RUI: Experimental and Theoretical Investigation of Threshold Energy Barriers and Substituent Effects for the 1,2-Halogen Interchange Reaction in Haloalkanes

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Bert Holmes and George Heard of the University of North Carolina at Asheville are supported by the Experimental Physical Chemistry Program to carry out a collaborative experimental and theoretical study of the kinetics of unimolecular reactions of chemically activated hydrohaloalkanes. The research builds on the PIs' previous investigations of an unusual gas phase mechanism involving the exchange of halogens on adjacent carbons. Focusing on hydrohaloalkanes, the plan is to determine threshold energy barriers and the effect of substituents on these energy barriers for various 1,2 halogen interchange reactions and for the 1,2-HX (where X = F, Cl, or Br) elimination reaction. Electronic structure calculations will give the frequencies and moments of inertia of the reactant and transition state, and these will be used with RRKM theory to calculate rate constants and permit the analysis of trends in the structure-reactivity relationships. Research outcomes from this project could improve the understanding combustion, incineration, and atmospheric chemical processes involving hydrochlorofluorocarbons. This research is expected to provide ample opportunities to enhance undergraduate education by involving students in research that is designed to develop analytical thinking skills and problem-solving ability, and encourage interest in pursuing advanced work in the chemical sciences.