Correlation and prediction of salt effects on vapor–liquid equilibrium in alcohol–water–salt systems

A modification of the solvation model of Ohe is proposed for the calculation of vapor–liquid equilibria (VLE) in alcohol–water–salt systems. The modified method employs the Bromley equation to calculate the activity of water in salt solutions, and a one-parameter empirical expression to calculate the activity of the alcohol. The single parameter is obtained by fitting ternary alcohol–water–salt data. The method is simple to use and does not require data on the vapor-pressures of alcohol–salt mixtures that are seldom available in the literature. Experimental data for 17 salts in 36 alcohol–water–salt systems, covering a temperature range from 298 to 375 K, and salt concentrations up to about 8 m, were correlated using the new approach. In all, 69 data sets and 1045 data points were correlated satisfactorily. The method was also used to predict VLE in four ternary alcohol–alcohol–salt systems and one quaternary alcohol–alcohol–water–salt system with satisfactory results.     

Phase equilibria in binary subsystems of urea–biuret–water system

Joint results of the differential scanning calorimetry (DSC) and thermogravimetry (TG) experiments were the basis for the fusion enthalpy and temperature determination of the biuret (NH₂CO)₂NH (synthesis by-product of the urea fertilizer (NH₂)₂CO). Recommended values are Δ_m H = (26.1 ± 0.5) kJ mol⁻¹, T _m = (473.8 ± 0.4) K. The DSC method allowed for the phase diagrams of “water–biuret,” “water–urea,” “urea–biuret” binary systems to be studied; as a result, liquidus and solidus curves were precisely defined. Stoichiometry and decomposition temperature of the biuret hydrate identified, composition of the compound in “urea–biuret” system was suggested.     

Premicellar aggregation in water–salt solutions of sodium alkyl sulfonates and dodecyl sulfate

The features of premicellar aggregation in aqueous solutions of sodium n-octyl, n-nonyl, and n-decyl sulfonate, as well as sodium n-dodecyl sulfate, at a constant ionic strength maintained by adding NaCl are studied by potentiometry using modified ion-selective electrodes reversible with respect to the ions of these surfactants. For the studied surfactants, the critical micelle concentrations are refined, the compositions of the products of premicellar aggregation are determined, and the stability constants of aggregates are evaluated.     

Molecular thermodynamics of salt effect in vapor–liquid equilibrium of ethanol–water systems

Scaled particle theory was used to derive a general expression for the salt effect parameter, K, of isobaric vapor–liquid equilibrium for ethanol–water-1-1 type electrolytic systems, which appears in the Furter equation. This expression was essentially a sum of two terms: 1, the hard sphere interaction term calculated by Masterton–Lee's equation, 2, the soft sphere interaction term calculated by Y. Hu's molecular thermodynamical model, in which the diameters of nacked ions were replaced by that of solvated ions, the solvation coefficients (i.e., in the radio of the latter to the former) were taken to be adjustable parameters, their magnitude implies the ionic solvation rules. A correlation equation for the local dielectrical constant around central ions with liquid concentration was obtained by mapping out experimental points. The calculated salt effect parameters of 9 ethanol–water-1–1 type electrolytic systems were in good agreement with the literature values within the wide range of liquid concentration.     

Synthesis and thermal decomposition of Cr–urea complex

In this work, Cr–urea complex ([Cr(NH₂CONH₂)₆](NO₃)₃) was synthesized by direct solid-state reaction of chromium nitrate and urea, and its thermal decomposition reaction was studied for the first time to explore the possibilities of using the complex as precursor to nanosized chromium oxide. The formation of [Cr(NH₂CONH₂)₆](NO₃)₃ is confirmed from infrared spectroscopy and elemental analysis. Thermogravimetric and differential thermal analysis of the compound show a three-stage thermal decomposition in the temperature range from 190 to 430 °C. The result of X-ray diffraction (XRD) shows that the [Cr(NH₂CONH₂)₆](NO₃)₃ decompose at ~300 °C into α-Cr₂O₃ nanopowder with an average crystallite size of 33 nm.     

