(Vapor-liquid) equilibria and excess Gibbs free energy functions of (ethanol + glycerol), or (water + glycerol) binary mixtures at several temperatures

The vapor pressures of (ethanol + glycerol) and (water + glycerol) binary mixtures were measured by means of two static devices at temperatures between (273 and 353 (or 363)) K. The data were correlated with the Antoine equation. From these data, excess Gibbs free energy functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker method. The (ethanol + glycerol) binary system exhibits positive deviations in G^E where for the (water + glycerol) mixture, the G^E is negative for all temperatures investigated over the whole composition. Additionally, the NRTL, UNIQUAC and Modified UNIFAC (Do) models have been used for the correlation or prediction of the total pressure.     

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.     

Phase equilibrium properties of binary aqueous solutions containing ethanediamine, 1,2-diaminopropane, 1,3-diaminopropane,or 1,4-diaminobutane at several temperatures

The vapour pressures of {ethanediamine (EDA) + water}, {1,2-diaminopropane (1,2-DAP) + water}, {1,3-diaminopropane (1,3-DAP) + water} or {1,4-diaminobutane (1,4-DAB) + water} binary mixtures, and of pure EDA, 1,2-DAP, 1,3-DAP, 1,4-DAB, and water components were measured by means of two static devices at temperatures between (293 and 363) K. The data were correlated with the Antoine equation. From these data, the excess Gibbs function (G^E) was calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The {ethanediamine (EDA) + water}, and {1,2-diaminopropane (1,2-DAP) + water} binary systems show negative azeotropic behaviour. The aqueous solutions of EDA, 1,2-DAP, or 1,3-DAP exhibit negative deviations in G^E for all investigated temperatures over the whole composition range whereas the (1,4-DAB + water) binary mixture shows negative G^E for temperatures (293.15 < T/K < 353.15) and a sinusoidal shape for G^E at T = 363.15 K.     

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.     

Thermodynamics of the solubility of reserpine in {{2-(2-ethoxyethoxy)ethanol + water}} mixed solvent systems at different temperatures

Thermodynamics of solubility of the bioactive compound reserpine in various {2-(2-ethoxyethoxy)ethanol + water} mixed solvent systems was investigated in this study. The solubility of reserpine was determined from T = (298.15 to 338.15) K at atmospheric pressure using the reported method of Higuchi and Connors. Values of the measured solubility of reserpine were correlated with the ideal and Yalkowsky models. The root mean square deviations (RMSD) were observed to be less than 0.020 by an ideal model. However, the RMSD values were observed as less than 0.050 by the Yalkowsky model. The mole fraction solubility of reserpine was observed highest in pure 2-(2-ethoxyethoxy)ethanol (7.69 · 10⁻⁴ at T = 298.15 K) and lowest in pure water (9.71 · 10⁻⁷ at T = 298.15 K) at each temperature investigated. The results of the Van’t Hoff and Krug analysis (thermodynamic studies) indicated endothermic and spontaneous dissolution of reserpine in all {2-(2-ethoxyethoxy)ethanol + water} mixed solvent systems.     

Phase equilibrium properties of binary mixtures containing 1,3-pentanediamine (or 1,5-diamino-2-methylpentane) and water at several temperatures

The vapor pressures of (1,3-pentanediamine + water), or (1,5-diamino-2-methylpentane + water) binary mixtures, and of pure 1,3-pentanediamine or 1,5-diamino-2-methylpentane components were measured by means of a static device at temperatures between (273 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 three order Redlich–Kister equation using the Barker’s method. The (1,3-pentanediamine + water) or (1,5-diamino-2-methylpentane + water) binary systems exhibit negative deviations in G^E for all investigated temperatures over the whole composition. Additionally, the NRTL UNIQUAC and Modified UNIFAC (Do) models have been used for the correlation or prediction of the total pressure.     

Measurement and correlation of (vapor + liquid) equilibria for the {2-propoxyethanol (C3E1) + n-hexane} and the {2-propoxyethanol (C3E1) + n-heptane} systems

2-Propoxyethanol (C₃E₁) is one of nonionic surfactants which are a particularly interesting class of substances due to both inter-molecular and intra-molecular association. Binary (vapor + liquid) equilibrium data were measured for {2-propoxyethanol (C₃E₁) + n-hexane} and {2-propoxyethanol (C₃E₁) + n-heptane} systems at temperatures ranging from (303.15 to 323.15) K. A static apparatus was used in this study. The experimental data were correlated well with a lattice fluid equation of state that combines the multi-fluid non-random lattice fluid model with Veytsman statistics for (intra + inter)-molecular association.     

