### Abstract

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 ≤ P_{0}, k = 2.04 × 10^{9} × P^{0.51} × e^{(-9745.70/T)}; for P > P _{0}, k = 9.43 × 10^{13} × 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 P_{0} = 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.

Original language | English (US) |
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Pages (from-to) | 207-212 |

Number of pages | 6 |

Journal | Theoretical Chemistry Accounts |

Volume | 117 |

Issue number | 2 |

DOIs | |

State | Published - Feb 2007 |

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### Keywords

- Butyl radical
- CBS method
- G3 method
- Hydrocarbon cracking
- Rate constant

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

**The application of composite energy methods to n-butyl radical β-scission reaction kinetic estimations.** / Zheng, Xiaobo; Blowers, Paul.

Research output: Contribution to journal › Article

*Theoretical Chemistry Accounts*, vol. 117, no. 2, pp. 207-212. https://doi.org/10.1007/s00214-006-0129-x

}

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

VL - 117

SP - 207

EP - 212

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

SN - 1432-881X

IS - 2

ER -