Prediction and experimental verification of the salt effect on the vapour–liquid equilibrium of water–ethanol–2-propanol mixture

Experimental vapour–liquid equilibria of water–ethanol–2-propanol saturated with NaNO₃, NaCl, KCl and containing 0.05 mol CH₃COOK/mol total solvent compared well with those predicted by Tan–Wilson and Tan–non-random two liquid (NRTL) models for multicomponent solvent–solute mixture using a set of solvent–solvent interaction parameters obtained from the regression of the vapour–liquid equilibrium of the solvent mixture without the dissolved solute and a set of solute–solvent interaction parameters calculated from the bubble points of the individual solvent components saturated or containing the same molar ratio of solute/total solvents as the mixture. The results also showed that a solvent component i is salted-in or out of the liquid phase relatively more than solvent component j would depend on whether A_sj/A_si (Tan–Wilson model) or exp(τ_is−τ_js) (Tan–NRTL model) is less or greater than 1. This is consistent with earlier publications on the effect of dissolved solutes (electrolytes and non-electrolytes) on the binary solvents mixtures. These findings confirmed that Tan–Wilson and Tan–NRTL models for multicomponent solvent–solute system can provide an accurate and rapid screening of electrolytes and non-electrolytes for their suitability in facilitating solvent separation by salt distillation of ternary solvent mixtures simply by determining the relative ratios of the solute–solvent interaction parameters from the respective bubble points of the solvent components containing the dissolved solute. The results also suggest that this may also be extended to other multicomponent solvent mixtures.     

TG–DTA, UV and FTIR spectroscopic studies of urea–thiourea mixed crystal

A mixed crystal of urea–thiourea was grown by slow evaporation of aqueous solution at room temperature. The bright and transparent crystals obtained were characterized by thermogravimetric–differential thermal analysis (TG–DTA), UV and FTIR spectroscopic analyses. A fitting decomposition pattern for the title compound was formulated on the TG curve which shows a two stage weight loss between 200 and 750 °C. In this temperature range DTA curve shows exothermic peaks supporting the formulated decomposition pattern. The UV and FTIR spectra show the characteristic absorption, vibration frequencies due to urea–thiourea mixed crystals. Detailed structural analysis of the compound is under progress.     

Bubble points of hydrogen chloride–water–isopropanol and hydrogen chloride–water–isopropanol–benzene systems and liquid–liquid equilibria of hydrogen chloride–water–benzene and hydrogen chloride–water–isopropanol–benzene systems

Bubble points of the HCl–water–isopropanol and the HCl–water–isopropanol–benzene systems and liquid–liquid equilibria (LLE) of the HCl–water–benzene and the HCl–water– isopropanol–benzene systems were measured at 25–85°C and 30–70°C, respectively. The electrolyte nonrandom two-liquid model proposed by Chen et al. [C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, AIChE J. 28 (1982) 588–596] can satisfactorily correlate bubble points and liquid–liquid equilibria of the present mixed-solvent electrolyte systems over the entire range of temperature and concentrations using only binary adjustable parameters.     

Synthesis,growth and characterization of nonlinear optical urea–ammonium chloride crystals

Semi-organic nonlinear optical urea–ammonium chloride (UAC) crystals have been grown from aqueous solution by slow evaporation technique. The lattice parameters of the grown crystals were determined by X-ray diffraction studies. The presence of functional groups was determined using Fourier transform infrared (FTIR) analysis. The thermal analysis studies indicate that the material possess optimum thermal stability. Optical absorption studies show low absorption in the entire visible region and UV cut – off is found to be at 240 nm. The presence of second harmonic generation (SHG) for the grown crystal was confirmed by Kurtz powder technique.     

