TY - JOUR
T1 - Application of compound models for estimating rate constants of hydrocarbon thermal cracking reactions
T2 - The neopentyl radical β-scission reaction
AU - Zheng, Xiaobo
AU - Blowers, Paul
AU - Zhang, Nianliu
N1 - Funding Information:
This work was funded by the State of Arizona through the Office of the Vice President for Research at the University of Arizona. Supercomputer time was provided by the National Computational Science Alliance and used the NCSA HP/Convex Exemplar SPP-2000 at the University of Illinois at Urbana-Champaign. Part of the supercomputer time was provided by National Partnership for Advanced Computational Infrastructure and used the IBM pSeries 690 and pSeries 655 at Boston University.
PY - 2005/8/10
Y1 - 2005/8/10
N2 - In this work, neopentyl radical β-scission reaction kinetics and energetics are investigated using quantum chemical G3 and Complete Basis Set (CBS) compound models. Experimental thermodynamic and kinetic data are employed to assess the accuracy of these calculations. The CBS model proves to have good agreement with the experimental data, indicating it is a good method for studying other hydrocarbon cracking reactions involving large species. A kinetic model of the reaction with pressure and temperature effects is proposed. For P ≤ P0, k [s-1] = 1.44 × 1012 × P0.29 × exp(-13890.20/T); for P > P0, k[s -1] = 1.04 × 1014 × exp(-16075.80/T), where P is in the units of kPa, T in the units of Kelvin, and P0 = 2.54 × 106 × exp(-7536.55/T). These equations can be easily applied to different reaction conditions without performing additional costly calculations.
AB - In this work, neopentyl radical β-scission reaction kinetics and energetics are investigated using quantum chemical G3 and Complete Basis Set (CBS) compound models. Experimental thermodynamic and kinetic data are employed to assess the accuracy of these calculations. The CBS model proves to have good agreement with the experimental data, indicating it is a good method for studying other hydrocarbon cracking reactions involving large species. A kinetic model of the reaction with pressure and temperature effects is proposed. For P ≤ P0, k [s-1] = 1.44 × 1012 × P0.29 × exp(-13890.20/T); for P > P0, k[s -1] = 1.04 × 1014 × exp(-16075.80/T), where P is in the units of kPa, T in the units of Kelvin, and P0 = 2.54 × 106 × exp(-7536.55/T). These equations can be easily applied to different reaction conditions without performing additional costly calculations.
KW - CBS method
KW - Hydrocarbon cracking
KW - Neopentyl radical
KW - Rate constant
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U2 - 10.1080/08927020500108437
DO - 10.1080/08927020500108437
M3 - Article
AN - SCOPUS:23744441529
SN - 0892-7022
VL - 31
SP - 615
EP - 621
JO - Molecular Simulation
JF - Molecular Simulation
IS - 9
ER -