Quaternary Liquid–Liquid Equilibria for Aqueous Systems Containing Dimethyl Carbonate at 298.15 K

Experimental tie-line data for two ternary systems, water + dimethyl carbonate + methanol or ethanol, and two quaternary systems, water + dimethyl carbonate + toluene + methanol or ethanol were investigated at 298.15 K and atmospheric pressure. The experimental liquid–liquid equilibrium data were correlated using a modified UNIQUAC activity coefficient model with binary and ternary as well as quaternary parameters. The calculated results were further compared with those obtained from an extended UNIQUAC model.     

Quaternary Liquid–Liquid Equilibria for Fuel Additive Systems Containing Diethyl Carbonate or 1,1-Dimethylethyl Methyl Ether at 298.15 K and Atmospheric Pressure

Liquid–liquid equilibrium tie line data were determined for three quaternary systems water + ethanol + diethyl carbonate+n-heptane, water + ethanol + 1,1-dimethylethyl methyl ether + diethyl carbonate, and water + 1,1-dimethylethyl methyl ether + diethyl carbonate+n-heptane at 298.15 K and atmospheric pressure. The experimental liquid–liquid equilibria results have been correlated using a modified UNIQUAC model and an extended UNIQUAC model, both with multicomponent interaction parameters in addition to the binary ones.     

The Cloud Point Behaviors and the Liquid–Liquid Equilibrium of L31—Inorganic Sodium Salt Aqueous Two-Phase Systems

The cloud point (CP) of triblock-copolymer L31 aqueous solution was determined with salting-out salts (Na₂SO₄/Na₂CO₃/NaF/NaCl/NaBr). The results show that all these salts can decrease the CP of L31 aqueous solution and form aqueous two-phase system (ATPS). With increasing concentrations of Na₂SO₄ and Na₂CO₃, an obvious phase inversion could be observed and phase inversion points were found. This was mainly due to the change in density, the salt-rich phase shifted from the top phase to the bottom phase. Meanwhile, the liquid-liquid equilibrium (LLE) data for L31-Na₂SO₄/Na₂CO₃/NaF/NaCl/NaBr ATPSs were measured at 288.15 K. The salt ability to decrease the CP and to induce the phase separation is as follows: Na₂SO₄?>?Na₂CO₃, NaF?>?NaCl?>?NaBr. Finally, the order of anions that reduced the CP and caused phase separation was obtained as follows: SO₄^2? >CO₃^2?, F^??>?Cl^??>?Br^?.     

Liquid–Liquid Equilibria of Oxygenate Fuel Additives with Water at 25°C: Ternary and Quaternary Aqueous Systems of Methyl tert-Butyl Ether and tert-Amyl Methyl Ether with Methanol or Ethanol

Experimental tie-line data have been determined for the ternary system water + methyl tert-butyl ether + tert-amyl methyl ether and the quaternary systems water + methanol + methyl tert-butyl ether + tert-amyl methyl ether, and water + ethanol + methyl tert-butyl ether + tert-amyl methyl ether at 25°C and ambient pressure. The experimental results have been satisfactorily correlated using the modified UNIQUAC and extended UNIQUAC models with ternary and quaternary, in addition to binary parameters.     

Characterization of Phenosafranine–Hemoglobin Interactions in Aqueous Solution

Binding of the drug phenosafranine to hemoglobin (Hb) in aqueous solutions was investigated by fluorescence, UV/vis and circular dichroism (CD) spectral methods at pH=7.4. The fluorescence data showed that fluorescence quenching of Hb by phenosafranine is the result of formation of a phenosafranine–Hb complex with a 1:1 molar ratio. Thermodynamic analysis implied that hydrophobic, electrostatic and hydrogen bond interactions are all involved in stabilizing the complex. The molecular distance (r=4.29 nm) between the donor (Hb) and acceptor (phenosafranine) was calculated according to Förster’s theory. The features of phenosafranine-induced secondary structure changes of Hb have been studied by synchronous fluorescence, CD and three-dimensional fluorescence spectroscopy. This study improves our knowledge of the interaction dynamics of phenazinium drugs to the physiologically important protein Hb.     

