The influence of the organolithium reagent nature on the possibility of the O→C<Subscript>sp</Subscript> migration of the R<Subscript>3</Subscript>Si group in propynes HC≡CCH<Subscript>2</Subscript>OSiR<Subscript>3</Subscript>

A possibility of the O→C_sp 1,4-migration of the R₃Si group in silyl ethers of terminal acetylenic alcohols upon treatment with organolithium reagents (RLi) was studied. In the case of 3-trimethylsilyloxypropyne, depending on the nature of RLi, the heterolysis of the Si—O bond occurs either by the action of acetylide formed as a result of deprotonation with the formation of 3-trimethylsilylprop-2-yn-1-ol trimethylsilyl ether, or by the action of the metalation agent with the formation of propargyl alcohol. The realization of the O→C_sp 1,4-migration of the Me₃Si group requires the use of mild organolithium reagents (lithium hexamethyldisilazanide and diisopropylamide). Silyl ethers having steric hindrance at the carbon atom bonded to the reaction center or around the silicon atom do not react with the studied organolithium reagents.     

Photochemistry of the IrCl<Subscript>6</Subscript><Superscript>2−</Superscript> complex in aqueous solutions in the presence of the bromide anions

Laser flash photolysis (308 nm) was applied to study photochemistry of the IrCl₆ ²⁻ complex in aqueous solutions in the presence of the Br⁻ anions. The formation of the Br₂ ^·− radical anions in the reaction between the Br⁻ ion and secondary radical pair formed after the photon absorption by the initial complex was observed. The Br₂ ^·− radical anions decay both in recombination and in the reaction with the initial IrCl₆ ²⁻ complex.     

Pulse radiolysis study of the oxidation of the I<Superscript>−</Superscript> ions with the radical anions Br<Subscript>2</Subscript><Superscript>·−</Superscript> in an aqueous solution: formation and properties of the radical anion BrI<Superscript>·−</Superscript>

The radiation chemical redox transformations in solutions of bromides in the presence of minor additives of iodides were studied by pulse radiolysis. The change in the concentrations of the Br⁻ and I⁻ ions changes the ratio of the formed short-lived radical anions Br₂ ^·−, BrI^·−, and I₂ ^·−. The spectrum of the mixed radical anion BrI^·− contains a broad optical band at 370 nm with ɛ₃₇₀ = 9650 L mol⁻¹ cm⁻¹. The reduction potential of the BrI^·−/Br⁻, I⁻ pair is 1.25 V. The rate constants for the forward and backward reactions Br₂ ^·− + I⁻ ⇌ BrI^·− + Br⁻ are k _f = 4.3·10⁹ and k _r = 1.0·10⁵ L mol⁻¹ s⁻¹, respectively; for the reactions BrI^·− ⇌ Br⁻ + I^·, k _f = 5.7·10⁸ s⁻¹ and k _r = 1.0·10¹⁰ L mol⁻¹ s⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1787–1792, September, 2008.     

State of active components on the surface of the PdCl<Subscript>2</Subscript>-CuCl<Subscript>2</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst for the low-temperature oxidation of carbon monoxide

The state of the active constituents of the freshly prepared PdCl₂-CuCl₂/γ-Al₂O₃ catalyst for the low-temperature oxidation of the carbon monoxide by molecular oxygen was studied by X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and diffuse reflectance IR Fourier transform spectroscopy (DRIFTS). It was shown that copper in the form of a crystalline phase of Cu₂Cl(OH)₃ with the structure of the mineral paratacamite and palladium chloride in an amorphous state occurred on the surface of γ-Al₂O₃. According to XAS data, the local environment of palladium consisted of four chlorine atoms, which formed a flat square with an increased distance between palladium and one of the chlorine atoms. The evolution of the local environments of copper and palladium upon a transition from the initial salts to the impregnating solutions and chlorides on the surface of γ-Al₂O₃ was considered. The role of γ-Al₂O₃ in the formation of the Cu₂Cl(OH)₃ phase was discussed. It was found by the DRIFTS method that linear (2114 cm⁻¹) and bridging (1990 and 1928 cm⁻¹) forms of coordinated carbon monoxide were formed upon the adsorption of CO on the catalyst surface. The formation of CO₂ upon the interaction of coordinated CO with atmospheric oxygen was detected. Active sites including copper and palladium were absent from the surface of the freshly prepared catalyst.     

