Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

Abstract

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 NO(x). 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 NO(x). 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.

Theoretical studies on the kinetics of the hydrogen-abstraction reactions from 1,3,5-trioxane and 1,4-dioxane by OH radicals

“…2 The gasphase kinetics of the reactions of cyclic ethers such as 1,3,5-trioxane (C 3 H 6 O 3 ) and 1,4-dioxane (C 4 H 8 O 2 ) have been studied to understand the impacts of the structures of these compounds on their atmospheric reactivity and degradation pathways. [3][4][5][6][7][8][9][10] As a consequence, the kinetics of the reactions of 1,3,5-trioxane and 1,4-dioxane with OH radicals (known as atmospheric detergents) have been the subject of some experimental studies. [5][6][7][8][9][10] To date, three experimental measurements of the rate coefficients for the C 3 H 6 O 3 + OH reaction have been reported.…”

1,3-Dioxan-5-ol

“…4 Other methods include oxidation of dioxane and dioxane derivatives to form the title compound. 6 In these cases, a mixture of products is formed.…”