Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane
Abstract
We present a combined experimental and theoretical investigation of the autoignition chemistry of a prototypical cyclic hydrocarbon, cyclopentane. Experiments using a high-pressure photolysis reactor coupled to time-resolved synchrotron VUV photoionization mass spectrometry directly probe the short-lived radical intermediates and products in cyclopentane oxidation reactions. We detect key peroxy radical intermediates ROO and OOQOOH, as well as several hydroperoxides, formed by second O2 addition. Automated quantum chemical calculations map out the R + O2 + O2 reaction channels and demonstrate that the detected intermediates belong to the dominant radical chain-branching pathway: ROO (+ O2) → γ-QOOH + O2 → γ-OOQOOH → products. ROO, OOQOOH, and hydroperoxide products of second-O2 addition undergo extensive dissociative ionization, making their experimental assignment challenging. We use photoionization dynamics calculations to aid in their characterization and report the absolute photoionization spectra of isomerically pure ROO and γ-OOQOOH. Here, a global statistical fit of the observed kinetics enables reliable quantification of the time-resolved concentrations of these elusive, yet critical species, paving the way for detailed comparisons with theoretical predictions from master-equation-based models.
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1787521
- Report Number(s):
- SAND-2021-5038J
Journal ID: ISSN 1089-5639; 695828
- Grant/Contract Number:
- AC04-94AL85000; NA0003525; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 125; Journal Issue: 20; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxides; Ions; Oxidation; Molecular structure; Cations
Citation Formats
Sheps, Leonid, Dewyer, Amanda Lee, Demireva, Maria Plamenova, and Zádor, Judit. Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane. United States: N. p., 2021.
Web. doi:10.1021/acs.jpca.1c02001.
Sheps, Leonid, Dewyer, Amanda Lee, Demireva, Maria Plamenova, & Zádor, Judit. Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane. United States. https://doi.org/10.1021/acs.jpca.1c02001
Sheps, Leonid, Dewyer, Amanda Lee, Demireva, Maria Plamenova, and Zádor, Judit. Tue .
"Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane". United States. https://doi.org/10.1021/acs.jpca.1c02001. https://www.osti.gov/servlets/purl/1787521.
@article{osti_1787521,
title = {Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane},
author = {Sheps, Leonid and Dewyer, Amanda Lee and Demireva, Maria Plamenova and Zádor, Judit},
abstractNote = {We present a combined experimental and theoretical investigation of the autoignition chemistry of a prototypical cyclic hydrocarbon, cyclopentane. Experiments using a high-pressure photolysis reactor coupled to time-resolved synchrotron VUV photoionization mass spectrometry directly probe the short-lived radical intermediates and products in cyclopentane oxidation reactions. We detect key peroxy radical intermediates ROO and OOQOOH, as well as several hydroperoxides, formed by second O2 addition. Automated quantum chemical calculations map out the R + O2 + O2 reaction channels and demonstrate that the detected intermediates belong to the dominant radical chain-branching pathway: ROO (+ O2) → γ-QOOH + O2 → γ-OOQOOH → products. ROO, OOQOOH, and hydroperoxide products of second-O2 addition undergo extensive dissociative ionization, making their experimental assignment challenging. We use photoionization dynamics calculations to aid in their characterization and report the absolute photoionization spectra of isomerically pure ROO and γ-OOQOOH. Here, a global statistical fit of the observed kinetics enables reliable quantification of the time-resolved concentrations of these elusive, yet critical species, paving the way for detailed comparisons with theoretical predictions from master-equation-based models.},
doi = {10.1021/acs.jpca.1c02001},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 20,
volume = 125,
place = {United States},
year = {Tue May 18 00:00:00 EDT 2021},
month = {Tue May 18 00:00:00 EDT 2021}
}
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