Study on the Phase equilibrium in the Systems Sodium Selenate — Cadmium Selenate — Water and Sodium Selenate — Manganese Selenate — Water at 25 °C

The phase equilibrium in the systems Na₂SeO₄ CdSeO₄ H₂O and Na₂SeO₄ MnSeO₄ H₂O were studied and it was established that new phases were obtained — double salts with a composition: Na₂Cd(SeO₄)₂ · 2 H₂O and Na₂Mn(SeO₄)₂ · 2 H₂O. The fields of phase equilibrium of the double salts in the triple systems were determined. The composition of the new phases and the number of the water molecules of crystallization were investigated, respectively by the Schreinemackers' method of physico-chemical analysis and thermogravimetrical analysis. An X-ray diffraction analysis of the new phases obtained was done.     

On the (MgxNi1–x)SeO4 · 6 H2O and (MgxCu1–x)SeO4 · 5 H2O mixed crystal formation

Mixed crystals (Mg_xNi_1–x)SeO₄ · 6 H₂O and (Mg_xCu_1–x)SeO₄ · 5 H₂O have been prepared studying the solubility in the MgSeO₄–NiSeO₄–H₂O and MgSeO₄–CuSeO₄–H_2O systems at 25 °C. It has been shown that the monoclinic structure of MgSeO₄ · 6 H₂O is unstable and undergoes a change into tetragonal structure due to the included nickel ions (about 4 at %). The lattice parameters of (Mg_{xNi 1–x})SeO₄ 6 H₂O have been calculated. It has been established that the magnesium ions incorporate isodimorphously in the crystal structure of CuSeO₄ · 5 H₂O which could be an indication of the existence of MgSeO₄ · 5 H₂O isostructural with the triclinic CuSeO₄ 5 H₂O. The distribution coefficients of the salt components between the liquid and solid phases have been calculated.     

Phase Equilibrium in the System HgSeO4 – H2SeO4 – H2O at 100°C

The solubility of the system HgSeO₄ – H₂SeO₄ – H₂O was studied at 100 °C. The fields of crystallization of HgSeO₄ H₂O and HgSeO₄ were established. The compounds obtamed were identified by means of chemical, X-ray and crystal-optical analysis. The mechanism of the thermal dissociation of the compounds obtained was studied.     

Double Salt Formation in the Cu(HCOO)2–Sr(HCOO)2–H2O System

The solubility in the Cu(HCOO)₂–Sr(HCOO)₂–H₂O system has been studied by the method of physico-chemical analysis at 25 and 50 °C. It has been established that two double salts are formed in the system: CuSr₂(HCOO)₆ · H₂O at 25 °C and CuSr(HCOO)₄ · 4 H₂O at 50 °C. The latter salt has not yet been described in the literature. It has been characterized by X-ray powder diffraction and DT and TG analysis. CuSr(HCOO)₄ · 4 H₂O crystallizes in the triclinic system with lattice parameters a = 12.376(6) Å, b = 13.394(4) Å, c = 11.508(6) Å, α = 93.38(3)°, β = 94.01(3)°, γ = 75.04(3)°. Dehydration proceeds in two stages.     

Thermal expansion,pyroelectricity and linear optical properties of Li2SeO4·H2O and Li2SO4·H2O

Large single crystals of polar Li₂SeO₄·H₂O were grown at 343 K from aqueous solution. Temperature dependent thermal expansion coefficients of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were determined within the temperature range 133 K–313 K and coefficients of the pyroelectric effect within the temperature range 183–343 K. Refractive indices between 365 nm and 1530 nm as well as unpolarized absorption spectra of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were measured and phase‐matching curves for second harmonic generation were calculated. Both compounds allow type I and type II phase‐matching at wavelengths from about 650 nm to the near infrared region. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties of non‐centrosymmetric mixed crystals K2(La1‐x Cex)(NO3)5 · 2 H2O (x = 0.0 – 1.0)

Large single crystals of optical quality of the non‐centrosymmetric orthorhombic potassium rare earth nitrate mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O were grown at 38 °C from diluted HNO₃. For crystals with x = 0.0, 0.19, 0.38 and 0.66 refractive indices and their dispersion were determined with an error less than 1 · 10^–4 in the wavelength range 0.404 – 1.083 μm by the prism method. Phase matching conditions for collinear SHG frequency conversion were analysed in detail, including calculation of the effective nonlinear optical susceptibility. By an appropriate choice of the fraction x of cerium the mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O allow an adjustment of non‐critical type I phase matching conditions to a desired wavelength of the fundamental wave within the range 1.055(4) – 1.107(6) μm. Non‐critical type II phase matching can be tuned in the wavelength range 0.949(2) – 0.931(2) μm. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation of Phase Equilibria in Systems with Double Salts

The method of expansion of the relative activity coefficients has been extended to systems with double salts formation. This use of resulting theoretical equations has been demonstrated on the systems NH₄Al(SO₄)₂ – (NH₄)₂SO₄ – H₂O and NH₄Al(SO₄)₂ – Al₂(SO₄)₃ – H₂O. The fit of the experimental data taken from the literature and of the calculated data is very good.     