Regime of superhigh reactivity of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + δ</Subscript> superconductor toward the components of air

Physicochemical features of the YBa₂Cu₃O_{6 + δ} superconductor synthesized via ceramic route and subjected to a kind of modification by long-term exposure to an atmosphere with low pH₂O have been studied by X-ray diffraction, thermal analysis, and magnetometry. The resulting material had a high degree of saturation with air components at room temperature and 30% humidity, up to 1.5 wt % in 30 days, which is not inherent in YBa₂Cu₃O_{6 + δ}.     

Kinetics of the <Emphasis Type="Italic">n,γ</Emphasis>-radiolysis of the N<Subscript>2</Subscript>O<Subscript>4</Subscript>-NO system over the temperature range 200–400°C and the pressure range 0.1–16.0 MPa

The kinetics of formation of dinitrogen and dinitrogen oxide under the action of reactor n,γ-radiation was studied at 150–400°C, 0.1–16.0 MPa, and doses of 1.44 × 10⁵?1.29 × 10⁶ Gy. The radiation-chemical yields of N₂ and N₂O were determined. A comparative kinetic analysis of the experimental data was performed.     

Role of the HO<Stack><Subscript>2</Subscript><Superscript>•</Superscript></Stack> radical in hydrogen oxidation at the third self-ignition limit

It is demonstrated by simultaneous analysis of experimental data and the results of numerical simulation that, at 100 kPa, the H₂/O₂ mixture self-ignites only owing to the occurrence of a chain avalanche. Self-heating becomes significant in the course of chain combustion and strengthens the chain avalanche. The accelerating decomposition of H₂O₂, which results from the reaction between HO₂^• and H₂, contributes to chain branching and determines the character of the chain thermal explosion. The role of the HO₂^• radical depends on the chain process conditions, consisting of chain termination as a result of the partial loss of HO₂^• at the initial self-acceleration stage, H atom regeneration, and participation in the second branched cycle under conditions of accelerated H₂O₂ decomposition.     

Regularities of formation of complex oxides with the fluorite structure in the ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The crystal and local structures of the complex oxides (1–x)ZrO₂ ? xY₂O₃ (YSZ) (x = 0.08–0.40) prepared by precipitation from solutions of metal salts followed by heat treatment in air were comprehensively studied by X-ray diffraction and Raman spectroscopy. Despite the same crystal structure type of the YSZ powders (cubic system, space group \(Fm\overline 3 m\) (225)), there are differences in the local structure of the samples. Comparison of the Raman spectra recorded at different laser excitation wavelengths provided the conclusion that the peaks observed in the Raman spectra of the YSZ samples with high yttrium content (x = 0.18–0.40) are likely to be due to luminescence of the powders.     

Reactivity of the oxides in the ternary V<Subscript>2</Subscript>O<Subscript>5</Subscript>-CuO-α-Sb<Subscript>2</Subscript>O<Subscript>4</Subscript> system in air

In this work it has been established which compounds finally are formed in air in the two-component CuO-V₂O₅ and CuO-α-Sb₂O₄ systems. Unknown thermal properties of CuV₂O₆, Cu₂V₂O₇ and Cu₁₁V₆O₂₆ have been established. Reactivity of the oxides and phase relations in the ternary V₂O₅-CuO-α-Sb₂O₄ system in air have been studied by using XRD and DTA methods. The results have showed the reaction of V₂O₅, CuO with α-Sb₂O₄ does not produce any compound where all the three oxides would be involved. It has been established that the α-Sb₂O₄ reacts and forms binary phases independently with CuO or V₂O₅. On the base of these results the investigated system was divided into subsidiary subsystem in which CuSb₂O₆ remains at equilibrium in the solid state with other phases formed in corresponding binary systems.     

