Specific features of the thermodynamics of activation in the LaNi<Subscript>5</Subscript>-H<Subscript>2</Subscript> and CeNi<Subscript>5</Subscript>-H<Subscript>2</Subscript> systems

Using heat conducting Tian—Calvet calorimetry and volumetric measurements, the first hydrogen absorption—desorption cycles in the LaNi₅-H₂ and CeNi₅-H₂ systems were studied. The pressure—composition isotherms were plotted, the equilibrium pressures of hydrogen along the absorption and desorption branches and in the region of hysteresis for different activation steps were determined, and the enthalpies of phase transitions α → β and β → α were calculated. The profiles of the heat evolution curves were analyzed. It was concluded that the mechanism of the reactions studied changes upon activation.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 134–139, January, 2005.     

Complexation processes in KF-SbF<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system studied by calorimetric titration

Complexation in a KF-SbF₃-H₂O system is studied in a range of molar ratios of fluorides KF : SbF₃= (0.1–2) : 1 by calorimetric titration. The equilibrium formation constants of complexes KSb₂F₇, KSbF₄, and K₂SbF₅ (5.8×10⁵±800, 3.3×10⁴±500, and 1.9×10⁶± 950, respectively) and the changes in enthalpy (–31.75± 0.74, –28.15±0.44, and –25.5±0.64 J mol^–1, respectively) and entropy (4±7, –8±5, and –35±9 J mol^–1 K^–1, respectively) are determined. The thermodynamic stability of the antimony(III) fluoride complexes is found to increase on going from KSb₂F₇ to K₂SbF₅.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 168–171.Original Russian Text Copyright © 2005 by Kovaleva, Zemnukhova, Lebedeva, Fedorishcheva.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Interaction of Cl<Subscript>2</Subscript> and SO<Subscript>2</Subscript> with Finely Divided In<Subscript>2</Subscript>O<Subscript>3</Subscript>

The effect of O₂, Cl₂, and SO₂ on electrophysical and sorption properties of powdered In₂O₃ with a large specific area is studied at 23–200°C. The specimen is most sensitive to Cl₂ and SO₂ at near-room temperatures.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 529–536.Original Russian Text Copyright © 2005 by Vinokurova, Derlyukova.     

Ionic conduction of a high-temperature modification of Lu<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>

A nanoceramic product of the composition Lu₂Ti₂O₇ is synthesized by a coprecipitation method with a subsequent sublimation drying and an annealing at 650–1650°C. The conduction of Lu₂Ti₂O₇ synthesized at 1650°C is ionic (10^–3 S cm^–1 at 800°C). Thus, a new material with a high ionic conduction has been discovered. The ordering in Lu₂Ti₂O₇ is studied by methods of RFA, RSA, IK spectroscopy, electron microscopy, and impedance spectroscopy. The existence of a low-temperature phase transition fluorite-pyrochlore at 800°C and a high-temperature conversion order-disorder at 1650°C are established.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 298–303.Original Russian Text Copyright © 2005 by Shlyakhtina, Ukshe, Shcherbakova.     

Temperature dependence of the polarization resistance of the O<Subscript>2</Subscript>,Au/La<Subscript>0.88</Subscript>Sr<Subscript>0.12</Subscript>Ga<Subscript>0.82</Subscript>Mg<Subscript>0.18</Subscript>O<Subscript>2.85</Subscript> electrode system

The impedance of a porous gold electrode in contact with solid electrolyte La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 and the effect of the manufacture conditions on its polarization resistance are studied at 600–800°C in air. The overall oxygen reaction rate on a gold electrode is described as the sum of two partial constituents, namely, the oxygen exchange at the gas/electrolyte interface at the gold/gas/electrolyte triple-phased boundary.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 190–197.Original Russian Text Copyright © 2005 by Shkerin, Sokolova, Khlupin, Beresnev.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Behavior of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> System at High Temperatures

The system Al₂O₃-ZrO₂ at temperatures of up to 2100°C was studied by differential thermal analysis.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 353–356.Original Russian Text Copyright © 2005 by Kamaev, Archugov, Mikhailov.     

