Excess Molar Enthalpies of the Ternary Systems (Acetonitrile+methyl Isobutyrate+Toluene) and (Propionitrile+methyl Isobutyrate+ethylbenzene) at 298.15 K

Excess molar enthalpies were measured at 298.15 K with a flow calorimeter built in our laboratory for the two ternary systems (acetonitrile+methyl isobutyrate+toluene) and (propionitrile+methylisobutyrate+ethylbenzene). Experimental data were nicely predicted by some empirical andsemi empirical procedures, exception made for UNIFAC group contribution method. The latter equation proved unsatisfactory for all mixtures containing methyl isobutyrate. The first ternary set proved a good model system to simulate mixing enthalpies reported in the literature for mixtures of poly(styrene-co-acrylonitrile) with polymethylmethacrylate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Application of Different Group Contribution Models and Empirical Methods to Excess Enthalpies of Ternary Mixtures

Studies were previously made of the excess molar enthalpies, H_m ^E, at 298.15 K and normal atmospheric pressure of the ternary mixtures (ethyl propanoate or 3-pentanone) + (n-hexane) + (n-decane, n-dodecane or n-tetradecane) and (1-propanol) + (3-pentanone) + (n-hexane, n-heptane, n-octane, 1-hexanol or 1-heptanol). In the present work, experimental values of H_m ^E were correlated through use of the Cibulka and Nagata equations, and a new correlation equation is proposed. Experimental data were compared with the predictions of the UNIFAC I (version of Tassios), UNIFAC II (version of Larsen) and Nitta-Chao group contribution models. H_m ^E values were used to test several empirical predictive methods, both symmetric (Kohler, Jacob-Fitzner, Colinet and Knobeloch-Schwartz), and asymmetric (Tsao-Smith, Toop, Scatchard, Hillert and Mathieson-Tynne). This revised version was published online in July 2006 with corrections to the Cover Date.     

Excess molar volume of dimethyl carbonate +p-xylene + n-decane at 288.15 and 298.15 k

Densities for dimethyl carbonate + p-xylene + n-decane ternary system, at 288.15 and 298.15 K and at atmospheric pressure, were measured. The corresponding excess molar volumes were calculated from the experimental data and were fitted by means of Cibulka equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Excess Enthalpies of (2,2,4-Trimethylpentane or Cyclohexane) + Methyl tert-Butyl Ether + tert-Amyl Methyl Ether at 25°C

Microcalormetric measurements of excess molar enthalpies at 25°C are reported for two ternary mixtures 2,2,4-trimethylpentane + methyltert-butyl ether +tert-amyl methyl ether and cyclohexane + methyltert-butyl ether +tert-amyl methyl ether. Smooth representations of the results are presented and used to construct constant-enthalpy contours on Roozeboom diagrams. Comparisons of the experimental results with estimates based on the Flory theory of mixtures are also described.     

Enthalpies of mixing of binary and ternary mixtures containing diisopropylether,benzene and cyclohexane at 303.15 K

Enthalpies of mixing H have been measured for liquid binary mixtures of diisopropylether (DIPE)+benzene or cyclohexane and for liquid ternary mixtures diisopropylether+benzene+cyclohexane at 303.15 K and constant pressure using a C80 calorimeter. A Redlich-Kister type equation was used to correlate experimental results.     

Volumetric Properties of the Ternary System 1,4-Dioxane + Butyl Acrylate + Ethyl Acrylate and Its Binary Butyl Acrylate + Ethyl Acrylate at 298.15 K

Densities of the ternary system 1,4-dioxane + butyl acrylate + ethyl acrylate and its binary butyl acrylate + ethyl acrylate have been measured in the whole composition range, at 298.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densimeter. The calculated excess molar volumes of the binary system are positive and were correlated with the Redlich–Kister equation and with a series of Legendre polynomials. Several models were used to correlate the ternary behavior from the excess molar volume data of their constituent binaries and were found equally good to fit the data. The best fit was based on a direct approach, without information on the component binary systems.     

