Über die quasi-binären Systeme NaNO2/Na2O und NaCN/Na2O. Phasendiagramme und Natrium-Ionenleitung in Na3O(NO2) und Na3O(CN)

On the Quasi-Binary Systems NaNO₂/Na₂O and NaCN/Na₂O. Phase Diagrams and Sodium Ion Conductivity of Na₃O(NO₂) and Na₃O(CN) Measurements of the electrical conductivities of Na₃O(NO₂) and Na₃O(CN) show sharp increases in conductivity at temperatures between 200° and 250°C, According to the phase diagrams of the quasi-binary systems NaNO₂/Na₂O and NaCN/Na₂O this is not an effect established by fusion. It seems to be a consequence of a “melting” of the sodium sublattice or the rotational disorder of complex anions.     

Die Verbindung Natriumphenolat · 2 Phenol im binären System ihrer Komponenten

The Compound Sodium Phenoxide · 2 Phenol in the System of its Components In the whole system of sodiumphenoxide/phenol the substance sodium phenoxide · 2 phenol is found to be the only compound between the two components. Single crystalls could be obtained by using the growing method according to Bridgman-Stockbarger. The crystal structure of PhONa · 2PhOH contains two different chains. In both of them sodium is coordinated in form of a distorted tetrahedron; in the first one by 4 oxygen, in the second one by 3 oxygen atoms and a phenoxid molecule, which is linked to sodium via its π-electrons. In the result of this realizations conclusions concerning the Kolbe-Schmitt-Synthesis are possible.     

Phasenbeziehungen im System LiGa?Sn und die Kristallstrukturen der intermediären Phasen LiGaSn und Li2Ga2Sn

Phase Relations in the System LiGa? Sn and the Crystal Structures of the Intermediate Compounds LiGaSn and Li₂Ga₂Sn The quasibinary system LiGa? Sn contains the intermediate ternary phases Li₇Ga₇Sn₃, Li₂Ga₂Sn, Li₅Ga₅Sn₃, Li₃Ga₃Sn₂ and LiGaSn. Single crystals of LiGaSn (a = 632.9(4) pm, Fd3m, Z = 4), Li₃Ga₃Sn₂ (a = 445.4(3), c = 1 090.0(2) pm, hP*), Li₅Ga₅Sn₃ (a = 447.0(4), c = 4 220.0(9) pm, hP*) and Li₂Ga₂Sn (a = 441.1(2), c = 2 164.5(7) pm, P6₃/mmc, Z = 4) have been grown from the melt. The crystal structures of LiGaSn and Li₂Ga₂Sn have been determined by single crystal X-ray methods (R = 0.029 bzw. 0.107 respectively). The crystal structure of LiGaSn contains a sphalerite-type Ga/Sn-arrangement, the Ga/Sn-arrangement of Li₂Ga₂Sn corresponds to a stacking variant of the wurtzite- and sphalerite-type. The compounds can be classified in terms of the Zintl concept.     

Na10Zn4O9 – ein neues Oxozinkat mit trigonal-planar koordiniertem Zink

Na₁₀Zn₄O₉, a Novel Oxozincate with Trigonal Planar Coordinated Zinc Using a new preparation method for sodium oxometallates we have succeeded in the synthesis of the new ternary oxide Na₁₀Zn₄O₉. Active ZnO reacted with Na₂O generated in situ from NaN₃ and NaNO₂. The compound consists of ZnO₄ tetrahedra which are connected via edges and corners to form layers of the composition ZnO₂. Furthermore, the structure was found to contain isolated, trigonal planar ZnO₃ units. 21 of 60 Na⁺ ions within the unit cell are disordered. Na₁₀Zn₄O₉ crystallizes in the space group R3 m (Nr. 166). The lattice constants are: a = 10.815(3), c = 17.930(7) Å; Z = 6; 8056 reflections; R = 0.062. The sodium ion conductivity at 400°C is 6 × 10^?3 Ω^?1 cm^?1.     

Zur Synthese und Kristallstruktur der ternären Carbide Na2PdC2 und Na2PtC2

Syntheses and Crystal Structures of Ternary Carbides Na₂PdC₂ and Na₂PtC₂ Na₂PdC₂ and Na₂PtC₂ were synthesized by the reaction of sodium carbide with palladium and platinum respectively. The crystal structures could be solved from X-ray powder diffraction data (space group: P3 m1, Z = 1). Both compounds crystallize in a new structure type with [M(C₂)_2/2^2?] chains (M?Pd, Pt) as the characteristic structural unit. The existence of a C? C triple bond was confirmed by Raman spectroscopy.     

