Insights on keto-hydroperoxide formation from O2 addition to the beta-tetrahydrofuran radical

Lockwood, Katherine S.; Labbe, Nicole J.

doi:10.1016/j.proci.2020.06.357

Insights on keto-hydroperoxide formation from O₂ addition to the beta-tetrahydrofuran radical

Journal Article · Sat Sep 12 00:00:00 EDT 2020 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2020.06.357· OSTI ID:1778229

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Univ. of Colorado, Boulder, CO (United States); CU Boulder
Univ. of Colorado, Boulder, CO (United States)

Cyclic ethers provide an interesting case study of low-temperature oxidation chemistry, especially in relevance to biofuels. A recent experimental study revealed new questions regarding the low-temperature oxidation mechanism of tetrahydrofuran (THF) concerning the formation of keto-hydroperoxides. In particular, keto-hydroperoxides originating from the THF-β radical were not captured accurately by current literature models, motivating this work to calculate the energetics of the first and second O₂-addition pathways for THF radicals. Electronic structure calculations at the CCSD(T)/cc-pV∞Z//M06-2X/cc-pVTZ level of theory were used to generate potential energy surfaces for the α-C and β-C THF radicals and subsequent pathways to the formation of the keto-hydroperoxide isomers. These are the first theoretical calculations of the second O₂-addition radical pathways for the THF-β radical. Results from the theorical work provided further insight into the low-temperature oxidation of THF. This included identifying the pathways most likely to form the keto-hydroperoxide isomers observed in prior experimental work; and detecting that the shortcomings in prior models are likely due to uncertainties in R + THF abstraction reaction rates. Here, these conclusions will motivate future work for accurate THF kinetic model development.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0018627

OSTI ID:: 1778229

Alternate ID(s):: OSTI ID: 1777042

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 38; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Keto-hydroperoxides
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Insights on keto-hydroperoxide formation from O2 addition to the beta-tetrahydrofuran radical

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Insights on keto-hydroperoxide formation from O₂ addition to the beta-tetrahydrofuran radical