Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether
Type
ArticleAuthors
Moshammer, KaiJasper, Ahren W.
Popolan-Vaida, Denisia M.
Lucassen, Arnas
Diévart, Pascal
Selim, Hatem
Eskola, Arkke J.
Taatjes, Craig A.
Leone, Stephen R.
Sarathy, Mani

Ju, Yiguang
Dagaut, Philippe

Kohse-Höinghaus, Katharina
Hansen, Nils
KAUST Department
Chemical Engineering ProgramChemical Science Program
Clean Combustion Research Center
Combustion and Pyrolysis Chemistry (CPC) Group
Physical Science and Engineering (PSE) Division
Date
2015-03-05Online Publication Date
2015-03-05Print Publication Date
2015-07-16Permanent link to this record
http://hdl.handle.net/10754/566096
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Show full item recordAbstract
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.Citation
Moshammer, K., Jasper, A. W., Popolan-Vaida, D. M., Lucassen, A., Diévart, P., Selim, H., … Hansen, N. (2015). Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether. The Journal of Physical Chemistry A, 119(28), 7361–7374. doi:10.1021/acs.jpca.5b00101Publisher
American Chemical Society (ACS)PubMed ID
25695304ae974a485f413a2113503eed53cd6c53
10.1021/acs.jpca.5b00101
Scopus Count
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