Kinetics and mechanism of the pyrolysis of pentachloroethane

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Abstract
The rate of the inhibited pyrolysis of pentachloroethane was studiedover the temperature range of 820 to 865°K using the toluene‐carrier technique in a stirred‐flow reactor. The pyrolysis rate was found to be first order in reactant, and the rate constant is described by k=1011.6±0.7 exp [(−48,200±2600)/RT] sec−1. An increase by a factor of 6.6 in the surface/volume of the reactor had a negligible effect on the rate. This observation, in addition to a reevaluation of earlier kinetic data for the pyrolysis of pentachloroethane, lead to the following conclusions concerning the pyrolysis mechanism. The initiation and termination as well as the propagation reactions were homogeneous, the termination involved both Cl and C2Cl5 radicals (crosstermination), and autocatalysis was caused by interaction between chlorine and pentachloroethane rather than by dissociation of molecular chlorine.

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