Component interactions in the Cs2CdBr4-Cs2ZnBr4-CsBr ternary system

Component interactions in the Cs₂CdBr₄-Cs₂ZnBr₄-CsBr ternary system have been studied by differential thermal analysis and X-ray powder diffraction. The liquidus surface is comprised of three crystallization fields: CsBr, a solid solution of Cs₂CdBr₄ with Cs₂ZnBr₄ (??), and a Cs₃ZnBr₅-based solid solution (??). The ternary eutectic coordinates are as follows: ??53.5 mol % Cs₂CdBr₄, 1.5 mol % Cs₂ZnBr₄, 45 mol % CsBr, and ??450°C. A Cs₂CdBr₄-Cs₃ZnBr₅ triangulating section, which is characterized by peritectic interaction with peritectic (p) coordinates of 20 mol % Cs₃ZnBr₅ and 480°C, divides the Cs₂CdBr₄-Cs₂ZnBr₄-CsBr ternary system into two ternary systems: Cs₂CdBr₄-CsBr-Cs₃ZnBr₅ and Cs₂CdBr₄-Cs₃ZnBr₅-Cs₂ZnBr₄.     

Interaction of components in the Cs2HgBr4-Cs2ZnBr4-CsBr ternary system

The interaction of components in the Cs₂HgBr₄-Cs₂ZnBr₄-CsBr ternary system was studied by differential thermal and X-ray powder diffraction analyses. The liquidus surface consists of the crystallization fields of three phases: CsBr, a solid solution of Cs₂HgBr₄ with Cs₂ZnBr₄ (??), and solid solution ?? based on Cs₃ZnBr₅. The ternary eutectic near Cs₂HgBr₄ has the coordinates ??83 mol % Cs₂HgBr₄, 2 mol % Cs₂ZnBr₄, and 15 mol % CsBr and the melting point ??415°C. The triangulating section Cs₂HgBr₄-Cs₃ZnBr₅ is characterized by the eutectic interaction with the eutectic that is degenerate near Cs₂HgBr₄, contains ??3 mol % Cs₃ZnBr₅, and melts at 420°C. This section divides the Cs₂HgBr₄-Cs₂ZnBr₄-CsBr ternary system into two ternary systems Cs₂HgBr₄-CsBr-Cs₃ZnBr₅ and Cs₂HgBr₄-Cs₃ZnBr₅-Cs₂ZnBr₄.     

Interaction of components in the HgBr2-CdBr2-PbBr2 ternary system

The interaction in the HgBr₂-CdBr₂-PbBr₂ ternary system was studied by differential thermal analysis; the isoconcentration section of the system at 50 mol % CdBr₂ was investigated. Based on the results of the study, a projection of the liquidus surface of the HgBr₂-CdBr₂-PbBr₂ ternary system to the composition triangle was constructed; the boundaries of the primary crystallization fields were determined for three phases: HgBr₂ (degenerate field), solid solution α based on CdBr₂, and solid solution β based on PbBr₂; and isotherms were drawn. A ternary eutectic has the composition 93 mol % HgBr₂-1 mol % CdBr₂-6 mol % PbBr₂ and melts at 235°C.     

CsBr—Cs<Subscript>2</Subscript>ZnBr<Subscript>4</Subscript>—Cs<Subscript>2</Subscript>CdBr<Subscript>4</Subscript>—Cs<Subscript>2</Subscript>HgBr<Subscript>4</Subscript> Four-component system

Component interactions in the CsBr—Cs₂ZnBr₄—Cs₂CdBr₄—Cs₂HgBr₄ system were studied using differential thermal analysis (DTA) and powder X-ra y diffraction. The system is characterized by a continuous solid solution series. New compounds have not been found.     

Interaction in the ternary system HgBr<Subscript>2</Subscript>-PbBr<Subscript>2</Subscript>-CsBr

Several vertical sections are investigated in the HgBr₂-PbBr₂-CsBr system by the methods of physicochemical analysis. Six compounds, namely, CsHg₂Br₅, CsHgBr₃, Cs₂HgBr₄, CsPb₂Br₅, CsPbBr₃, and Cs₄PbBr₆, are formed in the bordering binaries of the ternary system. By the results of investigation, the projection of the liquidus surface of the HgBr₂-PbBr₂-CsBr system on the composition triangle is constructed, and the fields of primary crystallization of nine phases are plotted, namely, HgBr₂, PbBr₂, CsBr, CsHg₂Br₅, CsHgBr₃, Cs₂HgBr₄, CsPb₂Br₅, CsPbBr₃, and Cs₄PbBr₆. An immiscibility region is found in the system. This region occupies a considerable part of the primary crystallization field of PbBr₂. The coordinates of invariant points are determined, and isotherms are plotted.     

