Kinetic isotope effect in the thermal dissociation of ethane

Abstract
The rate constants for the dissociation of ethane and ethane-d6 have been measured at temperatures from 778 to 878 K and over pressures between 1.33 and 214 kN m–2. The secondary kinetic isotope effect, (kD 1/kH 1), is greater than unity under all conditions studied. The results mirror the temperature dependence of the corresponding equilibrium constant ratio and are in line with measurements of (kD –1/kH –1) for methyl recombination at room temperature. The results are higher than a prediction for the infinite pressure limit by an adiabatic open channel theory of unimolecular dissociation.

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