Ab initio Calculations and RRKM/Master Equation Modeling of Chloroalkanes ¿ Alkenes + HCl Reactions for Use in Comparative Rate Studies

Published

November 23, 2011

Author(s)

Donald R. Burgess Jr., Jeffrey A. Manion

Abstract

The computations reported in this paper were done in conjunction with an experimental study involving single pulse shock tube measurements of the thermal decomposition of three chloroalkanes, and that work is reported in an accompanying preceding paper. The overall aim of the combined work is to provide a well-defined and reliable set of rate constants over an extended temperature range (a self-consistent temperature standard) for use as reference reactions in comparative rate studies. In this largely computational work, we review the literature for thermochemical and chemical kinetic data for HCl elimination reactions from six alkyl chlorides: chloroethane, 1-chloropropane, 2-chloropropane, 2-chlorobutane, chlorocyclopentane, and chlorocyclohexane. We discuss the fundamental nature of these types of reaction (four-centered "semi-ion pair" transition states). We employ quantum chemical methods to compute the structure and energies of reactants, products, and transition states and employ this information, in conjunction with experimentally-determined rate constants, in RRKM/Master Equation modeling to develop a set of rate expressions which should be valid over a range of different pressures (low pressure to high pressure limits) and an extended range of temperatures.

Citation

International Journal of Chemical Kinetics

Pub Type

Journals

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Citation

Burgess Jr., D. and Manion, J. (2011), Ab initio Calculations and RRKM/Master Equation Modeling of Chloroalkanes ¿ Alkenes + HCl Reactions for Use in Comparative Rate Studies, International Journal of Chemical Kinetics, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=906919 (Accessed April 25, 2024)