TY - JOUR
T1 - Determination of rate constants for a thermoneutral H-abstraction reaction
T2 - 38th International Symposium on Combustion, 2021
AU - Huang, Can
AU - Zhang, Peng
AU - Wang, Jiaxing
AU - Kang, Shiqing
AU - Zhang, Feng
AU - Law, Chung K.
AU - Yang, Bin
N1 - Funding Information:
This work is supported by the National Natural Science Foundation of China ( 91741109 , 51876199 ). This work was also supported by the Fundamental Research Funds for the Central Universities ( WK2320000038 ).
PY - 2021
Y1 - 2021
N2 - Thermoneutral H-abstraction reactions, which involve the abstraction by resonantly stabilized radicals from olefins to form other resonantly stabilized radicals, have recently been found to be important in high temperature combustion. They will shift the distribution of resonantly stabilized radicals and affect the molecular weight growth kinetics, thus changing the prediction for aromatic species. A typical thermoneutral H-abstraction reaction: C3H5-A + 1,5- C6H10 = C3H6 + C6H9-A (R1), was studied. A rapid compression machine, together with a fast sampling technique, was used to study the high temperature kinetics of 1,5-hexadiene. Experimental conditions that could be used to derive the rate constant of R1 were first identified by sensitivity analysis of a kinetic model for 1,5-hexadiene combustion. The concentration of propene was highly sensitive to the rate constant of R1 over the temperature range of 893 K–1007 K at 25 bar. By fitting the measured propene profiles, the rate constant of R1 was deduced under selected conditions. Also, the concentration profiles of propene in 1,5-hexadiene pyrolysis from a flow reactor measurement and oxidation from a jet stirred reactor measurement were also used to derive the rate constant of R1 over wider temperature ranges. The rate coefficient of R1 was further calculated by ab initio transition state theory, with energies obtained at the level of DLPNO-CCSD(T)/aug-cc-pVTZ//B2PLYP/cc-pVTZ. The theoretical predictions were in good agreement with the experimentally derived rate constants.
AB - Thermoneutral H-abstraction reactions, which involve the abstraction by resonantly stabilized radicals from olefins to form other resonantly stabilized radicals, have recently been found to be important in high temperature combustion. They will shift the distribution of resonantly stabilized radicals and affect the molecular weight growth kinetics, thus changing the prediction for aromatic species. A typical thermoneutral H-abstraction reaction: C3H5-A + 1,5- C6H10 = C3H6 + C6H9-A (R1), was studied. A rapid compression machine, together with a fast sampling technique, was used to study the high temperature kinetics of 1,5-hexadiene. Experimental conditions that could be used to derive the rate constant of R1 were first identified by sensitivity analysis of a kinetic model for 1,5-hexadiene combustion. The concentration of propene was highly sensitive to the rate constant of R1 over the temperature range of 893 K–1007 K at 25 bar. By fitting the measured propene profiles, the rate constant of R1 was deduced under selected conditions. Also, the concentration profiles of propene in 1,5-hexadiene pyrolysis from a flow reactor measurement and oxidation from a jet stirred reactor measurement were also used to derive the rate constant of R1 over wider temperature ranges. The rate coefficient of R1 was further calculated by ab initio transition state theory, with energies obtained at the level of DLPNO-CCSD(T)/aug-cc-pVTZ//B2PLYP/cc-pVTZ. The theoretical predictions were in good agreement with the experimentally derived rate constants.
KW - 1,5-hexadiene
KW - Allyl radical
KW - Allylic hydrogen abstraction
KW - Rapid compression machine
KW - Transition state theory
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U2 - 10.1016/j.proci.2020.07.054
DO - 10.1016/j.proci.2020.07.054
M3 - Conference article
AN - SCOPUS:85091464564
SN - 1540-7489
VL - 38
SP - 861
EP - 869
JO - Proceedings of the Combustion Institute
JF - Proceedings of the Combustion Institute
IS - 1
Y2 - 24 January 2021 through 29 January 2021
ER -