Solubility phase diagrams of Me 2SO4-NiSO4-H2O systems and the growth of Me 2Ni(SO4)2 · n H2O crystals [ Me = Na, Rb, Cs; n = 4, 6]

On the basis of the physicochemical analysis of the solubility phase diagrams for the Me ₂SO₄-NiSO₄-H₂O ternary systems (Me = Na, Rb, or Cs), the optimum concentration and temperature conditions for the crystallization of the Me ₂Ni(SO₄)₂ · nH₂O solid phases were found. Techniques for growth of single crystals of these binary salts have been developed. Such techniques allow application of mother liquors containing hydrates or anhydrous sulfates of Na, Rb, Cs, and Ni as raw materials. Na₂Ni(SO₄)₂ · 4H₂O, Rb₂Ni(SO₄)₂ · 6H₂O, and Cs₂Ni(SO₄)₂ · 6H₂O single crystals (28–34) × (8–13) × (5–10) mm³ in size have been grown from aqueous solutions in the dynamic regime. Original Russian Text ? L.V. Soboleva, 2007, published in Kristallografiya, 2007, Vol. 52, No. 6, pp. 1141–1144.     

Vibrational behavior of matrix‐isolated ions in Tutton compounds IV. Infrared spectroscopic study of NH4+ and SO42‐ ions included in nickel sulfates and selenates

Infrared spectra of K₂Ni(SeO₄)₂·6H₂O and (NH₄)₂Ni(SeO₄)₂·6H₂O containing SO₄^2‐ ions and those of K₂Ni(SO₄)₂·6H₂O and K₂Ni(SeO₄)₂·6H₂O containing NH₄⁺ ions are presented and discussed in the region of ν₃ and ν₁ of the sulfate ions and in the region of ν₄ of the NH₄⁺ ions, respectively. The SO₄^2‐ ions matrix‐isolated in the selenate matrices (approximately 1 mol%) exhibit three bands for ν₃ and one band for ν₁ in agreement with the low site symmetry C₁ of the host selenate ions. The NH₄⁺ guest ions included in the potassium sulfate matrix are characterized also with three bands for ν₄. However, the ammonium ions in (NH₄)₂Ni(SeO₄)₂·6H₂O as well as those included in K₂Ni(SeO₄)₂·6H₂O display four infrared bands corresponding to ν₄ due probably to some kind of disorder of the ammonium ions. The extent of energetic distortion of the isomorphously included sulfate ions as deduced from the values of Δν₃ and Δν_max is commented. The spectroscopic experiments reveal that the SO₄^2‐ guest ions are weaker distorted in the selenate matrices as compared to the same ions in the neat sulfates due to the larger unit‐cell volumes of the selenate compounds. The band positions of the water librations in the host potassium compounds are affected by the included ammonium cations. The formation of hydrogen bonds between the NH₄⁺ guest ions and the XO₄^2‐ host ions leads to a decrease in the proton acceptor capabilities of the anions and as a result the hydrogen bonds weaken on going from the neat potassium compounds to the mixed crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Effect of Different Inorganic Salts on the Growth Rate of NaCl Crystallized from Sea Water

A comprehensive experimental study on the effect of fourteen different inorganic salts on the growth rate of NaCl single crystals is presented. The fourteen different inorganic salts are chosen as they are present in Chinese sea water. The impurity content of each salt has been varied according to its presence in the natural sea water. The impurities are differentiated in groups related to their effect on the growth rate of NaCl. The examined impurities are: MgCl₂ · 6 H₂O, KCl, SrCl₂, NaBr, Nal, NaF, Na₂SO₄, NaBO₂ · 4 H₂O, Na₂CO₃, Na₂SiO₃ · 9 H₂O, ZnSO₄, CuSO₄ · 5 H₂O, PbCl₂, and K₄Fe(CN)₆.     

The Double Salts Cd(C6H5COO)2 · CdCl2 and Cd(C6H5COO)2 · CdBr2

The systems Cd(C₆H₅COO)₂ CdCl₂ H₂O and Cd(C₆H₅COO) ₂ CdBr₂ H₂O have been studied at 25 °C. Formation of the double salts Cd(C₆H₅COO)₂ · CdCl₂ and Cd(C₆H₅COO)₂ · CdBr₂(1:1:0) has been established and their chemical individuality has been confirmed by chemical, X-ray, and DT-analyses. Proceeding from data on the structure of Cd(C₆H₅COO)₂ · 2 H₂O and the composition of the 1:1:0 double salts as well as using Pauling's rules for the most probable spacial disposition of the ions, the crystal structure type of the double salts obtained are predicted.     