Potential of magnesium salt–monoalkylpolyethylene glycol–water systems for use in micellar extraction

Solubilities in MgCl₂ (MgSO₄, Mg(NO₃)₂)–syntanol DS-10 (syntanol ALM-10)–water systems have been studied by the visual-polythermal method and the isothermal section method. The liquid–liquid phase separation region was shown to change its topology depending on temperature and the salting-out agent. The salting-out agent anion was shown to influence the cloud point of syntanol solutions. The effect of structure on the ability of syntanol to be salted out by magnesium salts was studied. Optimal temperature and concentration parameters of boron extraction in the studied systems were determined.     

Calorimetric studies of interactions of some peptides with electrolytes,urea and ethanol in water at 298.15 K

The standard molar enthalpies of solution at infinite dilution \Updelta_\textsol H_\textm^￥ \Updelta_{\text{sol}} H_{\text{m}}^{\infty } of glycylglycine, dl-alanyl-dl-alanine and glycylglycylglycine in aqueous solutions of potassium chloride and ethanol as well as of glycylglycine and glycylglycylglycine in the solutions containing urea and water have been determined by calorimetry at the temperature 298.15 K. Changes of solution enthalpy, expressed in a form so-called heterotactic interaction coefficients, h_\textxy h_{\text{xy}} were used for analysis of interactions occurring between the investigated solutes in water. The group contributions illustrating the interactions of KCl, urea and ethanol with selected functional groups in the peptide molecules, namely CH₂, “pep,” and “ion” groups, were calculated and discussed.     

Surface tension isotherms of the dioxane–acetone–water and glycerol–ethanol–water ternary systems

The results of the experimental and theoretical studies of the concentration dependence of surface tension of aqueous solutions of the 1,4-dioxane–acetone–water and glycerol–ethanol–water ternary systems were given. The studies were performed by the hanging-drop method on a DSA100 tensiometer. The maximum error of surface tension was 1%. The theoretical models for calculating the surface tension of the ternary systems of organic solutions were analyzed.     

Solvation thermodynamics of benzene,nitrobenzene, and aniline in water–acetonitrile mixtures

The enthalpies of dissolution of benzene, nitrobenzene, and aniline in water–acetonitrile mixtures are determined via calorimetry. The concentration dependences of the standard enthalpies of solvation of solutes are calculated. It is found that the concentration dependences of the standard enthalpies of solvation pass through maxima. The height of the observed maxima is shown to depend largely on the nature of the substituent. In the presence of a hydrophilic amino group capable of forming strong hydrogen bonds with water molecules, the value of a maximum falls; in the presence of a nitro group, it rises. The enthalpy parameters of pair interaction between molecules of water and benzene and its derivatives are calculated.     

Liquid–liquid equilibrium behavior of tetrabutylammonium bromide,benzene, and water mixture

Tetrabutylammonium bromide (QBr) is a weak organic salt and used as a phase-transfer catalyst in phase-transfer catalytic reaction producing the desired product of benzyl bromide in the organic phase. The distribution of QBr between the organic phase (benzene is the organic phase solvent) and the aqueous phase is the important factor influencing benzyl bromide yield. In this study, the liquid–liquid equilibrium of benzene, water, and QBr ternary mixture were measured at 318.15, 328.15, and 338.15 K, respectively. The experimental results exhibited that the solubility of QBr is very large in this heterogeneous liquid mixture and the amount of aqueous phase increases whenever more QBr was added at constant temperature. The concentration of QBr in aqueous phase decreased with the increasing temperature. The organic phase composition did not vary obviously since the solubilities of water and QBr in benzene are very low. An empirical parameter was introduced to represent the degree of dissociation of QBr in solvent while the experimental data were correlated since it is very difficult to measure the degree of dissociation of QBr attributed to the partial dissociation of a weak organic salt. Finally, the experimental data were correlated with the NRTL model of Renon and Prausnitz taking account ion–molecule and molecule–molecule interactions.     

