Excess enthalpies of binary and ternary mixtures of acetonitrile with methanol,ethanol and benzene

Excess molar enthalpies are measured for the binary mixtures methanol—acetonitrile and ethanol—acetonitrile at 25 and 35°C and for the ternary mixtures methanol—acetonitrile—benzene and ethanol—acetonitrile—benzene at 25°C using an isothermal dilution calorimeter. The binary results are well reproduced with an association model which contains four equilibrium constants for the association of alcohol, two equilibrium constants for that of acetonitrile, and two solvation equilibrium constants between alcohol and acetonitrile molecules. The ternary results are compared with those calculated from the model with binary parameters.     

Excess enthalpies and complex formation of acetonitrile with acetone,chloroform, and benzene

Excess enthalpies of binary systems of acetonitrile—acetone, chloroform—acetone and chloroform—benzene, and ternary systems of acetonitrile—chloroform—acetone and acetonitrile—chloroform—benzene are reported at 25°C. The results are analyzed with thermodynamic association theory for complex ternary liquid mixtures. The theory involves two types of self-association of acetonitrile, formation and binary complexes for component pairs of a ternary system, and a nonspecific interaction term expressed by the NRTL equation between various chemical species.     

Measurement of vapor-liquid equilibrium in systems with components of very different volatility by the total pressure static method

To make feasible the experimental study of vapor-liquid equilibrium (VLE) in the systems mentioned in the title, a static apparatus for accurate measurement of total vapor pressures of solutions was constructed. Mixtures of known composition are prepared synthetically in a thermostated equilibrium cell by weight from pure degassed components and the total pressure is measured by a quartz Bourdon gage. A procedure was developed for degassing pure liquids to a degree corresponding to the high precision of pressure determination required. The static assembly was tested by comparing obtained isothermal vapor pressures and calculated excess Gibbs free energies with literature data for the benzene - cyclohexane system at 14 and 20°C, respectively. Additional experimental vapor-pressure data are presented for pure cyclohexane, benzene, and N-methylpyrrolidone (abbreviated throughout this paper as NMP) at 6–24°C and for the binary systems of benzene-cyclohexane at 8°C and cyclohexane - NMP and benzene - NMP at 8, 14, and 20°C over the entire composition range. The binary data were reduced by a modified Barker's method to evaluate excess Gibbs free energies and vapor phase compositions.     

Quaternary liquid—liquid equilibrium. Cyclohexane—ethanol—benzene—acetonitrile

Nagata, I., 1986. Quaternary liquid—liquid equilibrium. Cyclohexane—ethanol—benzene—acetonitrile. Fluid Phase Equilibria, 26: 59–68.Experimental liquid—liquid equilibrium results are presented for the ternary acetonitrile—ethanol—cyclohexane and the quaternary cyclohexane—ethanol—benzene—acetonitrile systems at 25°C. The results agree well with the calculated values derived from the extended UNIQUAC equation (Nagata) with parameters from phase equilibrium data for the constituent binary mixtures or ternary tie-line data sets.     

Isothermal vapor—liquid equilibrium of ternary mixtures formed by 1-propanol,acetonitrile and benzene

Vapor—liquid equilibrium data are presented for the ternary system 1-propanol-acetonitrile-benzene, at 45°C. The experimental vapor—liquid equilibrium results of the three constituent binary systems are well reproduced with the UNIQUAC associated-solution model and the ternary results are compared with those calculated from the model with binary parameters alone. Ternary prediction of liquid—liquid equilibria is given for the 1-propanol-acetonitrile-n-hexane and 1-propanol—acetonitrile-n-heptane systems at 25°C.     

Mutual solubilities and vapor pressures for binary and ternary aqueous systems containing benzene,toluene, m-xylene,thiophene and pyridine in the region 100–200°C

An apparatus has been constructed to measure mutual solubilities and vapor pressures for aqueous—organic liqui—liquid systems in the region of 200°C. Both liquid phases are sampled and analyzed using gas chromatography. Special care must be taken to ensure reliable sampling because mutual solubilities are very small; it is especially important to avoid entrainment, phase change (due to temperature gradients or pressure drop) and adsorption when removing samples for chemical analysis.Experimental results are reported for the temperature range 100–200°C for binary aqueous mixtures containing benzene, toluene, m-xylene and thiophene, and for ternary aqueous mixtures containing benzene and pyridine. The binary results are in good agreement with diverse data reported in the literature.     

