The application of composite energy methods to n-butyl radical β-scission reaction kinetic estimations

Xiaobo Zheng, Paul Blowers

Research output: Contribution to journalArticle

5 Citations (Scopus)

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 ≤ 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.

Original languageEnglish (US)
Pages (from-to)207-212
Number of pages6
JournalTheoretical Chemistry Accounts
Volume117
Issue number2
DOIs
StatePublished - Feb 2007

Fingerprint

energy methods
Reaction kinetics
cleavage
reaction kinetics
Hydrocarbons
composite materials
Composite materials
crude oil
Petroleum refineries
Pressure effects
Petroleum industry
hydrocarbons
Thermal effects
Reaction rates
Rate constants
pressure effects
Thermodynamics
temperature effects
Kinetics
industries

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.

In: Theoretical Chemistry Accounts, Vol. 117, No. 2, 02.2007, p. 207-212.

Research output: Contribution to journalArticle

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