Synthesis of Crystalline Americium Hydroxide, Am(OH)3 and Determination of its Enthalpy of Formation; Estimation of the Solubility-Product Constants of Actinide(III) Hydroxides

This paper reports a new synthesis of pure, microcrystalline Am(OH){sub 3}, its characterization by x-ray powder diffraction and infrared spectroscopy, and the calorimetric determination of its enthalpy of solution in dilute hydrochloric acid. From the enthalpy of solution the enthalpy of formation of Am(OH){sub 3} has been calculated to be {minus}1371.2{plus_minus}7.9 kj{center_dot}mol{sup {minus}1}, which represents the first experimental determination of an enthalpy of formation of any actinide hydroxide. The free energy of formation and solubility product constant of Am(OH){sub 3} (K{sub sp} = 7 {times} 10{sup {minus}31}) have been calculated from our enthalpy of formation and entropy estimates and are compared with literature measurements under near-equilibrium conditions. Since many properties of the tripositive lanthanide and actinide ions (e.g., hydrolysis, complex-ion formation, and thermochemistry) change in a regular manner, these properties can be interpreted systematically in terms of ionic size. This paper compares the thermochemistry of Am(OH){sub 3} with thermochemical studies of lanthanide hydroxides. A combined structural and acid-base model is used to explain the systematic differences in enthalpies of solution between the oxides and hydroxides of the 4f{sup n} and 5f{sup n} subgroups and to predict solubility-product constants for the actinide(III) hydroxides of Pu through Cf.