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    Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

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    Type
    Article
    Authors
    Moshammer, Kai
    Jasper, Ahren W.
    Popolan-Vaida, Denisia M.
    Lucassen, Arnas
    Diévart, Pascal
    Selim, Hatem
    Eskola, Arkke J.
    Taatjes, Craig A.
    Leone, Stephen R.
    Sarathy, Mani cc
    Ju, Yiguang
    Dagaut, Philippe cc
    Kohse-Höinghaus, Katharina
    Hansen, Nils
    KAUST Department
    Chemical Engineering Program
    Chemical Science Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Physical Science and Engineering (PSE) Division
    Date
    2015-03-05
    Online Publication Date
    2015-03-05
    Print Publication Date
    2015-07-16
    Permanent link to this record
    http://hdl.handle.net/10754/566096
    
    Metadata
    Show full item record
    Abstract
    In this paper we report the detection and identification of the keto-hydroperoxide (hydroperoxymethyl formate, HPMF, HOOCH2OCHO) and other partially oxidized intermediate species arising from the low-temperature (540 K) oxidation of dimethyl ether (DME). These observations were made possible by coupling a jet-stirred reactor with molecular-beam sampling capabilities, operated near atmospheric pressure, to a reflectron time-of-flight mass spectrometer that employs single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation. On the basis of experimentally observed ionization thresholds and fragmentation appearance energies, interpreted with the aid of ab initio calculations, we have identified HPMF and its conceivable decomposition products HC(O)O(O)CH (formic acid anhydride), HC(O)OOH (performic acid), and HOC(O)OH (carbonic acid). Other intermediates that were detected and identified include HC(O)OCH3 (methyl formate), cycl-CH2-O-CH2-O- (1,3-dioxetane), CH3OOH (methyl hydroperoxide), HC(O)OH (formic acid), and H2O2 (hydrogen peroxide). We show that the theoretical characterization of multiple conformeric structures of some intermediates is required when interpreting the experimentally observed ionization thresholds, and a simple method is presented for estimating the importance of multiple conformers at the estimated temperature (∼100 K) of the present molecular beam. We also discuss possible formation pathways of the detected species: for example, supported by potential energy surface calculations, we show that performic acid may be a minor channel of the O2 + CH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OCHOOH intermediate, which predominantly leads to the HPMF. © 2015 American Chemical Society.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry A
    DOI
    10.1021/acs.jpca.5b00101
    PubMed ID
    25695304
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jpca.5b00101
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; Chemical Engineering Program; Clean Combustion Research Center

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