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Issue 9, 2011
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A shock tube and theoretical study on the pyrolysis of 1,4-dioxane

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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) × 1059 × 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.

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

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Article information


Submitted
18 Aug 2010
Accepted
04 Nov 2010
First published
24 Dec 2010

Phys. Chem. Chem. Phys., 2011,13, 3686-3700
Article type
Paper

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

X. Yang, A. W. Jasper, B. R. Giri, J. H. Kiefer and R. S. Tranter, Phys. Chem. Chem. Phys., 2011, 13, 3686
DOI: 10.1039/C0CP01541E

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