TY - JOUR
T1 - Experimental and modeling investigation of the low-temperature oxidation of n-heptane
AU - Herbinet, Olivier
AU - Husson, Benoit
AU - Serinyel, Zeynep
AU - Cord, Maximilien
AU - Warth, Valérie
AU - Fournet, René
AU - Glaude, Pierre Alexandre
AU - Sirjean, Baptiste
AU - Battin-Leclerc, Frédérique
AU - Wang, Zhandong
AU - Xie, Mingfeng
AU - Cheng, Zhanjun
AU - Qi, Fei
N1 - Funding Information:
This study was supported by the European Commission through the “Clean ICE” Advanced Research Grant of the European Research Council. This work was granted access to the HPC resources of CINES under the allocation 2011086686 made by GENCI (Grand Equipement National de Calcul Intensif).
PY - 2012/12
Y1 - 2012/12
N2 - The low-temperature oxidation of n-heptane, one of the reference species for the octane rating of gasoline, was investigated using a jet-stirred reactor and two methods of analysis: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, that are not stable enough to be detected using gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of temperature (500-1100. K), at a residence time of 2. s, at a pressure of 800. Torr (1.06. bar) and under stoichiometric conditions. The fuel was diluted in an inert gas (fuel inlet mole fraction of 0.005). Attention was paid to the formation of reaction products involved in the low-temperature oxidation of n-heptane, such as olefins, cyclic ethers, aldehydes, ketones, species with two carbonyl groups (diones), and ketohydroperoxides. Diones and ketohydroperoxides are important intermediates in the low-temperature oxidation of n-alkanes, but their formation have rarely been reported. Significant amounts of organic acids (acetic and propanoic acids) were also observed at low temperatures. The comparison of experimental data and profiles computed using an automatically generated detailed kinetic model is satisfactory overall. A route for the formation of acetic and propanoic acids was proposed. Quantum calculations were performed to refine the consumption routes of ketohydroperoxides toward diones.
AB - The low-temperature oxidation of n-heptane, one of the reference species for the octane rating of gasoline, was investigated using a jet-stirred reactor and two methods of analysis: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, that are not stable enough to be detected using gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of temperature (500-1100. K), at a residence time of 2. s, at a pressure of 800. Torr (1.06. bar) and under stoichiometric conditions. The fuel was diluted in an inert gas (fuel inlet mole fraction of 0.005). Attention was paid to the formation of reaction products involved in the low-temperature oxidation of n-heptane, such as olefins, cyclic ethers, aldehydes, ketones, species with two carbonyl groups (diones), and ketohydroperoxides. Diones and ketohydroperoxides are important intermediates in the low-temperature oxidation of n-alkanes, but their formation have rarely been reported. Significant amounts of organic acids (acetic and propanoic acids) were also observed at low temperatures. The comparison of experimental data and profiles computed using an automatically generated detailed kinetic model is satisfactory overall. A route for the formation of acetic and propanoic acids was proposed. Quantum calculations were performed to refine the consumption routes of ketohydroperoxides toward diones.
KW - Jet-stirred reactor
KW - Ketohydroperoxide
KW - Low-temperature oxidation
KW - N-Heptane
KW - Organic acids
UR - http://www.scopus.com/inward/record.url?scp=84867917238&partnerID=8YFLogxK
U2 - 10.1016/j.combustflame.2012.07.008
DO - 10.1016/j.combustflame.2012.07.008
M3 - Article
C2 - 23712100
AN - SCOPUS:84867917238
SN - 0010-2180
VL - 159
SP - 3455
EP - 3471
JO - Combustion and Flame
JF - Combustion and Flame
IS - 12
ER -