Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.

doi:10.1016/j.proci.2014.05.004

Title: Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

Journal Article · Fri Jul 04 00:00:00 EDT 2014 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2014.05.004· OSTI ID:1122140

^[1]; Savee, John D. ^[1]; Osborn, David L. ^[1]; Taatjes, Craig A. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH₃)₂CCHCH₂OH) and isoprenol (3-methyl-3-buten-1-ol, CH₂C(CH₃)CH₂CH₂OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. These results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O₂ addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O₂. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O₂. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO₂-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.

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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1122140

Alternate ID(s):: OSTI ID: 1251888

Report Number(s):: SAND-2013-10349J; PII: S1540748914000078

Journal Information:: Proceedings of the Combustion Institute, Vol. 35, Issue 1; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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References (29)

Kinetics of elementary reactions in low-temperature autoignition chemistry Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X. Progress in Energy and Combustion Science, Vol. 37, Issue 4 https://doi.org/10.1016/j.pecs.2010.06.006	journal	August 2011
Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol Welz, Oliver; Zádor, Judit; Savee, John D. Physical Chemistry Chemical Physics, Vol. 14, Issue 9 https://doi.org/10.1039/c2cp23248k	journal	January 2012
Low-temperature combustion chemistry of biofuels: Pathways in the low-temperature (550–700K) oxidation chemistry of isobutanol and tert-butanol Welz, Oliver; Savee, John D.; Eskola, Arkke J. Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.05.058	journal	January 2013
The reaction of hydroxyethyl radicals with O2: A theoretical analysis and experimental product study Zádor, Judit; Fernandes, Ravi X.; Georgievskii, Yuri Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.05.020	journal	January 2009
Gas phase oxidation of alkenes—Part II. The oxidation of 2-methylbutene-2 and 2,3-dimethylbutene-2 Ray, D. J. M.; Waddington, D. J. Combustion and Flame, Vol. 20, Issue 3 https://doi.org/10.1016/0010-2180(73)90024-2	journal	June 1973
Gas-phase oxidation of alkenes: decomposition of hydroxy-substituted peroxyl radicals Ray, David J. M.; Redfearn, Alan; Waddington, David J. Journal of the Chemical Society, Perkin Transactions 2, Issue 5 https://doi.org/10.1039/p29730000540	journal	January 1973
Unconventional Peroxy Chemistry in Alcohol Oxidation: The Water Elimination Pathway Welz, Oliver; Klippenstein, Stephen J.; Harding, Lawrence B. The Journal of Physical Chemistry Letters, Vol. 4, Issue 3 https://doi.org/10.1021/jz302004w	journal	January 2013
A comprehensive chemical kinetic combustion model for the four butanol isomers Sarathy, S. Mani; Vranckx, Stijn; Yasunaga, Kenji Combustion and Flame, Vol. 159, Issue 6 https://doi.org/10.1016/j.combustflame.2011.12.017	journal	June 2012
A comprehensive experimental and modeling study of iso-pentanol combustion Mani Sarathy, S.; Park, Sungwoo; Weber, Bryan W. Combustion and Flame, Vol. 160, Issue 12 https://doi.org/10.1016/j.combustflame.2013.06.022	journal	December 2013
Metabolic engineering of Escherichia coli for high-specificity production of isoprenol and prenol as next generation of biofuels Zheng, Yanning; Liu, Qiang; Li, Lingling Biotechnology for Biofuels, Vol. 6, Article No. 57 https://doi.org/10.1186/1754-6834-6-57	journal	January 2013
Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature Rodriguez, Diana; Rodriguez, Ana; Soto, Amparo Journal of Atmospheric Chemistry, Vol. 59, Issue 3 https://doi.org/10.1007/s10874-008-9101-6	journal	March 2008
Products and mechanism of the reaction of Cl atoms with unsaturated alcohols Rodríguez, Ana; Rodríguez, Diana; Soto, Amparo Atmospheric Environment, Vol. 50 https://doi.org/10.1016/j.atmosenv.2011.12.030	journal	April 2012
