Abstract
The rapid development of powerful UV‐laser sources allows the investigation of macroscopic and microscopic details of elementary chemical reactions important in combustion processes. Experimental results on the effect of selective translational and vibrational excitation of reactants in elementary combustion reactions using laser photolysis and time‐resolved atomic line resonance absorption, laser‐induced fluorescence and CARS spectroscopy are compared with the results of theoretical studies on ab initio potential energy surfaces and thermal rate parameters. Thermal elimination of hydrogen chloride from 1,2‐dichloroethane and 1,1,1‐chlorodifluoroethane is a main industrial route to some important monomer compounds. Inducing these radical chain reactions by UV‐exciplex laser radiation offers the advantage that a monomolecular process with low activation energy becomes the rate determining step. This allows lower process temperatures with decreasing energy expense and avoiding the high temperature formation of byproducts.
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