The influence of reaction conditions on the photooxidation of diisopropyl ether

The hydroxyl radical initiated oxidation of diisopropyl ether has been studied in the large-volume outdoor European Photoreactor (EUPHORE) and in a small, laboratory-based reactor system. The product distributions determined from the experiments were found to be significantly dependent on the reaction conditions and provide strong evidence for the existence of three distinct regimes within the reaction system. In the presence of NO chi, the peroxy radicals react with NO to produce chemically activated (CH3)(2)CHOC(O)(CH3)(2) alkoxy radicals which undergo decomposition by C-C bond scission to yield isopropyl acetate and formaldehyde as the major products. Under conditions where the self-reaction of peroxy radicals dominates, thermoneutral (CH3)(2)CHOC(O)(CH3)(2) radicals are produced, which appear to undergo two reaction pathways; C-C bond scission to yield isopropyl acetate and formaldehyde and isomerisation to form acetone, acetic acid and formaldehyde. Under conditions where the reaction between peroxy and hydroperoxy radicals dominates, unstable hydroperoxides are produced which decompose to yield acetone as the only major reaction product. The results of our study are used to construct chemical mechanisms for the gas-phase photooxidation of diisopropyl ether under various tropospheric conditions. (c) 2005 Elsevier B.V. All rights reserved.