Quantification of Key Peroxy and Hydroperoxide Intermediates in the Low-Temperature Oxidation of Dimethyl Ether

Dimethyl ether (DME) oxidation is a model chemical system with a small number of prototypical reaction intermediates that also has practical importance for low-carbon transportation. Although it has been studied experimentally and theoretically, ambiguity remains in the relative importance of competing DME oxidation pathways in the low-temperature autoignition regime. To focus on the primary reactions in DME autoignition, we measured the time-resolved concentration of five intermediates, CH₃OCH₂OO (ROO), OOCH₂OCH₂OOH (OOQOOH), HOOCH₂OCHO (hydroperoxymethyl formate, HPMF), CH₂O, and CH₃OCHO (methyl formate, MF), from photolytically initiated experiments. We performed these studies at P = 10 bar and T = 450-575 K, using a high-pressure photolysis reactor coupled to a time-of-flight mass spectrometer with tunable vacuum-ultraviolet synchrotron ionization at the Advanced Light Source. Our measurements reveal that the timescale of ROO decay and product formation is much shorter than predicted by current DME combustion models. The models also strongly underpredict the observed yields of CH₂O and MF and do not capture the temperature dependence of OOQOOH and HPMF yields. Adding the ROO + OH → RO + HO₂ reaction to the chemical mechanism (with a rate coefficient approximated from similar reactions) improves the prediction of MF. Increasing the rate coefficients of ROO ↔ QOOH and QOOH + O₂ ↔ OOQOOH reactions brings the model predictions closer to experimental observations for OOQOOH and HPMF, while increasing the rate coefficient for the QOOH → 2CH₂O + OH reaction is needed to improve the predictions of formaldehyde. To aid future quantification of DME oxidation intermediates by photoionization mass spectrometry, we report experimentally determined ionization cross-sections for ROO, OOQOOH, and HPMF.