Topological transformation of the phase diagram of the potassium nitrate-water-<Emphasis Type="Italic">n</Emphasis>-butoxyethanol ternary system

Phase equilibria and critical phenomena in the potassium nitrate-water-n-butoxyethanol ternary system were studied by the visual polythermal method over the temperature range 10–150°C. In this system, the boundary binary liquid system is characterized by the presence of a closed stratification region. The temperature of the formation of a critical tie line of monotectic equilibrium (18.3°C) and solution compositions corresponding to the critical solubility points at various temperatures were determined. The n-butoxyethanol distribution coefficients between the aqueous and organic phases of the monotectic state were calculated at eight temperatures. n-Butoxyethanol salting out from aqueous solutions by potassium nitrate increased as the temperature grew. The generalized scheme of topological transformations of salt-binary solvent ternary system phase diagrams with salting out was substantiated and augmented.     

The salting out action of alkali metal nitrates on the water-diethylamine binary system

The results of a polythermal study of the salting out action of alkali metal (Na, K, and Cs) nitrates on the water-diethylamine binary system characterized by stratification with a lower critical solution point (LCSP) were comparatively analyzed. Alkali metal nitrates experiencing homoselective solvation in aqueousorganic solvents were found to decrease the LCSP of this binary system, that is, have a salting out action. A decrease in the radius of the cation in the series CsNO₃-KNO₃-NaNO₃ decreased the temperature of critical tie line formation in the monotectic state of salt-water-diethylamine ternary systems (69.3, 48.1, and 22.9°C, respectively). In all ternary systems, first and foremost in the system with potassium nitrate, the effect of diethylamine salting out from aqueous solutions grew stronger as the temperature increased. The conclusion was drawn that, among the salts studied, sodium nitrate had the strongest salting out effect at 22.9–88.4°C, and potassium nitrate, at 88.4–150.0°C.     

Topological transformation of the phase diagram of a potassium perchlorate-water-tetrahydrofuran ternary system in the temperature range of 40 to 140°C

Phase equilibria and critical phenomena in a potassium perchlorate-water-tetrahydrofuran ternary system are studied by visual polythermal means in the range of 40 to 140°C; the solubility diagram of the liquid subsystem is characterized by the presence of isolated binodal curve. The temperature of formation for the critical node of the monotectic state (107.3°C) and the dependences of the composition that corresponds to the critical points of solubility in the delayering field vs. temperature in the ranges of 70.3 to 107.3°C and 137.1 to 140.2°C are determined. The topological transformation of the investigated ternary system’s phase diagram upon a change in temperature is studied using isothermal sections of the system’s temperature concentration prism, plotted at nine temperatures. It is found that potassium perchlorate has only a salting-in effect on mixtures of water and tetrahydrofuran at temperatures below 107.3°C; at higher temperatures, it has both a salting-in and a salting-out effect, depending on its concentration and the composition of mixed solvent. It is shown that potassium perchlorate’s effect of salting tetrahydrofuran out of aqueous solutions grows slightly with an increase in temperature.     

Phase equilibria and critical phenomena in the cesium nitrate-water-diethylamine ternary system

Phase equilibria and critical phenomena in the cesium nitrate-water-diethylamine ternary system were studied by the visual-polythermal method over the temperature range 60–150 °C, where the boundary binary liquid system was characterized by stratification with a lower critical solution temperature (LCST). The introduction of cesium nitrate into the water-diethylamine system decreased the LCST of this system from 146.1 to 69.3°C and lowered the mutual solubility of the components. The diethylamine distribution coefficients between the aqueous and organic phases were calculated for monotectic equilibria at various temperatures. The salting out of diethylamine with cesium nitrate grew stronger as the temperature increased. The conclusion was drawn that the isotherms of the phase states of the system substantiated the generalized scheme of topological transformations of phase diagrams for salt-binary solvent ternary systems with salting out. The salting out effects of cesium and potassium nitrates on the water-diethylamine binary system were compared.     