(Vapour + liquid) equilibria and excess molar enthalpies for mixtures with strong complex formation. Trichloromethane or 1-bromo-1-chloro-2,2,2-trifluoroethane (halothane) with tetrahydropyran or piperidine

Isothermal (vapour  +  liquid) equilibria were measured for (trichloromethane  +  tetrahydropyran or piperidine) at T =  333.15 K and {1-bromo-1-chloro-2,2,2-trifluoroethane (halothane)  +  tetrahydropyran or piperidine} atT =  323.15 K with a circulation still. The results were verified by effective statistical procedures and used to calculate activity coefficients and excess molar Gibbs free energiesG_m^E . Excess molar enthalpiesH_m^E for these mixtures were determined at T =  298.15 K by means of an isothermal CSC microcalorimeter equipped with recently reconstructed flow mixing cells. Reliable performance of the calorimetric setup was proved by the good agreement of H_m^Efor (hexane  +  cyclohexane), (2-propanone  +  water), and (methanol  +  water), with the best literature results. The trichloromethane- or halothane-containing mixtures exhibit strong negative deviations from Raoult’s law and are highly exothermic, thus indicating that complex formation via hydrogen bonding is a governing nonideality effect. A close similarity in the behaviour of corresponding mixtures with trichloromethane and halothane is observed, but for halothane-containing mixtures,G_m^E and H_m^Eare consistently more negative, confirming that halothane is a more powerful proton donor than chloroform.     

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.     

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.     

(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.     

Equilibrium solubility of sodium 3-sulfobenzoate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures at temperatures from (278.15 to 323.15) K

The solubility of sodium 3-sulfobenzoate 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 by a steady-state method. The results of these experiments were correlated by a modified Apelblat equation. The dissolution enthalpy and entropy of sodium 3-sulfobenzoate in aqueous solutions of different mole fraction were obtained.     

High-pressure (vapour + liquid) equilibria for ternary systems composed by {(E)-2-hexenal or hexanal + carbon dioxide + water}: Partition coefficient measurement

A new apparatus based on a static–analytic method assembled in this work was utilised to perform high-pressure (vapour + liquid) equilibria measurements of aqueous ternary systems. This work includes values of isothermal partition coefficients between CO₂ and water of two apple aroma constituents, (E)-2-hexenal and hexanal. Additionally, this work reports new experimental (vapour + liquid) equilibria measurements for the ternary systems (CO₂ + (E)-2-hexenal + water) and (CO₂ + hexanal + water), at fixed liquid phase composition (600 mg · kg⁻¹), at temperatures of (313, 323 and 333) K and at pressures from (8 to 19) MPa. Vapour liquid interphase was checked and monitored visually for all the systems studied in this work. No liquid immiscibility was observed at the composition, temperatures and pressures studied. In order to suggest reasonable operation conditions for fractionation of aromas with dense carbon dioxide, partition coefficients of the aroma compounds between CO₂ and water along with their separation factors from water were calculated. Partition coefficients of (E)-2-hexenal between CO₂ and water were in the range of (6 to 91) and where found to be near six times higher than those of hexanal (9 to 17). Very high separation factors from water were observed (∼10⁴) especially for (E)-2-hexenal. The highest separation factor, for both compounds, was found at a temperature of 313 K and pressures from (12 to 14) MPa.     

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.     

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.     

Isothermal (vapour + liquid) equilibria for binary mixtures of diisopropyl ether with (methanol,or ethanol,or 1-butanol): Experimental data,correlations, and predictions

A glass dynamic recirculating still was employed for the measurement of isothermal (vapour + liquid) equilibrium (VLE) data for the binary mixtures of diisopropyl ether (DIPE) + alcohol, viz. (DIPE + methanol), (DIPE + ethanol), and (DIPE + 1-butanol) at T = (305.15, 315.15, and 325.15) K, T = (313.15, 323.15, and 333.15) K and T = (318.15, and 338.15) K, respectively. The combined standard uncertainties in the reported system pressures, temperatures and phase compositions are ±0.2 kPa, ±0.1 K and ±0.003, respectively. Maximum pressure azeotropes were observed for all isotherms of the (DIPE + methanol) and (DIPE + ethanol) systems. The experimental results were correlated using both the γ–ϕ and ϕ–ϕ approaches. For the correlation of the VLE data with the γ–ϕ approach, the Wilson, NRTL and UNIQUAC G^E models with the truncated two-term virial equation of state (Hayden and O’Connell correlation for second virial coefficient computation) were used. In the ϕ–ϕ correlation approach, the Peng–Robinson equation of state was used with the Wong–Sander mixing rules incorporating the same G^E models used in the γ–ϕ approach. Comparisons between the experimental values and predictions using UNIFAC (Dortmund) and the Predictive Soave–Redlich–Kwong (PSRK) model were performed to test the predictive capabilities of these models for the experimental data measured here. The thermodynamic consistency of the experimental data was checked with the Herington area test.     