Liquid—Liquid Equilibrium in Polydisperse Random Copolymer Blends

Continuous thermodynamics is applied to the liquid‐liquid equilibrium in random copolymer blends. Two copolymers are mixed, each consisting of two different monomer units. Hence, up to four monomer units may be present in the system. Both copolymers are characterized by divariate distribution functions with respect to molecular weight (chain length) and chemical composition. The basic relations necessary for phase equilibrium calculations are derived. The influences of both polydispersities and of the different parameters included in the model for the excess Gibbs free energy are discussed by calculating cloud‐point curves and shadow curves. Applications to practical systems are given.     

Volumetric and Surface Properties of Short Chain Alcohols in Aqueous Solution–Air Systems at 293?K

From measurements of the surface tension, density, viscosity and light scattering of aqueous solutions of methanol, ethanol and propanol at 293?K, their activity in the surface monolayer, surface excess concentration, and apparent and partial molar volume were determined. The surface excess concentration of alcohols at the water?Cair interface was determined from the Gibbs equation by using both the alcohol's activity and their molar fraction in the bulk phase and recalculated by using the Guggenheim?CAdam equation. The values of the surface excess concentration determined from the Gibbs equation were also applied to determine the standard Gibbs energy of alcohol adsorption at the water?Cair interface from Langmuir??s equation and compared to those determined from that of Aronson and Rosen.     

Influence of Temperature on Liquid–Liquid Equilibrium of Methanol + Toluene + Hexane Ternary Systems at Atmospheric Pressure

Phase equilibria of methanol?+?toluene?+?hexane ternary systems at (278.15, 283.15, 288.15 and 293.15) K at atmospheric pressure were investigated. The influence of temperature on the liquid–liquid equilibrium is discussed. All chemicals were quantified using gas chromatograph with a thermal conductivity detector coupled to a ChemStation and nitrogen as gas carrier, their mass fractions were higher than 0.999. From literature are found two articles from the same system at different temperatures studied here. Experimental data are compared with literature values. Values calculated using the NRTL and UNIQUAC equations are compared with the experimental data and it is found that the UNIQUAC equation fitted the experimental data better than the NRTL model for this ternary system.     

Liquid–Liquid Equilibrium Data for 1-Ethyl-3-methylimidazolium Acetate–Thiophene–Diesel Compound: Experiments and Correlations

Extraction of thiophene from cyclohexane, isooctane and toluene were performed using the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) at T=298.15 K. The liquid?Cliquid equilibrium (LLE) experiments were performed on three systems, namely: [EMIM][OAc]?Cthiophene?Ccyclohexane, [EMIM][OAc]?Cthiophene?Cisooctane and [EMIM][OAc]?Cthiophene?Ctoluene. The LLE data showed that [EMIM][OAc] has a higher selectivity at low concentration of thiophene and also showed that the hydrocarbon-rich phase is free of ionic liquid. This implies that there will be no cross contamination and the ionic liquid will be a non-pollutant in fuel after extraction. Further, the amount of hydrocarbon in the ionic-liquid-rich phase is very small. This implies that ionic liquid can be regenerated with negligible loss of fuel. LLE data was then correlated using the NRTL and UNIQUAC models. These showed root mean square deviation (RMSD) values of 0.82?% and 1.46?% for the isooctane system, 1.37?% and 1.57?% for the cyclohexane system and 1.39?% and 1.53?% for the toluene system.     

DNA Effect on Cis–Trans Equilibrium and Fluorescent Properties of 3,3′-Diethyl-9-thiomethylthiacarbocyanine Iodide in Aqueous Solution

The influence of DNA on the cis–trans equilibrium and fluorescent properties of 3,3-diethyl-9-thiomethylthiacarbocyanine iodide (DTTC) in a phosphate buffer (pH 7) was studied by various photochemical techniques. The interaction of dye molecules with DNA leads to the formation of stable noncovalently bonded complexes. Data obtained from DTTC absorption and fluorescence spectra suggest that complexation proceeds primarily through the cis-form of the dye. Complexation with DNA leads to a substantial increase in the quantum yield of the triplet state of DTTC molecules. The rate constant for quenching the dye triplet state by oxygen turned out to be significantly lower than the diffusion-controlled value.     

