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.     

Densities and Excess Molar Volumes of Binary and Ternary Mixtures of Aqueous Solutions of 2,2,2-Trifluoroethanol with Acetone and Alcohols at the Temperature of 298.15 K and Pressure of 101 kPa

Excess molar volumes V_m^E of the binary mixtures of (trifluoroethanol + 1-propanol), (trifluoroethanol + 2-propanol), (acetone + water), (methanol + water), (ethanol + water), (1-propanol + water), (2-propanol + water), and the ternary mixtures of (trifluoroethanol + methanol + water), (trifluoroethanol + ethanol + water), (trifluoroethanol~+ 1-propanol + water), (trifluoroethanol + 2-propanol + water) and (trifluoroethanol + acetone + water) were measured with a vibrating tube densimeter at the temperature of 298.15 K and the pressure 101 kPa. The extrema in V_m^E of trifluoroethanol mixtures occur at –0.690 cm³-mol^–1 for (trifluoroethanol + 1-propanol), at –0.990~cm³-mol^–1 for (trifluoroethanol + 2-propanol); at 0.562 and –0.973 cm³-mol^–1 for (trifluoroethanol + methanol + water), at 0.629 and –0.973 cm³-mol^–1 for (trifluoroethanol + ethanol + water), at 1.082 and –0.659 cm³-mol^–1 for (trifluoroethanol~+ 1-propanol + water), at 0.998 and –0.991 cm³-mol^–1 for (trifluoroethanol~+ 2-propanol + water), and at 0.515 and –1.472 cm³-mol^–1 for (trifluoroethanol + acetone + water). The experimental ternary V_m^E values were predicted by empirical expressions using binary solution data.     

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.     

Thermodynamics of aqueous mixtures of nonelectrolytes. IV. Excess volumes of water-acetonitrile mixtures from 15 to 35°C

Excess volumes of water-acetonitrile mixtures were obtained from measurements of density over the entire mole fraction range and at 5 degree intervals from 15 to 35°C. Partial molar excess volumes at the five temperatures, excess coefficients of thermal expansion at 25°C and partial molar excess expansibilities at 25°C were derived from the results. The values of the various volumetric properties are compared with data from the literature.Issued as NRCC No. 19500     

Determination of experimental excess molar properties for MTBE+1-propanol+octane

Summary Experimental excess molar enthalpies and densities have been measured for the ternary mixture x₁MTBE+x₂1-propanol+(1-x₁-x₂)octane and the involved binary mixtures at 298.15 K and atmospheric pressure. In addition, excess molar volumes were determined from the densities of the pure liquids and mixtures. A standard Calvet microcalorimeter was employed to determine the excess molar enthalpies. Densities were measured using a DMA 4500 Anton Paar densimeter. The UNIFAC group contribution model (in the versions of Larsen et al., and Gmehling et al.) has been used to estimate excess enthalpies values. Experimental data were also used to test several empirical expressions for estimating ternary properties from experimental binary results.     

Experimental and predicted excess molar volumes of the ternary system.

Summary Experimental excess molar volumes for the ternary system x₁MTBE+x₂1-propanol+(1-x₁-x₂) heptane and the three involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The ternary mixture shows maximum values around the binary mixture MTBE+heptane and minimum values for the mixture MTBE+propanol. The ternary contribution to the excess molar volume is negative, with the exception of a range located around the rich compositions of 1-propanol. Several empirical equations predicting ternary mixture properties from experimental binary mixtures have been applied.     

Analysis of Excess Molar Volumes of the Ternary Systems Containing a Propyl Alkanoate and Two Alkanes with Some Predictive Methods

Abstract

Excess molar volumes at 298.15 K of the ternary mixtures (propyl ethanoate + n-heptane + n-decane), (propyl propanoate + n-heptane + n-decane) and (propyl butanoate + n-heptane + n-decane) were determined using a DMA 60/602 Anton Paar densimeter. All the experimental values were compared with the results obtained with empirical expressions for estimating ternary properties from binary data and with the Nitta-Chao group-contribution model. For these ternary mixtures the same behaviour that had been observed in ester + n-alkane binary systems was found: excess volumes decrease when the ester length increases.     

