RbBr/CsBr-CH3OH/C2H5OH-H2O三元体系的溶解度

采用自制的相平衡研究装置, 测定了RbBr-CH3OH/C2H5OH-H2O和CsBr-CH3OH/C2H5OH-H2O四个三元体系在25、35、45 ℃三个温度下的平衡溶解度;同时得到了四个三元体系饱和溶液中不同盐浓度下的折光率数据. 实验结果表明,在所有的体系中, 随着甲醇或乙醇质量分数的增加, RbBr和CsBr 在水中的溶解度逐渐降低; 并且折光率也逐渐减小. 用经验关联方程对溶解度进行了拟合, 同时给出了CH3OH 和C2H5OH 分别对RbBr和CsBr的盐析率曲线.     

RbBr/CsBr-CH3OH/C2H5OH-H2O三元体系的溶解度

采用自制的相平衡研究装置,测定了RbBr-CH_3OH/C_2H_5OH-H_2O和CsBr-CH_3OH/C_2H_5OH-H_2O四个三元体系在25、35、45℃三个温度下的平衡溶解度;同时得到了四个三元体系饱和溶液中不同盐浓度下的折光率数据.实验结果表明,在所有的体系中,随着甲醇或乙醇质量分数的增加,RbBr和CsBr在水中的溶解度逐渐降低;并且折光率也逐渐减小.用经验关联方程对溶解度进行了拟合,同时给出了CH_3OH和C_2H_5OH分别对RbBr和CsBr的盐析率曲线.     

Equilibrium Phase Behavior of Ethylene Glycol/Glycerin＋RbNO3/CsNO3＋H2O at 288.15 and 298.15 K

The solubilities, densities and refractive indices for the four ternary systems ethylene glycol/glycerin＋ RbNOJCsNO3＋H20 were measured with mass fractions of ethylene glycol or glycerin in a range of 0 to 1.0 at 288.15 and 298.15 K. In all the cases, the presence of either ethylene glycol or glycerin significantly reduces the solubilities of the rubidium nitrate and cesium nitrate in aqueous solution, but the refractive indices increase with the increase of mass fraction of either ethylene glycol or glycerin. The density, refractive index and solubility of the saturated ternary systems were correlated with each other via polynomial equations. In addition, the refractive indices and densities of unsaturated solutions were also determined for the four ternary systems with different salt concentrations, which were correlated with the salt concentration and proportion of ethylene glycol or glycerin in the solution.     

硝酸铷在醇水混合溶剂中的溶解度

本文通过简单精确的分析方法测定了硝酸铷在水、水＋甲醇以及在水＋乙醇中在不同温度下的溶解度。在甲醇和乙醇存在的情况下，硝酸铷在水的溶解度都明显降低。通过四参数方程对试验数据拟和，取得了满意的结果。同时也测定了三元体系在“饱和”和“非饱和”状态下的折光率，并对折光率和醇及盐的浓度进行关联。     

Solubilities,densities and refractive indices for the ternary systems ethylene glycol + MCl + H2O (M = Na,K, Rb,Cs) at (15 and 35) °C

The solubilities, densities and refractive indices data for the four ternary systems ethylene glycol + MCl + H₂O (M = Na, K, Rb, Cs) at different temperatures were measured, with mass fractions of ethylene glycol in the range of 0 to 1.0. In all cases, the presence of ethylene glycol significantly reduces the solubility of the salts in aqueous solution. The experimental data of density, refractive index and solubility of saturated solutions for these systems were correlated using polynomial equations as a function of the mass fraction of ethylene glycol. On the other hand, the refractive index and density of unsaturated solutions was also determined for the four ternary systems with varied unsaturated salt concentrations. Values for both the properties were correlated with the salt concentrations and proportions of ethylene glycol in the solutions.     

25℃时KCl-RbCl-1/2-C3H7OH-H2O四元体系的液-液-固相平衡研究

本文研究了25℃时,K+,Rb+,//Cl-1/2C3H7OH,H2O两个四元体系的相平衡。测定了KCl＋RbCl＋H2O三元体系液-固相间的关系和KCl/RbCl不同质量比（1/0、0.75/0.25、0.5/0.5、0.25/0.75和0/1）在1/2-C3H7OH-H2O两种溶剂存在时的5组四元体系的液-液-固相关系。绘制出全相图。探讨了盐析效应,并采用一个五元参数方程对双液线数据进行了关联,此外采用一个经过修改Eisen-Joffe方程对结线数据和饱和平衡数据进行拟合,得到的结果令人满意。     