Crystal chemistry of the salts Me+Cl · Me2+Cl2 · 2 H2O

The crystal chemistry of the double salts Me⁺Cl · Me²⁺Cl₂ · 2 H₂O (where (Me⁺ = K, Rb, Cs; Me²⁺ = Mn, Fe, Co, Ni) is considered. It is concluded that these salts crystallize in three types of structures, the Me⁺ ion size being decisive for the structure type. Salts containing the large Cs⁺ ions crystallize in an orthorhombic structure in which [Me²⁺ (H₂O)₂Cl₄] octahedra form chains having common Cl⁻ corners. Salts with the smaller K⁺ ions crystallize in a tricline system, the [Me²⁺ (H₂O)₂Cl₄] octahedra being connected by a common Cl–Cl edge and forming dimers. When the intermediate in size Rb⁺ ions are present in the salts, either of the above structures is possible as well as a monoclinic structure which is intermediate in symmetry. The expected isostructure of the cesium salts was checked by studing the CsCl · NiCl₂ · 2 H₂O–CsCl · MnCl₂ · 2H₂O–H₂O system. A continuous series of mixed crystals is found.     

Thermal dehydration of the double salts K2Be(XO4)2·2H2O (X = S,Se)

The thermal dehydration of the title compounds was studied by TG, DTA and DSC methods and the enthalpies of dehydration were calculated (87.6 kJ mol^–1 and 167.5 kJ mol^–1 for the sulfate and selenate compound, respectively). The larger value of ΔH_deh of K₂Be(SeO₄)₂·2H₂O is due to the stronger hydrogen bonds formed in the selenate as compared to those formed in the respective sulfate owing to the stronger proton acceptor capabilities of the SeO₄^2– ions. The enthalpies of formation (ΔH_f⁰) of the dihydrates are also calculated from the DSC measurements (– 4467.4 kJ mol^–1 and – 3447.1 kJ mol^–1 for the sulfate and selenate compound, respectively). The anhydrous double salt, K₂Be(SO₄)₂, forms tetragonal crystals with lattice parameters: a = 7.232(2) Å; c = 14.168(2) Å; V = 741.0 ų, while the anhydrous salt, K₂Be(SeO₄)₂, forms monoclinic crystals with lattice parameters: a = 9.217(3) Å; b = 10.645(3) Å; c = 8.989(2) Å; β = 108.52(4)°; V = 836.2 ų. Vibrational spectra (infrared and Raman) of both the dihydrates and the anhydrous compounds are also presented and discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron Paramagnetic Resonance of VO2+ in M2Zn(SeO4)2 · 6H2O(M=K,Rb) Single Crystals

The EPR spectrum of VO²⁺ has been studied in single crystals of K₂Zn(SeO₄)₂ · 6H₂O and Rb₂Zn(SeO₄)₂ ∼ 6H₂O at ∼9.45 GHz. VO²⁺ substitutes for Zn²⁺ have preferential orientations in the lattice. The V = O of the intense vanadyl center is nearly along the longest Zn H₂O direction. Spin-Hamiltonian parameters have been evaluated from single crystal as well as from powder spectra.     

On the Mixed Crystals Formation in the Fe(Zn) (HCOO)2–Cd(HCOO)2–H2O System

The solubility in the Fe(HCOO)₂–Cd(HCOO)₂–H₂O and Zn(HCOO)₂–Cd(HCOO)₂–H₂O systems have been studied by the method of physico-chemical analysis at 25 °C and mixed crystals of the type Fe_1-xCd_x(HCOO)₂.2 H₂O and Zn_1-xCd_x (HCOO)₂. 2 H₂O have been obtained. The lattice parameters of the mixed crystals have been calculated. It has been established that the isostructural Fe(HCOO)₂. 2 H₂O and Cd(HCOO)₂. 2 H₂O form isomorphous mixed crystals, whereas the isostructural Zn(HCOO)₂. 2 H₂O and Cd(HCOO)₂. 2 H₂O yield isodimorphous mixed crystals. The difference in the behaviour of the two pairs of formate salts has been attributed to the difference in the Me–O_m, bond lengths in the coordination octahedra, forming the crystal structures.     

