corresponding ROO radical and rate constants for the reactions of OOQOOH isomers were determined. The constructed model was validated against the recent data of ignition delay times provided in literature by Werler et al. (2015). The agreement is good over the temperature range 500-1300 K and pressure range 1-40 bar, although, open questions remain regarding the non-consensus at 900-1150 K and 40 bar. Reaction-path and sensitivity analyses attribute the importance of the reactivity at the alpha site to the decrease of the C H bond dissociation energy due to the ether oxygen atom. (C) 2016 by The Combustion Institute. Published by Elsevier Inc.