Phase Equilibria and Critical Phenomena in the Potassium Nitrate-Water-Diethylamine Ternary System

Phase equilibria and critical phenomena in the potassium nitrate—water—diethylamine ternary system were studied by the visual polythermal method over the temperature range 40–150°C. The corresponding boundary binary liquid system was characterized by stratification with the lower critical temperature of solution. The introduction of potassium nitrate into the water—diethylamine system lowered its lower critical temperature of solution from 146.1 to 48.1°C and decreased the mutual solubility of the components. The diethylamine distribution coefficients between the aqueous and organic monotectic equilibrium phases at various temperatures were calculated. The effect of the salting out of diethylamine from aqueous solutions under the action of potassium nitrate was found to strengthen as the temperature increased. The constructed isotherms of the phase states of the system substantiated the generalized topological scheme of the transformation of phase diagrams of salt-binary solvent ternary systems with salting out.     

Equilibrium of two liquid phases and critical phenomena in a ternary system of cyclohexane-pyridine-acetic acid in the 10–55°C range

A visual polythermal method is used to study the mutual solubility of components and critical phenomena in a ternary system of cyclohexane-pyridine-acetic acid in the 10.0–55.0°C range. It is noted that the isothermal solubility diagrams of the system in the 10.0–52.5°C range is characterized by the occurrence of a closed separation region. A temperature dependence of the mixture composition, which corresponds to the critical point of solubility, is determined. It is found that with the increase in the temperature a two-liquid phase region disappears through a non-critical point.     

Salting out of triethylamine from aqueous solutions by potassium nitrate

By visual-polythermal method in the range 5–25°C we studied phase equilibria and critical phenomena in a ternary system potassium nitrate-water-triethylamine, where its component, binary liquid system, is stratified at the lower critical solution temperature.     

A comparative analysis of the solubility diagrams of iodine-water-alkanol ternary systems at 25°C

The solubilities of the components of the iodine-water-propanol (1-C₃H₇OH) ternary system at 25°C and atmospheric pressure were measured for the first time. The solubility diagram of this system is a ternary system diagram with salting out. Iodine stratifies water-propanol mixtures containing 16.2–73.0 wt % alcohol. The solubility of crystalline iodine increases as the content of alcohol in the mixed solvent grows and is maximum in a mixture containing 79.0 wt % alcohol. A comparative analysis of the phase diagrams of the iodine-water-alkanol (ethanol, propanol-1, and propanol-2) systems was performed. The differences between them can likely be explained by an increase in the electron donor ability of the alcohols, which is also in agreement with the enthalpies of solution of the alcohols in water.     

Topological transformation of the cesium nitrate-water-isopropanol ternary phase diagram

Phase equilibria and critical phenomena in the cesium nitrate-water-isopropanol system, where the liquid binary subsystem does not separate over the entire temperature range of its liquid state, were studied within 70–120°C using visual polythermal analysis. The temperature at which the monotectic critical tie-line appears (79.0°C) and the compositions of the solutions at critical solution points at various temperatures were determined. Isopropanol distribution coefficients between aqueous and organic monotectic phases were calculated for five temperatures. The salting out of isopropanol by cesium nitrate from aqueous solutions is enhanced by temperature elevation. The phase isotherms validated a previously reported fragment of the general scheme of the topological transformation of ternary phase diagrams for salt-binary solvent systems with salting out. Original Russian Text ? D.G. Cherkasov, V.F. Kurskii, S.I. Sinegubova, K.K. Il’in, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 6, pp. 1032–1036.     

Phase equilibria and critical phenomena in the rubidium nitrate-water-acetonitrile system

Phase equilibria and critical phenomena were studied from -5 to 120°C in the rubidium nitrate-water-acetonitrile system, in which the liquid binary subsystem is characterized by liquid-liquid phase separation with an upper critical solution point (UCSP), using a visual polythermal method. We found that rubidium nitrate has a salting out effect on water-acetonitrile solutions and causes them to demix at any temperature in the specified range. Acetonitrile distribution coefficients between aqueous and organic monotectic phases were calculated for various temperatures. The minimum value was observed for 20.0°C. Six isothermal phase diagrams of the system were plotted to verify a fragment of the global scheme of the topological transformation of phase diagrams for salt-binary solvent ternary systems with salting out. The salting out effects of potassium, rubidium, and cesium nitrates on water-acetonitrile mixtures were comparatively analyzed.     