Thermal, UV and FTIR spectral studies of urea–thiourea zinc chloride single crystal

A single crystal of urea–thiourea was grown by slow evaporation of aqueous solution at room temperature. The bright and transparent crystals obtained were characterised by TG–DTA, UV and FTIR spectral analyses. A fitting decomposition pattern for the title compound was formulated on the TG curve which shows a two stage mass loss between 200 and 750 °C. DTA curve shows exothermic peaks supporting the formulated decomposition pattern in this temperature range. The UV and FTIR spectra show the characteristic absorption, vibration frequencies due to urea–thiourea zinc chloride crystals. Detailed structural analysis of the compound is under progress.     

Characteristics of sodium alginate membranes for the pervaporation dehydration of ethanol–water and isopropanol–water mixtures

Alginate membranes for the pervaporation dehydration of ethanol–water and isopropanol–water mixtures were prepared and tested. The sodium alginate membrane was water soluble and mechanically weak but it showed promising performance for the pervaporation dehydration. To control the water solubility the sodium alginate membrane was crosslinked ionically using various divalent and trivalent ions. Among them the alginate membrane crosslinked with Ca²⁺ ion showed the highest pervaporation performance in terms of the flux and separation factors.     

Temperatures of liquid–liquid separation and excess molar volumes of {N-methylpiperidine–water} and {2-methylpiperidine–water} systems

Partial miscibility in binary systems {N-methylpiperidine–water} and {2-methylpiperidine–water} was studied. The temperatures of liquid–liquid separation were determined as function of composition using both calorimetric technique and phase equilibrium cell. The densities of {amine–water} mixtures were determined in the domain of total miscibility at temperatures between 288 K and 338 K. Excess molar volumes were derived from experimental density data and fit to a Redlich–Kister polynomial.     

Volume properties and structure of aqueous solutions of urea at 263–348 K

The apparent molar volume of urea ? in aqueous solution in the range T = 273–323 K and m = 1–10 (molality) depends linearly on m ^1/2. An equation for ?(m, T) was derived. The partial molar characteristics of urea ? ₂ and water ? ₁ (volume, dilatability, and temperature coefficients of volumes) were calculated. The ?(T) dependences have characteristic points (extrema, inflection points), shifted to the region of lower temperatures for dilute solutions. The ? ₁(T) dependences for 2m and 4m of the urea solution retain the characteristics of the Y ₁(T) of pure water. In these solutions, the proper structure of water is preserved.     

Comparison of thermal curing behavior of liquid and solid urea–formaldehyde resins with different formaldehyde/urea mole ratios

This study was undertaken to compare thermal cure kinetics of urea–formaldehyde (UF) resins, in both liquid and solid forms as a function of formaldehyde/urea (F/U) mole ratio, using multi-heating rate methods of differential scanning calorimetry. The requirement of peak temperature (T _p), heat of reaction (ΔH) and activation energy (E) for the cure of four F/U mole ratio UF resins (1.6, 1.4, 1.2 and 1.0) was investigated. Both types of UF resins showed a single T _p, which ranged from 75 to 118 °C for liquid resins, and from 240 to 275 °C for solid resins. As the F/U mole ratio decreased, T _p values increased for both liquid and solid resins. ΔH values of solid resins were much greater than those of liquid resins, indicating a greater energy requirement for the cure of solid resins. The ΔH value of liquid UF resins increased with decreasing in F/U mole ratio whereas it was opposite for solid resins, with much variation. The activation energy (E _a) values calculated by Kissinger method were greater for solid UF resins than for liquid resins. The activation energy (E _α ) values calculated by isoconversional method which showed that UF resins in liquid or solid state at F/U mole ratio of 1.6 followed a multi-step reaction in their cure kinetics. These results demonstrated that thermal curing behavior of solid UF resin differed greatly from that of liquid resins, because of a greater branched network structure in the former.