TY - JOUR
T1 - The application of composite energy methods to n-butyl radical β-scission reaction kinetic estimations
AU - Zheng, Xiaobo
AU - Blowers, Paul
PY - 2007/2
Y1 - 2007/2
N2 - Hydrocarbon cracking reactions are key steps in petroleum refinery processes and understanding reaction kinetics has very important applications in the petroleum industry. In this work, G3 and complete basis set (CBS) composite energy methods were applied to investigate butyl radical β-scission reaction kinetics and energetics. Experimental thermodynamic and kinetic data were employed to evaluate the accuracy of these calculations. The CBS compound model proved to have excellent agreement with the experimental data, indicating that it is a reliable method for studying other large hydrocarbon cracking reactions. Furthermore, a reaction kinetic model with pressure and temperature effects was proposed. For P ≤ P0, k = 2.04 × 109 × P0.51 × e(-9745.70/T); for P > P 0, k = 9.43 × 1013 × e (-15135.70/T), where k is the reaction rate constant in units of s-1; P is pressure in units of kPa, T is temperature in units of Kelvin, and the switching pressure is P0 = 1.53 × 10 9 × e(-10610.24/T). This model can be easily applied to different reaction conditions without performing additional expensive and complicated calculations.
AB - Hydrocarbon cracking reactions are key steps in petroleum refinery processes and understanding reaction kinetics has very important applications in the petroleum industry. In this work, G3 and complete basis set (CBS) composite energy methods were applied to investigate butyl radical β-scission reaction kinetics and energetics. Experimental thermodynamic and kinetic data were employed to evaluate the accuracy of these calculations. The CBS compound model proved to have excellent agreement with the experimental data, indicating that it is a reliable method for studying other large hydrocarbon cracking reactions. Furthermore, a reaction kinetic model with pressure and temperature effects was proposed. For P ≤ P0, k = 2.04 × 109 × P0.51 × e(-9745.70/T); for P > P 0, k = 9.43 × 1013 × e (-15135.70/T), where k is the reaction rate constant in units of s-1; P is pressure in units of kPa, T is temperature in units of Kelvin, and the switching pressure is P0 = 1.53 × 10 9 × e(-10610.24/T). This model can be easily applied to different reaction conditions without performing additional expensive and complicated calculations.
KW - Butyl radical
KW - CBS method
KW - G3 method
KW - Hydrocarbon cracking
KW - Rate constant
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U2 - 10.1007/s00214-006-0129-x
DO - 10.1007/s00214-006-0129-x
M3 - Article
AN - SCOPUS:33846575087
SN - 1432-881X
VL - 117
SP - 207
EP - 212
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 2
ER -