K<Subscript>2</Subscript>SO<Subscript>4</Subscript>-K<Subscript>2</Subscript>HPO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O phase diagram in the region of heterogeneous supercritical fluids

Our experimental study of phase equilibria in the K₂SO₄-K₂HPO₄-H₂O system at temperatures up to 500°C and pressures up to 100 MPa was directed to determine the sequence of phase transformations that generate heterogeneous supercritical fluids whose existence region propagates from the K₂SO₄-K₂HPO₄-H₂O subsystem into the ternary system. We found that supercritical fluids become heterogeneous as a result of addition of K₂HPO₄ starting with l ₁-l ₂ critical phenomena in saturated solutions, with the attendant amalgamation of the stable immiscibility region that propagates from the K₂HPO₄-H₂O system and the metastable liquid-liquid phase separation that originates from the K₂SO₄-H₂O system. Our experimental results and the topological analysis of phase equilibria in the vicinity of the critical point of water gave us the full scenario of the phase behavior of the title ternary system in the region of the subcritical and supercritical parameters of state.     

K<Subscript>2</Subscript>SO<Subscript>4</Subscript>-KCl-H<Subscript>2</Subscript>O phase diagram in the area of heterogenization of homogeneous supercritical fluids

The experimental investigations of phase equilibria in the K₂SO₄-KCl-H₂O system at temperatures to 500°C and pressures to 100 MPa were directed to elucidate the phase transformation sequence that leads to the heterogenization of the supercritical fluid whose existence field propagates from the K₂SO₄-H₂O binary subsystem to the ternary system. We suggest that fluid heterogenization in the title ternary system is accompanied by the transformation of the metastable immiscibility field to stable equilibria at elevated temperatures (near 460°C) and unexpectedly high pressures (～60 MPa), despite the presence of a vapor phase.     

Phase equilibria and critical phenomena in the Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>-K<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system at 380-400°C: Specifics of ternary phase diagrams with type 2 (p-Q) boundary subsystems

Phase equilibria in Li₂SO₄-KLiSO₄-H₂O and K₂SO₄-KLiSO₄-H₂O ternary systems, which contain type 2 salts (Li₂SO₄, KLiSO₄, and K₂SO₄), were studied at temperature of 380 to 400°C and pressures up to 90 MPa. Homogeneous supercritical (SC) fluids, which propagate from type 2 water-salt subsystems into a three-component region, change to heterogeneous liquid-phase equilibria as a result of the transformation of metastable immiscibility regions into stable equilibria. The heterogenization of SC fluids starts with critical phenomena in saturated solutions. In the K₂SO₄-KLiSO₄-H₂O system, the monovariant critical curve (l₁ = l₂ - s_KLiSO4 )(l_1 = l_2 - s_{KLiSO_4 } ) reveals a temperature maximum at the invariant double critical end point (DCE).     

High-temperature equilibria and critical phenomena in the Na2CO3-NaCl-H2O and Na2CO3-Na2WO4-H2O systems

Phase equilibria in the Na₂CO₃-NaCl-H₂O and Na₂CO₃-Na₂WO₄-H₂O ternary systems formed by type 1 salts (NaCl, Na₂WO₄) and a type 2 salt (Na₂CO₃) were experimentally studied at temperatures from 425 to 500°C and pressures from 30 to 160 MPa with the contents of type 1 salts from 10 to 30 wt %. Transition from supercritical homogeneous fluid equilibria of the Na₂CO₃-H₂O system to heterogeneous equilibria of the title ternary systems was studied in the presence or absence of liquid phase immiscibility in the type 1 subsystems.     

KF–KBr–K<Subscript>2</Subscript>SO<Subscript>4</Subscript> system

The KBr–D (K₃FSO₄) quasi-binary system and the KF–KBr–K₂SO₄ ternary system were studied by differential thermal analysis. The melting points and compositions of eutectic mixtures were determined. In-, mono-, and divariant equilibria were described.     

Glass formation in the Al<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript>-Al(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system

Glass formation boundaries in the Al₂(SO₄)₃-Al(NO₃)₃-H₂O system were determined. IR spectra were studied. Schemes of structural rearrangements within the boundaries of a second glass formation region in the Al(NO₃)₃-H₂O binary subsystem are suggested. A structure is suggested for glassy Al(NO₃)₃H₂O.     