Phase equilibria in a ternary fullerenol-d(C<Subscript>60</Subscript>(OH)<Subscript>22–24</Subscript>)–SmCl<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 25°C

The solubility in a ternary fullerenol-d (C₆₀(OH)_22–24)–SmCl₃–H₂O system at 25°C is studied via isothermal saturation in ampules. The solubility diagram is shown to be a simple eutonic one that consists of two branches corresponding to the crystallization of fullerenol-d (C₆₀(OH)_22–24 · 30H₂O) and samarium(III) chloride SmCl₃ · 6H₂O crystallohydrates and contains one nonvariant eutonic point corresponding to saturation with both crystallohydrates. The long branch of C₆₀(OH)_22–24 · 30H₂O crystallization shows the effect of fullerenol-d salting out of saturated solutions; in contrast, the short branch of SmCl₃ · 6H₂O crystallization shows the pronounced salting-in effect of samarium(III) chloride.     

298.15和308.15 K时1,2-丙二醇+MCl (M=Na,K, Rb,Cs)+H2O三元体系的溶解度、密度和折光率

系统研究了1,2-丙二醇+MCl (M=Na, K, Rb, Cs)+H₂O三元体系在298.15 和308.15 K时的等温相平衡. 采用硝酸汞滴定法测定了体系中无机盐的含量, 采用安东帕RXA170 折光率仪及DMA4500 密度计测定了所有体系的折光率和密度数值. 报道了1,2-丙二醇质量分数从0增加到0.9过程中饱和及不饱和三元溶液体系的等温溶解度、密度和折光率数据. 实验结果发现, 随着1,2-丙二醇的不断加入, 饱和溶液的溶解度和密度均呈现出减小的趋势, 而折光率的变化则呈现出相反的趋势. 采用经验方程关联了不同醇水比条件下不饱和溶液的密度和折光率实验数据, 获得了较为理想的拟合结果. 本研究的开展充实了碱金属盐在混合溶剂中的热力学数据, 为相关溶液化学研究奠定了基础.     

On the Double Salt Formation in the Systems Rb2SeO4=ZnSeO4=H2O andCs2SeO4=ZnSeO4=H2O at 25°C

 The solubilities in the systems Rb₂SeO₄=ZnSeO₄=H₂O and Cs₂SeO₄=ZnSeO₄=H₂O at 25°C were studied by the method of isothermal decrease of supersaturation. Comparatively wide crystallization fields of the double salts Rb₂Zn(SeO₄)₂ċ6H₂O and Cs₂Zn(SeO₄)₂ċ6H₂O are observed in the solubility diagrams. The double salts form monoclinic crystals which are isostructural with those of the corresponding rubidium and cesium zinc sulfate hexahydrates. TG and TDA measurements indicate that the double salts lose their crystallization water in one step in the temperature intervals of 50–160°C (rubidium salt) and 70–150°C (cesium salt).     

On the Double Salt Formation in the Systems Rb2SeO4=ZnSeO4=H2O andCs2SeO4=ZnSeO4=H2O at 25°C

Summary.  The solubilities in the systems Rb₂SeO₄=ZnSeO₄=H₂O and Cs₂SeO₄=ZnSeO₄=H₂O at 25°C were studied by the method of isothermal decrease of supersaturation. Comparatively wide crystallization fields of the double salts Rb₂Zn(SeO₄)₂ċ6H₂O and Cs₂Zn(SeO₄)₂ċ6H₂O are observed in the solubility diagrams. The double salts form monoclinic crystals which are isostructural with those of the corresponding rubidium and cesium zinc sulfate hexahydrates. TG and TDA measurements indicate that the double salts lose their crystallization water in one step in the temperature intervals of 50–160°C (rubidium salt) and 70–150°C (cesium salt). Received March 14, 2000. Accepted (revised) June 5, 2000     

Solid–liquid equilibria in the NaCl–SrCl2–H2O system at 288.15 K

The phase equilibria in the ternary system NaCl–SrCl₂–H₂O at 288.15 K were studied with the isothermal equilibrium solution method. The phase diagram and refractive index diagram were plotted for this system at 288.15 K. The phase diagram contains one invariant solubility point, two univariant solubility curves, and two crystallization fields of NaCl and SrCl₂ · 6H₂O. The refractive indices of the equilibrium solution change regularly with w(NaCl) increase. The calculated refractive index data are in good agreement with the experimental data. Combining the experimental solubility data of the ternary system, the Pitzer binary parameters for NaCl at 288.15 K and SrCl₂ at 298.15 K, the Pitzer mixing parameters θ_{Na, Sr}, Ψ_{Na, Sr, Cl} and the solubility equilibrium constants Ksp of solid phases existing in the ternary system at 288.15 K were fitted using the Pitzer and Harvie-Weare (HW) models. The mean activity coefficients of sodium chloride and strontium chloride, and the solubilities for the ternary system at 288.15 K were presented. A comparison between the calculated and measured solubilities shows that the predicted data agree well with the experimental results.     

