An experimental and theoretical kinetic study of the reaction of OH radicals with 1,4-dioxane

Fethi KHALED, Binod Giri, Milán Szőri, John R. Barker, Aamir Farooq

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

This work reports the rate coefficients for the hydrogen abstraction reaction of 1,4-dioxane by OH radicals. The reaction is investigated in the shock tube behind the reflected shock wave in the temperature range of 886 - 1334 K and pressures near 1.5 atm. We monitored the progress of the reaction by detecting OH radicals near 307 nm using a UV laser absorption technique. OH radicals were produced by rapid thermal decomposition of tert-butyl hydroperoxide (TBHP). High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical (QC) calculations combined with RRKM/ME methods were performed to explore the chemistry of the 1,4-dioxane + OH reaction. We found that the chair conformer of 1,4-dioxane dominates over the twist-boat conformer over the entire T-range of our study. However, we found that the twist-boat conformer constitutes a significant fraction of 1,4-dioxane at T ≥ 1000 K. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of 1,4-dioxane with OH radicals at high temperatures.
Original languageEnglish (US)
Title of host publication10th U.S. National Combustion Meeting
PublisherEastern States Section of the Combustion Institute
StatePublished - Jan 1 2017

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