Zur Kenntnis des quasi-binären Systems InBr—SnBr2

On the Quasi-binary System InBr—SnBr₂ The phase diagram of the quasi-binary system InBr—SnBr₂ is derived from DTA and X-ray investigations. A 1:2, 1:1 and a 3:1 compound are found. InSn₂Br₅ crystallizes tetragonal with the NH₄Pb₂Br₅-type structure. InSnBr₃ shows a new structure type. This compound is stable in a very narrow temperature range only. In₃SnBr₅ can be attributed to the low-temperature-Tl₃PbBr₅-type structure.     

Chemischer Transport und Sauerstoffionenleitfähigkeit von Mischkristallen im System In2O3/SnO2

Chemical Transport of Solid Solutions. 8. Transport Phenomena and Ionic Conductivity in the In₂O₃/SnO₂ System Chemical transport reactions are a suitable pathway to the preparation of In₂O₃‐rich and SnO₂‐rich mixed crystals coexisting in the In₂O₃/SnO₂ system (Cl₂ as transport agent, 1050 → 900 °C). Experiments are consistent with thermodynamic calculations. The existence of other phases in the system In₂O₃/SnO₂ could not be confirmed. The ionic conductivity of In₂O₃(SnO₂) was investigated.     

A4N2O5 (A = Na,K), neue Oxidnitrite der Alkalimetalle und eine Bemerkung zum quasi-binären System K3NO3/K3OBr

A₄N₂O₅ (A = Na, K) Novel Alkali Metal Oxide Nitrites, and a Comment on the System K₃NO₃/K₃OBr K₄N₂O₅ and Na₄N₂O₅ have been prepared for the first time: the respective alkali metal nitrites and -oxides in molar ratios 2 : 1 have been reacted in the solid state. Their crystal structure (for crystallographic data see ?Inhaltsübersicht”?) derive from the anti-K₂NiF₄ type of structure. Na₄N₂O₅ undergoes two phase transitions (at ?15°C and ?60°C) upon cooling. The behavior of solid solutions in the system K₃NO₃/K₃OBr at cooling gives support for the phase transition being driven by the OK₃-framework, where as in Na₃NO₃ order-disorder transitions of the NO₂^? group seem to induce the phase transitions.     

The Binary System BaF2/AlF3

The system BaF₂/AlF₃ is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF₅, Ba₃Al₂F₁₂, Ba₅AlF₁₉, polymorphic Ba₃AlF₉ and Ba₅AlF₁₃. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Zur thermischen Zersetzung von TeSeO4 und Te3SeO8 – Koexistenzbeziehungen im ternären System TeO2/SeO2/Bi2SeO5

Thermal Decomposition of TeSeO₄ and Te₃SeO₈ – Phase Relations in the Ternary System TeO₂/SeO₂/Bi₂SeO₅ The saturation decomposition pressure of TeSeO₄ and Te₃SeO₈ were determined in a membran zero manometer. From the equilibrium data are derived the Enthalpies of formation and the Standard Entropies: Data see Inhaltsübersicht. Thus the coexistence ranges in the ternary triangle TeO₂/SeO₂/Bi₂SeO₅ can be determined. Informations about the melting diagram obtained by thermal analysis of the condensed compositions TeO₂/SeO₂.     

Untersuchungen zum quasibinären System Bi2Se3/BiI3

Investigations on the Pseudobinary System Bi₂Se₃/BiI₃ The phase diagram of the pseudobinary system Bi₂Se₃/BiI₃ was investigated by DTA, total pressure measurements and x-ray phase analysis. Only BiSeI exist as a ternary phase in this system. The compound melts incongruently at 545 °C. Heat of formation and standard entropy were calculated from vapor pressure data.ΔH_B° (BiSeI, f, 298) = (–23.4 ± 1.9) kcal/mol S°(BiSeI, f, 298) = (38.7 ± 3.5) cal/K · mol     

Liquidus Temperatures of System Na3AlF6-K3AlF6-AlF3 for Aluminum Electrolysis at Lower Temperature

Liquidus temperatures in the molten salt system Na3AlF6-K3AlF6-AlF3 of interest for aluminum electrolysis were determined by thermal analysis method. The results were presented and an empirical equation describing liquidus temperatures for primary crystallization was derived t=1003.5–0.081×A2.3159–5.87×B0.657–0.024×A2.22×B1.14+ 0.035×A2.17×B1.084, where t is the liquidus temperature in degree Celsius, A denotes the mass fraction of AlF3 in system Na3AlF6-K3AlF6- AlF3, and B denotes K3AlF6/(Na3AlF6+K3AlF6 ) in mass(%, the value was defined as KR in this paper). The composition limitations are 0相似文献   

Phase Analysis of the Binary System of Cryolite (Na3AlF6) and Sodium Metasilicate (Na2SiO3)

The phase analysis of cryolite (Na₃AlF₆) and sodium metasilicate (Na₂SiO₃) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na₂SiO₃ between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na₂SiO₃ reacts with Na₃AlF₆ due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds.     

