Investigation of Organic Compound Reactivity in Liquid and Frozen Aqueous Systems Using Relative Rate Experiments

Previous studies have shown that snow and ice are highly reactive media where photochemical reactions occur. These reactions can have important consequences for the environment, including the production of organic compounds, halogens and nitrogen oxides that impact surface boundary layer chemistry. Laboratory-based studies have shown that the nature of the sample and the physical location of solutes play a large role in determining the reactivity of a particular compound. During the freezing of aqueous solutions, most solute molecules become excluded from the ice crystal lattice, increasing their apparent concentrations as they accumulate in liquid-like layers, micropockets, and microveins within the ice (freeze-concentration effect). In an effort to better understand how the physicochemical properties of solutes may impact reactivity in frozen solutions, we have examined the relative reaction rates of various organic compounds with hydroxyl radical in both liquid and frozen conditions. Solutions containing two target organic compounds and hydrogen peroxide were made in liquid and frozen phases, and then irradiated using a Q-Panel 340 lamp to simulate natural sunlight. Relative rates of reaction were then obtained for the two compounds in both liquid and ice conditions. In most cases the reactions proceeded more quickly in liquid samples, and the relative rates of reaction were different in liquid and frozen conditions. We will discuss the potential role of a compound's physicochemical properties and the influence of the physical nature of the sample with respect to observed reactivity differences.