Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition

Zhou, Chong-Wen; Simmie, John M.; Pitz, William J.; Curran, Henry J.

doi:10.1021/acs.jpca.6b03994

Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition

Journal Article · Thu Aug 25 04:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b03994· OSTI ID:1336987

Zhou, Chong-Wen ^[1]; Simmie, John M. ^[1]; Pitz, William J. ^[2]; Curran, Henry J. ^[1]

National Univ. of Ireland Galway (Ireland). School of Chemistry and Combustion Chemistry Center
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. We present calculated thermodynamic and kinetic data for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. Furthermore, these radicals can be formed via H atom abstraction reactions by H and Ö atoms and OH, HO₂, and CH₃ radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when OH is involved, but the reverse holds true for HO₂ radicals. We also determined the subsequent β-scission of the radicals formed, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1336987

Report Number(s):: LLNL-JRNL--690702

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 36 Vol. 120; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

The Impact of Resonance Stabilization on the Intramolecular Hydrogen-Atom Shift Reactions of Hydrocarbon Radicals Wang, Kun; Villano, Stephanie M.; Dean, Anthony M. ChemPhysChem, Vol. 16, Issue 12 https://doi.org/10.1002/cphc.201500396	journal	July 2015
Thermochemische Untersuchungen an cyclischen Ketonen Wolf, G. Helvetica Chimica Acta, Vol. 55, Issue 5 https://doi.org/10.1002/hlca.19720550510	journal	July 1972
Multiple-Well, multiple-path unimolecular reaction systems. I. MultiWell computer program suite Barker, John R. International Journal of Chemical Kinetics, Vol. 33, Issue 4 https://doi.org/10.1002/kin.1017	journal	January 2001
Computational studies on the reactions of 3-butenyl and 3-butenylperoxy radicals: Reactions of 3-Butenyl and 3-Butenylperoxy Radicals Miyoshi, Akira International Journal of Chemical Kinetics, Vol. 42, Issue 5 https://doi.org/10.1002/kin.20478	journal	March 2010
Computational Kinetic Study for the Unimolecular Decomposition of Cyclopentanone: KINETIC STUDY FOR THE UNIMOLECULAR DECOMPOSITION OF CYCLOPENTANONE Zaras, Aristotelis M.; Thion, Sebastien; Dagaut, Philippe International Journal of Chemical Kinetics, Vol. 47, Issue 7 https://doi.org/10.1002/kin.20921	journal	April 2015
Molpro: a general-purpose quantum chemistry program package: Molpro Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82	journal	July 2011
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Basis-set convergence in correlated calculations on Ne, N2, and H2O Halkier, Asger; Helgaker, Trygve; Jørgensen, Poul Chemical Physics Letters, Vol. 286, Issue 3-4 https://doi.org/10.1016/S0009-2614(98)00111-0	journal	April 1998
Impact of a pressurized hot water treatment on the quality of bio-oil produced from aspen Le Roux, Étienne; Chaouch, Mounir; Diouf, Papa Niokhor Biomass and Bioenergy, Vol. 81 https://doi.org/10.1016/j.biombioe.2015.07.005	journal	October 2015
Intermolecular C–H⋯O interactions in cyclopentanone: An inelastic neutron scattering study Vaz, Pedro D.; Nolasco, Mariela M.; Ribeiro-Claro, Paulo J. A. Chemical Physics, Vol. 427 https://doi.org/10.1016/j.chemphys.2013.08.004	journal	December 2013
A comprehensive combustion chemistry study of 2,5-dimethylhexane Sarathy, S. Mani; Javed, Tamour; Karsenty, Florent Combustion and Flame, Vol. 161, Issue 6 https://doi.org/10.1016/j.combustflame.2013.12.010	journal	June 2014
Kinetics of oxidation of cyclohexanone in a jet-stirred reactor: Experimental and modeling Serinyel, Z.; Togbé, C.; Zaras, A. Proceedings of the Combustion Institute, Vol. 35, Issue 1 https://doi.org/10.1016/j.proci.2014.06.150	journal	January 2015
Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling Al Rashidi, Mariam J.; Thion, Sébastien; Togbé, Casimir Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.036	journal	January 2017
Excited-State Ring-Opening Mechanism of Cyclic Ketones: A MS-CASPT2//CASSCF Study Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu The Journal of Physical Chemistry A, Vol. 119, Issue 15 https://doi.org/10.1021/acs.jpca.5b00302	journal	April 2015
