An experimental and theoretical high temperature kinetic study of the thermal unimolecular dissociation of fluoroethane

Binod Giri, John H. Kiefer, Hui Xu, Stephen J. Klippenstein, Robert S. Tranter

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

The thermal dissociation of fluoroethane has been studied using shock tube (ST)/time-of-flight mass spectrometry (TOF-MS) at 500 and 1200 Torr over the temperature range 1200-1550 K. The ST/TOF-MS experiments confirm that elimination of HF is the only reaction channel and rate coefficients for this reaction were extracted from concentration/time profiles derived from the mass spectra. Results from a novel diaphragmless shock tube coupled to the TOF-MS are also presented and demonstrate the unique ability of this apparatus to generate sufficiently reproducible shock waves that signal averaging can be performed over multiple experiments; something that is not possible with a conventional shock tube. The dissociation is also studied with ab initio transition state theory based master equation simulations. A modest increase in the calculated barrier height (i.e., by 1 kcal mol-1) yields predicted high pressure rate coefficients that are in good agreement with the existing literature data. The present pressure dependent observations are accurately reproduced for a downwards energy transfer for neon at 1200 to 1500 K of ∼270 cm -1, which is somewhat smaller than that found in previous studies on fluorinated ethanes with the same bath gases.

Original languageEnglish (US)
Pages (from-to)6266-6273
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume10
Issue number41
DOIs
StatePublished - Oct 27 2008

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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