Phase relationships of the lithium halide spinels Li2MCl4-Li2MBr4 with M = Mn,Fe, Cd

The sections Li₂MCl_4?4xBr_4x of the quaternary systems LiCl-LiBr-MCl₂-MBr₂ with M = Mn, Cd, and Fe were studied by high-temperature X-ray diffraction patterns and DTA and DSC measurements. In the quasibinary lithium manganese halide system complete series of solid solutions exist between the inverse spinels Li₂MnCl₄ and Li₂MnBr₄. Li₂MnBr₄ and solid solutions with x > 0.54 undergo phase transitions to tetragonal spinels at lower temperatures. In the nonquasibinary system with M = Cd, only at temperatures near 400°C a complete series of mixed crystals is formed. At lower temperatures the system is mainly two-phase with rock salt-type Li_1?yCd_0.5yCl_1?xBr_x and cadmium chloride-type Cd_1?yLi_2yCl_2?2xBr_2x solid solutions in equilibrium. The lithium iron halide system is similar to that of cadmium, but spinel-type Li₂FeBr₄ does not exist at any temperature. The manganese and cadmium halide spinels and spinel solid solutions undergo phase transitions to NaCl defect structures at elevated temperatures.     

Glass formation along the CsHgBr3-CsPbBr3, Cs2HgBr4-CsPbBr3, and CsHg2Br5-CsPbBr3 sections of the HgBr2-PbBr2-CsBr ternary system

Glass formation is studied along the CsHgBr₃-CsPbBr₃, Cs₂HgBr₄-CsPbBr₃, and CsHg₂Br₅-CsPbBr₃ sections of the HgBr₂-PbBr₂-CsBr ternary system. The glass formation region is demarcated. Characteristic temperatures are determined by differential thermal analysis; the ratio T _g/T _m and the Hruby factor H _R for glassy samples are determined. The data are analyzed, and the most promising glass compositions along the specified sections are determined.     

Study on the equilibria in the ZnBr2(CdBr2)?H2O?C2H5OH Systems at 25°C

The solubility isotherms of the three-component systems: ZnBr₂? H₂O? C₂H₅OH and CdBr₂? H₂O? C₂H₅OH at 25°C have been studied. Crystallization fields of the equilibrium coexistence of the salts ZnBr₂ · 2H₂O, ZnBr₂, CdBr₂ · 4H₂O, CdBr₂ and CdBr₂ · 1.5 C₂H₅OH in water-ethanol solvent have been found. The dehydration processes of crystalline hydrates and the probable solvation of Zn²⁺ and Cd²⁺ ions in the saturated solutions have been discussed.     

Li+ ion conductivity in the system Li4SiO4Li3VO4

Two ranges of solid solutions were prepared in the system Li₄SiO₄Li₃VO₄: Li_4?xSi_1?xV_xO₄, 0 < x ? 0.37 with the Li₄SiO₄ structure and Li_3+yV_1?ySi_yO₄, 0.18 ? y ? 0.53 with a γ structure. The conductivity of both solid solutions is much higher than that of the end members and passes through a maximum at ～40Li₄SiO₄ · 60Li₃VO₄ with values of ～1 × 10^?5 ohm^?1 cm^?1 at 20°C, rising to ～4 × 10^?2 ohm^?1 cm^?1 at 300°C. These conductivities are several times higher than in the corresponding Li₄SiO₄Li₃(P,As)O₄ systems, especially at room temperature. The solid solutions are easy to prepare, are stable in air, and maintain their conductivity with time. The mechanism of conduction is discussed in terms of the random-walk equation for conductivity and the significance of the term c(1 ? c) in the preexponential factor is assessed. Data for the three systems Li₄SiO₄Li₃YO₄ (Y = P, As. V) are compared.     

Phasendiagramm des quasibinären Systems NiCr2S4–NiGa2S4, Kristallstruktur des NiGa2S4

Phase Relationship of the Quasibinary System NiCr₂S₄? ;NiGa₂S₄, Crystal Structure of NiGa₂S₄ The quaternary system NiCr_2–2xGa_2xS₄ was studied with the help of X-ray powder Guinier photographs of quenched samples. The crystal structure of ternary NiGa₂S₄, not found formerly, was determined using single crystal data. The structure (trigonal space group P3 m1, Z = 1, a = 362.49(2), c = 1199.56(5) pm) consists of hexagonal close-packed sulfur with Ni and Ga in one fourth of the octahedral and tetrahedral holes, respectively (FeGa₂S₄ type). The S? ;S distance of the S? ;Ni? ;S layered units is unusually small, vic. 321.1 pm. The infrared spectrum of NiGa₂S₄ and a group theoretical treatment of the FeGa₂S₄ type lattice modes are given. Up to 20 mol % Ga of the layered NiGa₂S₄ can be substituted by Cr whereby Ni is possibly transfered from octahedral to tetrahedral sites. The phase width of monoclinic Cr₃S₄ type NiCr₂S₄ is very small possibly due to the metal-metal interaction in this NiAs defect structure. In the range 0.18 ? x ? 0.35 quaternary spinel type mixed crystals are formed.     

