Ternary and quaternary (liquid + liquid) equilibria for (water + ethanol + α-pinene, +β-pinene,or +limonene) and (water + ethanol + α-pinene + limonene) at the temperature 298.15 K

(Liquid + liquid) equilibria and tie-lines for the ternary (water + ethanol + α-pinene, or β-pinene or limonene) and quaternary (water + ethanol + α-pinene + limonene) mixtures have been measured at T = 298.15 K. The experimental multicomponent (liquid + liquid) equilibrium data have been successfully represented in terms of the modified UNIQUAC model with binary parameters.     

(Vapour + liquid) equilibria and excess Gibbs free energies of (cyclohexanone + 1-chlorobutane and + 1,1,1-trichloroethane) binary mixtures at temperatures from (298.15 to 318.15) K

The vapour pressures of binary (cyclohexanone + 1-chlorobutane, + 1,1,1-trichloroethane) mixtures were measured at the temperatures of (298.15, 308.15, and 318.15) K. The vapour pressures vs. liquid phase composition data have been used to calculate the excess molar Gibbs free energies G^E of the investigated systems, using Barker’s method. Redlich–Kister, Wilson, UNIQUAC, and NRTL equations, taking into account the vapour phase imperfection in terms of the 2-nd virial coefficient, have represented the G^E values. No significant difference between G^E values obtained with these equations has been observed.     

Experimental (vapour + liquid) equilibrium data of (methanol + water), (water + glycerol) and (methanol + glycerol) systems at atmospheric and sub-atmospheric pressures

Experimental (vapour + liquid) equilibrium results for the binary systems, (methanol + water) at the local atmospheric pressure of 95.3 kPa and at sub-atmospheric pressures of (15.19, 29.38, 42.66, 56.03, and 67.38) kPa, (water + glycerol) system at pressures (14.19, 29.38, 41.54, 54.72, 63.84, and 95.3) kPa and the (methanol + glycerol) system at pressures (32.02 and 45.3) kPa were obtained over the entire composition range using a Sweitoslwasky-type ebulliometer. The relationship of the liquid composition (x₁) as a function of temperature (T) was found to be well represented by the Wilson model. Computed vapour phase mole fractions, activity coefficients and the measured values along with optimum Wilson parameters are presented.     

Experimental and theoretical study of quaternary (liquid + liquid) equilibria for mixtures of (methanol or water + ethanol + toluene + n-decane)

Experimental (liquid + liquid) equilibrium data were obtained for the extraction of toluene from n-decane by mixed-solvents (ethanol + water) and (ethanol + methanol) at three temperatures (298.15, 303.15, and 313.15) K and ambient pressure.The measured tie-line data for two quaternary mixtures of {(ethanol +  water) + toluene + n-decane} and {(ethanol + methanol) + toluene + n-decane} are presented. The experimental quaternary (liquid + liquid) equilibrium data have been correlated using the NRTL activity coefficient model to obtain the binary interaction parameters of these components. The NRTL models predict the equilibrium compositions of the quaternary mixtures with small deviations. The partition coefficients and the selectivity factor of the mixed-solvents used were calculated and presented. From our experimental and calculated results, we conclude that for the extraction of toluene from n-decane mixtures the mixed-solvent (ethanol + methanol) has a higher selectivity factor than the other mixed-solvent at the three temperatures studied.     

Experimental determination of the isothermal (vapour + liquid) equilibria of binary aqueous solutions of sec-butylamine and cyclohexylamine at several temperatures

The vapour pressures of (sec-butylamine + water), (cyclohexylamine + water) binary mixtures, and of pure sec-butylamine and cyclohexylamine components were measured by means of two static devices at temperatures between 293 (or 273) K and 363 K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The (cyclohexylamine + water) system shows positive azeotropic behaviour for all investigated temperatures. The two binary mixtures exhibit positive deviations in G^E for all investigated temperatures over the whole composition range.     

