Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether.

We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C-O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.

Study of Low- and Intermediate-Temperature Oxidation Kinetics of Diethyl Ether in a Supercritical Pressure Jet-Stirred Reactor.

Growing demand for low-emission and high-efficiency propulsion systems spurs interest in understanding low-temperature and ultra-high-pressure combustion of alternative biofuels like diethyl ether (DEE). In this study, DEE oxidation experiments are performed at 10 and 100 atm, over a temperature range of 400-900 K, at fuel-lean, stoichiometric, and fuel-rich conditions by using a supercritical pressure jet-stirred reactor (SP-JSR). The experimental data show that DEE is very reactive and exhibits an uncommon low-temperature oxidation behavior with two negative temperature coefficient (NTC) zones. The first NTC zone is mainly governed by the competition reactions of QOOH + O2 = O2QOOH and QOOH = 2CH3CHO + OH, while the second one is mainly governed by the competition reactions of R + O2 = RO2 and the ß-scission reaction of fuel radical R. It is shown that the increase of pressure stabilizes RO2 and promotes HO2 chemistry. Moreover, the branching ratios of ß-scission reactions of R and QOOH decrease. As a result, it is shown that, with the increase of pressure, both NTC zones become weaker at 100 atm. In addition, the intermediate-temperature oxidation is shifted considerably to lower temperature at 100 atm. The existing DEE model in the literature well predicts the experimental data at low temperature; however, it underpredicts the fuel consumptions at intermediate temperature. The H2/O2 subset in the existing DEE model is updated in this study based on the Princeton updated HP-Mech, including the singlet/triplet competing channels of HO2 related reactions. The updated model improves the overall predictability of key species, especially at intermediate temperature.