Experimental excess molar volumes of the ternary mixture and comparisonwith several empirical methods

Experimental excess molar volumes for the ternary system {x₁MTBE+x₂1-propanol+(1–x₁–x₂)nonane} and the three involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The ternary mixture shows maximum values around the binary mixture MTBE+nonane and minimum values for the mixture MTBE+propanol. The ternary contribution to the excess molar volume is negative, with the exception of a range located around the rich compositions of 1-propanol. Several empirical equations predicting ternary mixture properties from experimental binary mixtures have been applied.     

Measurement and Calculation of Heat Capacity of Heavy Distillation Cuts Under Pressure up to 40 MPa

Isobaric heat capacities of natural mixtures were determined up to 40 MPa with a modified C-80 Setaram calorimeter equipped with cells designed for high pressures. The systems investigated were heavy distillation cuts with respective boiling points of 150, 200, 250 and 300°C. These experimental data were used as discriminatory values to test thermodynamic models and more precisely to choose among the great number of equations of state and mixing rules proposed in the literature, the most appropriate for the characterization of the heavy components.This revised version was published online in November 2005 with corrections to the Cover Date.     

Correlation and prediction of ternary excess enthalpy data

Methods for predicting ternary excess enthalpies from excess enthalpy data for the three binary mixtures involved are examined and tested for forty-two sets of ternary data. In order to study the relation between the performance of the methods and the characteristics of the components in the mixture, the sets of data were classified into four groups according to the chemical nature of their components. The asymmetric equations proposed by Scatchard, Toop, and Hillert are shown to provide accurate predictions. The ratio of the standard deviations between experimental and predicted excess enthalpies and the maximum absolute value of this magnitude is 0.05 or less for most of the systems. These equations are asymmetric with respect to the numbering of components. A rule is given for selecting which component is to be designated as component 1 for systems showing endothermic mixing, exothermic mixing, or a combination of endothermic and exothermic mixing. Correlation methods are also examined and a partial differential approximant is proposed to represent the ternary contribution to the excess enthalpy.     

Excess properties and vapor-liquid equilibrium data for the chloroform + tetrahydrofuran binary system at 30°C

Excess molar volume, excess viscosity, excess molar enthalpy, and excess molar Gibbs free energy were calculated from the experimental density, viscosity, heat of mixing and vapor-liquid equilbrium data, respectively, for the chloroform + tetrahydrofuran system at 30°C over the complete molar fraction range. The results have been satisfactorily interpreted by assuming the existence of three species A, AB, and B in mutual equilibrium and that these species mix ideally. Values are given for the equilibrium constant and heat of formation of AB.     

Measurements and analysis of excess molar volumes for the ternary mixture MTBE + 1-pentanol + decane

Summary 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+decane and for the involved binary mixtures MTBE+1-pentanol and 1-pentanol+decane. The excess molar volumes for the binary mixture MTBE+decane was reported in an earlier work [1]. 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. The empirical expressions of Kohler [18], Jacob and Fitzner [19], Colinet [20], Knobeloch and Schwartz [21], Tsao and Smith [22], Toop [23], Scatchard et al. [24], Hillert [25], Mathieson and Thynne [26] were applied to estimate ternary properties from binary results.     

Study on volumetric measurement and correlations for MTBE+1-propanol+decane at 298.15 K and atmospheric pressure

Summary Experimental densities for the ternary mixture x₁MTBE+x₂1-propanol+(1-x₁-x₂)decane and the binary mixtures xMTBE +(1-x)1-propanol and x1-propanol+(1-x)decane have been measured at 298.15 K and atmospheric pressure, using a DMA 4500 Anton Paar densimeter. Excess molar volumes were determined from the densities of the pure liquids and mixtures. Attending to the symmetry of the studied mixtures, suitable fitting equations have been used in order to correlate adequately the experimental data. For the ternary mixture, experimental data were also used to test several empirical expressions for estimating ternary properties from experimental binary results.     