Solubility and thermodynamic function of a new anticancer drug ibrutinib in 2-(2-ethoxyethoxy)ethanol + water mixtures at different temperatures

Ibrutinib is a recently approved anticancer drug recommended for the treatment of mantle cell lymphoma and chronic lymphocytic leukemia. It has been reported as practically insoluble in water and hence it is available in the market at higher doses. Poor solubility of ibrutinib limits its development to oral solid dosage forms only. In this work, the solubilities of ibrutinib were measured in various 2-(2-ethoxyethoxy)ethanol (Carbitol) + water mixtures at T = (298.15 to 323.15) and p = 0.1 MPa. The solubility of ibrutinib was measured using an isothermal method. The thermodynamics function of ibrutinib was also studied. The measured solubilities of ibrutinib were correlated and fitted with Van’t Hoff, the modified Apelblat and Yalkowsky models. The results of curve fitting of all three models showed good correlation of experimental solubilities of ibrutinib with calculated ones. The mole fraction solubility of ibrutinib was observed highest in pure 2-(2-ethoxyethoxy)ethanol (2.67 · 10⁻² at T = 298.15 K) and lowest in pure water (1.43 · 10⁻⁷ at T = 298.15 K) at T = (298.15 to 323.15) K. Thermodynamics data of ibrutinib showed an endothermic, spontaneous and an entropy-driven dissolution behavior of ibrutinib in all 2-(2-ethoxyethoxy)ethanol + water mixtures. Based on these results, ibrutinib has been considered as practically insoluble in water and freely soluble in 2-(2-ethoxyethoxy)ethanol. Therefore, 2-(2-ethoxyethoxy)ethanol could be used as a physiologically compatible cosolvent for solubilization and stabilization of ibrutinib in an aqueous media. The solubility data of this work could be extremely useful in preformulation studies and formulation development of ibrutinib.     

Thermodynamic properties of (n-alkoxyethanols + organic solvents). XII. Total vapour pressure measurements for (n-hexane,n-heptane or cyclohexane + 2-methoxyethanol) at different temperatures

Total pressure measurements are reported for (n -hexane  +  2-methoxyethanol) at T =  (313.15 and 323.15) K, (n -heptane  +  2-methoxyethanol) at T =  323.15 K, and (cyclohexane  +  2-methoxyethanol) at T =  (303.15, 313.15, and 323.15) K. Results were obtained by using a Van Ness type apparatus and were fitted with the five-parameter modified Margules equation by Barker’s method. Measurements are represented to within an average absolute deviation of approximately 0.02 kPa. Mixtures show positive deviation from Raoult’s law and show azeotropic behaviour at the temperatures considered in this work.     

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.     

Excess molar volume and viscosity study for the ternary system tetrahydrofuran (1) + 1-chlorobutane (2) + 2-butanol (3) at 283.15, 298.15 and 313.15 K

This work reports the measured density, ρ, and viscosity, η, values of liquid mixtures of tetrahydrofuran (1) + 1-chlorobutane (2) + 2-butanol (3) at temperatures of 283.15, 298.15 and 313.15 K over a range of mole fractions and atmospheric pressure. Excess molar volume, V^E, viscosity deviations, Δη, and excess free energies of activation of viscous flow, ΔG^*E, have been calculated from experimental data and fitted to Cibulka, Singh et al. and Nagata and Sakura equations. The results were analyzed in terms of the molecular interaction between the components of the mixtures. Excess molar volumes and viscosity deviations were predicted from binary contributions using geometrical solution models, Tsao and Smith; Jacob and Fitzner; Kholer; Rastogi et al.; Radojkovic et al. Finally, experimental results are compared with those obtained by applying group-contribution method proposed by Wu.