期刊
CHEMPHYSCHEM
卷 11, 期 18, 页码 3980-3986出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201000503
关键词
alkoxy radicals; atmospheric oxidation; cyclic ethers; 1,3-dioxane
资金
- European Commission [ENV4-CT97-0414]
The products of the hydroxyl (OH) radical and chlorine (Cl) atom initiated oxidation of 1,3-dioxane are determined under various reaction conditions in a 50 L teflon reaction chamber using FTIR spectroscopy for analysis. The major products detected in all experiments are (2-oxoethoxy)methyl formate, formic acid and methylene glycol diformate with average molar yields of 0.50 +/- 0.05, 0.41 +/- 0.02 and 0.03 +/- 0.01 respectively for the OH initiated oxidation in the presence of NOx. The yields of these products do not vary significantly with O-2 partial pressure or oxidising agent (OH or Cl). However, the yield of formic acid decreased by at least a factor of two in the absence of NOx. The results of these experiments are used to elucidate a simplified gas-phase atmospheric degradation scheme for 1,3-dioxane and also provide valuable information on the atmospheric fate of the cyclic and linear alkoxy radicals produced in these and similar reactions. The available experimental data suggests that the relative importance of the competing pathways (reaction with O-2 and ring opening by C-C or C-O bond fission) is a strong function of the ring strain in the cycloalkoxy radicals.
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