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31 May 1984 Formation Of Vinyl Chloride And Vinylidene Fluoride By UV-Laser Induced Chain Reactions
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Proceedings Volume 0458, Applications of Lasers to Industrial Chemistry; (1984) https://doi.org/10.1117/12.939411
Event: 1984 Los Angeles Technical Symposium, 1984, Los Angeles, United States
Abstract
Thermal elimination of hydrogen chloride from 1,2-dichloroethane and 1,1,1-chlorodifluoroethane is a main industrial route to some important monomer compounds. Two reaction paths are possible - unimolecular four-center-elimination and a radical chain mechanism. The latter is started by the endothermic C-Cl bond rupture, followed by the chain consisting of an abstraction reaction and a monomolecular decomposition step. Inducing the chain by photo-initiation offers the advantage that the monomolecular process becomes the rate determining step leading to a lower activation energy for the total reaction. This allows lower process temperatures, therefore decreasing energy expense and avoiding the high temperature formation of byproducts. In our investigation we used as photolysis source several lines of an UV-Exciplex-Laser which provide short pulses of monochromatic UV-radiation with high energy. It was possible to study the effects of initial radical concentration on the quantum yield 0 as function of the temperature. Long reaction chains and a decrease of 0 inversely proportional to the square root of irradiation intensity were observed. The formation of the monomers was detected by a time-resolved UV-absorption technique. Experimental results were analysed in order to yield information about the temperature and pressure dependence of the rate determining reaction. By application of our data in computer simulations wP were able to extrapolate the reaction behaviour to various technical conditions.
© (1984) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.
J Wolfrum and M Schneider "Formation Of Vinyl Chloride And Vinylidene Fluoride By UV-Laser Induced Chain Reactions", Proc. SPIE 0458, Applications of Lasers to Industrial Chemistry, (31 May 1984); https://doi.org/10.1117/12.939411
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