Complex-radical terpolymerization of phenanthrene,maleic anhydride,and trans-stilbene

The radical terpolymerization of the donor-acceptor-donor monomer system, phenanthrene (P)—maleic anhydride (M)—trans-stilbene (S), was studied. These monomers are known to be nonhomopolymerizable. The terpolymerization was carried out in p-dioxane and/or toluene at 70°C in the presence of benzoyl peroxide used as the initiator. P and S were found to form charge transfer complexes (CTC) with M in p-dioxane at 35°C. The results obtained are discussed in terms of the free monomer and complex propagation models. It is shown that terpolymerization is carried out at a stage close to binary copolymerization of two complexomers. The reactivity ratio of P … M and S … M complexes was estimated by the Kelen-Tüdös method. Absorbance ratios at 1770 cm^?1 (v_C=0 of anhydride group), 764 cm^?1 (δ_CH in monosubstituted benzene of S), and 820 cm^?1 (δ_CH in disubstituted benzene of P) as a function of terpolymer composition were established. P—M—S terpolymers are shown to have high thermal stabilities. © 1995 John Wiley & Sons, Inc.     

Dielectric relaxation study of binary mixture of sulfolane and N,N-dimethylformamide in benzene solution using microwave absorption data

The dielectric constant (???) and dielectric loss (???) for dilute solutions of the binary mixture of different molar concentrations of sulfolane and DMF in benzene solution has been measured at 9.885 GHz and different temperatures (25, 30, 35, 40°C) by using standard microwave techniques. Following the single frequency concentration variational method, the dielectric relaxation time (??) and dipole moment (??) have been calculated. It is found that dielectric relaxation process can be treated as the rate process, just like the viscous flow. The presence of solute-solute molecular associations in benzene solution has been proposed. Energy parameters (??H _?, ??F _?, ??S _?) for dielectric relaxation process of binary mixture at 50% mole fraction in benzene at 25, 30, 35, and 40°C have been calculated and compared with the corresponding energy parameters (??H _??, ??F _??, ??S _??) for the viscous flow.     

Measurement of vapor-liquid equilibria and determination of azeotropic point

Hiaki, T., Tochigi, K. and Kojima, K., 1986. Measurement of vapor—liquid equilibria and determination of azeotropic point. Fluid Phase Equilibria, 26: 83–102.To measure the azeotropic point, a liquid-vapor ebullition type equilibrium still is developed. Vapor-liquid equilibria at 101.325 kPa are measured for the ternary azeotropic system benzene - cyclohexane - n-propanol, and the three constituted binary azeotropic systems. A method is introduced for graphical determination of the binary azeotropic point on the basis of experimental binary vapor-liquid equilibrium data. Also, a method is evolved for determination of the binary and ternary azeotropic points by using the extended Redlich-Kister equation applicable to the condition of constant pressure, and the azeotropic points are determined for three binary and one ternary systems.     

Determination of H o , G o , and S o of the interaction of ions with carrier antibiotics by computerized microcalorimetry

ΔH°, ΔG°, and ΔS° — and thereby the equilibrium constant of the interaction of carrier antibiotics with ions — are determined using a microcalorimeter on-line with a dedicated computer. Thermodynamic data of the interaction of monensin, macrotetrolides and valinomycin with sodium and potassium ions in methanol at 25°C are given.     