Measurements and modeling of LLE and HE for (methanol + 2,4,4-trimethyl-1-pentene), and LLE for (water + methanol + 2,4,4-trimethyl-1-pentene)

Excess enthalpy (H^E) for the binary system of (methanol + 2,4,4-trimethyl-1-pentene) (TMP-1) is reported at T = 298.15 K and 101 kPa. (Liquid + liquid) equilibrium (LLE) for the same system is measured at atmospheric pressure (101 kPa). LLE for ternary system of (water + methanol + 2,4,4-trimethyl-1-pentene) is measured at T = (283 and 298) K.The parameters of Non-Random Two-Liquid (NRTL) model were regressed for the system of (methanol + TMP-1) using H^E and LLE from this work combined with isobaric (101 kPa) and isothermal (T = 331 K) VLE data from literature. The NRTL parameters for the binary system of (water + TMP-1) were fitted to a binary LLE data set from literature. NRTL parameters for the binary system of (water + methanol) were taken from ASPEN PLUS. The LLE for the ternary system was modeled by the three binary NRTL interaction parameters systems. The binary and ternary models were compared against the measured data.     

Effect of temperature on the excess molar volumes of some alcohol + aromatic mixtures and modelling by cubic EOS mixing rules

Densities of the (methanol + benzene), (ethanol + benzene), (methanol + chlorobenzene) and (ethanol + chlorobenzene) mixtures have been measured at six temperatures (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15 K) and 101.33 kPa. Excess molar volumes V^E were determined and fitted by the Redlich–Kister equation. It was observed that in all cases V^E increases with rising of temperature. The values of limiting excess partial molar volumes have been calculated, as well. The obtained results have been analysed in terms of specific molecular interactions present in these mixtures taking into considerations effect of temperature on them. The correlation of V^E binary data was performed with the Peng–Robinson–Stryjek–Vera cubic equation of state (PRSV CEOS) coupled with the van der Waals (vdW1) and CEOS/G^E mixing rule introduced by Twu, Coon, Bluck and Tilton (TCBT). The experimental values of V^E were compared with those estimated by both mixing rules at the temperature range and on each temperature, separately.     

(Liquid + liquid) equilibria of (water + ethanol + dimethyl glutarate) at several temperatures

(Liquid + liquid) equilibrium (LLE) data of (water + ethanol + dimethyl glutarate) have been determined experimentally at T=(298.15,308.15 and 318.15) K. The reliability of the experimental tie-line data was ascertained by using the Othmer and Tobias correlation. The LLE data of the ternary mixture were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

Equilibrium solubility of sodium 2-naphthalenesulfonate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures at temperatures from (278.15 to 323.15) K

The equilibrium solubility of sodium 2-naphthalenesulfonate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures was measured at elevated temperatures from (278.15 to 323.15) K using a steady-state method. With increasing temperatures, the solubility increases in aqueous solvent mixtures. The results of these results were regressed by a modified Apelblat equation. The dissolution entropy and enthalpy determined using the method of the least-squares and the change of Gibbs free energy calculated with the values of Δ_diffS^o and Δ_diffH^o at T = 278.15 K.     

Investigation of the isothermal (vapour + liquid) equilibria of aqueous 2-amino-2-methyl-1-propanol (AMP), N-benzylethanolamine,or 3-dimethylamino-1-propanol solutions at several temperatures

The vapour pressures of (2-amino-2-methyl-1-propanol (AMP) + water), (N-benzylethanolamine + water), or (3-dimethylamino-1-propanol + water) binary mixtures, and of pure AMP and 3-dimethylamino-1-propanol components were measured by means of two static devices at temperatures between 283 K and 363 K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The {2-amino-2-methyl-1-propanol (AMP) + water} binary mixture exhibits negative deviations in G^E (at T < 353.15 K) and a sinusoidal shape for G^E for the higher temperatures over the whole composition range. For the aqueous N-benzylethanolamine solution, a S shape is observed for the G^E for all investigated temperatures over the whole composition range. The (3-dimethylamino-1-propanol + water) binary mixture exhibits negative deviations in G^E (at T < 293.15 K), positive deviations in G^E (for 293.15 K < T < 353.15 K) and a sinusoidal shape for G^E for the higher temperatures over the whole composition range.     

Thermodynamics of isomeric hexynes + MTBE binary mixtures

The vapor pressures of liquid hex-1-yne or hex-2-yne + methyl 1,1-dimethylethyl ether (MTBE) binary mixtures and of the three pure components were measured by a static method at several temperatures between 263 and 343 K. These data were correlated with the Antoine equation. Excess molar Gibbs energies G^E were calculated for several constant temperatures, taking into account the vapor-phase imperfection in terms of the second molar virial coefficients, and were fitted to the Redlich–Kister equation. Calorimetric excess enthalpy H^E measurements, for these binary mixtures, are also reported at 298.15 K. The experimental VLE and H^E data were used, examining the binary mixtures hex-1-yne or hex-2-yne + MTBE in the framework of the DISQUAC and modified UNIFAC (Do) models. The DISQUAC calculations, reporting a new set of interaction parameters for the contact carbon–carbon triple bond/oxygen ether, is regarded as a preliminary approach.     

