Excess Molar Volumes of Binary Mixtures of Propyl Ethanoate with some n-Alkanes at 298.15 K and 308.15 K

Abstract

Excess molar volumes v^E have been measured for the binary liquid mixtures of propyl ethanoate with five n-alkanes (n-hexane, n-heptane, n-octane, n-nonane and n-decane) at 298.15 and 308.15 K, using an Anton Paar densimeter. All the mixtures studied present positive v^E values that increase with the length of the chain of the alkane and with the temperature. The experimental results are compared with the predictions of the Nitta—Chao model.     

Temperature dependence of the derived properties of mixtures containing chlorobenzene and aliphatic linear alkanes (C6–C12)

This article reports experimental densities, refractive indices and speeds of sound of the binary mixtures chlorobenzene?+?(n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane or n-dodecane) and speeds of sound of the ternary mixtures chlorobenzene?+?n-hexane?+?(n-undecane or n-dodecane) at 298.15?K and atmospheric pressure, over the whole concentration range. The corresponding derived properties were computed from the experimental data. The results were fitted by means of the Redlich–Kister equation for binary mixtures and the Nagata equation for ternary mixtures. A set of estimation methods were applied, and an interpretation in terms of structure and length of molecular chain of the n-alkane molecules was made.     

Excess Enthalpies of Ternary Mixtures: (2-Methyltetrahydrofuran or Di-n-Butyl ether) + 3-Methylpentane + n-Decane at 25°C

Measurements of excess molar enthalpies at 25°C in a flow microcalorimeter are reported for the two ternary mixtures 2-methyltetrahydrofuran + 3-methylpentane + n-decane and di-n-butyl ether + 3-methylpentane + n-decane. 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.     

Liquid–Liquid Equilibria of Oxygenate Fuel Additives with Water at 298.15 K: Ternary and Quaternary Aqueous Systems of Diisopropyl Ether and Hydrocarbons with 2-Propanol

Experimental tie-line data were determined for one ternary system, water + diisopropyl ether + n-heptane and two quaternary systems, water + diisopropyl ether + 2-propanol + n-heptane or toluene at 298.15 K and ambient pressure. The experimental liquid–liquid equilibrium data were successfully correlated using a modified UNIQUAC model with ternary and quaternary mixture parameters, in addition to the binary ones. The calculated results were also compared with those obtained from an extended UNIQUAC model of Nagata [Fluid Phase Equilib. 54, 191 (1990)].     

Densities and Viscosities of the Binary Mixtures Decanol + Some n-Alkanes at 298.15 K

Abstract

Densities and viscosities of four binary liquid systems decanol +n-heptane, +n-octane, +n-nonane, +n-decane, have been determined at 298.15 K and atomospheric pressure, over the complete composition ranges. The excess values of molar volume, viscosity and Gibbs free energy for the activation of flow were evaluated. The Grunberg-Nissan parameter was also calculated. The viscosity data were fitted to the equations of McAllister and Auslander.     

Excess enthalpies of the ternary mixtures: tetrahydrofuran + (diisopropyl ether or 2-methyltetrahydrofuran) + n-heptane at 298.15 K

Excess molar enthalpies, measured at 298.15 K in a flow microcalorimeter, are reported for the ternary mixtures (tetrahydrofuran + diisopropyl ether + n-heptane) and (tetrahydrofuran + 2-methyltetrahydrofuran + n-heptane). Smooth representations of the results are described and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. The latter are compared with diagrams obtained when the model of Liebermann and Fried is used to estimate the excess enthalpies of the ternary mixtures from the physical properties of the components and their binary mixtures.     

Excess Enthalpies of 2-Methyltetrahydrofuran + 2,2,4-Trimethylpentane + (Decane or Dodecane) 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 + n-decane and 2-methyltetrahydrofuran + 2,2,4-trimethylpentane + n-dodecane. 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.     

Analog calorimetry and UNIQUAC group contributions approaches to the miscibility of pvc with eva copolymers

The miscibility of blends of poly(vinyl-chloride) (PVC) with poly(ethylene-co-vinyl acetate) (EVA) was investigated through analog calorimetry and a group contribution procedure based on the UNIQUAC model. The group contribution parameters quantifying the pair interactions between the structural features of the above polymers were calculated from experimental excess enthalpies of a series of binary mixtures of chlorocompounds, esters and hydrocarbons. Enthalpy data were also collected for the ternary mixtures (2-chloropropane+ethyl acetate+n-heptane) and (2-chlorobutane + methyl acetate+n-heptane), chosen as possible models for the studied macromolecular mixtures. The miscibility window of the PVC-EVA blends is fairly predicted by the group contribution method. It is also acceptably predicted by the enthalpic behaviour of the first ternary set, but only when the latter is calculated with binary data. A slightly narrower miscibility range is predicted by the binary interaction model. The results of these procedures are compared and the higher reliability of the group contribution procedure is emphasized in terms of its capability to reproduce the exact structure of the macromolecules and the non-univocal choice of the model molecules involved in the analog calorimetry approach. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamics of binary mixtures of aliphatic linear alkanes (C6–C12) at 298.15 K

This article reports experimental values of speeds of sound, densities and refractive indices on mixing of the binary mixtures n-hexane + (n-heptane, n-octane, n-nonane, n-decane, n-undecane, or n-dodecane) at 298.15?K and atmospheric pressure, over the whole concentration range. The corresponding excess and derived properties were computed from the experimental data. The results were fitted by means of the Redlich–Kister equation, such parameters being gathered. Different estimation methods (equations of state, mixing rules, Collision Factor and Free Length Theory) were applied, qualitative agreement between the experimental and theoretical values both in magnitude and sign being obtained.     

