Kinetic measurements of the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solutions

摘要

pstrongAbstract./strong Free radical reactions are an important degradation process for organic compounds within the aqueous atmospheric environment. Nevertheless, non-radical oxidants such as hydrogen peroxide and ozone also contribute to the degradation and conversion of these substances (Tilgner and Herrmann, 2010). In this work, kinetic investigations of non-radical reactions were conducted using UV / Vis spectroscopy (dual-beam spectrophotometer and stopped flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics to reactions of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acid as well as methacrolein (MACR) and methyl vinyl ketone (MVK) with Hsub2/subOsub2/sub and ozone at 298 K. The measurements indicate rather small rate constants at room temperature of ik/isub2nd/sub 3 Msupa??1/sup ssupa??1/sup (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (ik/isubOH•/sub ~10sup9/sup Msupa??1/sup ssupa??1/sup). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated first-order conversion rate constants change the picture towards Hsub2/subOsub2/sub reactions becoming more important, especially when compared to the nitrate radical. For some reactions mechanistic suggestions are also given./p.