Theoretical study on the reaction mechanism of the OH-initiated oxidation of CH2=C(CH3)CH2CH2OH Du, Benni; Zhang, Weichao Structural Chemistry, Vol. 22, Issue 3 https://doi.org/10.1007/s11224-011-9742-y	journal	January 2011
Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates Battin-Leclerc, F. Progress in Energy and Combustion Science, Vol. 34, Issue 4 https://doi.org/10.1016/j.pecs.2007.10.002	journal	August 2008
Hydrocarbon radical reactions with oxygen: comparison of allyl, formyl, and vinyl to ethyl Bozzelli, Joseph W.; Dean, Anthony M. The Journal of Physical Chemistry, Vol. 97, Issue 17 https://doi.org/10.1021/j100119a030	journal	April 1993
Oxidation of allyl radicals: kinetic parameters for the reactions of allyl radicals with HO₂and O₂between 400 and 480 °C Lodhi, Zulfiqar H.; Walker, Raymond W. J. Chem. Soc., Faraday Trans., Vol. 87, Issue 15 https://doi.org/10.1039/FT9918702361	journal	January 1991
Detailed chemical kinetic modeling of the effects of CC double bonds on the ignition of biodiesel fuels Westbrook, C. K.; Pitz, W. J.; Sarathy, S. M. Proceedings of the Combustion Institute, Vol. 34, Issue 2 https://doi.org/10.1016/j.proci.2012.05.025	journal	January 2013
The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics Osborn, David L.; Zou, Peng; Johnsen, Howard Review of Scientific Instruments, Vol. 79, Issue 10 https://doi.org/10.1063/1.3000004	journal	October 2008
“Imaging” combustion chemistry via multiplexed synchrotron-photoionization mass spectrometry Taatjes, Craig A.; Hansen, Nils; Osborn, David L. Phys. Chem. Chem. Phys., Vol. 10, Issue 1 https://doi.org/10.1039/B713460F	journal	January 2008
Absolute photoionization cross-section of the propargyl radical Savee, John D.; Soorkia, Satchin; Welz, Oliver The Journal of Chemical Physics, Vol. 136, Issue 13 https://doi.org/10.1063/1.3698282	journal	April 2012
Simplified CCSD(T)-F12 methods: Theory and benchmarks Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3054300	journal	February 2009
Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar Peterson, Kirk A.; Adler, Thomas B.; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 128, Issue 8 https://doi.org/10.1063/1.2831537	journal	February 2008
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
A complete basis set model chemistry. VI. Use of density functional geometries and frequencies Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W. The Journal of Chemical Physics, Vol. 110, Issue 6 https://doi.org/10.1063/1.477924	journal	February 1999
A complete basis set model chemistry. VII. Use of the minimum population localization method Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W. The Journal of Chemical Physics, Vol. 112, Issue 15 https://doi.org/10.1063/1.481224	journal	April 2000
Infrared Absorption Probing of the Cl + C₃H₆ Reaction: Rate Coefficients for HCl Production between 290 and 800 K Pilgrim, Jeffrey S.; Taatjes, Craig A. The Journal of Physical Chemistry A, Vol. 101, Issue 32 https://doi.org/10.1021/jp971405h	journal	August 1997
Pressure Dependence of the Reaction Cl + C₃H₆ Kaiser, E. W.; Wallington, T. J. The Journal of Physical Chemistry, Vol. 100, Issue 23 https://doi.org/10.1021/jp960406r	journal	January 1996
Infrared Absorption Probing of the Cl + C₂H₄ Reaction: Direct Measurement of Arrhenius Parameters for Hydrogen Abstraction Pilgrim, Jeffrey S.; Taatjes, Craig A. The Journal of Physical Chemistry A, Vol. 101, Issue 23 https://doi.org/10.1021/jp970117i	journal	June 1997
Absolute and Site-Specific Abstraction Rate Coefficients for Reactions of Cl with CH₃CH₂OH, CH₃CD₂OH, and CD₃CH₂OH between 295 and 600 K Taatjes, Craig A.; Christensen, Lene K.; Hurley, Michael D. The Journal of Physical Chemistry A, Vol. 103, Issue 48 https://doi.org/10.1021/jp992465l	journal	November 1999

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
low-temperature oxidation
autoignition
alcohols
resonance stabilization
peroxy radicals

Title: Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

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