In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Margerum will continue his studies of the rates and mechanisms of rapid reactions in aqueous solution. A number of these reactions are of importance in environmental chemistry. An apparatus that allows the study of reactions that are over in a few millionths of a second will be used and improved in this work. Mechanistic studies of rapid non-metal redox, hydrolysis, and disproportionation reactions of halogens and their compounds with oxygen, nitrogen, and sulfur will be examined. The importance of halogen-cation transfer mechanisms, the correlation of reactivities with nucleophilicity, and the determination of the role of acid-base catalysis will be emphasized. The pulsed-accelerated-flow apparatus will be used to monitor the reactions; this instrumentation was developed by the Margerum group, and will be improved by position-resolved observation. The latter will incorporate charge-coupled device technology, accelerated flow, and orthogonal observation to expand the ability to study rapid multi-step and other complex reactions in solution.
