Equilibrium Isotope Effects in the Preparation and Isothermal Decomposition of Ternary Hydrides Pd(HxD1−x)y (0 < x < 1 and y > 0.6)

Abstract

A Sieverts' apparatus coupled with a residual gas analysis is used to measure the concentration variations of hydrogen isotopes in the gas and solid phases during exchange and isothermal decomposition of mixed hydrides. beta-phase palladium hydrides with known ratios of H:D, Pd(H x D 1- x ) y (0 < x < 1, y > 0.6), are prepared by H 2 with PdD y or D 2 with PdH y exchange, and their desorption isotherms are reported here at 323 K. A higher equilibrium pressure in isothermal desorption of mixed hydrides is associated with a higher ratio of D/H in the initial mixed hydrides in beta-phase. The composition of the gas desorbed from a mixed hydride varies; i.e., the ratio of D/H in gas decreases with the sum of (H + D) in Pd. The values of the separation factor alpha during desorption at 323 K and during H-D exchange at 248 K are discussed and compared with those in the literature. Desorption isotherms of mixed isotope hydrides are between those of the single isotope hydrides of H-Pd and D-Pd, however, plateaus slope more than those of pure isotope hydrides. The origin of the plateau sloping in the mixed hydrides can be attributed to the compositional variations during desorption, i.e., the equilibrium pressure is greater when D/H ratio in solid is greater. A simple model is proposed in this study that agrees well with experimental results.