Fuel-specific influences on the composition of reaction intermediates in premixed flames of three C5H10O2 ester isomers

Yang, Bin; Westbrook, Charles K.; Cool, Terrill A.; Hansen, Nils; Kohse-Höinghaus, Katharina

doi:10.1039/c0cp02065f

Fuel-specific influences on the composition of reaction intermediates in premixed flames of three C5H10O2 ester isomers

Journal Article · Fri Dec 31 23:00:00 EST 2010 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c0cp02065f· OSTI ID:1060397

Yang, Bin ^[1]; Westbrook, Charles K.; Cool, Terrill A.; Hansen, Nils; Kohse-Höinghaus, Katharina

Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551

Measurements of the composition of reaction intermediates in low-pressure premixed flat flames of three simple esters, the methyl butanoate (MB), methyl isobutanoate (MIB), and ethyl propanoate (EP) isomers of C5H10O2, enable further refinement and validation of a detailed chemical reaction mechanism originally developed in modeling studies of similar flames of methyl formate, methyl acetate, ethyl formate, and ethyl acetate. Photoionization mass spectrometry (PIMS), using monochromated synchrotron radiation, reveals significant differences in the compositions of key reaction intermediates between flames of the MB, MIB, and EP isomers studied under identical flame conditions. Detailed kinetic modeling describes how these differences are related to molecular structures of each of these isomers, leading to unique fuel destruction pathways. Despite the simple structures of these small esters, they contain structural functional groups expected to account for fuel-specific effects observed in the combustion of practical biodiesel fuels. The good agreement between experimental measurements and detailed reaction mechanisms applicable to these simple esters demonstrates that major features of each flame can be predicted with reasonable accuracy by building a hierarchical reaction mechanism based on three factors: (1) unimolecular decomposition of the fuel, especially by complex bond fission; (2) H-atom abstraction reactions followed by beta-scission of the resulting radicals, leading to nearly all of the intermediate species observed in each flame; (3) the rates of H-atom abstraction reactions for each alkoxy or alkyl group (i.e., methoxy, ethoxy, methyl, ethyl, propyl) are effectively the same as in other ester fuels with the same structural groups.

Research Organization:: Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)

Sponsoring Organization:: USDOE

DOE Contract Number:: FG02-01ER15180

OSTI ID:: 1060397

Report Number(s):: DOE-ER15180-3

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 15 Vol. 13; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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