Abstract
The constants of the equilibrium between H held in the surface layer and H dissolved in the bulk of Pd-H)-electrodes coated with different surface layers have been galvanostatically measured within 0 and 30°C, in 1 NH 2SO 4. The enthalpy change ΔH 0 and entropy change ΔS 0 have been estimated from van't Hoff plots. A physical effect in the linear correlation between ΔH 0 and ΔS 0 data has been detected. The dependence of ΔH 0, ΔS 0 and ΔG 0 298 on the roughness factor ( f w = 2–60) explains the tendency of H to accumulate spontaneously in the surface layer. The schematic diagram of the potential energy of Pd/solution interface is compared with data on Pd/H 2 gas interface. The difference is ascribed to the specific adsorption of anions connected with the high density of defects in the surface layer.
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