Densities and Viscosities of the Ternary Mixture (Benzene + 1-Propanol + Ethyl Acetate) at 298.15 K

Abstract

Densities and viscosities of the ternary mixture (benzene + 1-propanol + ethyl acetate) and the corresponding binary mixtures (benzene + 1-propanol, benzene + ethyl acetate and 1-propanol + ethyl acetate) have been measured at the temperature 298.15 K. From these measurements excess volumes, V^E , excess viscosities, η^E, and excess Gibbs energies of activation for viscous flow, G*^E , have been determined. The equation of Redlich-Kister has been used for fitting the excess properties of binary mixtures. The excess properties of the ternary system were fitted to Cibulka's equation.     

Excess molar enthalpies of the ternary system MTBE+ethanol+octane

Excess molar enthalpies of the ternary mixture {x ₁ tert-butyl methyl ether (MTBE)+x ₂ ethanol+(1–x ₁–x ₂) octane} and the involved binary mixture {x ethanol+(1–x) octane} have been measured at 298.15 K and atmospheric pressure, over the whole composition range, using a Calvet microcalorimeter. The results were fitted by means of different variable degree polynomials.     

Prediction of ternary excess enthalpy data by the UNIFAC Group Contribution method

The UNIFAC Group Contribution method is applied to predict ternary excess enthalpies H ^E . In order to improve previous predictions, values for the group interaction parameters are determined from binary excess enthalpy data. These parameters are used to estimate sixty-four sets of ternary H ^E data which are compared with data from the literature. Results are also compared with those obtained using methods to predict ternary excess enthalpies from the binary H ^E data for the three binary system involved.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Speeds of sound and isentropic compressibil- ities of cyclohexane+1,3-dioxolane+2-butanol and n-hexane+1,3-dioxolane+2-butanol

Speeds of sound of the ternary mixtures cyclohexane+1,3-dioxolane+2-butanol and n-hexane+1,3-dioxolane+2-butanol have been measured at the temperatures of 298.15 and 313.15 K. Isentropic compressibilities and excess isentropic compressibilities have been calculated from experimental data. We have also compared the experimental isentropic compressibilities with calculated values from the free length theory and the collision factor theory. Experimental results show positive values of excess isentropic compressibilities in almost the whole composition range for the ternary mixture containing cyclohexane, meanwhile they are negative for the mixture containing n-hexane. Such different behaviour of these systems is related to the large free volume shown by n-hexane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ternary mixture MTBE+1-pentanol+nonane at 298.15 K and atmospheric pressure

Densities at 298.15 K and atmospheric pressure have been measured, using a DMA 4500 Anton Paar densimeter, for the ternary mixture methyl tert-butyl ether (MTBE)+1-pentanol+nonane and for the involved binary mixture 1-pentanol+nonane. In addition, excess molar volumes were determined from the densities of the pure liquids and mixtures. Suitable fitting equations have been used in order to correlate adequately the excess molar volumes. Experimental data were also used to test several empirical expressions for estimating ternary properties from experimental binary results.     

Excess molar enthalpies of the ternary system mtbe+ethanol+hexane

Excess molar enthalpies of the ternary mixture {x₁ tert-butyl methyl ether (MTBE)+x₂ ethanol+(1–x₁–x₂) hexane} and, the involved binary mixtures {x tert-butyl methyl ether (MTBE)+(1–x) ethanol}, {x tert-butyl methyl ether (MTBE)+(1–x) hexane} and {x ethanol+( 1–x) hexane} have been measured at 298.15 K and atmospheric pressure, over the whole composition range, using a Calvet microcalorimeter. The results were fitted by means of different variable degree polynomials.     

Isothermal vapour–liquid equilibria in the ternary system tert-butyl methyl ether + tert-butanol + 2,2,4-trimethylpentane and the three binary subsystems

Vapour–liquid equilibrium data are reported for the ternary tert-butyl methyl ether+tert-butanol+2,2,4-trimethylpentane and the three binary tert-butyl methyl ether+tert-butanol, tert-butyl methyl ether+2,2,4-trimethylpentane, tert-butanol+2,2,4-trimethylpentane subsystems. The data were measured isothermally at 318.13, 328.20, and 339.28 K covering pressure range 15–100 kPa. Azeotropic data are presented for the tert-butanol+2,2,4-trimethylpentane system. Molar excess volumes at 298.15 K are given for the three binary systems. The binary vapour–liquid equilibrium data were correlated using Wilson, NRTL, and Redlich–Kister equations; the parameters obtained were used for calculation of phase behaviour in ternary system and for subsequent comparison with experimental data.     