Glass formation in the Al(IO<Subscript>3</Subscript>)<Subscript>3</Subscript>-Al<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript>-HIO<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system

On the basis of experimental data obtained in the study of glass-formation boundaries in the Al₂(SO₄)₃-HIO₃-H₂O, Al(IO₃)₃-Al₂(SO₄)₃-H₂O, and Al(IO₃)₃-HIO₃-H₂O systems and using geometrical analysis, we predict the positions of glass-formation boundaries in the Al(IO₃)₃-Al₂(SO₄)₃-HIO₃-H₂O four-component system along 60, 40, and 25 wt % H₂O sections.     

Phase equilibria in the Na,K∥SO<Subscript>4</Subscript>, CO<Subscript>3</Subscript>, F-H<Subscript>2</Subscript>O system at 25°C

Phase equilibria in the Na, K∥SO₄, CO₃, F-H₂O system at 25°C are studied using the translation technique. Twenty four divariant fields, 22 univariant curves, and seven invariant points are found in the system. The complete phase diagram (the phase complex) of the system is designed on the basis of these data.     

Phase Equilibria in the K,Cа∥SO<Subscript>4</Subscript>,CO<Subscript>3</Subscript>,HCO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O System at 25°С

Phase equilibria in the system K,Cа∥SO₄,CO₃,HCO₃–H₂O have been studied at 25°С. This system at 25°С involves 7 invariant points, 21 monovariant curves, and 22 divariant fields. The data gained served to plot the first phase diagram (phase complex) of the studied system at 25°С.     

Phase diagram of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-MoO<Subscript>3</Subscript>-Ag<Subscript>2</Subscript>O system

The results concerning the synthesis, structure and thermal properties of V₂O₅-MoO₃-Ag₂O samples in the vanadium rich region of ternary system are presented in the form of quasi-binary phase diagrams in which at constant V₂O₅/MoO₃ molar ratios, equal 9:1, 7:3 and 1:1, the content of Ag₂O was variable. A new ternary phase isostructural with NaVMoO₆ has been detected in the investigated system.     

System NaOH-Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-Na<Subscript>2</Subscript>S

The NaOH-Na₂SO₄-Na₂S system has been studied. Refined phase diagrams have been designed for the boundary binaries and for four radiating sections, as well as the liquidus surface for the ternary system.     

Solubility in the ternary system CaSO<Subscript>4</Subscript> + Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> + H<Subscript>2</Subscript>O at 298.15 K

The solubility in the ternary system, aqueous mixture of CaSO₄ and Na₂SO₄, at T = 298.15 K comprises five different salts: calcium sulfate dihydrate, mirabilite, thenardite, glauberite and labile salt. Using the Extended Pitzer’s Ion Interaction model for pure and mixed electrolyte solutions and criteria of phase equilibria, predicted solubility behavior of salts was compared with experimental results from literature. The agreement between calculated and experimental solubilities was excellent in the ionic strength range up to 10.9062 mol kg⁻¹.     

Solubility isotherm for the Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

Solubility in the Na₂MoO₄-Na₂SO₄-H₂O system was studied using isothermal saturation at 5–100°C. The boundaries of crystallization fields were determined for sodium sulfate and sodium molybdate. Solid solutions were not observed within the range of the temperatures studied. The density, refractive index, and dynamic viscosity of the saturated solutions of the system were determined, and these data were used to calculate the molar volume, kinematic viscosity, and apparent molar volume of the sum of salts in these solutions. All property isotherms of solutions are in a strict correlation with the solubility in the system; this correlation is represented as an isobaric-isothermal diagram.     

Calculation of phase behavior and chemical transformations in H<Subscript>2</Subscript>O-NH<Subscript>3</Subscript>-CO<Subscript>2</Subscript> system using a modified hole quasichemical model

A technique for calculation of phase equilibria over a wide range of temperatures and pressures for fluid systems, where chemical interactions lead to the formation of ionic species, was developed. A hole quasichemical model was modified to account for chemical reactions and electrostatic interactions in the liquid phase. The densities and dielectric permittivity as function of a solution composition was taken into account in describing the electrostatic contribution to the Gibbs energy (Pitzer approximation) and Born contribution, that is required for thermodynamic consistency of simulation results. A method of assessing the appropriate relationships for mixtures of ammonia-water and ternary solutions was suggested. Calculations of the phase behavior of the H₂O-NH₃ system in the entire range of concentrations in the temperature interval 373–588 K at pressures up to 200 bar, and also of H₂O-NH₃-CO₂ system containing NH₃ to 30 mol% and CO₂ up to 14 mol% in the temperature range 373–473 K at pressures to 88 bar gave satisfactory agreement with experimental data. Concentrations of the molecular and ionic individuals in the liquid phase, depending on the overall composition of the mixture were evaluated.     

