Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) 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...
Published in: | The Journal of Physical Chemistry A |
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American Chemical Society (ACS)
2015
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Online Access: | http://hdl.handle.net/10754/566096 https://doi.org/10.1021/acs.jpca.5b00101 |
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ftkingabdullahun:oai:repository.kaust.edu.sa:10754/566096 2023-12-31T10:05:51+01:00 Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether 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 Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils Chemical Engineering Program Chemical Science Program Clean Combustion Research Center Combustion and Pyrolysis Chemistry (CPC) Group Physical Science and Engineering (PSE) Division 2015-03-05 application/pdf image/jpeg http://hdl.handle.net/10754/566096 https://doi.org/10.1021/acs.jpca.5b00101 unknown American Chemical Society (ACS) https://www.osti.gov/biblio/1369819 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.5b00101 doi:10.1021/acs.jpca.5b00101 1089-5639 1520-5215 The Journal of Physical Chemistry A 25695304 http://hdl.handle.net/10754/566096 This document is the Accepted Manuscript version of a Published Work that appeared in final form in [JournalTitle], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [ArticleLink]. This file is an open access version redistributed from: https://www.osti.gov/biblio/1369819 2016-03-05 Article 2015 ftkingabdullahun https://doi.org/10.1021/acs.jpca.5b00101 2023-12-02T20:18:10Z 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. Article in Journal/Newspaper Carbonic acid King Abdullah University of Science and Technology: KAUST Repository The Journal of Physical Chemistry A 119 28 7361 7374 |
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King Abdullah University of Science and Technology: KAUST Repository |
op_collection_id |
ftkingabdullahun |
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unknown |
description |
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. |
author2 |
Chemical Engineering Program Chemical Science Program Clean Combustion Research Center Combustion and Pyrolysis Chemistry (CPC) Group Physical Science and Engineering (PSE) Division |
format |
Article in Journal/Newspaper |
author |
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 Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils |
spellingShingle |
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 Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
author_facet |
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 Ju, Yiguang Dagaut, Philippe Kohse-Höinghaus, Katharina Hansen, Nils |
author_sort |
Moshammer, Kai |
title |
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_short |
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_full |
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_fullStr |
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_full_unstemmed |
Detection and Identification of the Keto-Hydroperoxide (HOOCH 2 OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether |
title_sort |
detection and identification of the keto-hydroperoxide (hooch 2 ocho) and other intermediates during low-temperature oxidation of dimethyl ether |
publisher |
American Chemical Society (ACS) |
publishDate |
2015 |
url |
http://hdl.handle.net/10754/566096 https://doi.org/10.1021/acs.jpca.5b00101 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
https://www.osti.gov/biblio/1369819 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.5b00101 doi:10.1021/acs.jpca.5b00101 1089-5639 1520-5215 The Journal of Physical Chemistry A 25695304 http://hdl.handle.net/10754/566096 |
op_rights |
This document is the Accepted Manuscript version of a Published Work that appeared in final form in [JournalTitle], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [ArticleLink]. This file is an open access version redistributed from: https://www.osti.gov/biblio/1369819 2016-03-05 |
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_ |
1786837573785616384 |