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.     

Total pressure and excess Gibbs energy for the ternary mixture di-isopropyl ether + 1-propanol + benzene and its corresponding binary systems at 313.15 K

Total pressure measurements are reported for the ternary system ‘di-isopropyl ether + 1-propanol + benzene’ and two of the binary systems involved ‘di-isopropyl ether + 1-propanol’ and ‘1-propanol + benzene’ at 313.15 K. 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 properties of ternary (IL + 2-propanol or 1-butanol or 2-butanol + ethyl acetate) systems and binary (IL + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate) systems

The experimental densities for the binary or ternary systems were determined at T = (298.15, 303.15, and 313.15) K. The ionic liquid methyl trioctylammonium bis(trifluoromethylsulfonyl)imide ([MOA]⁺[Tf₂N]⁻) was used for three of the five binary systems studied. The binary systems were ([MOA]⁺[Tf₂N]⁻ + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate). The ternary systems were {methyl trioctylammonium bis(trifluoromethylsulfonyl)imide + 2-propanol or 1-butanol or 2-butanol + ethyl acetate}. The binary and ternary excess molar volumes for the above systems were calculated from the experimental density values for each temperature. The Redlich–Kister smoothing polynomial was fitted to the binary excess molar volume data. Virial-Based Mixing Rules were used to correlate the binary excess molar volume data. The binary excess molar volume results showed both negative and positive values over the entire composition range for all the temperatures.The ternary excess molar volume data were successfully correlated with the Cibulka equation using the Redlich–Kister binary parameters.     

Excess enthalpies of ternary mixtures of (oxygenated additives + aromatic hydrocarbon) mixtures in fuels and bio-fuels: (Dibutyl-ether + 1-propanol + benzene), or toluene,at T = (298.15 and 313.15) K

New experimental excess molar enthalpy data of the ternary systems (dibutyl ether + 1-propanol + benzene, or toluene), and the corresponding binary systems at T = (298.15 and 313.15) K at atmospheric pressure are reported. A quasi-isothermal flow calorimeter has been used to make the measurements. All the binary and ternary systems show endothermic character at both temperatures. The experimental data for the systems have been fitted using the Redlich–Kister rational equation. Considerations with respect the intermolecular interactions amongst ether, alcohol and hydrocarbon compounds are presented.     

Volumetric behavior of the ternary system (methyl tert-butyl ether + methylbenzene + butan-1-ol) and its binary sub-system (methyl tert-butyl ether + butan-1-ol) within the temperature range (298.15 to 328.15) K

Values of the density and speed of sound were measured for the ternary system (methyl tert-butyl ether + methylbenzene + butan-1-ol) within the temperature range (298.15 to 328.15) K at atmospheric pressure by a vibrating-tube densimeter DSA 5000. Two binary sub-systems were studied and published previously while the binary sub-system (methyl tert-butyl ether + butan-1-ol) is a new study in this work. Excess molar volume, adiabatic compressibility, and isobaric thermal expansivity were calculated from the experimental values of density and speed of sound. The excess quantities were correlated using the Redlich–Kister equation. The experimental excess molar volumes were analyzed by means of both the Extended Real Associated Solution (ERAS) model and the Peng–Robinson equation of state. The novelty of this work is the qualitative prediction of ternary excess molar volumes for the system containing auto-associative compound and two compounds that can hetero-associate. The combination of the ERAS model and Peng–Robinson equation of state could help to qualitatively estimate the real behavior of the studied systems because the experimental results lie between these two predictions.     

Isobaric (vapour + liquid + liquid) equilibrium data for (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) systems at 100 kPa

Isobaric (vapour + liquid + liquid) equilibria were measured for the (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) system at 100 kPa.The apparatus used for the determination of (vapour + liquid + liquid) equilibrium data was an all-glass dynamic recirculating still with an ultrasonic homogenizer couple to the boiling flask.The experimental data demonstrated the existence of a heterogeneous ternary azeotrope for both ternary systems. The (vapour + liquid + liquid) equilibria data were found to be thermodynamically consistent for both systems.The experimental data were compared with the estimation using UNIQUAC and NRTL models and the prediction of UNIFAC model.     

(Vapour + liquid) equilibrium and excess Gibbs functions of ternary mixtures containing 1-butanol or 2-butanol,n-hexane,and 1-chlorobutane at T = 298.15 K

Isothermal (vapour + liquid) equilibrium data for the ternary mixtures 1-butanol + n-hexane + 1-chlorobutane and 2-butanol + n-hexane + 1-chlorobutane have been studied with a recirculating still at T = 298.15 K. The experimental data were satisfactorily checked for thermodynamic consistency using the method of van Ness. Activity coefficients and excess Gibbs function have been correlated with the Wilson equation. The G^E values obtained for the two ternary systems are very similar.     