Refinement of Phase Formation in the Na2MoO4-Hf(MoO4)2 System. Crystal Structure of the New Binary Molybdate Na8Hf(MoO4)6

Phase equilibria in the subsolidus region of the Na₂MoO₄-Hf(MoO₄)₂ system have been investigated. The existence of Na₂Hf(MoO₄)₃ was confirmed, and a new binary molybdate, Na₈Hf(MoO₄)₆, has been found, whose crystal structure with dimensions a = 20.661(3) Å, b = 9.816(1) Å, c = 13.796(3) Å, β = 113.47(1)°, Z = 4, space group C2/_c, _R = 0.023 is similar to that of K₈Hf(MoO₄)₆. In the structure, each HfO₆ octahedron is linked (through common vertices) to six MoO₄ tetrahedra, forming [Hf(MoO₄)₆]⁸⁻ cluster groups. Between the groups are Na⁺ ions having considerably distorted tetragonal pyramidal or octahedral oxygen surroundings; c.n. of sodium here is 5 or 6 versus c.n. = 7–9 of potassium in K₈Hf(MoO₄)₆. The open irregular environment of sodium and the continuous three-dimensional openwork of oxygen polyhedra around sodium suggest that Na₈Hf(MoO₄)₆ or its analogs may be good ion conductors.Original Russian Text Copyright © 2004 by S. F. Solodovnikov, B. G. Bazarov, L. V. Balsanova, Z. A. Solodovnikova, and Zh. G. Bazarova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1044–1048, November–December, 2004.     

273 K下Na2CO3-Na2SO4-Na2B4O7-H2O四元体系介稳相平衡的实验研究

采用等温蒸发法研究了四元体系Na2CO3-Na2SO4-Na2B4O7-H2O在273 K时的介稳相平衡及平衡液相的密度. 利用溶解度数据绘制了该四元体系273 K下的相图. 研究结果表明, 该四元体系有异成分复盐2Na2SO4·Na2CO3形成. 相图中有2个共饱点、5条单变量曲线和4个结晶相区. 4个结晶相区分别为盐Na2CO3·10H2O, Na2SO4·10H2O, Na2B4O7·10H2O和2Na2SO4·Na2CO3的结晶区. 复盐2Na2SO4·Na2CO3同时存在于包含Na2CO3-Na2SO4-H2O三元体系的其它四元体系或高元体系中. 在273 K介稳平衡相图中, 碳酸钠以Na2CO3·10H2O形式析出; 硫酸钠以Na2SO4·10H2O的形式析出; 硼酸钠的完整分子式为Na2B4O5(OH)4·8H2O. Na2CO3对Na2B4O7有盐析作用.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Zur Kenntnis von Na4Br(NH2)3: Ein Amidbromid im System NaNH2/NaBr

Na₄Br(NH₂)₃: An Amide Bromide in the System NaNH₂/NaBr The pseudobinary system NaNH₂/NaBr was investigated by X-ray methods. The crystal structure of Na₄Br(NH₂)₃ was solved by single crystal data: Pnnm, Z = 4, a = 6.579(2) Å, b = 12.755(4) Å, c = 8.776(2) Å Z(F_o) with (F_o)² ≥ 3σ = (F_o)² = 503, Z(parameter) = 39, R/R_w = 0.082/0.106. It is a new type of structure, built up by a three-dimensional network of [Na₄(NH₂)₃⁺] containing the bromide ions.     

Na5Br(OH)4: Darstellung und Kristallstruktur einer Verbindung im System NaOH/NaBr

Na₅Br(OH)₄: Synthesis and Structure of a Compound in the System NaOH/NaBr The pseudobinary system NaOH/NaBr is investigated by X-ray methods. The structure of the compound Na₅Br(OH)₄ was solved by single crystal data: Na₅Br(OH)₄: Pnma, Z = 8, a = 11.846(2) Å, b = 18.782(4) Å, c = 6.431(1) Å, Z(F_o) = 1 202 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 100, R/R_w = 0.030/0.035 The compound crystallizes in a new type of structure. Pairs of octahedra around O by 5 Na and 1 H to [Na₅(OH)]₂ are orientated in such a way to one another that two ions OH^? form a parallelogram hinting to unusual bent hydrogen bridge bonding.     

Na4AuTl,die erste ternäre Verbindung im System Natrium/Gold/Thallium

Na₄AuTl, the First Ternary Compound in the System Sodium/Gold/Thallium Silver coloured, brittle single crystals of Na₄AuTl were obtained by the reaction of NaN₃, gold sponge and TlN₃ at 773 K. The structure was determined from X-ray single-crystal diffractometry data: Na₄AuTl crystallizes in a new structure type with separated gold and thallium partial structures. These consist of linear [Au_2/2] chains and [Tl₂] dumb-bells. Structural relationships between Na₂Au and the Na Au partial structure of Na₄AuTl are discussed.