[en] This paper systematically treats the thermochemical properties of binary and complex oxides of the lanthanides and actinides, in terms of other well-characterized species and thermochemical cycles. Since the trivalent lanthanides provide a reference series against which the lanthanide and actinide sesquioxides can be compared, the trivalent-ion energetics are considered first. Recent interest in monoxides, prompted by high-pressure synthesis of lanthanide monoxides and interest in divalent actinide metals and oxides, has led us to include a treatment of the relative stabilities of monoxides and sesquioxides. The important tetravalent state is viewed from the perspective of the dioxides as well as the perovskites BaMO³. Since there are no higher-valent lanthanides, systematic trends in pentavalent and hexavalent complex actinide oxides are not treated in this review. 79 references, 10 figures, 4 tables

[en] Recently-obtained calorimetric data on the sesquioxides and dioxides of americium and curium are summarized. These data are combined with other properties of the actinide elements to elucidate the stability relationships among these oxides and to predict the behavior of neighboring actinide oxides. 45 references, 4 figures, 5 tables

[en] The enthalpy of formation of hexagonal Am₂O₃ at 298.15 K has been determined to be -1690.4 +- 7.9 kj mol^-1 by solution microcalorimetry. Systematic comparison of the measured enthalpies of formation of hexagonal Pu₂O₃ and Am₂O₃, monoclinic Cm₂O₃, and all lanthanide sesquioxides has been utilized to develop a predictive understanding of stability relationships among all actinide sesquioxides and other actinide species

[en] The Chemistry of the Actinide Elements is an exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

[en] The Chemistry of the Actinide Elements is a comprehensive, contemporary and authoritative exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

[en] This article reviews recent research on the structural, thermodynamic, magnetic, and spectroscopic properties of ternary and other complex oxides containing actinide ions. Since complex oxides often exhibit unusual coordination sites and oxidation states for transition elements, the unique properties of complex oxides are emphasized. For completeness, a brief summary of properties of the binary oxides is also given. Properties of isostructural and isoelectronic series of oxides are compared in terms of structure-stability relationships, magnetochemistry, spectroscopy (photoelectron, Moessbauer, vibrational, and electronic), and synthetic procedures. 110 references, 8 tables

[en] This paper reports the first determination of the enthalpy of formation of a complex actinide(IV) oxide: ΔH⁰/sub f/ (BaUO₃, s, 298 K) = -1690 +- 10 kJ mol^-1. The preparation and properties of this and other actinide(IV) complex oxides are described and are compared with other perovskites BaMO₃. The relative stabilities of tetravalent and hexavalent uranium in various environments are compared in terms of the oxidation-reduction behavior of uranium in geological nuclear waste storage media; in perovskite, uranium(IV) is very unstable in comparison with uranium(VI)

[en] A systematic treatment of the thermochemical properties of binary and complex oxides of the lanthanides and actinides in terms of other well-characterized species and thermochemical cycles is given in this paper. Since the trivalent lanthanides provide a reference series with which the lanthanide and actinide sesquioxides can be compared, the trivalent ion energetics are considered first. Recent interest in monoxides, prompted by high pressure synthesis of lanthanide monoxides and interest in divalent actinide metals and oxides, has led the author to include a treatment of the relative stabilities of monoxides and sesquioxides. The important tetravalent state is viewed from the perspective of the dioxides as well as the perovskites BaMO₃. Since there are no higher valent lanthanides, systematic trends in pentavalent and hexavalent complex actinide oxides are not treated in this review. (Auth.)

[en] The enthalpy of formation of BaPuO₃ at 298.15 K has been determined by solution microcalorimetry to be -1,656.0 ± 5.6 kJ mol^-1. The ΔH degree of solid-state complex formation at 298.15 K, BaO(s) + PuO₂(s) = BaPuO₃(s), has been calculated to be -51.8 ± 5.7 kJ mol^-1. These results are compared with those for other f-element dioxides and ternary (perovskite) oxides and are used to estimate thermodynamic properties for potential dissolution reactions in a nuclear waste repository. The results indicate that the perovskite structure is not suitable for immobilization of plutonium unless reducing (oxygen-free) conditions are maintained

[en] This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for σ- and π-bonded compounds, and some concluding remarks on the superheavy elements