Oxidation of diethyl ether: Extensive characterization of products formed at low temperature using high resolution mass spectrometry

The oxidation of a stoichiometric diethyl ether-oxygen-nitrogen mixture containing 5000 ppm fuel was studied in jet-stirred reactor at 10 atm and residence times 1 s. Experimental temperatures varied stepwise for 440 to 740 K products were quantified by gas chromatography with TCD FID, chromatography-mass spectrometry, FTIR. Other experiments the temperature range 480 570 performed characterizing elusive cool flame products. To this end, samples trapped acetonitrile flow injection analyses liquid spectrometry (Orbitrap Q-Exactive?). For ionization, we used positive negative atmospheric pressure chemical ionization (APCI). Among fuel-specific products, hydroperoxides diols (C4H10O3), carbonyl (C4H8O4), acetic acid, di-keto ethers (C4H6O3), cyclic (C4H8O2) highly oxygenated molecules, i.e., keto-dihydroperoxides (C4H8O6), keto-trihydroperoxides (C4H8O8), di-keto-hydroperoxides (C4H6O5), diketo-dihydroperoxides (C4H6O7), detected. confirm presence –OH or –OOH groups H/D exchange D2O used. DNPH derivatization identify carbonyls present samples, especially those molecular weight below 50 amu which cannot be detected directly mass spectrometer. Chemical kinetic modeling using mechanism taken from literature performed. Although reasonable agreement between data simulations observed several species, some discrepancies experimental computed mole fractions observed.