Mathematical description of the softening temperature of poly(vinyl chloride) blends with solid-state chlorinated polyethylene

Summary Excess molar volumes of methyl tert-butyl ether (MTBE)+1-pentanol+octane and the binary mixtures MTBE+1-pentanol and 1-pentanol+octane, were measured at 298.15 K and atmospheric pressure, using a DMA 4500 Anton Paar densimeter. All the experimental values were compared with the results obtained by empirical expressions for estimating ternary properties from binary results.     

Excess molar enthalpy of binary mixtures of hexane+ethyl benzene, <Emphasis Type="Italic">o</Emphasis>-xylene, <Emphasis Type="Italic">m</Emphasis>-xylene and <Emphasis Type="Italic">p</Emphasis>-xylene at 298.15 K

Summary This paper reports excess molar enthalpies of the binary systems hexane+ethyl benzene, hexane+o-xylene, hexane+m-xylene and hexane+p-xylene at 298.15 K and atmospheric pressure, over the whole composition range. The data was measured directly using a Calvet microcalorimeter. The excess magnitude was correlated to a Redlich-Kister type equation for each mixture. Also, we will discuss the results for the four mixtures studied here and by comparison with the same binary systems but containing propyl propanoate as first component. Finally, we will correlate our results with the Nitta-Chao and the three UNIFAC theoretical approximations.     

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.     

Thermodynamic properties of the mixture [x1,3-dioxane+(1-x) 1,4-dioxane] at the temperature 298.15 K

Excess enthalpies, excess heat capacities, excess volumes and sound velocities of the mixture of dioxane isomers, 1,3-dioxane and 1,4-dioxane, were measured. One of the isomers, 1,4-dioxane is considered as non-polar liquid and the other as polar liquid. Excess enthalpies are positive and small, less than 55 J mol^-1. Excess heat capacities are also very small and the curve is W-shaped, and the values are from 0.03 to -0.08 J mol^-1 K^-1. Excess volumes and excess isentropic compressibilities are small and positive, and less than 0.03 cm³ mol^-1 and 0.8 TPa^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Densities and Excess Molar Volumes of (Benzene <Emphasis Type="Bold">+</Emphasis> Propionitrile) in the Presence of Chloroform or Carbon Tetrachloride at the Temperature 298.15 K

The excess molar volumes V^E_m for ternary pseudo-binary mixtures of [(benzene+chloroform or carbon tetrachloride)+(propionitrile+chloroform or carbon tetrachloride)] have been determined over the full composition range, by measuring the densities with a vibrating-tube densimeter at 298.15 K and atmospheric pressure. The experimental and calculated quantities are compared to those for the binary mixture (benzene+propionitrile), and the mixing behavior of the components is discussed. The results show that adding the third component, chloroform or carbon tetrachloride, to the binary mixture has a small effect on the interaction between benzene and propionitrile.     

Comments regarding ‘density,speed of sound,refractive index and derivatives properties of the binary mixture n-hexane + n-heptane (or n-octane or n-nonane), T = 288.15–313.15 K’

Communication shows that not all of the measured excess molar data reported in the paper is consistent with the cited literature reference as the authors had claimed.     

含醇溶液的热力学研究Ⅲ.超额体积

根据先前提出的含醇溶液形成的热力学模型，利用充上和释放两个组分间引力 势能的方法，建立了一个含醇溶液超额体积方程．该方程有清晰的物理意义，不仅 能描述各种各样含醇溶液的超额体积随组成的变化规律，而且还能显示自缔合、交 叉缔合和组分间的van der Waals引力对超额体积的贡献．