The effect of the synthesis method on the morphological and luminescence characteristics of α-Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>

A promising yellow phosphor, α-Zn₂V₂O₇, was synthesized at temperatures below the phase transition temperature (610 ± 5°C) by three different methods: solid-phase and microwave processes and thermolysis of a water–salt composition. According to powder X-ray diffraction, the structures of all samples belonged to space group C/2c. Depending on the method of synthesis, the particle size varied from 500 nm (thermolysis of a water–salt composition) to 5–8 μm (ceramic and microwave methods). The excitation spectra of all samples are in the UV region (220–400 nm) and the emission spectra are in the 400–750 nm wavelength range. The photoluminescence spectra of the samples are non-elementary, which is caused by specific features of the electronic charge transfer in the structural VO₄ tetrahedra.     

Study of the effect of methods for liquid-phase synthesis of nanopowders on the structure and physicochemical properties of ceramics in the CeO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Two alternative chemical synthesis methods—cryotechnological coprecipitation of hydroxides and cocrystallization of salts—were used for preparing (CeO₂)_1–x (Y₂O₃) _x nanopowders (x = 0.10, 0.15, 0.20) with a mean coherent scattering domain size of ~7–11 nm and S _sp = 2.1–97.5 m²/g. From these nanopowders, ceramic nanomaterials with mean coherent scattering domain sizes of ~61–85 nm were synthesized. It was studied how the phase composition, microstructure, and electrical transport properties of the produced samples depend on the Y₂O₃ content of a CeO₂-based solid solution and on the synthesis method. It was shown that, in the series (CeO₂)_1–x (Y₂O₃) _x (x = 0.10, 0.15, 0.20), the solid solution (CeO₂)_0.90(Y₂O₃)_0.10 has the highest ionic conductivity with the ion transport number t _i = 0.73 (600°C). In its physicochemical characteristics, this ceramic can be used as a solid electrolyte of intermediate-temperature fuel cells.     

A study of the hydrolysis of ZrF<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack> and the structure of intermediate hydrolysis products by <Superscript>19</Superscript>F and <Superscript>91</Superscript>Zr NMR in the 9.4 T field

The high-field ¹⁹F and ⁹¹Zr NMR method is used to study the hydrolysis and polycondensation of hexafluorozirconate ZrF₆²⁻ in aqueous and water-peroxide solutions. During hydrolysis in aqueous solutions only ZrF₆²⁻ and F⁻ ions were observed by NMR, however, in the water-peroxide medium, an intermediate product of hydrolysis ([F₅Zr-OO-ZrF₅]⁴⁻ dimer) was detected. The dimer structure is confirmed by ¹⁹F and ⁹¹Zr NMR. In high fields (¹⁹F NMR frequency > 200 MHz), the fluorine exchange between ZrF₆²⁻ and F⁻ is slow in the ¹⁹F NMR scale and has a multisite character.     

Heat-Treatment-Induced Evolution of the Mesostructure of Finely Divided Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> Produced by the Sol–Gel Method

A method was developed for the low-temperature sol–gel synthesis of one of the most popular components of functional and structural materials—nanostructured yttrium aluminum garnet Y₃A_l5O₁₂—using precursors from the class of alkoxoacetylacetonates produced from the corresponding acetylacetonates. It was determined that increasing duration of heat treatment of yttrium-aluminum-containing xerogen in air to 6 h reduces the crystallization temperature of the Y₃A_l5O₁₂ phase from 920–930 to 750–800°C, which was confirmed by IR spectroscopy and X-ray powder diffraction analysis. The microstructure of nanocrystalline yttrium aluminum garnet obtained at 800°С was studied; it was found that the size of crystallites is 30–40 nm, the size of particles is 30–50 nm, and the size of pores is 20–30 nm. Small-angle neutron scattering demonstrated that, in the powders synthesized at 700–800°C, there is structural ordering of the short-range type, whereas in the nanocrystalline samples heat-treated at a higher temperature (850°С), there is no such ordering.     