Excess enthalpies of binary and ternary mixtures containing dibutyl ether (DBE), 1-butanol,and heptane at T = 298.15 K and 313.15 K

Experimental excess molar enthalpies of the ternary systems {dibutyl ether (DBE) + 1-butanol + heptane} and the corresponding binary systems at T = 298.15 K and T = 313.15 K at atmospheric pressure are reported. A quasi-isothermal flow calorimeter has been used to make the measurements. All the binary and the ternary systems show endothermic character. The experimental data for the binary and ternary systems have been fitted using the Redlich–Kister equation, the NRTL and UNIQUAC models. The values of the standard deviation indicate good agreement between the experimental results and those calculated from the equations.     

Experimental and predicted excess molar enthalpies for 1,4-dioxane + octane + cyclohexane at 303.15 K

Excess molar enthalpies for the ternary system 1,4-dioxane (1) + n-octane (2) + cyclohexane (3) and for the three constituent binary systems have been measured by a Calvet microcalorimeter at 303.15 K and ambient pressure. The experimental binary results were fitted by the Redlich–Kister equation. The excess molar enthalpies of the ternary system were correlated using the Cibulka equation. The DISQUAC group contribution model was applied to predict the excess molar enthalpy for this mixture.     

Salt effect on (liquid + liquid) equilibrium of (water + tert-butanol + 1-butanol) system: Experimental data and correlation

(Liquid + liquid) equilibrium data for the quaternary systems (water + tert-butanol + 1-butanol + KBr) and (water + tert-butanol + 1-butanol + MgCl₂) were experimentally determined at T = 293.15 K and T = 313.15 K. For mixtures with KBr, the overall salt concentrations were 5 and 10 mass percent; for mixtures with MgCl₂, the overall salt concentrations were 2 and 5 mass percent. The experimental results were used to estimate molecular interaction parameters for the NRTL activity coefficient model, using the Simplex minimization method and a concentration-based objective function. The correlation results are extremely satisfactory, with deviations in phase compositions below 1.7%.     

Isothermal and isobaric (vapour + liquid) equilibria of (N,N- dimethylformamide + 2-propanol + 1-butanol)

The isothermal and isobaric (vapour  +  liquid) equilibria (v.l.e.) for (N, N - dimethylformamide  +  2-propanol  +  1-butanol) and the binary constituent mixtures were measured with an inclined ebulliometer. The experimental results are analyzed using the UNIQUAC equation with temperature-dependent binary parameters. The comparison between the experimental and literature results for binary systems is given. The ternary v.l.e. values are predicted from the binary results.     

Estimation of (vapour + liquid) equilibrium of binary systems (tert-butanol + 2-ethyl-1-hexanol) and (n-butanol + 2-ethyl-1-hexanol) using an artificial neural network

(Vapour + liquid) equilibrium (VLE) data are important for designing and modelling of process equipment. Since it is not always possible to carry out experiments at all possible temperatures and pressures, generally thermodynamic models based on equations of state are used for estimation of VLE. In this paper, an alternate tool, i.e. the artificial neural network technique has been applied for estimation of VLE for the binary systems viz. (tert-butanol + 2-ethyl-1-hexanol) and (n-butanol + 2-ethyl-1-hexanol). The temperature range over which these models are valid is (353.2 to 458.2) K at atmospheric pressure. The average absolute deviation for the temperature output was in range 2% to 3.3%. The results were then compared with experimental data.     

Excess volumes of mixing in (N,N-dimethylacetamide + methanol + water) and (N,N-dimethylacetamide + ethanol + water) at the temperature 313.15 K

Precise excess volumes of mixing measurements at T = 313.15 K are reported over the whole composition range for binary mixtures: (N,N-dimethylacetamide + water), (N,N-dimethylacetamide + methanol), (N,N-dimethylacetamide + ethanol) and for the ternary mixtures (N,N-dimethylacetamide + methanol + water) and (N,N-dimethylacetamide + ethanol + water). For all the systems, large negative deviations from ideality are observed. The binary results have been fitted using the Redlich–Kister type polynomial. The possibility of predicting the ternary results from the binary ones was examined.     

Quaternary (liquid + liquid) equilibria for (methanol + 2,2,4-trimethylpentane + toluene + 1,1-dimethylpropyl methyl ether or 1,1-dimethylethyl methyl ether) at T = 298.15 K

The experimental equilibrium tie-lines of two quaternary mixtures for (methanol + 1,1-dimethylpropyl methyl ether + toluene + 2,2,4-trimethylpentane) and (methanol + 1,1-dimethylethyl methyl ether + toluene + 2,2,4-trimethylpentane) were measured at the temperature 298.15 K and ambient pressure. The quaternary experimental results and their constituent ternaries have been satisfactorily predicted using binary parameters alone obtained by an associated-solution model that takes into account association of methanol molecules and solvation between (methanol + polar molecules) with allowance for a non-polar interaction given by an extended form of the UNIQUAC model. The results are further compared with those correlated by modified and extended forms of the UNIQUAC models that include multi-body interaction parameters in addition to binary ones.     

