Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

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 coup...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-07, Vol.119 (28), p.7361-7374
Main 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, S. Mani, Ju, Yiguang, Dagaut, Philippe, Kohse-Höinghaus, Katharina, Hansen, Nils
Format: Article
Language:English
Subjects:
10 SYNTHETIC FUELS
Chemical Sciences
Engineering Sciences
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
jet-stirred reactor, keto-hydroperoxide , dimethyl ether, low-temperture oxidation
or physical chemistry
Reactive fluid environment
Theoretical and
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 + ĊH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OĊHOOH intermediate, which predominantly leads to the HPMF.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.5b00101