NaCl-NaBO2-Na2CO3-NaMoO4 quaternary system

The NaCl-NaBO₂-Na₂CO₃-Na₂MoO₄ quaternary system was studied by a calculation-experimental method and differential thermal analysis. The coordinates of one ternary eutectic and two quaternary eutectics were determined: E ₇: 572°C, 29 mol % NaCl, 10 mol % NaBO₂, 32 mol % Na₂CO₃, and 29 mol % Na₂MoO₄; ɛ₁: 562°C, 36 mol % NaCl, 10 mol % NaBO₂, 30.5 mol % Na₂CO₃, and 23.5 mol % Na₂MoO₄; and ɛ₂: 536°C, 17 mol % NaCl, 10 mol % NaBO₂, 27 mol % Na₂CO₃, and 46 mol % Na₂MoO₄.     

Korrektur zur Kristallstruktur von „Cs4PbO3”︁ und die Strukturverwandtschaft zwischen den Modifikationen von Cs4PbO4

Correction of the Crystal Structure of “Cs₄PbO₃” and the Structural Relationship between the Modifications of Cs₄PbO₄ The compound that has been described as Cs₄PbO₃ really is Cs₄PbO₄. It does not crystallize in the space group P2₁, as assumed, but in P2₁/c. The observed fictitiuous violation of the extinction law for the c glide plane is due to twinning. The structure was refined using the original data as well as new data from an untwinned crystal. The denomination β-Cs₄PbO₄ is used to distinguish this structure from another known modification (α-Cs₄PbO₄). Both structures, α-Cs₄PbO₄ and β-Cs₄PbO₄, can be derived from the sphere packing of γ-plutonium when certain voids in its packing are occupied with oxygen atoms.     

Electric conductivity of solid solutions in Cs2 ? 2x Fe2 ? x A x O4 systems (A = P, V)

Solid solutions based on CsFeO₂ in Cs_{2 ? 2x} Fe_{2 ? x} A _x O₄ systems (A = P, V) were synthesized. Their crystal structure and the temperature and concentration dependences of the total conductivity and its electronic component were studied. The ranges of temperature and composition in which cesium-cation conductivity was dominant were determined. The obtained data were compared with the results of studies of other cesium-conducting solid electrolytes.     

A new semiconducting quaternary mixed halogenide: pentathallium dimercury pentabromide tetraiodide,Tl5Hg2Br5I4

A novel quaternary mixed halogenide, Tl₅Hg₂Br₅I₄, was synthesized by fusion of thallium bromide and mercury iodide in a 5:2 molar ratio. The crystal structure of Tl₅Hg₂Br₅I₄ represents a new series of composite structures described by the general formula nTlBr*mTl₂[HgBr₂I₂]; in this case, n = 4 and m = 8. Electronic structure calculations indicate that the title compound is a semiconductor.     

Multicomponent systems LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript> and LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>

Phase equilibria in the LiCl–LiBr–Li₂SO₄ ternary system and the LiCl–LiBr–Li₂SO₄–Li₂MoO₄ quaternary system were studied by differential thermal analysis. The compositions and temperatures of minima in the ternary and quaternary systems were determined to be (31.2 mol % LiCl, 46.8 mol % LiBr, 22.0 mol % Li₂SO₄, 460°C) and (25.2 mol % LiCl, 30.2 mol % LiBr, 14.6 mol % Li₂SO₄, 30.0 mol % Li₂MoO₄, 411°C), respectively.     

