Abstract
Rate constantsk and translational temperaturesT have been determined for the decompositions of ethyl acetate and perfluorocyclobutane at various pressures induced by a continuous (cw) CO2 laser. Arrhenius plots give activation energies in good agreement with those reported for thermal rate constantsk 1. The ratiosk/k 1 become progressively larger than unity with decreasing reactant pressure, indicative of laser induced non-thermalization, but the values ofk/k t appear to reach limiting values at low pressures, similar to effects reported elsewhere for CH3CF2Cl. Analysis of the data suggests important general features of vibrational-translational energy transfer in polyatomic compounds.
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