Physical Properties of the Ternary Mixture Ethanol+Water+1-Butyl-3-Methylimidazolium Chloride at 298.15 K

In this work densities, refractive indices, speeds of sound and isentropic compressibilities of the ternary mixture ethanol+water+1-butyl-3-methylimidazolium chloride ([C₄mim][Cl]), and of the binary subsystems containing the ionic liquid, have been measured at 298.15 K and atmospheric pressure.     

Solubilities of imidazolium-based ionic liquids in aqueous salt solutions at 298.15 K

The solubilities of ionic liquids in the ternary systems (ionic liquid + H₂O + inorganic salt) were reported at 298.15 K and atmospheric pressure. The examined ionic liquids are [C₄mim][PF₆] (1-n-butyl-3-methylimidazolium hexafluorophosphate), [C₈mim][PF₆] (1-n-octyl-3-methylimidazolium hexafluorophosphate), and [C₈mim][BF₄] (1-n-octyl-3-methylimidazolium tetrafluoroborate). The examined inorganic salts are the chloride-based salts (sodium chloride, lithium chloride, potassium chloride, and magnesium chloride) and the sodium-based salts (sodium thiocyanate, sodium nitrate, sodium trifluoroacetate, sodium bromide, sodium iodide, sodium perchlorate, sodium acetate, sodium hydroxide, sodium dihydrogen phosphate, sodium phosphate, sodium tetrafluoroborate, sodium sulfate, and sodium carbonate). The effects of the cations and the anions of the ionic liquids and of the inorganic salts on the solubility of the ionic liquids in the ternary solutions were systematically compared and discussed.     

Measurement of the Diffusivity of Cesium Ion in Aqueous Rubidium Chloride Solution

For the first time cesium diffusivity in aqueous solutions of rubidium chloride is being reported here in the concentration range from 0.001 to 4.00 mol⋅dm⁻³. The measurement use a radioactive tracer technique employing a sliding cell mechanism. These diffusivity values were utilized to understand the transport mechanism of Cs ion in the RbCl–H₂O system using the Onsager-Gosting-Harned equation and the extended Debye-Hückel equation. The observed deviation between the theoretical and experimental diffusivities are explained by introducing the concept of Field-Dielectric-Gradient forces and energies that exist around an ion, which takes care of the finite size of the ion, ion-water interaction and the ion-ion interaction in a continuum basis.     

An isothermal (30 °C) study of heterogeneous equilibria in the sucrose (C12H22O11)-calcium hydroxide (Ca(OH)2)-water system

Solid-liquid equilibria in the C₁₂H₂₂O₁₁-Ca(OH)₂-H₂O system have been determined at 30 °C. Two phases C₁₂H₂₂O₁₁·3Ca(OH)₂ and C₁₂H₂₂O₁₁·2Ca (OH)₂ have been evidenced, and solubility (liquidus) curves have been determined. It is thus shown that these ternary phases exhibit incongruent solubilities at 30 °C. These solid phases were characterized using Infrared Spectroscopy (IR), Scanning Electron Microscopy (SEM) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES).     

The phase diagrams and Pitzer model representations for the system KCl + MgCl2 + H2O at 50 and 75°C

The solubilities in the KCl-MgCl₂-H₂O system were determined at 50 and 75°C and the phase diagrams and the diagram of refractive index vs composition were plotted. Two invariant point, three univariant curves, and three crystallization zones, corresponding to potassium chloride, hexahydrate (MgCl₂ · 6H₂O) and double salt (KCl · MgCl₂ · 6H₂O) showed up in the phase diagrams of the ternary system, The mixing parameters ??_{K, Ca} and ??_{K, Ca, Cl} and equilibrium constant K _sp were evaluated in KCl-MgCl₂-H₂O system by least-squares optimization procedure, in which the single-salt Pitzer parameters of KCl and MgCl₂ ??⁽⁰⁾, ??⁽¹⁾, ??⁽²⁾, and C ^? were directly calculated from the literature. The results obtained were in good agreement with the experimental data.     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