Effect of the sequence of chemical transformations on the spatial segregation of components and formation of periclase-spinel nanopowders in the MgO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–H<Subscript>2</Subscript>O System

Specific features of the process in which oxide nanopowders are formed in a hydrothermal treatment of coprecipitated magnesium and iron oxides were studied. It was shown that the rate at which oxide nanoparticles are formed increases when reagents structurally close to the final product are used. It was found that, with the hydrothermal treatment of coprecipitated magnesium and iron hydroxides at 450°C combined with the subsequent thermal treatment in air at temperatures of 400–600°C, it is possible to obtain a homogeneous mixture of nanocrystalline powders based on an iron-containing spinel phase and magnesium oxide.     

Tensimetric investigation of the CrCl<Subscript>3</Subscript>—Cl<Subscript>2</Subscript> system in the temperature range of 600–1200 K

The sublimation pressure of chromium trichloride was measured by the static method with a quartz membrane-gauge manometer in the temperature range of 875–1230 K. An approximating equation for the sublimation pressure vs. temperature was found. The enthalpy (259.4±4 kJ mol^–1) and the entropy (224.2±3.5 J mol^–1 K^–1) of sublimation at 298 K were calculated. For the process 2 CrCl₃(g) + Cl₂(g) = 2 CrCl₄(g), the following values were obtained: _r H°₂₉₈ = –207.1±11.6 kJ mol^–1 and _r S°₂₉₈ = –173.6±10 5 J mol^–1 K^–1.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1561–1564, August, 2004.     

Diagram of the PbF<Subscript>2</Subscript>–SnF<Subscript>2</Subscript> system

A phase diagram of the PbF₂–SnF₂ system has been studied by differential thermal analysis and X-ray powder diffraction. The system forms Pb_1–хSn_хF₂ (х ≤ 0.33) solid solution and three compounds. Pb₂SnF₆ decomposes in solid state by a peritectoid reaction at 350°С; Pb₃Sn₂F₁₀ and PbSnF₄ melt by peritectic reactions at 565 and 380°С, respectively. The eutectic coordinates are 180°С, 90 mol % SnF₂.     

Thermodynamic Study of the 2PbTe–AgSbTe<Subscript>2</Subscript> System Using EMF Technique with the Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript> Solid Electrolyte

The work presents the results of studies of the 2PbTe–AgSbTe₂ system using the EMF technique with the Ag₄RbI₅ solid electrolyte in the temperature range of 300–430 K. Formation of a wide (0–80 mol % AgSbTe₂) region of PbTe-based solid solutions in the system is shown. Partial thermodynamic functions \(\left( {\overline {\Delta G} ,\overline {\Delta H} ,\overline {\Delta S} } \right)\) of alloyed silver are calculated on the basis of the equations of the temperature dependences of EMF. Potential-forming reactions are determined on the basis of the data on solid-phase equilibriums in the Ag₂Te–PbTe–Sb₂Te₃–Te system that are used to calculate standard thermodynamic functions of formation and standard entropies of (2PbTe) _x (AgSbTe₂)_1–x (x = 0.2; 0.4; 0.6; 08; 0.9) solid solutions.     

The effect of synthesis conditions on the structure of compounds formed in the Dy<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> system

Crystallization and phase transition processes taking place in the Dy₂O₃–TiO₂ system during the isothermal annealing of the precursors synthesized by co-precipitation were studied. The phase composition of the obtained powders is determined by not only the chemical composition of the precursor (Dy₂O₃: TiO₂ ratio) and annealing temperature but also by the procedure of precursor synthesis determining the uniformity of Dy and Ti distribution in the precursor precipitate. Higher homogeneity of precursor particles provides the formation of almost single-phase nanocrystaline dysprosium titanate (Dy₂TiO₅, Dy₂Ti₂O₇) powders at annealing temperatures of 800–1000°C.