Thermodynamic Investigation of Phase Equilibria in Metal Carbonate–Water–Carbon Dioxide Systems

 Solubility measurements as a function of temperature have been shown to be a powerful tool for the determination of thermodynamic properties of sparingly-soluble transition metal carbonates. In contrast to calorimetric methods, such as solution calorimetry or drop calorimetry, the evaluation of solubility data avoids many systematic errors, yielding the enthalpy of solution at 298.15 K with an estimated uncertainty of ±3 kJ · mol⁻¹. A comprehensive set of thermodynamic data for otavite (CdCO₃), smithsonite (ZnCO₃), hydrozincite (Zn₅(OH)₆(CO₃)₂), malachite (Cu₂(OH)₂CO₃), azurite (Cu₃(OH)₂(CO₃)₂), and siderite (FeCO₃) was derived. Literature values for the standard enthalpy of formation of malachite and azurite were disproved by these solubility experiments, and revised values are recommended. In the case of siderite, data for the standard enthalpy of formation given by various data bases deviate from each other by more than 10 kJ · mol⁻¹ which can be attributed to a discrepancy in the auxiliary data for the Fe²⁺ ion. A critical evaluation of solubility data from various literature sources results in an optimized value for the standard enthalpy of formation for siderite. The Davies approximation, the specific ion-interaction theory, and the Pitzer concept are used for the extrapolation of the solubility constants to zero ionic strength in order to obtain standard thermodynamic properties valid at infinite dilution, T = 298.15 K, and p = 10⁵ Pa. The application of these electrolyte models to both homogeneous and heterogeneous (solid-solute) equilibria in aqueous solution is reviewed.     

Thermodynamic Investigation of Phase Equilibria in Metal Carbonate–Water–Carbon Dioxide Systems

Summary.  Solubility measurements as a function of temperature have been shown to be a powerful tool for the determination of thermodynamic properties of sparingly-soluble transition metal carbonates. In contrast to calorimetric methods, such as solution calorimetry or drop calorimetry, the evaluation of solubility data avoids many systematic errors, yielding the enthalpy of solution at 298.15 K with an estimated uncertainty of ±3 kJ · mol⁻¹. A comprehensive set of thermodynamic data for otavite (CdCO₃), smithsonite (ZnCO₃), hydrozincite (Zn₅(OH)₆(CO₃)₂), malachite (Cu₂(OH)₂CO₃), azurite (Cu₃(OH)₂(CO₃)₂), and siderite (FeCO₃) was derived. Literature values for the standard enthalpy of formation of malachite and azurite were disproved by these solubility experiments, and revised values are recommended. In the case of siderite, data for the standard enthalpy of formation given by various data bases deviate from each other by more than 10 kJ · mol⁻¹ which can be attributed to a discrepancy in the auxiliary data for the Fe²⁺ ion. A critical evaluation of solubility data from various literature sources results in an optimized value for the standard enthalpy of formation for siderite. The Davies approximation, the specific ion-interaction theory, and the Pitzer concept are used for the extrapolation of the solubility constants to zero ionic strength in order to obtain standard thermodynamic properties valid at infinite dilution, T = 298.15 K, and p = 10⁵ Pa. The application of these electrolyte models to both homogeneous and heterogeneous (solid-solute) equilibria in aqueous solution is reviewed. Received June 26, 2001. Accepted July 2, 2001     

Liquid–Liquid Extraction of Sulfuric Acid from Aqueous Sulfate Waste Solution using Alamine 336/Kerosene/TBP Solvent

Generally the metallurgical industries generate huge amounts of harmful environmental wastes, which may be solids, liquids, or gases in their nature. The present study aims to recovery sulfuric acid (227 g/l) from wastes generated during hydrometallurgical digestion of titanium ores with sulfuric acid for TiO₂ production. For this purpose Alamine 336/kerosene solvent was used. Various extraction parameters as Alamine 336 concentration, shaking time, type of diluent, and O/A phase ratio were studied and optimized. Under the optimum conditions, Mc-Cabe Thiele diagram results indicated that, after four extraction stages the acid concentration in aqueous phase was reduced from the initial value of 227 g/l to about 17 g/l. Stripping of the loaded sulfuric acid from the organic phase was done with warm water (60°C). Stripping parameters as water temperature, stripping time, and A/O phase ratio were studied. Under the stripping the loaded acid concentration in organic phase was reduced from 210 to 6 g/l which matched theoretically by McCabe Thiele diagram.     