Synthesis of hydroxyapatite by hydrolysis of α-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Conditions for hydroxyapatite (HAP) synthesis in aqueous solutions by hydrolysis of α-Ca₃(PO₄)₂ were studied. Temperature exerts a substantial effect on the rate of α-Ca₃(PO₄)₂ hydrolysis and also changes the morphology of the reaction products. At 40 °C, the plate-like intersecting (perpendicular to the surface of the initial particles) crystals of HAP grow. Their maximum size after the 24-h hydrolysis is 1–2 µm. Needle like HAP crystals are formed upon boiling of the suspension. The morphology observed for the HAP particles agrees well with the conclusions obtained by analysis of the kinetics of tricalcium phosphate hydrolysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 78–85, January, 2005.     

ESR Study of the Formation of O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> Radical Anions on Oxidized CeO<Subscript>2</Subscript> and CeO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript> Adsorbing a CO + O<Subscript>2</Subscript> Mixture

It is demonstrated by ESR measurements that O ₂ ⁻ (CO + O₂) radical anions result from CO + O₂ adsorption on the oxidized surface of CeO₂. These radical anions are stabilized in the coordination sphere of Ce⁴⁺ cations located in isolated and associated anionic vacancies. This reaction shows an activation behavior determined by CO adsorption. The variation of O ₂ ⁻ (CO + O₂) concentration with CO adsorption temperature suggests that surface carbonates and carboxylates participate in this reaction. In the (0.5– 10.0)%CeO₂/ZrO₂ system, O ₂ ⁻ forms on supported CeO₂ and is stabilized on Ce⁴⁺ and Zr⁴⁺ cations. The stability of O ₂ ⁻ -Ce⁴⁺ complexes is lower on supported CeO₂ than on unsupported CeO₂, indicating a strong interaction between the cerium cations and the support.__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 423–429.Original Russian Text Copyright © 2005 by Il’ichev, Kuli-zade, Korchak.     

Polythermic Section B<Subscript>4</Subscript>C-LaB<Subscript>6</Subscript> in the Ternary System La-B-C

The interaction was studied and the polythermic section B₄C-LaB₆ was constructed for the ternary system La-B-C described by a eutectic phase diagram.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 338–340.Original Russian Text Copyright © 2005 by Ordan’yan, Yurchenko, Vikhman.     

Thermal Decomposition of Ti<Subscript>5</Subscript>(Se,Te)<Subscript>8</Subscript> in Argon and Nitrogen Atmospheres

Chalcogenides TiSe_1.60−x Te_x (0 ≤ x ≤ 1.60), forming a continuous series of hexagonal solid solutions, were prepared by the direct ampule procedure. The thermal decomposition of TiSe_1.60−x Te_x was studied for the samples with x = 0, 0.16, 0.80, 1.44, and 1.60 in Ar and N₂ atmospheres in the course of heating from 25 to 1000°C. The selenide undergoes no weight loss under Ar, in contrast to the telluride which disproportionates and loses weight owing to the formation of volatile TiTe₂. At high temperatures, tellurides are more sensitive than selenides to the presence of nitrogen: The disproportionation is accompanied by the reaction of TiTe₂ with N₂, yielding low-volatile titanium nitride and free tellurium. Titanium selenide and telluride as components of the solid solutions behave similarly to the corresponding individual chalcogenides.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1063–1067.Original Russian Text Copyright © 2005 by Pankratova, Zvinchuk, Suvorov, Hatanpaa, Kozlov, Leskela.     

Microstructure and Conduction of Composites Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> Near the Eutectic Melting Point

Microstructure and conduction of ceramic composites Bi₂CuO₄ + xBi₂O₃ (x = 5, 10, 15, 20 wt %) near the eutectic melting point (770°C) are studied. Bismuth oxide, initially randomly distributed over the ceramics bulk, after quenching from temperatures exceeding the eutectic melting point, becomes localized at triple junctions and grain boundaries in Bi₂CuO₄, which is caused by wetting grain boundaries and forming a liquid-channel structure. The jumpwise change in the composites’ conductivity near 730 and 770°C caused by polymorphic transformation of Bi₂O₃ and the eutectic melting with simultaneous formation of a liquid-channel structure. Transport numbers of the oxygen ion are measured at 770°C by coulomb-volumetric method. The conduction by oxygen ions increases in the composites with decreasing average size of Bi₂CuO₄ crystallites.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 596–601.Original Russian Text Copyright © 2005 by Lyskov, Metlin, Belousov, Tret’yakov.     