Phase equilibria for four binary systems containing propylene

Isothermal vapor—liquid equilibria (P−x, y) for four binary systems of propylene with methanol, acetone, diethyl ether and propylene oxide were measured using a swing method at 25°C. Also, the saturated molar volume of the liquid phase for each system was obtained by a weighing method. The data obtained were correlated by use of the Soave-Redlich-Wong equation. The P-x, y relations were described satisfactorily, except for the methanol—propylene     

Vapor-liquid equilibrium for the systems ethyl formate-methyl ethyl ketone,ethyl formate-toluene and ethyl formate-methyl ethyl ketone-toluene: new unifac parameters for interactions between the groups ACH/HCOO,ACCH2/HCOO and CH2Co/HCOO

Vapor-liquid equilibrium data are presented for the binary systems ethyl formate-methyl ethyl ketone (MEK) at 40°C and 50 °C and ethyl formate-toluene at 48°Cand 51°C and for the ternary system ethyl formate-MEK-toluene at 50°C. The measurements were carried out in a recirculation still similar to that proposed by Röck and Sieg. Vapor pressures of the pure substances were measured and the data correlated using the Antoine equation. The binary data were reduced by means of a maximum-likelihood procedure providing the relevant Margules, NRTL and UNIQUAC parameters.New UNIFAC interaction parameters between the groups ACH/HCOO, ACCH₂/HCOO and CH₂CO/HCOO have been obtained. These parameters have been used to predict the ternary data, and a comparison between the experimental and predicted values is presented.     

Thermogravimetric and FTIR studies of chitosan blends

Results of spectrophotometric and thermogravimetric studies of chitosan (CH) blends with polyvinyl alcohol (PVAL), starch (S) and hydroxypropylcellulose (HPC) obtained by casting from solutions in the form of transparent films containing 0–1.0 weight fraction of CH were discussed. Blends containing S are homogeneous only in the case of low-weight fraction of S (to 0.3).On the basis of results of thermodegradation in dynamic and isothermal conditions, thermal stability of the tested systems was estimated. Thermogravimetric measurements in dynamic conditions were carried out in the temperature range of 100–450 °C at constant heating rate 15 °C/min. From thermogravimetry (TG) and DTG curves the activation energy and characteristic parameters of degradation of the tested blends were determined. The observed growth of activation energy and T_p—temperature of initial weight loss, T_max—temperature of maximal rate and C_e—degree of conversion at the end of the measurement (at temperature 450 °C) along with the increase of polymer fraction (HPC and S) in the CH blend provides an evidence of improved thermal stability of the systems tested.Investigations in isothermal conditions in air at temperature from 100 to 200 °C confirmed appreciable improvement of CH thermal stability in the blends being tested.Infrared spectroscopic analysis of the blends showed a distinct stabilization of the process of chain scission. In the band at 1080 cm⁻¹ associated with absorption in –C–O–C– group during degradation of the blends at temperature 200 °C much smaller decrease due to molecular scission were observed than in the case of pure CH.     

Ternary liquid—liquid equilibria for acetonitrile—ethanol—cyclohexane and acetonitrile—2-propanol—cyclohexane

Liquid—liquid equilibrium data were obtained for two ternary systems: acetonitrile— ethanol—cyclohexane at 40°C, and acetonitrile—2-propanol—cyclohexane at 50°C. Binary vapor—Liquid equilibrium data were measured for acetonitrile—2-propanol at 50°C. The binary parameters of the Zeta and effective Zeta equations were evaluated from equilibrium data for binary pairs. The parameters obtained were used to predict the ternary liquid—liquid equilibrium data for six systems involving the present systems and the ternary vapor—liquid equilibrium data for one completely miscible system and two partially miscible systems without adding any ternary parameter. A heterogeneous area calculated by the Zeta equation is in general too large and does not decrease appreciably with increasing values of the third parameter ζ of the Zeta equation. However, the effective Zeta equation works much better than the original Zeta equation in data reduction.     

Compressed liquid densities of propane—normal butane mixtures between 10 and 60°C at pressures up to 9.6 MPa

Compressed liquid densities for propane—normal butane mixtures are reported at six temperatures between 10 and 60°C. For each isotherm, there are at least seven compositions ranging between 10 and 75 mol% propane at pressures from near saturation up to 9.65 MPa. The derived excess volumes are negative and represent a maximum of 0.5 percent of the mixture volume at 10°C. At 60°C, the excess volume can be up to 2.2% of the mixture volume. In addition to the binary data, limited density measurements were made on ternary mixtures containing up to 17 mol% ethane.     

