Local structural analyses on molten terbium fluoride in lithium fluoride and lithium–calcium fluoride mixtures

X-ray absorption fine structure (XAFS) measurements on terbium fluoride in molten lithium fluoride and in molten lithium–calcium fluoride mixtures, (e.g. 0.20TbF3–0.80LiF, 0.20TbF3–0.62LiF–0.18CaF2, 0.20TbF3–0.48LiF–0.32CaF2, 0.50TbF3–0.50LiF, and 0.50TbF3–0.38LiF–0.12CaF2), have been carried out. In the solid state, coordination number of terbium (Ni) and inter ionic distances between terbium and fluorine in the first neighbor (ri) are nearly constant in all mixtures. In 0.20TbF3–0.80LiF, 0.20TbF3–0.62LiF–0.18CaF2 and 0.50TbF3–0.50LiF mixtures, Ni's decrease from ca. 8 to 6 and ri's also decrease from ca. 2.29 to 2.26 Å on melting. On the other hands, in molten 0.20TbF3–0.48LiF–0.32CaF2 and 0.50TbF3–0.38LiF–0.12CaF2 mixtures, Ni's are slightly larger than 6 and ri's do not change. These facts correspond to the amount of F− supplied by solvent melts, i.e. the effect of CaF2 becomes predominant at bCaF2 > 0.32 in ternary 0.20TbF3–aLiF–bCaF2 mixtures and at bCaF2 > 0.12 in ternary 0.50TbF3–aLiF–bCaF2 mixtures

Interaction of FeII and Si under anoxic and reducing conditions: Structural characteristics of ferrous silicate co-precipitates

The interaction of FeII and Si is at the heart of many critical geochemical processes in diverse natural and engineered environments. The resulting FeII-silicate phases play important roles in regulating the concentrations and bioavailability of FeII and Si, as well as serve as sinks for trace and hazardous elements. Therefore, a detailed understanding of their structural characteristics and the underlying formation mechanisms may provide insights useful to predicting their reactivity and stability under different conditions. In this work, co-precipitates with different Si/FeII ratios (0.5, 1.0 and 2.0) were synthesized under anoxic and reducing conditions at different solution pH (7, 9 and 11). Thermodynamic calculations from solution chemistry data were carried out and co-precipitates were studied using X-ray diffraction (XRD), infrared (IR) spectroscopy and Fe K-edge extended X-ray absorption fine structure spectroscopy (EXAFS). Thermodynamic calculations predict the formation of phyllosilicate phases such as greenalite in all the samples. Solid characterization data, however, reveal significant structural variabilities and phase heterogeneity. Incipient phyllosilicate structures tend to be more pronounced in samples from pH 9 and 11, while at neutral pH conditions, polymeric silicate phases like amorphous SiO2 become predominant. These variabilities are possibly linked to heterogeneous formation processes arising from relative solubility differences between SiO2 and Fe(OH)2. High pH (>8) conditions favor the polymerization of Fe(OH)2 layers which likely serve as templates for layered silicate formation, while neutral pH conditions favor the precipitation of polymeric silicate phases like amorphous SiO2 to which aqueous Fe species may adsorb. In samples from Si/FeII = 0.5, relatively well developed Fe(OH)2 layers were identified from the EXAFS data. Increasing Si/FeII ratios lead to amorphous SiO2 precipitation and inhibition of Fe(OH)2 polymerization, resulting in smaller phyllosilicate domains embedded in a polymeric SiO2 matrix. The results of this work may be useful in interpreting structural variabilities of FeII-Si phases observed both in nature and in engineered environments. Such variabilities may influence subsequent phase recrystallization processes as well as reactivity towards environmentally relevant elements such as radionuclides

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

The refining of platinum group metals is based mainly on solvent extraction methods, whereas Ru is selectively recovered by distillation as RuO4. Replacement of distillation by extraction is expected to simplify the purification process. To develop an effective extraction system for Ru, we analyzed the Ru species in HCl with ultraviolet-visible (UV-Vis) and Ru K-edge extended X-ray absorption fine structure (EXAFS) spectroscopies, and we examined the properties of Ru extracted with N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide) amine (EHBAA) and trioctylamine (TOA). EXAFS and UV-Vis spectra of Ru in HCl solutions revealed that the predominant Ru species in 0.5–10 M HCl solutions changed from [RuCl4(H2O)2]− to [RuCl6]3− with the HCl concentration. The extraction percentages (E%) of Ru in the EHBAA system increased with increasing HCl concentration, reached 80% at [HCl] = 5 M, and decreased at higher HCl concentrations; the corresponding E% for TOA were low. EXAFS analysis of the extracted complex indicated that the Ru3+ had 5 Cl− and 1 H2O in its inner coordination sphere. The similarity of the dependence on HCl concentrations of the E% in the EHBAA system and the distribution profile of [RuCl5(H2O)]2− on [RuCln(H2O)6−n]3−n suggested that the EHBAA extracted the pentachlorido species