(Liquid + liquid) equilibrium of (water + 2-propanol + 1-butanol + salt) systems at T = 313.15 K and T = 353.15 K: Experimental data and correlation

(Liquid + liquid) equilibrium data for the quaternary systems (water + 2-propanol + 1-butanol + potassium bromide) and (water + 2-propanol + 1-butanol + magnesium chloride) were measured at T = 313.15 K and T = 353.15 K. The overall salt concentrations were 5 and 10 mass percent. Ternary (liquid + liquid) equilibrium data for the salt-free system (water + 2-propanol + 1-butanol) were also determined and found to be in good agreement with data from the literature. The NRTL model for the activity coefficient was used to correlate the data. New interaction parameters were estimated, using the Simplex minimization method and a concentration-based objective function. The results are very satisfactory, with root mean square deviations between experimental and calculated compositions of both phases being less than 0.5%.     

Phase equilibria in the ternary system isobutyl alcohol + isobutyl acetate + 1-hexanol and the binary systems isobutyl alcohol + 1-hexanol,isobutyl acetate + 1-hexanol at 101.3 kPa

Consistent vapor–liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system isobutyl alcohol (IBA) + isobutyl acetate (IBAc) + 1-hexanol and two constituent binary systems: IBA + 1-hexanol and IBAc + 1-hexanol. The IBA + 1-hexanol system exhibits no deviation from ideal behaviour and IBAc + 1-hexanol system show lightly positive deviation from Raoult's law. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL, UNIQUAC models. The ternary system is well predicted from binary interaction parameters. 1-Hexanol eliminates the IBA–IBAc binary azeotrope. However, the change of phase equilibria behaviour is small therefore this solvent is not an effective agent for that azeotrope mixture separation. In fact, the mean relative volatility on a solvent free basis is 1.28 (close to unity).     

Vapor–liquid equilibria in the ternary system isobutyl alcohol + isobutyl acetate + butyl propionate and the binary systems isobutyl alcohol + butyl propionate,isobutyl acetate + butyl propionate at 101.3 kPa

Consistent vapor–liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system isobutyl alcohol (IBA) + isobutyl acetate (IBAc) + butyl propionate (BUP) and two constituent binary systems: IBA + BUP and IBAc + BUP. The IBA + BUP system show lightly positive deviation from Raoult's law and IBAc + BUP system exhibits no deviation from ideal behaviour. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL, UNIQUAC models. The ternary system is very well predicted from binary interaction parameters. BUP eliminates the IBA–IBAc binary azeotrope. The change of phase equilibria behaviour is significant therefore this solvent seems to be an effective agent for that azeotrope mixture separation. In fact, the mean relative volatility on a solvent free basis is 1.8.The binary VLE data measured in the present study passed the thermodynamic consistency test of Fredenslund et al. [A. Fredenslund, J. Gmehling, P. Rasmussen, Vapor–Liquid Equilibria Using UNIFAC, A Group Contribution Method, Elsevier, Amsterdam, 1977], and were correlated by the Wilson, NRTL and UNIQUAC models to relate activity coefficients with mole fractions. The VLE data obtained for the ternary system passed both the Wisniak L–W [J. Wisniak, Ind. Eng. Chem. Res. 32 (1993) 1531–1533] and McDermott–Ellis [C. McDermott, S.R. Ellis, Chem. Eng. Sci. 20 (1965) 293–296] consistency test. The parameters obtained from binary data were utilized directly to predict the phase behaviour of the ternary system. The results showed an excellent agreement with experimental values.     

(Liquid + liquid) equilibria of (sulfolane + benzene + n-hexane), (N-formylmorpholine + benzene + n-hexane), and (sulfolane + N-formylmorpholine + benzene + n-hexane) at temperatures ranging from (298.15 to 318.15) K: Experimental results and correlation

The experimental (liquid + liquid) equilibrium (LLE) properties for two ternary systems containing (N-formylmorpholine + benzene + n-hexane), (sulfolane + benzene + n-hexane) and a quaternary mixed solvent system (sulfolane + N-formylmorpholine + benzene + n-hexane) were measured at temperature ranging from (298.15 to 318.15) K and at an atmospheric pressure. The experimental distribution coefficients and selectivity factors are presented to evaluate the efficiency of the solvents for extraction of benzene from n-hexane. The LLE results obtained indicate that increasing temperature decreases selectivity for all solvents. The LLE results for the systems studied were used to obtain binary interaction parameters in the UNIQUAC model by minimizing the root mean square deviations (RMSD) between the experimental and calculated results. Using the interaction parameters obtained, the phase equilibria in the systems were calculated and plotted. The calculated compositions based on the UNIQUAC model were found to be in good agreement with the experimental values. The result of the RMSD obtained by comparing the calculated and experimental two-phase compositions is 0.0163 for (N-formylmorpholine + benzene + n-hexane) system and is 0.0120 for (sulfolane + benzene + n-hexane) system.     

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.