Kinetics of decomposition of the liquid phase of the ternary system LiOH-H2O2-H2O in the presence of the solid phase of Li2O2 · H2O

The kinetics of decomposition of hydrogen peroxide in the liquid phase of the ternary system LiOH-H₂O₂-H₂O was studied in the presence the solid phase of Li₂O₂·H₂O and without it. The main kinetic parameters of the processes studied were determined.     

Study of the solubility of components in the system Mg(ClO3)2-2NH2C2H4OH · H3C6H5O7-H2O

The solubility of components in the system Mg(ClO₃)₂-2NH₂C₂H₄OH · H₃C₆H₅O₇-H₂O was studied from the complete freezing temperature ?59.4°C to 20.0°C. A polythermal solubility diagram was constructed, in which the crystallization fields were determined for ice, Mg(ClO₃)₂ · 16H₂O, Mg(ClO₃)₂ · 12H₂O, Mg(ClO₃)₂ · 6H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇ · H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇, and two new compounds, [(HOC(CH₂COOH)₂COO)₂Mg · 2H₂O] and [HOC(CH₂COO)₂MgCOOH · 2H₂O], which were identified by chemical and physicochemical analysis methods.     

Phase diagram and IR spectral investigations of the 2TeO2 · V2O5Li2O · V2O5 · 2TeO2 system

By means of X-ray phase analysis, IR spectroscopy, and DTA, the system 2TeO₂ · V₂O₅Li₂O · V₂O₅ · 2TeO₂ was investigated and its phase diagram was constructed. The formation of a new compound with composition Li₂O · 3V₂O₅ · 6TeO₂, melting incongruently was documented. A comparison of the bands in the IR spectrum was made. Stable glasses in the whole range of concentrations were prepared. From the IR spectra of the glasses, the corresponding crystallization products, and the data of known crystal structures, a model of the short-range order in the glasses was proposed.     

Study of the system Pr2O3-SeO2-H2O at 100°C and the properties of the compounds obtained

The solubility of the system Pr₂O₃-SeO₂-H₂O at 100°C was studied. The fields of crystallization of Pr₂(SeO₃)₃·H₂O, PrH(SeO₃)₂, Pr(HSeO₃)₃ were established. The compounds obtained were identified by means of chemical, X-ray and thermal analysis. The thermal decomposition of Pr₂(SeO₃)₃·H₂O, PrH(SeO₃)₂, and Pr(HSeO₃)₃ was determined.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal stability of Li2O–SiO2–TiO2 gels evaluated by the induction period of crystallization

To evaluate the thermal stability of materials, various criteria have been used. Not only the simple parameters, as characteristic temperatures, but also the combined criteria E/RT _p , k _f (T) and criterion based on the length of induction period of crystallization have been taken into account. Four gels with the composition Li₂O–2SiO₂–nTiO₂ (n = 0.00, 0.03, 0.062, and 0.1) were prepared and the validity of the criteria was tested by applying them to these gels. The results indicate that thermal stability of the studied gels decrease with amount of TiO₂.     

Synthesis and study of lithium triuranate Li2U3O10 · 6H2O

Li₂U₃O₁₀ · 6H₂O crystal hydrate was synthesized by the reaction between synthetic schoepite UO₃ · 2.25H₂O and aqueous lithium nitrate solution under hydrothermal conditions at 200°C. The composition and structure of the obtained compound were established, and its dehydration and thermal decomposition were studied, by chemical analysis, X-ray diffraction, IR spectroscopy, and scanning calorimetry.     

Structure and properties of glasses in the system Li2O–SnO–B2O3

Glasses in the system Li₂O–SnO–B₂O₃ system were prepared by a melt-quenching method. Thermal and viscous properties and local structure of these glasses were investigated. The SnO–B₂O₃ glasses exhibited relatively low glass-transition temperatures (T_g) around 350 °C and excellent thermal stability against crystallization. Viscosity measurements in the vicinity of T_g indicated that the glasses were considerably fragile compared to alkali borate glasses. Fraction of four-coordinated boron was maximized at the composition with 50 mol% SnO and that of nonbridging oxygen, which is not purely ionic in alkali borate systems but partially covalent, augmented with an increase in the SnO content. Correlation between glass properties and structure was discussed in the SnO–B₂O₃ binary system.     

Temperature dependence of the substrate selectivity in the hydroxylation of alkylbenzenes in the H2O2−H2SO4 system

The substrate selectivity in the hydroxylation of methylbenzenes in the H₂O₂−H₂SO₄ (70 wt.%) system was studied at 15–55 °C. The activation entropy correlates with the basicity of the arenes, while the substrate selectivity and activation enthalpy correspond both with the basicity and ionization potentials of ArH. We concluded that the structure of the reaction transition state is intermediate between a charge transfer complex and σ-complex. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 35, No. 1, pp. 39–43, January–February, 1999.     

Prediction of the solubility of HCl-MgCl2-H2O system at −5°C using the ion-interaction model

The component solubilities of the HCl-MgCl₂-H₂O system at −5°C were predicted by using the Pitzer ion interaction model and its extended Harvie and Weare model. The results indicated that the model supplies a good prediction of the above-mentioned system. The values of parameters of β⁽⁰⁾, β⁽¹⁾, and C ^φ of HCl and MgCl₂ were obtained by using the same optimization methods as in the literature, while those of θ_MgH and Ψ_MgHCl were derived by extrapolating the published data of 5, 15, 25, 35, and 45°C, as well as coupling the activity coefficients with the solubility data. The comparison between the calculated results and the experimental data indicated that the Pitzer ion interaction model and its extended Harvie and Weare model are quite reliable in the solubility prediction. The text was submitted by the authors in English     

Solid solutions of double phosphate hexahydrates in the MgNH4PO4 · 6H2O-Ni2+-H2O system and their dehydration products

Substitutional solid solutions Mg²⁺ ? Ni²⁺ of crystal hydrates Mg_{(1 ? x)}Ni _x NH₄PO₄ · 6H₂O and Mg_{(1 ? x)}Ni _x NH₄PO₄ · H₂O (where 0 < x ≤ 0.65), which have struvite structure and dittmarite structure, respectively, have been studied. Ion exchange Mg²⁺ ? Ni²⁺ influences the condition of M²⁺-H₂O (M²⁺ = Mg²⁺, Ni²⁺) coordination bonds and hydrogen bonds involving coordinated H₂O molecules, as probed by X-ray powder diffraction, thermal analysis, and FTIR spectroscopy. The coordination of water molecules to metal ions in those crystal hydrates is treated to be a factor that determines the propensity of the resulting crystal structures to polymorphism.     

An analysis of the vibrational frequencies and amplitudes of the H5O+2 ion in H4SiW12O40·6H2O (TSA·6H2O) and H3PW12O40·6H2O (TPA·6H2O)

The infrared, Raman and inelastic neutron scattering (INS) spectra of TSA·6H₂O and TPA·6H₂O are in agreement with those expected for the presence of H₅O⁺₂ ions. Force fields for different assignment schemes are compared with the observed vibrational frequencies and the INS spectral profile. All but two schemes are eliminated. Whilst low-resolution INS spectroscopy cannot distinguish between these two schemes, the orientations of the vibrational ellipsoids for one scheme are in better agreement with those reported from low-temperature crystallographic studies of the H₅O⁺₂ ion.