Vapour—liquid equilibrium of the system benzene + cyclohexane + 1-propanol at 760 mm Hg

Arce, A., Blanco, A. and Tojo, J., 1986. Vapour—liquid equilibrium of the system benzene + cyclohexane + 1-propanol at 760 mm Hg. Fluid Phase Equilibria, 26: 69–81.Vapour—liquid equilibrium data for the mixture benzene + cyclohexane + 1-propanol at a constant pressure of 760 mm Hg have been determined experimentally and predicted using the group contribution methods UNIFAC and ASOG and the NRTL, UNIQUAC and Wilson equations (with correlation parameters obtained from data for the corresponding binary mixtures). The various predictions are compared and evaluated in the light of the experimental results.     

Raman study of reorientational motion of liquid benzene

Raman spectra of the 943 cm^?1 band of liquid benzene-d₆ were measured at temperatures up to 120°C and at pressures up to 4000 bar. Rotational diffusion constants for tumbling and spinning motions were obtained from Raman band widths and NMR T₁ data. Experimental results were compared with theoretical diffusion constants computed on the basis of various models. It is found that the Hynes—Kapral—Weinberg theory gives the best prediction for the temperature and pressure dependence of the diffusion constants and for the rotational anisotropy in liquid benzene.     

Kinetic study of specific base catalyzed hydrolysis of ethyl acrylate in water-ethanol binary system

Kinetic study of hydroxide anion catalyzed hydrolysis of ethyl acrylate has been carried in ethanol-water (10–50% v/v) binary systems at the temperature range 30 ± 0.1, 35 ± 0.1, 40 ± 0.1, and 45 ± 0.1°C. Calculated specific rate constant values decreases with increasing proportion of ethanol at all temperatures. The observed retardation of a base catalyzed hydrolysis reaction is explained on the basis of fact that the formation of polarized transition state is disfavored with increase in % of ethanol. The relation between the change in dielectric constant due to variation in binary mixtures and change in specific rate constant are explained on the basis of electrostatic and non electrostatic contributions of solvent mixtures. The variation of ΔG*, ΔH*, ΔS* with solvent composition and the specific effect of water on the reaction rate kinetics are also discussed.     

Refractive index and molar refractivity of benzonitrile, chlorobenzene, benzyl chloride and benzyl alcohol with benzene at T = 298.15, 303.15, 308.15 and 313.15 K

Densities and refractive indices were measured for the binary liquid mixtures formed by benzonitrile, chlorobenzene, benzyl chloride, and benzyl alcohol with benzene at (T = 298.15, 303.15, 308.15 and 313.15 K) and atmospheric pressure over the whole concentration range. The Lorentz–Lorentz mixing rule, the Ramaswami and Anbananthan model, and the model devised by Glinski were used to study the refractive index and molar refractivity. These results have been discussed to study the type of mixing behavior between the mixing molecules. The measured data were fitted to the Redlich–Kister polynomial relation to estimate the binary coefficients and standard errors. Furthermore, the McAllister multibody interaction model is used to correlate the binary refractive index with the experimental findings. It is observed that molar refractivity, molecular interaction, and association constant can be better understood from these models.     

Thermophysical properties of supercritical fluids with special consideration of aqueous systems

Selected thermophysical properties of polar, dense supercritical fluids are discussed. The static dielectric constant of water and the freon R22 (CHClF₂) is shown in some detail. Examples of critical curves for binary systems with water and methanol are given. New experimental data of excess volumes up to 400 °C and 2000 bar are shown for water combined with H₂, CH₄ and benzene. Excess Gibbs energies and activity coefficients for water-benzene are also shown. Results of the solubility of anthracene in ten different high pressure fluids, obtained by UV-spectroscopy, are presented. The PVT-data of concentrated supercritical aqueous NaCl-solutions and the ion product of pure water to 1000 °C are discussed.