Abstract
The thermal unimolecular decomposition of chloroethane-2,2,2-d3 has been studied by means of very low-pressure pyrolysis (VLPP) over the temperature range 975-1213 K (gas/wall collisions only) and at 1173 K with COz as a collision bath gas. The experimental results are consistent with the reaction proceeding via the four-centerelimination of DC1. No firm evidence could be found for the three-center elimination of HC1 under the experimental conditions employed. Extrapolated high-pressure rate coefficients obtained via the application of RRKM theory with the incorporation of gas/wall energy-transfer efficiencies consistent with a recent VLPP study of chloroethane-2-dl are given by 1013.6e xp(-243 kJ mol-1/R7') s-l. Fitting of the pressure-dependent data by solution of the integrodifferential reaction-diffusion master equation gives a gas/gas average downward collision energy transfer value of ca. 1040 cm-l for C02/CD3CH2Cc1o llisions.
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