Thermal dissociation of ethylene glycol vinyl ether.

Abstract

The pyrolysis of ethylene glycol vinyl ether (EGVE), an initial product of 1,4-dioxane dissociation, was examined in a diaphragmless shock tube (DFST) using laser schlieren densitometry (LS) at 57 ± 2 and 122 ± 3 Torr over 1200-1800 K. DFST/time-of-flight mass spectrometry experiments were also performed to identify reaction products. EGVE was found to dissociate via two channels: (1) a molecular H atom transfer/C-O scission to produce C(2)H(3)OH and CH(3)CHO, and (2) a radical channel involving C-O bond fission generating ˙CH(2)CH(2)OH and ˙CH(2)CHO radicals, with the second channel being strongly dominant over the entire experimental range. A reaction mechanism was constructed for the pyrolysis of EGVE which simulates the LS profiles very well over the full experimental range. The decomposition of EGVE is clearly well into the falloff region for these conditions, and a Gorin model RRKM fit was obtained for the dominant radical channel. The results are in good agreement with the experimental data and suggest the following rate coefficient expressions: k(2,∞) = (6.71 ± 2.6) × 10(27) × T(-3.21)exp(-35512/T) s(-1); k(2)(120 Torr) = (1.23 ± 0.5) × 10(92) × T(-22.87)exp(-48 248/T) s(-1); k(2)(60 Torr) = (2.59 ± 1.0) × 10(88) × T(-21.96)exp(-46283/T) s(-1).

• Authors: Xueliang Yang, John H Kiefer, Robert S Tranter
• Journal: Physical chemistry chemical physics : PCCP (Phys Chem Chem Phys) Vol. 13 Issue 48 Pg. 21288-300 (Dec 28 2011) ISSN: 1463-9084 [Electronic] England
• PMID: 22024976 (Publication Type: Journal Article, Research Support, U.S. Gov't, Non-P.H.S.)

Chemical References

• Dioxanes
• Ethylene Glycols
• Vinyl Compounds
• Hydroxyl Radical
• ethylene glycol monovinyl ether
• 1,4-dioxane

Topics

• Dioxanes (chemistry)
• Ethylene Glycols (chemistry)
• Hydroxyl Radical (chemistry)
• Lasers
• Mass Spectrometry
• Temperature
• Vinyl Compounds (chemistry)