Abstract
The intramolecular kinetic isotope effect in the reaction of fluorine atoms with HD molecules, F+HD→kF+HDHF+D,F+DH→kF+DHDF+H,was measured as function of reaction temperature in the range of 159–413 °K. The measured isotope effect can be expressed as an Arrhenius-type equation: kF+HD/kF+DH = (1.26 ± 0.02) exp[(70 ± 6)/RT]. Experiments were carried out in a fast flow system with direct mass spectrometric analysis of reaction products. The experimental results for kF+HD/kF+DH, as well as results for kF+H2/kF+D2 which were reported in an earlier publication, are compared with calculations based on transition state theory, using empirical and semiempirical models.
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