Solubility of oxides in the KBr-BaBr2 eutectic melt (0.495: 0.505) at 973 K

Solubility products of MnO (pK _s,MnO = 6.32 ± 0.1), NiO (pK _s,NiO = 8.06 ± 0.2), and PbO (pK _s,PbO = 4.04 ± 0.2) in KBr-BaBr₂ (0.495: 0.505) melt at 973 K were determined by potentiometric titration using a Pt(O₂)|ZrO₂(Y₂O₃) membrane oxygen electrode. A significant increase in oxide solubilities compared to those of 2CsBr · KBr melt is attributed to the enhancement of acidic properties of cations in the series Cs⁺, K⁺-Ba²⁺, ensuring a greater degree of binding of oxide ions that results from dissociation of the oxide under study to the cationic framework of the melt. The solubilities of the investigated oxides in chloride and bromide melts with similar cationic compositions are virtually identical.     

Ultrasonic velocity for an equimolar mixture of molten AgI and NaCl in the biphasic region

The ultrasonic velocities of a molten stratifying mixture composed of 0.5 AgI and 0.5 NaCl (the composition corresponding to the top of the miscibility gap) were measured along the saturation line for a wide temperature range via the pulse method to establish the characteristics of mixing salts with different chemical bonds. We show that the difference, Δu, between the magnitudes of the sound velocities for the coexisting phases decreases with increasing temperature and becomes zero at 1064 K. This temperature corresponds to the critical phase transition point, T_c. The temperature dependence of the sound velocity difference, Δu, is described by the equation Δu ≈ (T_c − T)^Θ, where Θ = 0.896, which is less than that found for alkali halide melts (Θ = 1.02), in which long-range Coulomb forces between ions prevail. The results are discussed in terms of the peculiarity of the chemical bond in silver iodide.     

Consecutive recovery of uranium oxides from uranyl-containing molten alkali metal sulfate electrolytes

The oxygen coefficient (atomic ratio O/U) of a cathode product and the cathode current yield in consecutive recovery of uranium oxides from molten salt mixtures (nLi₂SO₄ + (1 ? n)Cs₂SO₄) + UO₂SO₄ and (Li,Na,K)₂SO₄ + UO₂SO₄ in air were analyzed as dependent on the electrolyte and the mean solvent-salt cation radius. The increasing mean solvent-salt cation radius and decreasing UO₂SO₄ concentration in the electrolyte during long-term electrolysis suppress the solvolysis of uranyl ions and decrease the oxygen coefficient in the cathode product. The cathode current yield decreases systematically during electrolysis and drops to zero long before the uranium is completely recovered from the melt. The ultimate uranium recovery increases as the mean solvent-salt cation radius increases.     

Solubility of Elemental Sulfur in Water at 298 K

Abstract

The solubility of elemental rhombic sulfur in water is 1.9(±0.6) × 10^?8 mole S₈·kg^?1. This value is in agreement with thermodynamic considerations on the solubility of sulfur and experimental data on sulfur hydrosols.     

Electroreduction of cerium ions on silver electrode in halide melts at 973 K

The mechanism of electroreduction of cerium ions in equimolar KCl-NaCl melt is explored at 973 K. The effect of the anionic composition of the melt on the electroreduction of cerium ions is studied. It is shown that the electrodeposition of metal cerium from halide melts on a silver electrode is the primary electrochemical process that occurs at potentials more positive than those corresponding to the supporting-electrolyte decomposition. The electroreduction of chloride complexes of cerium on a silver electrode in the melt in both steady-and non-steady-state polarization modes at rates below V ≤ 0.5 V/s is limited by the diffusion delivery; at higher polarization rates, the charge-transfer stage predominates.     

Interaction of rare-earth oxides with binary molten mixtures of zirconium and alkali metal fluorides

Isothermal saturation, inductively coupled plasma mass spectrometry (ICP-MS), and X-ray powder diffraction were used to study solubilities of La₂O₃, Sm₂O₃, and Ho₂O₃ in the eutectic mixtures of LiF-ZrF₄, NaF-ZrF₄, and KF-ZrF₄ systems at temperatures from 873 to 1073 K. The solubilities of rare earth oxides in the molten fluorozirconate systems studied decrease in the increasing order of Ln³⁺ ion radii and in the increasing order of alkali metal cation radii in the binary mixture. The thermodynamic parameters of dissolution calculated for the oxides imply the dominance of a chemical dissolution mechanism, and this implication was supported by X-ray powder diffraction data.     

Solubility of carbon dioxide in molten alkali-metal nitrates

The solubility of CO₂ in the series of molten alkali-metal nitrates is volumetrically measured on improved equipment, and the thermodynamic characteristics of dissolution are calculated.     

Solubility of water in a benzene-cyclohexane mixture

The solubility of a water molecule in a binary mixture of nonpolar cyclohexane and quadrupolar benzene is studied with the ab initio method. A novel self-consistent reaction field theory that properly accounts for benzene quadrupole moments in the continuum solvent framework is used to describe the solvation effects of the solvent mixture. The free energy of transfer from pure cyclohexane to the mixture solvent is obtained with the neglect of nonelectrostatic contributions. A reasonable agreement with experiments indicates that the theoretical method presented here provides a promising approach to electronic structure calculations in quadrupolar solvents and their mixtures with nonpolar solvents.     