Some Physicochemical Parameters of Saturated Ternary Solutions of Systems with Mixed Crystals in their Solid Phase

The measurements of density (ϱ), viscosity (η) and hydration number (n_h) of saturated solutions of ternary systems KCl KBr H₂O, K₂SO₄ (NH₄)₂SO₄ H₂O and KNO₃ NH₄NO₃ H₂O with mixed crystals in the solid phase have been conducted. It has been confirmed, that the occurence of the extremes on the curves of dependence of the properties (ϱ, η, n_h) on the composition of saturated solution may be the base for the supposition that beside mixed crystals the double salts have also been formed in the solid phase of a given system.     

DTA,DSC, and X-ray Powder Diffraction Studies on Some Zinc Selenate Hydrates

The thermal dehydration of ZnSeO₄ · 6 H₂O, ZnSeO₄ · 5 H₂O, and ZnSeO₄ · 3 H₂O has been studied by TG, DTA, and DSC-analyses. It has been established that the dehydration of ZnSeO₄ · 6 H₂O occurs stepwise and as intermidiate hydrates ZnSeO₄ · 5 H₂O, ZnSeO₄ · 3 H₂O and ZnSeO₄ · H₂O are produced. The enthalpy of dehydration of the observed phase transitions has been determined. The enthalpy of formation of ZnSeO₄ · 6 H₂O, ZnSeO₄ · 5 H₂O, ZnSeO₄ · 3 H₂O, and ZnSeO₄ · H₂O has been calculated on the basis of the DSC-data. ZnSeO₄ · 5 H₂O and ZnSeO₄ · 3 H₂O have been studied rentgenographically: ZnSeO₄ · 5 H₂O crystallizes in triclinic system with lattice parameters: a = 6.387(2) Å; b = 10.706(3) Å; c = 6.167(3) Å; α = 98.66(2)°; β = 109.32(3)° γ = 75.52(3)° V = 384.3(2) ų; SG P1 . ZnSeO₄ · 3 H₂O forms orthorhombic crystals with lattice constants: a = 8.165(4)Å; b = 11.314(5) Å; c = 12.465(7) Å; V = 1151.5(7) ų; SG Pbca.     

Zur Realstruktur von Ga1–xInxAs LPE-Schichten

Ga_1–xIn_xAs epitaxial layers (0.02 ≦ × ≦ 0.12) are grown on (111)-oriented GaAs substrates from nonstoichiometric melts. The etch pit densities – determined by chemical etching – yield values between 2 · 10⁵ cm⁻² and 3 · 10⁷ cm⁻² and were found to be dependent on composition, layer thickness and cooling rate. X-ray topography of cleaved {110}-planes gives information on layer quality and indicates the existence of stress in the substrate lattice near the heterojunction. The validity of Vegard's law in the investigated concentration range was confirmed by X-ray determination of the lattice constants. The half width of double crystal spectrometer rocking-curves, the epd and the relative intensity of photoluminescence show similar dependence on the composition of the mixed crystal layers.     

The double phosphates MIMIIPO4 (MI – Na,K; MII – Mg,Mn, Co,Ni, Zn) – synthesis from chloride melts and characterization

The particularities of the chemical interaction in systems M^IPO₃‐M^IIO(or Mn₂O₃)‐M^ICl (M^I – Na, K; M^II – Mg, Co, Ni, Zn) have been investigated at the temperature 1073 K and molar ratios P/M^x = 1 or 2 and M^ICl/(M^IPO₃ + M^IIO(or Mn₂O₃)) = 30. The conditions of formation of complex phosphates M^ІM^IIPO₄ and Na₄Ni₃(PO₄)₂P₂O₇ have been found. Influences of the nature of alkali and bivalent metals on the products composition were discussed. The advantages of chloride melts using (synthesis time reduction and temperature reducing) for preparing of complex phosphates were shown. The synthesized compounds have been characterized using the powder X‐ray diffraction, Fourier transform infrared and diffuse reflectance spectroscopies.     

Crystalloluminescence and Mechanoluminescence Spectra of Ba(ClO3)2 · H2O and 2 K2SO4 · Na2SO4 Crystals

Crystalloluminescence and mechanoluminescence of Ba(ClO₃)₂ · H₂O and 2 K₂SO₄ · Na₂SO₄ crystals are investigated. The crystalloluminescence spectra are almost similar to the photoluminescence spectra; however, they differ completely from the mechanoluminescence spectra. The crystalloluminescence excitations may take place due to the various processes: (i) the recombination of ions, (ii) from amorphous to crystalline transition, (iii) from the phase change during the crystallization, and (iv) from the dielectric breakdown by the electric field produced due to the creation of microfracture during the crystal growth. It is concluded that the crystalloluminescence excitation in Ba(ClO₃)₂ · H₂O and 2K₂SO₄ · Na₂SO₄ crystals may be chemical in origin.