Salting-Out of <Emphasis Type="Italic">n</Emphasis>-Propyl Alcohol with Potassium Nitrate from Aqueous Solutions

The solubility of components and critical phenomena in the ternary system constituted by potassium nitrate, water, and n-propyl alcohol were studied by the visual polythermal method in the temperature range 25–80°C. The temperature of formaiton of the critical node of the monotectic equilibrium (critical solution-solid phase) and the solution compositions corresponding to the critical solution points at different temperatures were determined. The isothermal solubility diagrams of the system were constructed and the distribution coefficients of n-propyl alcohol at different temperatures were calculated. A comparative analysis of the salting-out effect exerted by potassium nitrate on aqueous solutions of n-propyl alcohol and isopropyl alcohol was done.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 398–402.Original Russian Text Copyright © 2005 by Sinegubova, Cherkasov, Il’in.     

The solubility of C<Subscript>60</Subscript>Br<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 6, 8, 24) in organic solvents

The polythermal (over the temperature range 20–80°C) solubility of fullerene bromo derivatives C₆₀Brn (n = 6, 8, 24) in several solvents (o-xylene, o-dichlorobenzene, n-decanol-1, and enanthic acid) was studied. The corresponding solubility polytherms are given.     

Thermodynamic Properties and Melting Behavior of Bi–Sn–Zn Alloys

The partial and integral enthalpies of mixing of liquid Bi–Sn–Zn alloys were determined at 500°C by a drop calorimetric technique using a Calvet-type microcalorimeter. The ternary interaction parameters in the Bi–Sn–Zn system were fitted using the Redlich-Kister-Muggianu model for substitutional solutions, and isoenthalpy curves of the integral molar enthalpy of mixing at 500°C were constructed. Furthermore, a DSC technique was used to determine the liquidus temperatures in three sections (3, 5, and 7 at.% Zn) as well as the invariant reaction temperature of the ternary eutectic L ⇄ (Bi) + (Sn) + (Zn). The ternary eutectic reaction was found at 135°C.     

Thermodynamic Properties and Melting Behavior of Bi–Sn–Zn Alloys

Summary. The partial and integral enthalpies of mixing of liquid Bi–Sn–Zn alloys were determined at 500°C by a drop calorimetric technique using a Calvet-type microcalorimeter. The ternary interaction parameters in the Bi–Sn–Zn system were fitted using the Redlich-Kister-Muggianu model for substitutional solutions, and isoenthalpy curves of the integral molar enthalpy of mixing at 500°C were constructed. Furthermore, a DSC technique was used to determine the liquidus temperatures in three sections (3, 5, and 7 at.% Zn) as well as the invariant reaction temperature of the ternary eutectic L ⇄ (Bi) + (Sn) + (Zn). The ternary eutectic reaction was found at 135°C.     

Solubility of Acetaminophen and Ibuprofen in Polyethylene Glycol 600, N-Methyl Pyrrolidone and Water Mixtures

The solubility of acetaminophen and ibuprofen in binary and ternary mixtures of N-methyl pyrrolidone, polyethylene glycol 600 and water at 25 °C were determined and the solubilities are mathematically represented by the Jouyban–Acree model. The density of the solute-free solvent mixtures was measured and employed to train the Jouyban–Acree model and then the densities of the saturated solutions were predicted. The overall mean relative deviations (OMRDs) for fitting the solubility data of acetaminophen and ibuprofen in binary mixtures are 3.2% and 6.0%, respectively. The OMRDs for fitting the solubilities in ternary solvent mixtures for acetaminophen and ibuprofen are 15.0% and 28.6%, respectively, and the OMRD values for predicting all solubilities of acetaminophen and ibuprofen by a trained version of the Jouyban–Acree model are 9.4% and 17.8%, respectively. The prediction OMRD for the density of saturated solutions is 1.9%.     

