Temperature dependence of the intramolecular kinetic isotope effect in the reaction system Cl + HD

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Abstract
The relative rates of the two competing isotopic reactions, (1) Cl + HD → HCl + D and (2) Cl + DH → DCl + H were measured as a function of reaction temperature in the range of 297–443 °K. The ratio of rates can be expressed as an Arrhenius type equation; k1/k2 = (0.81 ± 0.04) × exp[(460 ± 50)/RT]. The very fast reaction of the hydrogen atoms formed with residual molecular chlorine, which under conventional experimental conditions would mask any isotope effect, was eliminated by adding NO2 as an efficient hydrogen atom scavenger to the stream of reactants in a fast flow reactor.