The Emission Characteristics of Laser Plume from the PbGa<Subscript>2</Subscript>S<Subscript>4</Subscript> Crystal Surface

Averaged spectra and oscilloscope traces of emission of laser plasma in vacuum produced by the impact of neodymium laser radiation (τ = 20 ns, λ = 1.06 µm, f = 12 Hz, W =10⁸–10⁹ W/cm²) on Pb, Ga, and polycrystalline PbGa₂S₄ targets were studied. From spectroscopic diagnostic data, the electron temperature, the recombination time of singly charged ions, and the number density of electrons in the laser plume of lead gallium sulfide were determined. An analysis of the results is given.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 5, 2005, pp. 396–400.Original Russian Text Copyright © 2005 by Shuaibov, Chuchman.     

Crystal Structure of Sodium Perchloratotriacetatoneptunate(V) Monohydrate Na<Subscript>3</Subscript>NpO<Subscript>2</Subscript>(OOCCH<Subscript>3</Subscript>)<Subscript>3</Subscript>ClO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The crystal structure of Na₃NpO₂(OOCCH₃)₃ClO₄ · H₂O was studied by single-crystal X-ray diffraction method. The structure is composed of the complex anions NpO₂(OOCCH₃)₃]²⁻, perchlorate anions, Na cations, and water molecules. The oxygen environment of Np(V) is a hexagonal bipyramid whose equatorial plane is formed by the oxygen atoms of three acetate ions. In addition to the acetate anions, the structure contains the perchlorate ion whose oxygen atoms, except for one, are included in the coordination environment of Na⁺ cations.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 8, 2005, pp. 636–640.Original Russian Text Copyright © 2005 by Charushnikova, Fedoseev, Starikova.     

Conduction and Ion Transport in LaYO<Subscript>3</Subscript> Doped with CaO

Values of partial conductions (ionic: protonic, oxygen, hole) and their activation energies in LaYO₃ are determined at 700–1050°C, pO₂ ranging from air to 10⁻¹⁵ Pa, and pH₂O = 0.04–13.5 kPa for different versions of doping with calcium (when introduced into the lanthanum or yttrium sublattices, or into both sublattices simultaneously). The conductivity increases in the series La_0.97Ca_0.03YO_{3 − α} < LaY_0.97Ca_0.03O_{3 − α} < La_0.985Y_0.985Ca_0.03O_{3 − α}, which means that the stoichiometric composition with a 1 : 1 ratio between Y and La has the highest conductivity.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 610–615.Original Russian Text Copyright © 2005 by Balakireva, Stroeva, Gorelov.     

Energetic aspects in description of metal—hydrogen—boron bonds in (B<Subscript>10</Subscript>H<Subscript>14</Subscript>)<Subscript>2</Subscript>Pt and (B<Subscript>8</Subscript>C<Subscript>12</Subscript>H<Subscript>14</Subscript>)<Subscript>2</Subscript>Pt complexes

The energies of formation of platinum complexes with borohydrides B₁₀H₁₄ and B₁₀H ₁₄ ^2- or carboranes B₈C₂H₁₄ and B₈C₂H ₁₄ ^2- were considered in terms of the structure—thermodynamics model. The thermodynamic stability of these complexes was substantiated.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 149–152. Original Russian Text Copyright © 2005 by Ionov, Kuznetsov.     

Decomposition in Prolonged Storage of KF · H<Subscript>2</Subscript>O<Subscript>2</Subscript> Stabilized with Carboxylic Acids

Decomposition of KF · H₂O₂ stabilized with carboxylic acids (maleic, fumaric, succinic, adipic) in storage for more than three years at 20°C was studied. Rate constants of decomposition of stabilized KF · H₂O₂ were determined in different time intervals. The chemical reactions in the system KF-H₂O₂-carboxylic acid in the stage of preparation of solid KF · H₂O₂ stabilized with carboxylic acid and those during prolonged storage of the final product are discussed.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 287–291.Original Russian Text Copyright © 2005 by Titova, Nikol’skaya, Buyanov, Pudova, Karzhavina.     

