Relative Rates of Reaction of Bromine Atoms with Isotopic Hydrogen Molecules

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Abstract
Kinetic isotope effects in the reaction of bromine atoms with isotopic hydrogen molecules were measured in this investigation. Rate constant ratios were determined by isotopic analysis of H2–HD, H2–HT, or H2—D2 mixtures before and after reaction with bromine atoms. Over the temperature range of 438° to 623°K, the ratios of the second-order rate constants were kH2/ΣkHD = (1.14±0.01) exp(591±4/RT), kH2/ΣkHT = (1.22±0.02) exp(658±16/RT), kH2/kD2 = (1.32±0.04) exp(1253±37/RT). A comparison of these results with the corresponding isotope effects obtained in the chlorine- and iodine-atom experiments reveals surprisingly little difference in kinetic isotope effects. The theoretical calculation of the kinetic isotope effects was carried out using Bigeleisen's theory of isotope effects on reaction rates. The calculations were made using various methods of constructing the potential energy surface and it was found that none of the semiempirical methods used gave agreement to better than 40% to 80%.

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