title: High-temperature oxidation chemistry of n-butanol--experiments in low-pressure premixed flames and detailed kinetic modeling.
abstract: An automated reaction mechanism generator is used to develop a predictive, comprehensive reaction mechanism for the high-temperature oxidation chemistry of n-butanol. This new kinetic model is an advancement of an earlier model, which had been extensively tested against earlier experimental data (Harper et al., Combust. Flame, 2011, 158, 16-41). In this study, the model's predictive capabilities are improved by targeting isomer-resolved quantitative mole fraction profiles of flame species in low-pressure flames. To this end, a total of three burner-stabilized premixed flames are isomer-selectively analyzed by flame-sampling molecular-beam time-of-flight mass spectrometry using photoionization by tunable vacuum-ultraviolet synchrotron radiation. For most species, the newly developed chemical kinetic model is capable of accurately reproducing the experimental trends in these flames. The results clearly indicate that n-butanol is mainly consumed by H-atom abstraction with H, O, and OH, forming predominantly the α-C(4)H(9)O radical (CH(3)CH(2)CH(2)˙CHOH). Fission of C-C bonds in n-butanol is only predicted to be significant in a similar, but hotter flame studied by Oßwald et al. (Combust. Flame, 2011, 158, 2-15). The water-elimination reaction to 1-butene is found to be of no importance under the premixed conditions studied here. The initially formed isomeric C(4)H(9)O radicals are predicted to further oxidize by reacting with H and O(2) or to decompose to smaller fragments via β-scission. Enols are detected experimentally, with their importance being overpredicted by the model.
authors: Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551, USA. nhansen@sandia.gov
authors: N
authors: N
authors: Hansen
authors: M R
authors: MR
authors: Harper
authors: W H
authors: WH
authors: Green
mesh_terms: D020001:1-Butanol / Q000737:chemistry*; D006358:Hot Temperature; D007700:Kinetics; D008956:Models, Chemical; D010084:Oxidation-Reduction; D011312:Pressure
chemical_list: D020001:1-Butanol