Isotope effects in the gas phase radiolysis of H2S and D2S

Abstract

Gas phase radiolysis studies have been carried out on mixtures of H2S and D2S using as irradiation sources, either a Gammacell or a Febetron 705 pulsed electron accelerator. Separation factors (α = (H/D)prod ÷ (H/D)react) were obtained for various values of xD (the mole fraction of D2S), dose rate and temperature, as well as with the addition of SF6. All of the observed α values, for 0.2 ≤ xD ≤ 0.8, fall on the following empirical straight line.[Formula: see text]The addition of neon to a D2S/H2S mixture gives a value of α which decreases as the partial pressure of neon increases. For a 70% D2S/30% H2S mixture, &([a-z]+); = 1.9 ± 0.1 for the pure mixture and 1.28 ± 0.08 when 90 kPa of neon has been added to 10 kPa of the mixture. The &([a-z]+); values described by eq. 1 are interpreted as arising from kinetic isotope effects in the reactions of (translationally) hot H or D atoms with H2S, HDS, or D2S to form H2, HD or D2.Hydrogen yields from the gas phase radiolysis of pure H2S and pure D2S have been determined for dose rates from 4 × 1016 to 2 × 1028 eV g−1 s−1. Using dose rates of up to 2 × 1027 eV g−1 s−1, ΔG = G(H2) − G(D2) = 0.5. For the highest dose rate used (2 × 1028 eV g−1 s−1), ΔG = 1.5. The larger value of ΔG at very high dose rates is thought to arise from the dissociative neutralization processes. A possible mechanism is discussed.