Solubilities of zinc oxide and cadmium oxide in KCl-LiCl eutectic melts

ZnO solubility (pP = 4.77 ± 0.1) and CdO solubility (pP = 1.46 ± 0.1) in KCl-LiCl melts at 700°C are determined using the sequential additions method with the potentiometric control of the equilibrium oxide ion concentration. Cadmium oxide is a strong base; it fully dissociates in unsaturated solutions. Zinc oxide is a weak base (pK _ZnO = 2.89 ± 0.15). As the acidic properties of an ionic solvent strengthen with a fixed anionic composition, the solubilities of the oxides increase in correlation with their basicity index; the surface energy at the interface between the solid oxide and ionic melt decreases in association.     

On the behaviour of Eu oxo-species in molten NaBr–NaI (0.77:0.23) mixture at 973 K

The interaction of Eu₂O₃ with molten NaBr–NaI (0.77:0.23) mixture at 973 K was studied by sequential addition method with the use of YSZ membrane oxygen electrode for controlling of course of the process. The Red-Ox process is accompanied with formation of EuO in the melt. The total solubility of EuO (sum of concentration of Eu²⁺, O^2–, non-dissociated EuO) in the molten NaBr–NaI at 973 K (mole fraction 2.7 × 10^–4) is considerably lower than in pure NaI melt (4.2 × 10^–4), which can be explained using the ‘hole’ model by reduction of a number of holes of comparable with EuO particle size because of addition of smaller bromide ion to the iodide melt.

The solubility of EuO is appreciably affected by its dispersity and the value of surface energy causing these solubility changes is estimated as 37 J m^–2.     

Solubility of metal oxides in molten equimolar KBr-NaBr mixture at 973 K

Solubility products (pK _s,MO, molality) are measured by potentiometric titration with a Pt(O₂)|ZrO₂(Y₂O₃) oxygen electrode in the molten KBr-NaBr equimolar mixture at 973 K for the following oxides: CaO (5.00 ± 0.3), MnO (7.85 ± 0.3), NiO (9.72 ± 0.04), PbO (5.20 ± 0.3), and SrO (3.81 ± 0.3). The correlation between pK _s,MeO and the polarization of the corresponding cations by Goldschmidt is obtained.     

The 5v 3 bands of 18O enriched ozone: line positions of 16O16O18O, 16O18O16O, 16O18O18O and 18O16O18O

The four 5v ₃ bands of ¹⁸O enriched ozone have been observed and analysed for the first time. Two species (¹⁶O¹⁸O¹⁶O and ¹⁸O¹⁶O¹⁸O) belong to the C_2v symmetry group and two other (¹⁸O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O) to the C_s symmetry group. They have been recorded at a resolution of 0.008 cm^?1 with a pathlength of 32.16 m. Despite the very weak absorptions observed, almost 250 energy levels have been derived for each of the 4 species, with J ? 35 and K _a ? 13, and suitable sets of Hamiltonian parameters have been determined. For 3 species it has been necessary to account for the resonance between the (005) and (311) states to correctly reproduce the spectra observed. These resonances, anharmonic for C_2v, and hybrid (both anhar-monic and Coriolis) for C_s symmetry confirm the accidentally extremely strong coupling between the (005) and (311) states for ¹⁶O₃, due in that case to the very close distance between unperturbed energy levels. This work also confirms the excellent prediction of band centres of these four species derived from the recently determined isotopically invariant molecular potential function.     

Kinetics of luminescence of CsI single crystals scavenged by Y3+

CsI single crystals were grown from the melt scavenged by Y³⁺ (YCl₃) addition in 6.7·10⁻⁴–6.7·10⁻³ mol·kg⁻¹ range. The addition of the scavenger amounts comparable with the total concentration of the oxygen‐containing admixtures in molten CsI results in complete destruction of the latter. Because of this, the intensity of the band with a maximum at 2.8 eV in radioluminescence spectra caused by the oxygen‐containing admixtures (anion vacancies) considerably decreases, and the fraction of the slow 2μs‐component corresponding to these admixtures becomes lower than 0.01 (0.007). The addition of larger quantities of YCl₃ leads to the appearance of a wide band with a maximum at 2.8 eV caused by cation vacancies, and the intensity of the slow 2μs‐component increases to 0.02. The maximum ratio of two faster components with the decay constants equal to 7 and 30 ns reaches 0.65:0.33 at Y³⁺ concentration in CsI melt equal to 6.7·10^‐3 mol·kg^‐1, the effective luminescence time of fastest components is ca 14 ns. The dependence of the ‘Fast/Total ratio’ on Y³⁺ concentration passes through its maximum (0.81) corresponding to the equivalence of Y³⁺ and O²⁻ concentrations in the growth CsI melt.     

The influence of the composition of CsCl-LiCl-YCl<Subscript>3</Subscript> melts on their acid properties at 973 K

The acid properties of CsCl-xLiCl and CsCl-LiCl + xYCl₃ melts were studied at 973 K by the potentiometric method with the use of a Pt(O₂)|ZrO₂(Y₂O₃) oxygen electrode. The acidity of these melts increased as x grew. The oxobasicity index values (pI _L) were estimated, they were 3.84 for 2CsCl-LiCl and 5.55 for 0.875(2CsCl + LiCl) + 0.125YCl₃ melts. The acid properties of mixed “alkali metal halide-rare-earth metal halide” melts were close to each other, and the presence of Li⁺ cations in such melts did not influence their pI _L values because of the leveling of their acid properties.     

On the center-focus problem for systems with a degenerate singular point

For an analytic system with nonzero cubic part and with a degenerate monodromic singular point, we indicate an algorithm for constructing the asymptotic expansion of the Poincaré map. We present closed-form expressions for the first four focus quantities and find two necessary conditions for a center.     

Water Spectra in the Region 4200-6250 cm, Extended Analysis of ν1+ν2, ν2+ν3, and 3ν2 Bands and Confirmation of Highly Excited States from Flame Spectra and from Atmospheric Long-Path Observations

Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm⁻¹ at resolutions (FWHM) between 0.0053 and 0.0080 cm⁻¹. The use of a White-type multireflection cell made large pressure × pathlength products possible up to 31.27 mbar×288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10⁻²⁶ cm⁻¹/molecule cm⁻² at T=296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H₂¹⁶O (bands ν₁+ν₂, ν₂+ν₃, and 3ν₂). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H₂O data was 5×10⁻³ cm⁻¹ for line positions and 7×10⁻³ cm⁻¹ for energy levels up to J_max=20 and K_a(max)=13. Particular attention was paid to water lines in the transparency window 4200-5000 cm⁻¹, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H₂¹⁶O (ν₁, ν₃, 2ν₂, ν₁+ν₂, ν₂+ν₃, 3ν₂, 4ν₂−ν₂, 2ν₂+ν₃−ν₂, ν₁+2ν₂−ν₂) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.