Temperature- and pH- Dependent OH Radical Reaction Kinetics of Tartaric and Mucic Acids in the Aqueous Phase.

Abstract

Tartaric acid and mucic acid are dicarboxylic acids (DCAs), a substance class often found in atmospheric aerosols and cloud droplets. The hydroxyl radical (•OH)-induced oxidation in the aqueous phase is known to be an important loss process of organic compounds such as DCAs. However, the study of •OH kinetics of DCAs in the aqueous phase is still incomplete. In the present study, the rate constants of the •OH reactions of tartaric acid and mucic acid in the aqueous phase were determined by the thiocyanate competition kinetics method as a function of temperature and pH. The following T-dependent Arrhenius expressions (in units of L mol-1 s-1) were first derived for the •OH reactions with tartaric acid─k(T, H2A) = (3.3 ± 0.1) × 1010 exp[(-1350 ± 110 K)/T], k(T, HA-) = (3.6 ± 0.1) × 1010 exp[(-580 ± 110 K)/T], and k(T, A2-) = (3.3 ± 0.1) × 1010 exp[(-1190 ± 170 K)/T]─as well as mucic acid─k(T, H2A) = (2.2 ± 0.1) × 1010 exp[(-1140 ± 150 K)/T], k(T, HA-) = (4.8 ± 0.1) × 1010 exp[(-1280 ± 170 K)/T], and k(T, A2-) = (2.1 ± 0.1) × 1010 exp[(-970 ± 70 K)/T]. A general trend of the •OH rate constant is found as > > . The pH- and temperature-dependent rate constants of the OH radical reactions allow an accurate description of the source and sink processes in the tropospheric aqueous phase.