Evaluated Kinetics of the Reactions of H and CH ₃ with n -Alkanes: Experiments with n -Butane and a Combustion Model Reaction Network Analysis Manion, Jeffrey A.; Sheen, David A.; Awan, Iftikhar A. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b01004	journal	February 2015
The path of chemical reactions - the IRC approach Fukui, Kenichi Accounts of Chemical Research, Vol. 14, Issue 12 https://doi.org/10.1021/ar00072a001	journal	December 1981
A kinetic investigation of the gas-phase reactions of hydroxyl radicals with cyclic ketones and diones: mechanistic insights Dagaut, Philippe; Wallington, Timothy J.; Liu, Renzhang The Journal of Physical Chemistry, Vol. 92, Issue 15 https://doi.org/10.1021/j100326a026	journal	July 1988
Comparison of the quadratic configuration interaction and coupled-cluster approaches to electron correlation including the effect of triple excitations Lee, Timothy J.; Rendell, Alistair P.; Taylor, Peter R. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a008	journal	July 1990
Thermochemical studies of carbonyl compounds. 5. Enthalpies of reduction of carbonyl groups Wiberg, Kenneth B.; Crocker, Louis S.; Morgan, Kathleen M. Journal of the American Chemical Society, Vol. 113, Issue 9 https://doi.org/10.1021/ja00009a033	journal	April 1991
Strange Kinetics of the C ₂ H ₆ + CN Reaction Explained ^† Georgievskii, Yuri; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp068430k	journal	May 2007
Kinetics and Thermochemistry of 2,5-Dimethyltetrahydrofuran and Related Oxolanes: Next Next-Generation Biofuels Simmie, John M. The Journal of Physical Chemistry A, Vol. 116, Issue 18 https://doi.org/10.1021/jp301870w	journal	April 2012
Computational Kinetic Study for the Unimolecular Decomposition Pathways of Cyclohexanone Zaras, Aristotelis M.; Dagaut, Philippe; Serinyel, Zeynep The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/jp506227w	journal	November 2014
Reactivity–Structure-Based Rate Estimation Rules for Alkyl Radical H Atom Shift and Alkenyl Radical Cycloaddition Reactions Wang, Kun; Villano, Stephanie M.; Dean, Anthony M. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/jp511017z	journal	January 2015
Benchmarking Compound Methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the Active Thermochemical Tables: A Litmus Test for Cost-Effective Molecular Formation Enthalpies Simmie, John M.; Somers, Kieran P. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/jp511403a	journal	January 2015
Low temperature (550–700 K) oxidation pathways of cyclic ketones: dominance of HO ₂ -elimination channels yielding conjugated cyclic coproducts Scheer, Adam M.; Welz, Oliver; Vasu, Subith S. Physical Chemistry Chemical Physics, Vol. 17, Issue 18 https://doi.org/10.1039/C4CP06097K	journal	January 2015
Gaussian-4 theory Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 126, Issue 8 https://doi.org/10.1063/1.2436888	journal	February 2007
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 103, Issue 11 https://doi.org/10.1063/1.470645	journal	September 1995
Chemical Kinetic Data Base for Combustion Chemistry. Part 3: Propane Tsang, Wing Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555806	journal	April 1988
Chemical Kinetic Data Sheets for High‐Temperature Reactions. Part II Cohen, N.; Westberg, K. R. Journal of Physical and Chemical Reference Data, Vol. 20, Issue 6 https://doi.org/10.1063/1.555901	journal	November 1991
Volatile organic compound production by organisms in the genus Ascocoryne and a re-evaluation of myco-diesel production by NRRL 50072 Griffin, M. A.; Spakowicz, D. J.; Gianoulis, T. A. Microbiology, Vol. 156, Issue 12 https://doi.org/10.1099/mic.0.041327-0	journal	August 2010
The production of myco-diesel hydrocarbons and their derivatives by the endophytic fungus Gliocladium roseum (NRRL 50072) Strobel, G. A.; Knighton, B.; Kluck, K. Microbiology, Vol. 154, Issue 11 https://doi.org/10.1099/mic.0.2008/022186-0	journal	November 2008
The Penetration of a Potential Barrier by Electrons Eckart, Carl Physical Review, Vol. 35, Issue 11 https://doi.org/10.1103/PhysRev.35.1303	journal	June 1930
Comprehensive Handbook of Chemical Bond Energies Luo, Yu-Ran https://doi.org/10.1201/9781420007282	book	March 2007
Heats of Combustion of Cyclic Ketones and Alcohols. Sellers, Peter; Sunner, Stig; Lundvik, Lars Acta Chemica Scandinavica, Vol. 16 https://doi.org/10.3891/acta.chem.scand.16-0046	journal	January 1962

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