Phase equilibrium properties of binary aqueous solutions of benzylamine, 1,2-bis(2-aminoethoxy)ethane,or 2-[2-(dimethylamino)ethoxy]ethanol

The vapour pressures of (benzylamine + water), {1,2-bis(2-aminoethoxy)ethane + water}, or {2-[2-(dimethylamino)ethoxy]ethanol + water} binary mixtures, and pure 2-[2-(dimethylamino)ethoxy]ethanol component were measured by means of two static devices at temperatures between (283.15 and 363.15 (or 323.15)) K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The (benzylamine + water) binary mixture exhibits positive deviations in G^E for (303.15 < T/K < 323.15) and a sinusoidal shape in G^E for T > 323.15 K over the whole composition range. The aqueous 1,2-bis(2-aminoethoxy)ethane or {2-[2-(dimethylamino)ethoxy]ethanol + water} solutions exhibit negative deviations in G^E for all investigated temperatures over the whole composition range.     

Isothermal (vapour + liquid) equilibria and excess Gibbs free energies in some binary (cyclopentanone + chloroalkane) mixtures at temperatures from 298.15 K to 318.15 K

The vapour pressures of binary (cyclopentanone + 1-chlorobutane, +1,3-dichloropropane, and +1,4-dichlorobutane) mixtures, were measured at the temperatures of (298.15, 308.15, and 318.15) K. The vapour pressures vs. liquid phase composition data have been used to calculate the excess molar Gibbs free energies G^E of the investigated systems, using Barker’s method. Redlich–Kister, Wilson and NRTL equations, taking into account the vapor phase imperfection in terms of the second virial coefficient, have represented the G^E values. No significant difference between G^E values obtained with these equations has been observed.     

Effect of ionic liquids on (vapor + liquid) equilibrium behavior of (water + 2-methyl-2-propanol)

Isobaric T, x, y data were reported for ternary systems of {water + 2-methyl-2-propanol (tert-butyl alcohol, TBA) + ionic liquid (IL)} at p = 100 kPa. When the mole fraction of TBA on IL-free basis was fixed at 0.95, measurements were performed at IL mass fractions from 0.6 down to 0.05, in a way of repeated synthesis. The vapor-phase compositions were obtained by analytical methods and the liquid-phase compositions were calculated with the aid of mass balances. Activity coefficients of water and TBA were obtained without the need of a thermodynamic model of the liquid-phase. Six ILs, composed of an anion chosen from [OAc]^? or [Cl]^?, and a cation from [emim]⁺, or [bmim]⁺, or [hmim]⁺, were studied. Relative volatility and activity coefficients were presented in relation with the IL mole fraction, showing the effect of the ILs on a molar basis. The effect of the ILs on relative volatility of TBA to water was depicted by the effect of anions and cations on, respectively, the activity coefficients of water and TBA. The results indicated that, among the six ILs studied, [emim][Cl] has the most significant effect on enhancement of the relative volatility, which reaches a value of 7.2 at an IL mass fraction of 0.58. Another IL, [emim][OAc], has also significant effect, with an appreciable value of 5.2 for the relative volatility when the IL mass fraction is 0.6. Considering the relatively low viscosity and melting point of [emim][OAc], it might be a favorable candidate as solvent for the separation of water and TBA by extractive distillation. Simultaneous correlation by the NRTL model was presented for both systems of (water + ethanol + IL) and (water + TBA + IL), using consistent binary parameters for water and IL.     

Temperature dependence on mutual solubility of binary (methanol + limonene) mixture and (liquid + liquid) equilibria of ternary (methanol + ethanol + limonene) mixture

Mutual solubility data of the binary (methanol + limonene) mixture at the temperatures ranging from 288.15 K close to upper critical solution temperature, and ternary (liquid + liquid) equilibrium (tie-lines) of the (methanol + ethanol + limonene) mixture at the temperatures (288.15, 298.15, and 308.15) K have been obtained. The experimental results have been represented accurately in terms of the extended and modified UNIQUAC models with binary parameters, compared with the UNIQUAC model. The temperature dependence of binary and ternary (liquid + liquid) equilibrium for the binary (methanol + limonene) and ternary (methanol + ethanol + limonene) mixtures could be calculated successfully using the extended and modified UNIQUAC model.     