Isothermal vapor–liquid equilibria and excess molar volumes for the ternary mixtures containing 2-methyl pyrazine

Isothermal vapor–liquid equilibrium (VLE) data at 353.15 K and excess molar volumes (V^E) at 298.15 K are reported for the binary systems of ethyl acetate (EA)+cyclohexane and EA+n-hexane and also for the ternary systems of EA+cyclohexane+2-methyl pyrazine (2MP) and EA+n-hexane+2MP. The experimental binary VLE data were correlated with common g^E model equations. The correlated Wilson parameters of the constituent binary systems were used to calculate the phase behavior of the ternary mixtures. The calculated ternary VLE data using Wilson parameters were compared with experimental ternary data. The experimental excess molar volumes were correlated with the Redlich–Kister equation for the binary mixtures, and Cibulka’s equation for the ternary mixtures.     

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.     

Changes of refractive indices of the ternary mixtures chlorobenzene + n-hexane + (n-nonane or n-decane) at 298.15 K

The measures of the refractive indices of the ternary mixtures chlorobenzene + n-hexane + (n-nonane or n-decane) have been done at 298.15?K and atmospheric pressure in the whole composition diagram. The composition dependence of the derived magnitude has been compared with the data obtained with several theoretical models. Attending to the accurate results of these models, the equation of state enclosing mixing rules are pointed out as simple procedures for a multicomponent estimation of refractive indices, the corresponding binary parameters could be used to other thermophysical studies.     

Volumetric properties of the binary mixture <Emphasis Type="Italic">n</Emphasis>-heptane+ethylbenzene mixtures at high temperatures and high pressures

New experimental data on the density of three (0.2393, 0.4856 and 0.7390 mole fraction of ethylbenzene) binary n-heptane+ethylbenzene mixtures have been measured with a constant-volume piezometer immersed in a precision liquid thermostat. These new experimental data covering a temperature range from 306 to 527 K and a pressure range of 0.1 to 11 MPa. The experimental data reported here have an uncertainty less than 0.06% for the density, 0.05% for the pressure, 15 mK for the temperature, and 0.012% for the concentration. Excess molar volumes were derived using measured values of density for the mixtures and for the pure components calculated with reference equation of state for n-heptane (Span and Wagner, 2003) and for the pure ethylbenzene (Frenkel et al., 2005). The derived values of excess molar volumes at atmospheric pressure were compared with the values reported by other authors in the literature. The effect of pressure on the excess molar volumes was studied.     

Viscosities and Densities of Solutions of n-Decane, or n-Tetradecane with Several Esters at 25°C

Viscosity and density data are reported for n-decane + propyl ethanoate, propyl propanoate, propyl butyrate, and n-tetradecane + propyl ethanoate, propyl propanoate, and propyl butyrate at 25°C and atmospheric pressure. Kinematic viscosities were determined using a capillary viscosimeter and densities were measured using vibrating-tube densimetry. The equations of Grunberg–Nissan, McAllister, Auslander, and Teja were fitted to the viscosity data. Excess molar Gibbs free energies of activation for flow were also evaluated. The experimental values obtained for excess volumes were compared with the Nitta et al. group contribution model.     

Excess volumes for n-alkanols + n-alkanes I. Binary mixtures of methanol,ethanol, n-propanol,and n-butanol + n-heptane

Excess volumes V^E measured at 298.15 K in a successive-dilution dilatometer are reported for binary mixtures of the n-alkanols C₁ to C₄ + n-heptane. For ethanol +, and n-butanol + n-heptane, the measurements were extended to high dilutions of alkanol. V^E is positive for all of the mixtures but decreases rapidly in magnitude for increasing chain length of the n-alkanol. The results were used to estimate the excess partial molar volumes of the components.     

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.     

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.     

Calorimetric effects of short-range orientational order in solutions of benzene or n-alkylbenzenes in n-alkanes

A Picker flow microcalorimeter was used to determine molar excess heat capacities, C^E_p, at 298.15 K, as function of concentration, for the eleven liquid mixtures: benzene+n-tetradecane; toluene+n-heptane, and +n-tetradecane; ethylbenzene+n-heptane, +n-decane, +n-dodecane; and +n-tetradecane; n-propylbenzene +n-heptane, and +n-tetradecane; n-butylbenzene+n-heptane, and +n-tetradecane. In addition, molar excess volumes, V^E, at 298.15 K, were obtained for each of these systems (except benzene+n-tetradecane) and for toluene+n-hexane. The excess volumes which are generally negative with a short alkane, increase and become positive with increasing chain length of the alkane. The excess heat capacities are negative in all cases. The absolute ¦C^E_p¦ increased with increasing chain length of the n-alkane. A formal interchange parameter, C_p12, is calculated and its dependence on n-alkane chain length is discussed in terms of molecular orientations.     

Isentropic compressibilities of the mixture chlorobenzene + n-hexane + (n-heptane or n-octane) at 298.15 K

In this work, the applicability of the free length and the collision factor theories (FLT and CFT, respectively) to predict multicomponent changes of isentropic compressibilities is analysed and compared. To this end, appropiate expansions for ternary mixtures were derived from the original works, and then applied to a mixture containing unlike compounds in terms of functional molecular groups. Experimental data of excess molar volumes from open literature and new experimental isentropic compressibilities of the mixture chlorobenzene?+?n-hexane?+?(n-heptane or n-octane) were used to compute the parameters. A good accuracy was obtained when ternary prediction is attempted in this partially soluble mixture at different temperatures by the collision factor theory. These results show the versatility of this model for estimation in complex multicomponent mixtures with phases splitting.     

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.