Enols Are Common Intermediates in Hydrocarbon Oxidation

Taatjes, Craig A.; Hansen, Nils; McIlroy, Andrew; Miller, James A.; Senosiain, Juan P.; Klippenstein, Stephen J.; Qi, Fei; Sheng, Liusi; Zhang, Yunwu; Cool, Terrill A.; Wang, Juan; Westmoreland, Phillip R.; Law, Matthew E.; Kasper, Tina; Kohse-Höinghaus, Katharina

doi:10.1126/science.1112532

Enols Are Common Intermediates in Hydrocarbon Oxidation

Journal Article · Fri Jun 24 04:00:00 EDT 2005 · Science

DOI:https://doi.org/10.1126/science.1112532· OSTI ID:886063

Taatjes, Craig A. ^[1]; Hansen, Nils ^[1]; McIlroy, Andrew ^[1]; Miller, James A. ^[1]; Senosiain, Juan P. ^[1]; Klippenstein, Stephen J. ^[1]; Qi, Fei ^[1]; Sheng, Liusi ^[1]; Zhang, Yunwu ^[1]; Cool, Terrill A. ^[1]; Wang, Juan ^[1]; Westmoreland, Phillip R. ^[1]; Law, Matthew E. ^[1]; Kasper, Tina ^[1]; Kohse-Höinghaus, Katharina ^[1]

Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, CA 94551–0969, USA.; JILA, National Institute of Standards and Technology and University of Colorado, 440CB, Boulder CO, 80309–0440 USA.; National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026, China.; School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853, USA.; Department of Chemical Engineering, University of Massachusetts, Amherst, MA 01003–9303, USA.

Models for chemical mechanisms of hydrocarbon oxidation rely on spectrometric identification of molecular structures in flames. Carbonyl (keto) compounds are well-established combustion intermediates. However, their less-stable enol tautomers, bearing OH groups adjacent to carbon-carbon double bonds, are not included in standard models. We observed substantial quantities of two-, three-, and four-carbon enols by photoionization mass spectrometry of flames burning representative compounds from modern fuel blends. Concentration profiles demonstrate that enol flame chemistry cannot be accounted for purely by keto-enol tautomerization. Currently accepted hydrocarbon oxidation mechanisms will likely require revision to explain the formation and reactivity of these unexpected compounds.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE National Nuclear Security Administration (NNSA); Sandia Corporation; Lockheed Martin Company; Chinese Academy of Sciences; National Natural Science Foundation of China; Deutsche Forschungsgemeinschaft

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 886063

Report Number(s):: LBNL--57997; BnR: KC0301020

Journal Information:: Science, Journal Name: Science Journal Issue: 5730 Vol. 308; ISSN 0036-8075

Publisher:: AAAS

Country of Publication:: United States

Language:: English

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