Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether
Moshammer K, Jasper AW, Popolan-Vaida DM, et al. Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether. The Journal of Physical Chemistry A . 2015;119(28):7361-7374. In this paper we report the detection and ide...
Published in: | The Journal of Physical Chemistry A |
---|---|
Main Authors: | , , , , , , , , , , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
American Chemical Society
2015
|
Subjects: | |
Online Access: | https://pub.uni-bielefeld.de/record/2773113 |
id |
ftubbiepub:oai:pub.uni-bielefeld.de:2773113 |
---|---|
record_format |
openpolar |
spelling |
ftubbiepub:oai:pub.uni-bielefeld.de:2773113 2023-05-15T15:52:53+02:00 Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether Moshammer, Kai Jasper, Ahren W. Popolan-Vaida, Denisia M. Lucassen, Arnas Dievarti, Pascal Selim, Hatem Eskola, Arkke J. Taatjes, Craig A. Leone, Stephen R. Sarathy, S. Mani Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils 2015 https://pub.uni-bielefeld.de/record/2773113 eng eng American Chemical Society info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b00101 info:eu-repo/semantics/altIdentifier/issn/1089-5639 info:eu-repo/semantics/altIdentifier/wos/000358337600030 info:eu-repo/semantics/altIdentifier/pmid/25695304 https://pub.uni-bielefeld.de/record/2773113 info:eu-repo/semantics/closedAccess http://purl.org/coar/resource_type/c_6501 info:eu-repo/semantics/article doc-type:article text 2015 ftubbiepub https://doi.org/10.1021/acs.jpca.5b00101 2022-02-08T22:34:18Z Moshammer K, Jasper AW, Popolan-Vaida DM, et al. Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether. The Journal of Physical Chemistry A . 2015;119(28):7361-7374. 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 vacuumultraviolet 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 (similar to 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 O-2 + CH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OCHOOH intermediate, which predominantly leads to the HPMF. Article in Journal/Newspaper Carbonic acid PUB - Publications at Bielefeld University The Journal of Physical Chemistry A 119 28 7361 7374 |
institution |
Open Polar |
collection |
PUB - Publications at Bielefeld University |
op_collection_id |
ftubbiepub |
language |
English |
description |
Moshammer K, Jasper AW, Popolan-Vaida DM, et al. Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether. The Journal of Physical Chemistry A . 2015;119(28):7361-7374. 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 vacuumultraviolet 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 (similar to 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 O-2 + CH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OCHOOH intermediate, which predominantly leads to the HPMF. |
format |
Article in Journal/Newspaper |
author |
Moshammer, Kai Jasper, Ahren W. Popolan-Vaida, Denisia M. Lucassen, Arnas Dievarti, Pascal Selim, Hatem Eskola, Arkke J. Taatjes, Craig A. Leone, Stephen R. Sarathy, S. Mani Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils |
spellingShingle |
Moshammer, Kai Jasper, Ahren W. Popolan-Vaida, Denisia M. Lucassen, Arnas Dievarti, Pascal Selim, Hatem Eskola, Arkke J. Taatjes, Craig A. Leone, Stephen R. Sarathy, S. Mani Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
author_facet |
Moshammer, Kai Jasper, Ahren W. Popolan-Vaida, Denisia M. Lucassen, Arnas Dievarti, Pascal Selim, Hatem Eskola, Arkke J. Taatjes, Craig A. Leone, Stephen R. Sarathy, S. Mani Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils |
author_sort |
Moshammer, Kai |
title |
Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_short |
Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_full |
Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_fullStr |
Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_full_unstemmed |
Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_sort |
detection and identification of the keto-hydroperoxide (hooch2ocho) and other intermediates during low-temperature oxidation of dimethyl ether |
publisher |
American Chemical Society |
publishDate |
2015 |
url |
https://pub.uni-bielefeld.de/record/2773113 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b00101 info:eu-repo/semantics/altIdentifier/issn/1089-5639 info:eu-repo/semantics/altIdentifier/wos/000358337600030 info:eu-repo/semantics/altIdentifier/pmid/25695304 https://pub.uni-bielefeld.de/record/2773113 |
op_rights |
info:eu-repo/semantics/closedAccess |
op_doi |
https://doi.org/10.1021/acs.jpca.5b00101 |
container_title |
The Journal of Physical Chemistry A |
container_volume |
119 |
container_issue |
28 |
container_start_page |
7361 |
op_container_end_page |
7374 |
_version_ |
1766387985877565440 |