The unimolecular decomposition of 1-chloroethyl radical

V. D. Knyazev, Á Bencsura, I. A. Dubinsky, D. Gutman, S. M. Senkan

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Abstract

The kinetics of the unimolecular decomposition of the 1-chloroethyl radical have been studied. The reaction was isolated for quantitative study in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were obtained in time-resolved experiments as a function of temperature (848-980 K) and bath gas density (3-22×1016 molecule cm-3) in He, Ar, and N2. The rate constants are in the falloff under the conditions of the experiments. The falloff behavior was analyzed using a Master Equation analysis. A transition state model was created to obtain values of the microcanonical rate constants, k(E), needed to solve the Master Equation. The transition state model provides the high-pressure limit rate constants for the decomposition reaction (k1 (CH3CHCl→CH2CHCl+H)=1.94×109 T1.22 exp(-19,510 K/T) s-1) and the reverse reaction (k-1 (H+CH2CHCl→CH3CHCl)=3.35×10-14 T0.86 exp(-75.3 K/T) cm3 molecule-1 s-1). Values of {ΔE}down for the energy loss probability were obtained for each experiment using the exponential-down model. The values of {ΔE}down display a pronounced positive temperature dependence with average values of 255 (He), 360 (Ar), and 261 (N2) cm-1. Parametrization of the temperature and pressure dependence of the unimolecular rate constant for the temperature range 298-1500 K and pressures 0.001-10 atmospheres is provided using the modified Lindemann-Hinshelwood expression.

Original languageEnglish
Pages (from-to)817-824
Number of pages8
JournalSymposium (International) on Combustion
Volume25
Issue number1
DOIs
Publication statusPublished - 1994

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ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Mechanical Engineering
  • Physical and Theoretical Chemistry
  • Fluid Flow and Transfer Processes

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