Densities and excess molar volumes of the binary system N-methyldiethanolamine + (2-aminoethyl)ethanolamine and its ternary aqueous mixtures from 283.15 to 363.15 K

Experimental density data of the binary mixtures of N-methyldiethanolamine + (2-aminoethyl)ethanolamine and the ternary mixtures of N-methyldiethanolamine + (2-aminoethyl)ethanolamine + water were reported at atmospheric pressure over the entire composition range at temperatures from 283.15 to 363.15 K. Density measurements were performed using an Anton Paar digital vibrating U-tube densimeter. Excess molar volumes were calculated from the experimental data and correlated as the Redlich-Kister equation for the binary mixtures, and as the Nagata-Tamura equation for the ternary mixtures. Several empirical models were applied to predict the excess molar volumes of ternary mixtures from the corresponding binary mixture values. It indicates that the best agreement with the experimental data was achieved by the Redlich-Kister, Kohler, and Jacob-Fitzner models.     

Excess Volume of Ternary Water + Diacetone Alcohol + 2-Propanol as a Function of Pressure,Temperature and Composition

Abstract

The excess volume V^E of the ternary water + diacetone alcohol (or DAA) + 2-propanol and of the three binaries water + DAA, water + 2-propanol and DAA + 2-propanol was evaluated from experimental density data (2772 values) as a function of the pressure P (between 0.1 MPa and 65 MPa), the temperature T (303.15K, 323.15K and 343.15K) and the composition. Various representative models are discussed. It is possible to account for the values of the density with an average absolute deviation of about 0.06% in the experimental P-T domain.     

Excess enthalpies of alcohol + amine mixtures. Experimental results and theoretical description using the ERAS-model

New experimental data of the molar excess enthalpy H^E of mixtures containing eight liquids - propylamine + methanol, ethanol, propan-1-ol, butan-1-ol, butylamine + methanol, ethanol, propan-1-ol, butan-1-ol - are presented using a quasi-isothermal flow calorimeter. The results are used for testing the ERAS-model which provides a theoretical concept accounting for the self-association and cross-association of alcohol and amine molecules, as well as for non-associative intermolecular interactions. Excess molar volumes V^E are also successfully described by the model. It turns out that the strong cross-association occurring between alcohol and amine molecules is the predominant reason for the remarkably low exothermic values of H^E observed for the mixtures studied.     

Excess Molar Volumes of Ternary Mixtures of 2-Butanone or 2-Pentanone with 1-Chloroctane + n-Octane at 25°C

Excess molar volumes at 25°C of the ternary systems 2-butanone + 1 -chlorooctane + octane and 2-pentanone + 1-chlorooctane + octane and of binary mixtures 2-butanone + octane, 2-pentanone + octane, and 1-chlorooctane + octane, were determined using an Anton Paar DMA 60/602 densimeter. All the experimental values were compared with the results obtained by empirical expressions for estimating ternary properties from binary data. Variable degree polynomials were fitted to the results.     

Excess Enthalpies of 2-Methyltetrahydrofuran + (2,2,4-Trimethylpentane or n-Heptane) + Methylcyclohexane at 25°C

Measurements of excess molar enthalpies at 25°C in a flow microcalorimeter, are reported for the two ternary mixtures 2-methyltetrahydrofuran + 2, 2, 4-trimethylpentane + methylcyclohexane and 2-methyltetrahydrofuran + n-heptane + methylcyclohexane. Smooth representations of the results are described and used to construct constant-enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann–Fried model using only the physical properties of the components and their binary mixtures.     

Excess heat capacities at T=298.15 K and excess enthalpies at T=293.15 and 298.15 K of aqueous solution of 2-methoxyethanol

Excess isobaric heat capacities of mixture (2-methoxyethanol+water) were measured at T=298.15 K and excess enthalpies at T=293.15 and 298.15 K. Excess enthalpies were extremely exothermic, up to -1290 J mol^-1 atT=293.15 K and -1240 J mol^-1 at T=298.15 K. Excess isobaric heat capacities were positive and very large, approximately 9 J K^-1 mol^-1 at the maximum. In contrast to the data reported by Page and coworkers, the excess heat capacity data were positive in the entire composition range and there was no change in their signs. Consistently, no crossing was found between the curves of excess enthalpies at T=298.15 and 293.15 K. This revised version was published online in July 2006 with corrections to the Cover Date.