A shock tube and theoretical study on the pyrolysis of 1,4-dioxane

X. Yang, A. W. Jasper, Binod Giri, J. H. Kiefer, R. S. Tranter

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17 Scopus citations

Abstract

The dissociation of 1, 2 and 4% 1,4-dioxane dilute in krypton was studied in a shock tube using laser schlieren densitometry, LS, for 1550-2100 K with 56 ± 4 and 123 ± 3 Torr. Products were identified by time-of-flight mass spectrometry, TOF-MS. 1,4-dioxane was found to initially dissociate via C-O bond fission followed by nearly equal contributions from pathways involving 2,6 H-atom transfers to either the O or C atom at the scission site. The 'linear' species thus formed (ethylene glycol vinyl ether and 2-ethoxyacetaldehyde) then dissociate by central fission at rates too fast to resolve. The radicals produced in this fission break down further to generate H, CH3 and OH, driving a chain decomposition and subsequent exothermic recombination. High-level ab initio calculations were used to develop a potential energy surface for the dissociation. These results were incorporated into an 83 reaction mechanism used to simulate the LS profiles with excellent agreement. Simulations of the TOF-MS experiments were also performed with good agreement for consumption of 1,4-dioxane. Rate coefficients for the overall initial dissociation yielded k123Torr = (1.58 ± 0.50) × 10 59 × T-13.63 × exp(-43970/T) s-1 and k58Torr = (3.16 ± 1.10) × 1079 × T-19.13 × exp(-51326/T) s-1 for 1600 < T < 2100 K.

Original languageEnglish (US)
Pages (from-to)3686-3700
Number of pages15
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number9
DOIs
StatePublished - Mar 7 2011

ASJC Scopus subject areas

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

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