Comparative Study of the Oxygen Storage Capacity of Pt/M<Subscript>x</Subscript>O<Subscript>y</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Systems

The oxygen storage capacity of 1% Pt/15% M_xO_y/Al₂O₃ systems containing a rare-earth or an alkaline-earth metal oxide or TiO₂ as the oxygen-storing component was studied. Oxygen storage capacity was evaluated as the amount of C₃H₈ reacting at 400°C with oxygen that was taken up by the catalyst during oxidative treatment. The systems containing a rare-earth metal oxide or TiO₂ possess the highest oxygen storage capacity among the catalysts examined (80 and 75 µmol C₃H₈/g Cat, respectively). Of the BaO and SrO systems, the latter is of interest, although its oxygen storage capacity (∼27 µmol C₃H₈/g Cat) is somewhat lower than the oxygen storage capacity of any rare-earth metal oxide or the TiO₂ system.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 585–589.Original Russian Text Copyright © 2005 by Sinel’nikov, Tolkachev, Stakheev.     

Enthalpy of formation of BaCe<Subscript>0.9</Subscript>In<Subscript>0.1</Subscript>O<Subscript>3−δ</Subscript>(s)

Enthalpy of formation of the perovskite-related oxide BaCe_0.9In_0.1O_2.95 has been determined at 298.15 K by solution calorimetry. Solution enthalpies of barium cerate doped with indium and mixture of BaCl₂, CeCl₃, InCl₃ in ratio 1:0.9:0.1 have been measured in 1 M HCl with 0.1 M KI. The standard formation enthalpy of BaCe_0.9In_0.1O_2.95 has been calculated as −1611.7±2.6 kJ mol⁻¹. Room-temperature stability of this compound has been assessed in terms of parent binary oxides. The formation enthalpy of barium cerate doped by indium from the mixture of binary oxides is Δ_ox H ⁰ (298.15 K)=−36.2±3.4 kJ mol⁻¹.     

On the Possibility of Using Protonic Solid Electrolyte CsHSO<Subscript>4</Subscript> in Hydrogen Fuel Cells

Electrochemical parameters of an H₂|air fuel cell with a membrane of solid electrolyte CsHSO₄ or composites (1 − x)CsHSO₄/xSiO₂ (x = 0.1–0.3) and different electrodes are measured at 175 °C. The maximal power (3.5 mW/cm² at a voltage of 0.6 V) is obtained for a cell with platinum-black electrodes and an intermediate layer of a mixture of platinum black and the electrolyte material. In the absence of a platinum catalyst, CsHSO₄ and composites CsHSO₄/SiO₂ are chemically stable in hydrogen at the operating temperature of the fuel cell.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 556–559.Original Russian Text Copyright © 2005 by Lavrova, Russkikh, Ponomareva, Uvarov.     

Interaction of solid electrolyte La<Subscript>0.88</Subscript>Sr<Subscript>0.12</Subscript>Ga<Subscript>0.82</Subscript>Mg<Subscript>0.18</Subscript>O<Subscript>2.85</Subscript> with hydrogen,water vapor,and carbon dioxide

The air,Au/La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85/Au,air cells are studied by an impedancemetry method before and after a week-long exposure at 700°C to atmospheres of hydrogen, humid air, and carbon dioxide. Blank specimens of the same electrolyte are examined by methods of x-ray diffraction, Raman scattering (RS), and x-ray photoelectron spectroscopy. The fact that the shape of the RS spectra and the shape of the electrode impedance dispersion alter unequivocally suggests that, at the very least, the electrode surface interacts with all the gases. The interaction in question is reversible in the case of hydrogen and carbon dioxide. In the case of water vapor, the interaction is irreversible.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 198–205.Original Russian Text Copyright © 2005 by Shkerin, Kovyazina, Beresnev, Kalashnikova, Martemyanova.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.