The kinetics of the heterogeneous catalytic gas-phase oxychlorination of ethylene to 1,2-dichloroethane was investigated, using a copper chloride on alumina catalyst at 180°C. The reaction rate increased with increasing partial pressures of ethylene and oxygen, but was independent of hydrogen chloride partial pressure. A reaction rate model based on the surface reaction of ethylene and oxygen to form an ethylene oxide intermediate as the rate-determining step provided the best fit of the experimental data. Mechanisms based on the Deacon reaction were not consistent with the data. The energy of activation for the rate expression was 24.5 kcal per mole. A study of the effect of process variables on chlorocarbon selectivity indicated that decreasing the hydrogen chloride partial pressure decreased side reactions to other chlorocarbons.
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