Reaction Pathways, Thermodynamics, and Kinetics of Cyclopentanone Oxidation Intermediates: A Theoretical Approach

Khanniche, Sarah; Green, William H.

doi:10.1021/acs.jpca.9b05806

Title: Reaction Pathways, Thermodynamics, and Kinetics of Cyclopentanone Oxidation Intermediates: A Theoretical Approach

Journal Article · Wed Sep 18 00:00:00 EDT 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.9b05806· OSTI ID:1763637

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Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Despite the promising role of cyclopentanone as a bio-derived fuel, thermodynamic and kinetic data are lacking for low temperature oxidation regimes. In this study, ab initio calculations at the CBS-QB3 level explore the subsequent reactivity that results from O₂-addition to 2- and 3-oxo cyclopentyl radicals, including expected reaction classes such as intra-H migration, HO₂-elimination, cyclic ether formation and β-scission along with their thermodynamic parameters. Some of the rates are similar to the analogous reactions of cyclopentane, but some other reactions of cyclopentanone are very different. The carbonyl group hinders H-migration from the α’ position but promotes HO₂-elimination. Enol peroxy formation from some hydroperoxy alkyl radicals of cyclopentanone is unexpectedly important, and so is HO₂-elimination by β-scission. Our calculations also indicated that at engine relevant conditions the α-RO₂ prefers to go back to reactants 2-oxo cyclopentyl radical and O₂. Therefore, the reactions resulting from HO2-addition to 2-oxo cyclopentyl is also provided. The lowest barrier channel identified on the singlet surface corresponds to an unexpected intra OH-migration path concerted with ring opening. In conclusion, this valuable information will advance the construction of improved kinetic models for the oxidation of cylopentanone.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: EE0007982

OSTI ID:: 1763637

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 123, Issue 45; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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