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 language||English (US)|
|Title of host publication||10th U.S. National Combustion Meeting|
|Publisher||Eastern States Section of the Combustion Institute|
|State||Published - Jan 1 2017|