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

Kai Moshammer; Ahren W. Jasper; Denisia M. Popolan-Vaida; Zhandong Wang; Vijai Shankar; Lena Ruwe; Craig A. Taatjes; Philippe Dagaut; Nils Hansen

doi:10.1021/acs.jpca.6b06634

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

Kai Moshammer, Ahren W. Jasper, Denisia M. Popolan-Vaida, Zhandong Wang, Vijai Shankar, Lena Ruwe, Craig A. Taatjes, Philippe Dagaut, Nils Hansen

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Abstract

This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015, 119, 7361–7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450–1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

Original language	English (US)
Pages (from-to)	7890-7901
Number of pages	12
Journal	The Journal of Physical Chemistry A
Volume	120
Issue number	40
DOIs	https://doi.org/10.1021/acs.jpca.6b06634
State	Published - Oct 4 2016

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This material is based upon work supported by the U.S.Department of Energy (DOE), Office of Science, Office ofBasic Energy Sciences. D.M.P.-V. is supported by the DOE Gas Phase Chemical Physics Program at Lawrence Berkeley National Laboratory, under Contract DEAC02-05CH11231. We thank Paul Fugazzi for technical assistance and Profs.Leone, Sarathy, and Kohse-Hoinghaus for continuing support of this project, and Prof. Lucchese for providing his code. P.D. received funding from the European Research Council under the European Community's Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement 291049-2G-CSafe. Z.W. and V.S.B.S. acknowledge competitive research funding given to the Clean Combustion Research Center from the King Abdullah University of Science and Technology. The Advance Light Source is supported by the Director, Office of Science,Office of Basic Energy Sciences, of the U.S. DOE under Contract DEAC02-05CH11231. Sandia is a multimission laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration under Contract DE-AC04-94-AL85000.

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title = "Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether",

abstract = "This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015, 119, 7361–7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450–1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.",

author = "Kai Moshammer and Jasper, {Ahren W.} and Popolan-Vaida, {Denisia M.} and Zhandong Wang and Vijai Shankar and Lena Ruwe and Taatjes, {Craig A.} and Philippe Dagaut and Nils Hansen",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This material is based upon work supported by the U.S.Department of Energy (DOE), Office of Science, Office ofBasic Energy Sciences. D.M.P.-V. is supported by the DOE Gas Phase Chemical Physics Program at Lawrence Berkeley National Laboratory, under Contract DEAC02-05CH11231. We thank Paul Fugazzi for technical assistance and Profs.Leone, Sarathy, and Kohse-Hoinghaus for continuing support of this project, and Prof. Lucchese for providing his code. P.D. received funding from the European Research Council under the European Community's Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement 291049-2G-CSafe. Z.W. and V.S.B.S. acknowledge competitive research funding given to the Clean Combustion Research Center from the King Abdullah University of Science and Technology. The Advance Light Source is supported by the Director, Office of Science,Office of Basic Energy Sciences, of the U.S. DOE under Contract DEAC02-05CH11231. Sandia is a multimission laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration under Contract DE-AC04-94-AL85000.",

year = "2016",

month = oct,

day = "4",

doi = "10.1021/acs.jpca.6b06634",

language = "English (US)",

volume = "120",

pages = "7890--7901",

journal = "The Journal of Physical Chemistry A",

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T1 - Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

AU - Moshammer, Kai

AU - Jasper, Ahren W.

AU - Popolan-Vaida, Denisia M.

AU - Wang, Zhandong

AU - Shankar, Vijai

AU - Ruwe, Lena

AU - Taatjes, Craig A.

AU - Dagaut, Philippe

AU - Hansen, Nils

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This material is based upon work supported by the U.S.Department of Energy (DOE), Office of Science, Office ofBasic Energy Sciences. D.M.P.-V. is supported by the DOE Gas Phase Chemical Physics Program at Lawrence Berkeley National Laboratory, under Contract DEAC02-05CH11231. We thank Paul Fugazzi for technical assistance and Profs.Leone, Sarathy, and Kohse-Hoinghaus for continuing support of this project, and Prof. Lucchese for providing his code. P.D. received funding from the European Research Council under the European Community's Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement 291049-2G-CSafe. Z.W. and V.S.B.S. acknowledge competitive research funding given to the Clean Combustion Research Center from the King Abdullah University of Science and Technology. The Advance Light Source is supported by the Director, Office of Science,Office of Basic Energy Sciences, of the U.S. DOE under Contract DEAC02-05CH11231. Sandia is a multimission laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration under Contract DE-AC04-94-AL85000.

PY - 2016/10/4

Y1 - 2016/10/4

N2 - This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015, 119, 7361–7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450–1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

AB - This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015, 119, 7361–7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450–1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

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U2 - 10.1021/acs.jpca.6b06634

DO - 10.1021/acs.jpca.6b06634

M3 - Article

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SN - 1089-5639

VL - 120

SP - 7890

EP - 7901

JO - The Journal of Physical Chemistry A

JF - The Journal of Physical Chemistry A

IS - 40

ER -

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

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