Thermodynamics of H in Disordered Pd−Ag Alloys from Calorimetric and Equilibrium Pressure−Composition−Temperature Measurements

Abstract

In this research, the thermodynamics of H2 solution and hydride formation in a series of disordered Pd-Ag alloys has been determined using both reaction calorimetry and equilibrium PH2-composition-T data. Trends of DeltaHH and DeltaSH with both H and Ag concentration have been determined. For the Pd0.76Ag0.24 alloy, which does not form a hydride phase, DeltaHH and DeltaSH both exhibit minima with H/(Pd0.76Ag0.24) followed by a linear increase of the former. A linear increase of DeltaHH is found for all of the alloys in the high H content region beyond the two-phase region or, if, there is no two-phase region, in the high H content region. DeltaHH degrees at infinite dilution of H decreases with atom fraction Ag, XAg, up to about 0.40 and then increases. Enthalpies for hydride formation/decomposition, 1/2H2(g) + dilute <--> hydride, have been determined calorimetrically for alloys which form two phases (303 K). The enthalpies for hydride formation become more exothermic with XAg while the corresponding entropy magnitudes are nearly constant, 46 +/- 2 J/K mol H.