(Vapour + liquid) equilibrium in (N,N-dimethylacetamide + ethanol + water) at the temperature 313.15 K

Total vapour pressures, measured at the temperature 313.15 K, are reported for the ternary mixture (N,N-dimethylacetamide + ethanol + water), and for binary constituent (N,N-dimethylacetamide + ethanol). The present results are also compared with previously obtained data for (amide + ethanol) binary mixtures, where amide = N-methylformamide, N,N-dimethylformamide, N-methylacetamide, 2-pyrrolidinone, and N-methylpyrrolidinone. We found that excess Gibbs free energy of mixing for binary (amide + ethanol) mixtures varies roughly linearly with the molar volume of amide.     

Thermodynamic properties of (tetradecane + benzene, + toluene, + chlorobenzene, + bromobenzene, + anisole) binary mixtures at T = (298.15, 303.15, and 308.15) K

Density ρ, viscosity η, and refractive index n_D, values for (tetradecane + benzene, + toluene, + chlorobenzene, + bromobenzene, + anisole) binary mixtures over the entire range of mole fraction have been measured at temperatures (298.15, 303.15, and 308.15) K at atmospheric pressure. The speed of sound u has been measured at T = 298.15 K only. Using these data, excess molar volume V^E, deviations in viscosity Δη, Lorentz–Lorenz molar refraction ΔR, speed of sound Δu, and isentropic compressibility Δk_s have been calculated. These results have been fitted to the Redlich and Kister polynomial equation to estimate the binary interaction parameters and standard deviations. Excess molar volumes have exhibited both positive and negative trends in many mixtures, depending upon the nature of the second component of the mixture. For the (tetradecane + chlorobenzene) binary mixture, an incipient inversion has been observed. Calculated thermodynamic quantities have been discussed in terms of intermolecular interactions between mixing components.     

Phase equilibria properties of binary and ternary systems containing di-isopropyl ether + isobutanol + benzene at 313.15 K

Isothermal vapour–liquid equilibrium data have been measured for the ternary system (di-isopropyl ether + isobutanol + benzene) and two of the binary systems involved (di-isopropyl ether + isobutanol) and (isobutanol + benzene) at 313.15 K. A static technique consisting of an isothermal total pressure cell was used for the measurements. Data reduction by Barker's method provides correlations for G^E using the Margules equation for the binary systems and the Wohl expansion for the ternary system. Wilson, NRTL and UNIQUAC models have been applied successfully to both the binary and the ternary systems.     

Volumetric study of (2-methoxyethanol + tetrahydrofuran + cyclohexane) at T=298.15 K

The excess molar volumes V_m^E at T=298.15 have been determined in the whole composition domain for (2-methoxyethanol + tetrahydrofuran + cyclohexane) and for the parent binary mixtures. Data on V_m^E are also reported for (2-ethoxyethanol + cyclohexane). All binaries showed positive V_m^E values, small for (methoxyethanol + tetrahydrofuran) and large for the other ones. The ternary V_m^E surface is always positive and exhibits a smooth trend with a maximum corresponding to the binary (2-methoxyethanol + cyclohexane). The capabilities of various models of either predicting or reproducing the ternary data have been compared. The behaviour of V_m^E and of the excess apparent molar volume of the components is discussed in both binary and ternary mixtures. The results suggest that hydrogen bonding decreases with alcohol dilution and increases with the tetrahydrofuran content in the ternary solutions.     

Excess properties and vapour pressure of (3-diethylaminopropylamine + n-alkanes)

The vapour pressures of liquid (3-diethylaminopropylamine (3-DEPA) + n-heptane) mixtures were measured by a static method between T = (303.15 and 343.15) K at 10 K intervals. The molar excess enthalpies H^E at T = 303.15 K were measured for the systems {3-DEPA + C_nH_2n+2 (n = 6, 7, 12)}. The molar excess Gibbs free energies G^E were obtained with Barker’s method and fitted to the Redlich–Kister equation. The Wilson equation was also used. Deviations between experimental and predicted G^E and H^E, by using group contribution UNIFAC (Gmehling version) model, were evaluated.