Der erste Vertreter des K2PtCl6-Typs bei Fluoriden A2[PtF6]: β-Cs2[PtF6]

The First Fluoride A₂[PtF₆] of the K₂PtCl₆ Type: β-Cs₂[PtF₆] For the first time, yellow cubic single crystals of Cs₂[PtF₆] have been obtained by solid state reaction, heating (Pt-tube, 35 d, 800°C) the fluorination product of an intimate mixture of (NH₄)₂PtCl₆ and 2 CsCl (diluted F₂, F₂:N₂ = 1:5, 10 d, 400°C). The new form is isostructural with K₂PtCl₆: Fm3 m; a = 905.5(2) pm; Z = 4 (Guinier-de Wolff data, CuKα₁); R = 2.32% (SHELX-76); 1398 I₀(hkl), Image-Plate diffractometer data (Stoe IPDS). It is compared with already known α-Cs₂[PtF₆] (K₂GeF₆-type, P3 m1). The Madelung-Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, and Mean Fictive Ionic Radii, MEFIR, are calculated and discussed in comparison with the data of further Hexafluoroplatinates(IV). A complete analysis of MAPLE was carried out for the title compound as well as for the α- and a hypothetical α′-form.     

From simple rings to one-dimensional channels with calix[8]arenes, water clusters, and alkali metal ions

The macrocycle 4-tert-butylcalix[8]arene (L) was reacted with alkali metal carbonates (Li₂CO₃, Na₂CO₃, K₂CO₃, Rb₂CO₃, and Cs₂CO₃) at the interface of a biphasic THF/water system. Needle-like crystals with a general formula [A_x(4-tert-butylcalix[8]arene-xH)(THF)_y(H₂O)_z] (with A=Li, Na, K, Rb, Cs, x=1, 2, y=4, 5, 8, and z=6, 7) were thereby obtained. The solid state structures were investigated by X-ray diffraction of single crystals and by TGA measurements. They do not appear to be maintained in solution.     

LiCl-LiBr-LiVO3-Li2MoO4 quaternary system

The phase equilibrium in the LiCl-LiBr-LiVO₃-Li₂MoO₄ quaternary system was studied by differential thermal analysis. The composition corresponding to the minimum in the curve of monovariant equilibria of the quaternary system was determined to be 10.6 mol % LiCl, 38.0 mol % LiBr, 30.3 mol % LiVO₃, and 21.1 mol % Li₂MoO₄, with the melting point at 389°C.     

Mo¨ssbauer studies of thiospinels. IV. The system FeCr2S4-Fe3S4

Spinel compounds of the composition Fe_1+xCr_2?xS₄, with 0 ≦ x ≦ 0.5, have been prepared in polycrystalline form. The ionic distribution Fe²⁺[Cr³⁺_2?xFe³⁺_x]S^2?₄ is derived from both X-ray and ⁵⁷Fe Mo¨ssbauer data. Room temperature Mo¨ssbauer spectra show the typical behavior of tetrahedral-site Fe²⁺ surrounded by different octahedral-site neighbors. Octahedral-site Fe³⁺ absorbs as a doublet with Δ ≈ 0.5 mm/s. Samples of overall composition FeCr₂S₄ consist mainly of a spinel Fe²⁺[Cr³⁺_2?yFe³⁺_y]S^2?₄, y ≈ 0.02.     

Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 44. Tricäsiumheptaphosphid Cs3P7: Darstellung,Struktur und Eigenschaften

Chemistry and Structural Chemistry of Phosphides and Ployphosphides. 44. Tricesium Heptaphosphide Cs₃P₇: Preparation, Structure, and Properties Tricesium heptaphosphide is prepared from the elements by a quantitative reaction at 1200 K in Nb ampoules. Slow cooling yield the bright yellow α-Cs₃P₇, quenching the yellow orange coloured β-Cs₃P₇. The crystalline α-Cs₃P₇ transforms at 552 K in a first order phase transition to the plastically crystalline β-Cs₃P₇. Both modifications are sensitive against moisture and oxygen and are completely soluble in ethylendiamine yielding a pale yellow solution. At room temperature the ³¹P nmr spectra of such solutions show only one singulett, which corresponds to the valence tautomerism of the P₇^3? anion. α-Cs₃P₇ crystallizes in a new structure type (P4₁, a = 904.6(1) pm; c = 1671.4(4) pm; Z = 4). The structure is formed by heptaphospha-nortricyclene anions P₇^3? and Cs⁺ cations. The cs atoms connect the anions forming a three-dimensional arrangement (d?(Cs? P) = 374 pm), not allowing the fragmentation into discrete Cs₃P₇ units. The P? P distances differ by their function in the nortricyclene anion. Each P₇ group is surrounded by 12 Cs atms. β-Cs₃P₇ crystallizes in the Li₃Bi type of structure (Fm3 M; a(573 K) = 1130.5(1)pm; Z = 4). The P atoms of the P₇^3? anions surround the Bi positions with an orienational disorder. The orientation has been investigated with a mixed crystal Ca₃(P₇)_2/3(P₁₁)_1/2 (Fm3 m; a (298 K) = 1149.5(9) pm; Z = 4).