Five solvates of a multicomponent pharmaceutical salt formed by berberine and diclofenac

A multicomponent pharmaceutical salt formed by the isoquinoline alkaloid berberine (5,6‐dihydro‐9,10‐dimethoxybenzo[g]‐1,3‐benzodioxolo[5,6‐a]quinolizinium, BBR) and the nonsteroidal anti‐inflammatory drug diclofenac {2‐[2‐(2,6‐dichloroanilino)phenyl]acetic acid, DIC} was discovered. Five solvates of the pharmaceutical salt form were obtained by solid‐form screening. These five multicomponent solvates are the dihydrate (BBR–DIC·2H₂O or C₂₀H₁₈NO₄⁺·C₁₄H₁₀Cl₂NO₂^?·2H₂O), the dichloromethane hemisolvate dihydrate (BBR–DIC·0.5CH₂Cl₂·2H₂O or C₂₀H₁₈NO₄⁺·C₁₄H₁₀Cl₂NO₂^?·0.5CH₂Cl₂·2H₂O), the ethanol monosolvate (BBR–DIC·C₂H₅OH or C₂₀H₁₈NO₄⁺·C₁₄H₁₀Cl₂NO₂^?·C₂H₅OH), the methanol monosolvate (BBR–DIC·CH₃OH or C₂₀H₁₈NO₄⁺·C₁₄H₁₀Cl₂NO₂^?·CH₃OH) and the methanol disolvate (BBR–DIC·2CH₃OH or C₂₀H₁₈NO₄⁺·C₁₄H₁₀Cl₂NO₂^?·2CH₃OH), and their crystal structures were determined. All five solvates of BBR–DIC (1:1 molar ratio) were crystallized from different organic solvents. Solvent molecules in a pharmaceutical salt are essential components for the formation of crystalline structures and stabilization of the crystal lattices. These solvates have strong intermolecular O…H hydrogen bonds between the DIC anions and solvent molecules. The intermolecular hydrogen‐bond interactions were visualized by two‐dimensional fingerprint plots. All the multicomponent solvates contained intramolecular N—H…O hydrogen bonds. Various π–π interactions dominate the packing structures of the solvates.     

Phase diagrams and physicochemical properties of Li<Superscript>+</Superscript>,K<Superscript>+</Superscript>(Rb<Superscript>+</Superscript>)//borate–H<Subscript>2</Subscript>O systems at 323 K

The phase and physicochemical properties diagrams of Li⁺,K⁺(Rb⁺)//borate–H₂O systems at 323 K were constructed using the experimentally measured solubilities, densities, and refractive indices. The Schreinemakers’ wet residue method and the X-ray diffraction were used for the determination of the compositions of solid phase. Results show that these two systems belong to the hydrate I type, with no solid solution or double salt formation. The borate phases formed in our experiments are RbB₅O₆(OH)₄ · 2H₂O, Li₂B₄O₅(OH)₄ · H₂O, and K₂B₄O₅(OH)₄ · 2H₂O. Comparison between the stable phase diagrams of the studied system at 288, 323, and 348 K show that in this temperature range, the crystallization form of salts do not changed. With the increase in temperature, the crystallization field of Li₂B₄O₅(OH)₄ · H₂O salt at 348 K is obviously larger than that at 288 K. In the Li⁺,K⁺(Rb⁺)//borate–H₂O systems, the densities and refractive indices of the solutions (at equilibrium) increase along with the mass fraction of K₂B₄O₇ (Rb₂B₄O₇), and reach the maximum values at invariant point E.     

Densities and Conductivities of Aqueous N,N,N-Alkyloctyldimethylammonium Chloride at Different Temperatures

The simple equations for predictions of the density and conductivity of mixed electrolyte solutions were extended to the related properties of mixed ionic liquid solutions. The densities and conductivities were measured for the ternary solutions OOAC (N,N,N-dioctyldimethylammonium chloride) + OPAC (N,N,N-octylpentyldimethylammonium chloride) + H₂O, OOAC + N,N,N-octylbutyldimethylammonium chloride (OBAC) + H₂O, OPAC + OBAC + H₂O and their corresponding binary subsystems OOAC + H₂O, OPAC + H₂O, and OBAC + H₂O at (298.15, 303.15, and 308.15) K, respectively. The results were used to test the predictability of the extended equations. Comparison of the results shows that these simple equations can be used to predict the density and conductivity of the mixed ionic liquid solutions from the properties of their binary subsystems of equal ionic strength.