Lamellar Liquid Crystals of Brij 97 Aqueous Solutions Containing Different Additives

Lamellar liquid crystals of Brij 97 aqueous solutions were investigated by means of rheological techniques and SAXS at 25 °C, in the presence of various additives including isopropyl myristate, oleic acid, ionic liquid bmim-PF₆ and bmim-BF₄. The lamellar phases show high elasticity as indicated by their mechanical and discrete relaxation spectra, which is expected to be an advantage when they are used as drug delivery vehicles. It is noted that in comparison with other systems, the lamellar phase formed in the Brij 97/water/IPM system has the lowest storage and loss moduli, implying that it has a weak network strength and less stable internal structure. The Brij 97/water/oleic acid system is the most shear resistance, whereas the Brij 97/water/bmim-PF₆ system exhibits fluid-like viscoelastic properties to some extent. These differences are analyzed through SAXS data for the different location of the additive in the lamellar phase.     

Simultaneous Calculation of Equilibrium Constants and Standard Formation Enthalpies from Calorimetric Data for Systems with Multiple Equilibria in Solution

The computer program HypΔH is a general-purpose Windows^® application designed to derive equilibrium constants and/or formation enthalpies of complexes from solution calorimetric data. Least-squares minimization is used with the analytically determined derivatives. The efficacy of the program is demonstrated by application to the calculation of formation constants and enthalpies for the formation of AgPy⁺ and AgPy ₂ ⁺ , and also of CH₃HgGly⁺, CH₃HgGlyH and (CH₃Hg)₂Gly²⁺. The results are compared with published data.     

Isomorphous Substitution of Metallic Elements for Zeolite Y in the Aqueous Solution

The substitutions of Ti, Fe and Zr into zeolite Y in the aqueous solutions of (NH4)2TiF6, (NH4)3ZrF7 and (NH4)3FeF6 were systematically Investigated. It was found that Ai atoms in the framework can be replaced by some metallic elements and the extent of substitution depends on the M/A1 ratio of the solution. The maximum allowable M/A1 ratio of the aqueous solution Is related with the radius of the M atom and the stability constant of the MFnm- complex. The substituted zeolite samples with crystallinity greater than 80% were characterized by means of XRD, IR, DTA, TPR and NH3-TPD measurements. The incorporation of Ti, Fe and Zr into the zeolite leads to an increase in the unit cell parameter, a lowering of thermal stability and a red shift of the asymmetric stretching frequency. The extent of these changes is apparently related with the ionic radius of the metallic element and the degree of substitution. The results of various characterization methods show that the het-eroatoms are readily Introduced int     

Electrical Double Layer on Liquid Sn–Ga Alloy in Aqueous Solutions

Double-layer parameters of a liquid Sn–Ga electrode in aqueous electrolyte solutions are studied. It is shown that Sn in the alloy with Ga is a surface-active component and is forced out onto a surface layer of the electrode. The double-layer parameters of an Sn–Ga electrode (8 at. % Sn), which are measured in the experimentally accessible range of charges, differ radically from the parameters of Ga electrodes and are close to those of Sn electrode. Hence, an Sn–Ga electrode containing 8 at. % Sn simulates electrochemical properties of a liquid Sn electrode. The difference between reciprocal electronic capacitances of Hg and Sn and a corrected electrochemical work function of Sn are determined. It is shown that the chemisorption interaction of an Sn–Ga electrode with water molecules is virtually absent at charges more negative than –7 C/cm². A potential drop on uncharged Sn, which is associated with water chemisorption, is –20 mV. Thus, the hydrophilicity of Sn is slightly higher than that of Hg, Bi–Ga, Pb–Ga, and Tl–Ga and significantly lower than that of In–Ga, Cd–Ga, and Ga.