DSC analysis of Cu–Zn–Sn shape memory alloy fabricated via electrodeposition route

Cu–Zn–Sn shape memory alloy strips with composition range of 13.70–46.30 mass% Sn were fabricated by electrodepositing Sn on a shim brass surface and then subsequently annealed at a constant temperature of 400 °C for 120 min under flowing nitrogen. Subjecting the Sn-plated strips to differential scanning calorimetry (DSC) analysis revealed that the austenitic start (A _s) temperature was essentially constant at 225 °C while the martensite start (M _s) temperature was consistently within the 221.5–222 °C interval. Austenite to martensite phase transformation showed two distinct peaks on the DSC thermogram which can be attributed to the non-homogeneity of the bulk Cu–Zn–Sn ternary alloy. The latent heats of cooling and heating were found to increase with the mass% Sn plated on the shim brass. Effect of annealing temperature was also investigated wherein strips with an essentially constant composition of 26 mass% Sn were annealed at a temperature range of 350–420 °C for 120 min under flowing nitrogen. Varying the annealing temperature has no significant effect on the transformation temperatures of the ternary alloy.     

Topological transformation of a phase diagram for the sodium nitrate-water-isopropanol ternary system

Phase equilibria and critical phenomena in the sodium nitrate-water-isopropanol ternary system, where a boundary binary liquid system shows no immiscibility over the entire temperature range of its liquid state, were studied in the range from 5 to 90°C using a visual polythermal method. The formation temperature of a monotectic critical tie-line was determined to be 6.1°C, and the solution compositions corresponding to critical solution points at various temperatures were determined. Isopropanol partition coefficients between the aqueous and organic phases of monotectic equilibrium were calculated for seven temperatures. The isopropanol salting out from aqueous solutions by sodium nitrate was shown to be enhanced by rising temperature. Isothermal phase diagrams of the title system were constructed to verify a fragment of the general scheme of topological transformations of phase diagrams for salt-binary solvent ternary systems with salting out.     

Diagramme Polythermique Du Systeme Ternaire KCl–FeCl2–H2O Entre 0 Et 70°C

Polytherm diagram of the ternary system KCl–FeCl₂ –H₂ O between 0 and 70°C. Phase equilibria in the KCl–FeCl₂ –H₂ O system were studied over the temperature range 0–70°C by conductimetric and analytical methods. A solubility polytherm of the system was constructed. We have observed the crystallization fields of the KCl and FeCl₂ 6H₂ O (at 0°C), KCl and FeCl₂ 4H₂ O (at 15, 30 and 40°C) and KCl, FeCl₂ 4H₂ O and of a double salt KClFeCl₂ 2H₂ O are obtained at 70°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Regularities of self-propagating high-temperature synthesis in the solid 8-hydroxyquinoline—chloramine B system

The regularities of chemical reactions in solid 8-hydroxyquinoline—chloramine B mixtures were studied under conditions of organic self-propagating high-temperature synthesis (SHS), isothermal reaction, and thermal explosion in the 20–220 °C temperature range. Comprehensive physicochemical analysis and microstructural study of the reaction products were carried out. The temperature of SHS initiation (58 °C), the heat of the reaction (129±9 kJ mol⁻¹), the stoichiometric coefficient (1), the maximum temperature (T _max=98–140 °C), and the velocity of SHS wave propagation (u=0.15–0.55 mm s⁻¹) were determined. Depending on the ratio of the reactants (n), a low-temperature non-degeerate stable gasless mode (n≤1,T _max=115 °C,E _a=42 kcal mol⁻¹) and a high-temperature mode (n>1,T _max=140 °C,E _a=0.4 kcal mol⁻¹) are possible for SHS. The SHS affords monohydroxy and monochloro derivatives of 8-hydroxyquinoline, benzenesulfonamide, NaCl, NaOH, and H₂O. The mechanism of the solid-phase reaction at temperatures below 58 °C includes surface, solid-phase, and gas-phase diffusion; that for SHS is capillary spreading of the hydroxyquinoline melt. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2271–2284, December, 1999.     

Formation of Diazepam–Lanthanides(III) Complexes in the 50–50 Volume % Ethanol–Water Solvent System and Study of the Effect of Temperature on the Complex Formation Constants

Diazepam (7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one) is an important derivative of the 1,4-benzodiazepine compound commercially distributed as Valium. The complex formation constants of diazepam with some light lanthanide(III) metal ions have been studied by potentiometric measurements. All titrations were performed in 50–50% (volume/volume) ethanol–water solvent mixtures at constant ionic strength (0.10 mol⋅dm⁻³). The ionic strength was maintained by using sodium perchlorate. The complex formation constants were determined at 25.00, 35.00 and 45.00 °C. With increasing temperature, a decrease was observed in the protonation constant (pK) of diazepam.