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Title: Fuel-Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C5H10O2 Ester Isomers

Abstract

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 C{sub 5}H{sub 10}O{sub 2}, 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 β-scissionmore » 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.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1065196
DOE Contract Number:  
SC0001198
Resource Type:
Journal Article
Journal Name:
Phys. Chem. Chem. Phys.
Additional Journal Information:
Journal Volume: 13; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biofuels (including algae and biomass), hydrogen and fuel cells, combustion, carbon capture

Citation Formats

Yang, B., Cool, T. A., Westbrook, Charles K., Hansen, N., and Kohse-Hoinghaus, K. Fuel-Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C5H10O2 Ester Isomers. United States: N. p., 2011. Web. doi:10.1039/c0cp02065f.
Yang, B., Cool, T. A., Westbrook, Charles K., Hansen, N., & Kohse-Hoinghaus, K. Fuel-Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C5H10O2 Ester Isomers. United States. doi:10.1039/c0cp02065f.
Yang, B., Cool, T. A., Westbrook, Charles K., Hansen, N., and Kohse-Hoinghaus, K. Sat . "Fuel-Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C5H10O2 Ester Isomers". United States. doi:10.1039/c0cp02065f.
@article{osti_1065196,
title = {Fuel-Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C5H10O2 Ester Isomers},
author = {Yang, B. and Cool, T. A. and Westbrook, Charles K. and Hansen, N. and Kohse-Hoinghaus, K.},
abstractNote = {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 C{sub 5}H{sub 10}O{sub 2}, 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 β-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.},
doi = {10.1039/c0cp02065f},
journal = {Phys. Chem. Chem. Phys.},
number = ,
volume = 13,
place = {United States},
year = {2011},
month = {1}
}