Solubility of freons in polar and non-polar liquids at 298.15 K

The cavity formation energy (CFE) is the free energy invested in rearrangement of the solvent molecules when a solute is inserted into a solvent, which is very important to the solubility studies. The CFE of liquid solvents; n-heptane, n-octane, cyclohexane, tetrachloromethane, benzene and water at 298.15 K has been determined. The solubility (in terms of Henry’s law constant), Gibb’s free energy of solution and ΔG_s^*, the thermodynamical quantities for the solvation process defined by Ben-Naim and Marcus of fluorine containing gases; freon-11, freon-12, freon-13, freon-14, freon-21, freon-c-318 and sulpherhexafluoride (SF₆) in above liquid solvents at 298.15 K also been calculated with this cavity formation energy. It yields good agreement with experimental results. The calculation shows importance of CFE in determining the solution properties.     

The electrochemical behavior of metal carbonyls in a mixture of a room temperature molten salt and benzene

The electrochemical oxidation of six metal carbonyls was studied in a mixture of the high Lewis acid, room temperature molten salt, composed of aluminum chloride and ethylpyridinium bromide (2:1 molar ratio) and benzene (50% v/v). Chromiuim hexacarbonyl was found to be reversibly oxidized to the seventeen electron cationo Cr(CO)⁺₆, isoelectronic with vanadium hexacarbonyl. Some stability was also found for the corresponding 17 electron cation of iron pentacarbonyl. The other carbonyl compounds studied Mo(CO)₆, W(CO)₆, Re₂(CO)₁₀, and Mn₂(CO)₁₀ exhibit electrochemical behavior characteristic of chemical and electrochemical reactions following the electron transfer reaction. Based on the large dependence of the oxidation potentials on the nature of the central metal atom in this solvent, it is proposed that the metal carbonyls interact with electron deficient species in the melt, decreasing the σ donor ability of the ligand, but increasing its π acceptor capabilities.     

Solubility of Solid Hexane and Cyclohexane in Liquid Argon at 87.3 K

The solubilities of solid hexane and cyclohexane in liquid argon at 87.3 K have been measured by the filtration method. The hexane and cyclohexane content in solution was determined using gas chromatography. The solubilities of the C₆ hydrocarbons in liquid argon at 87.3 K are (0.56 ± 0.11) × 10^-7 mole fraction for hexane and (1.04 ± 0.30) × 10^-7 mole fraction for cyclohexane. The Preston–Prausnitz method was used for calculation of the solubilities of solid hexane and cyclohexane in liquid argon in the temperature range 84–110 K. The values of the solvent–solute interaction constant l₁₂ were also calculated.     

Phase separation in metal oxides

A fascinating phenomenon, recently found to occur in certain transition-metal oxides, is phase separation wherein pure, nominally monophasic oxides of transition metals with well-defined compositions separate into two or more phases over a specific temperature range. Such phase separation is entirely reversible, and is generally the result of a competition between charge-localization and -delocalization, the two situations being associated with contrasting electronic and magnetic properties. Coexistence of more than one phase, therefore, gives rise to electronic inhomogeneity and a diverse variety of magnetic, transport, and other properties, not normally expected of the nominal monophasic composition. An interesting feature of phase separation is that it covers a wide range of length scales anywhere between 1-200 nm. While cuprates and manganates, especially the latter, provide excellent examples of phase separation, it is possible that many other transition-metal compounds with extended structures will be found to exhibit phase separation.     

Three-coordinate metal centers in extended transition metal oxides

The n = 3 Ruddlesden-Popper phase Sr3LaFe1.5Co1.5O10+/-delta is capable of sustaining O contents as low as O7.5 with a mean metal oxidation state of +2 and three coordination at the central site in the trilayer of originally octahedral transition metal sites. The shortening of the axial bonds to the flanking octahedral layers stabilizes the low oxidation state and consequent unusual low coordination number of the Fe2+ and Co2+ cations within the extended structure.     

Solubility of antimony metal in molten antimony(III) chloride-aluminum chloride and antimony(III) chloride-cesium chloride mixtures

The solubility of antimony metal in molten SbCl₃AlCl₃ and SbCl₃CsCl is reported. Measurements were made at many compositions and temperatures within the following ranges: SbCl₃AlCl₃ system, 1–90 mol% AlCl₃ at 235–430°C; SbCl₃CsCl system, 0.5–25 mol % CsCl at 405°C, 45–80 mol % CsCl at 628°C and 60 mol % CsCl at 562–642°C. The solubility is attributed to the reversible reaction of antimony metal with antimony(III) in the melts to form two types of species with oxidation states below 3+. One type is stabilized in SbCl₃AlCl₃ melts at high pCl (pCl = − log[Cl⁻]) and the other is stabilized in SbCl₃CsCl melts with low pCl. Both types are present in melts with a high concentration of SbCl₃, but it is in such melts that antimony metal has its lowest solubility.     

Ab initio molecular dynamics simulation of a water-hydrogen fluoride equimolar mixture.

Hydrogen fluoride and water can be mixed in any proportion. The resulting solutions have unique acidic properties. In particular, hydrogen fluoride undergoes a weak-to-strong acidity transition with increasing concentration of HF To supplement the knowledge already obtained on dilute or moderately concentrated solutions and gas-phase aggregates, an equimolar mixture is studied here by Car-Parrinello molecular dynamics. The natures of the ions and of the complexes formed in the equimolar liquid were determined. Specifically, H3O+, H5O2+, FH-OH2, and HF2- were spontaneously obtained while only hydronium and fluoride ions pre-exist in the equimolar crystal. The behaviour of the proton in the equimolar liquid was compared with mixtures of other proportions simulated previously in an attempt to relate proton dynamics to acidity. In the same way, the behaviour of HF2- was also examined. In this case, proton localization and transfer appeared to be driven by the fluctuating environment of the solvated ion.