Preparation and physicochemical study of nickel(II) thiostannate in the NiCl<Subscript>2</Subscript>-SnS<Subscript>2</Subscript>-H<Subscript>2</Subscript>O system

Nickel(II) thiostannate is prepared in the NiCl₂-SnS₂-H₂O system by precipitation from solutions. Its formation temperature and homogenization time are determined. The synthesis of NiSnS3 from the ammonium acetate buffer solution is found to last 6–8 h at 80–90°C. The elemental composition of ternary nickel(II) thiostannate is detrermined by chemical analysis.     

五元体系Li＋, K＋//, CO32- ,SO42- , B4O72- -H2O在288 K时的介稳相平衡研究

采用等温蒸发法研究了五元体系Li^＋, K^＋//, , -H₂O 在288 K时的介稳相平衡关系, 测定了该五元体系在288 K条件下的介稳平衡的溶解度和溶液密度, 根据实验数据绘制了相应的介稳平衡相图和水图. 相平衡研究结果表明该五元体系介稳相平衡中有复盐K₂SO₄•Li₂SO₄生成, 其介稳相图(Li₂CO₃饱和)有4个共饱和点, 9条单变量曲线, 6个Li₂CO₃饱和的结晶区分别为LiBO₂•8H₂O, K₂B₄O₇•4H₂O, K₂CO₃•3/2H₂O, K₂SO₄, Li₂SO₄•H₂O和复盐 K₂SO₄•Li₂SO₄.     

Phases in the system Tb<Subscript>2</Subscript>O<Subscript>3</Subscript>-SeO<Subscript>2</Subscript>-H<Subscript>2</Subscript>O at 100°C and their physicochemical study

Summary The solubility isotherm of the system Tb₂O₃-SeO₂-H₂O at 100° was studied. The compounds of the three-component system were identified by the Schreinemakers’ method as well as by chemical and X-ray phase analyses. Simultaneous TG and DTA analyses of all compounds of the system were made. The mechanism of thermal decomposition was described.     

Projection of the liquidus surface of the Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Gd<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> system

Phase equilibria in the Sb₂Te₃-Gd₂Te₃-Bi₂Te₃ ternary system have been studied using differential thermal analysis, namely, X-ray powder diffraction, microstructure examination, thermodynamic analysis, and microhardness and alloy density measurements. Phase diagrams of some polythermal joins and liquidus surface have been constructed. The regions of primary crystallization of phases and the coordinates of all invariant and univariant equilibria in the system under investigation have been established.     

Phase equilibria in the La<Subscript>2</Subscript>S<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> ternary system

Phase equilibria in the La₂S₃-Bi₂S₃-La₂O₃ ternary system were studied by differential thermal, X-ray powder diffraction, and microstructure analyses. Phase diagrams of five vertical sections and a liquidus surface projection were plotted for the La₂S₃-Bi₂S₃-La₂O₃ system. The regions of primary crystallization of phases and coordinates of non- and monovariant equilibria were determined for the system.     

K<Subscript>3</Subscript>VO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Formation conditions,crystal structure,and physicochemical properties

Potassium oxosulfatovanadate(V) K₃VO₂(SO₄)₂ has been obtained by solid-phase synthesis from K₂SO₄, K₂S₂O₇, and V₂O₅ (2: 1: 1), and its formation conditions, crystal structure, and physiochemical properties have been studied. The conversions of K₃VO₂(SO₄)₂ in contact with potassium vanadates and other potassium oxosulfatovanadates(V) are considered in terms of phase relations in the K₂O-V₂O₅-SO₃ system, which models the active component of vanadium catalysts for sulfur dioxide oxidation into sulfur trioxide. The X-ray diffraction pattern of K₃VO₂(SO₄)₂ is indexed in the monoclinic system (space group P2₁) with unit cell parameters of a = 10.0408(1) Å, b = 7.2312(1) Å, c = 7.3821(1) Å, β = 104.457(1)°, Z = 2, and V = 519.02 ų. The crystal structure of K₃VO₂(SO₄)₂ is built from [VO₂(SO₄)₂]^3? complex anions, in which the vanadium atom is in an octahedral oxygen environment formed by two terminal oxygen atoms (V-O(6) = 1.605(7) Å, V-O(10) = 1.619(7) Å and four oxygen atoms of the two chelating sulfate anions. The vibrational spectra of K₃VO₂(SO₄)₂ are analyzed using these structural data.