Thermophysical properties for (diethyl carbonate + p-xylene + octane) ternary system

The density and speed of sound of the ternary mixture (diethyl carbonate + p-xylene + octane) have been measured at atmospheric pressure and in the temperature range T = (288.15 to 308.15) K. Besides, surface tension has been also determined for the same mixture at T = 298.15 K. The experimental measurements have allowed the calculation of the corresponding derived properties: excess molar volumes, excess isentropic compressibilities, and surface tension deviations. Excess properties have been correlated using Nagata and Tamura equation and correlation for the surface tension deviation has been done with the Cibulka equation. Good accuracy has been obtained. Based on the variations of the derived properties values with composition, a qualitative discussion about the intermolecular interactions was drawn.     

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.     

Thermodynamic study of binary mixtures containing 1-butylpyridinium tetrafluoroborate and methanol, or ethanol

Densities and speeds of sound have been determined for the binary mixture (1-butylpyridinium tetrafluoroborate + methanol, or ethanol) over the temperature range 293.15 K to 323.15 K. From experimental values, excess volume and excess isentropic compressibility have been calculated. The mixtures give negative values for the excess properties. Besides, (vapour + liquid) equilibrium in isothermal conditions has been obtained for these systems at T = 303.15 K and T = 323.15 K, which has allowed us to derive activity coefficients and excess Gibbs functions. Positive deviations from Raoult’s law have been found. A detailed analysis and interpretation of results have been carried out in structural and energetic terms using thermodynamic information of the pure compounds.     

Physicochemical properties of {1-methyl piperazine (1) + water (2)} system at T = (298.15 to 343.15) K and atmospheric pressure

Densities (ρ) and viscosities (η) of aqueous 1-methylpiperazine (1-MPZ) solutions are reported at T = (298.15 to 343.15) K. Refractive indices (n_D) are reported at T = (293.15 to 333.15) K, and surface tensions (γ) are reported at T = (298.15 to 333.15) K. Derived excess properties, except excess viscosities (Δη), are found to be negative over the entire composition range. The addition of 1-MPZ reduces drastically the surface tension of water. The temperature dependence of surface tensions is explained in terms of surface entropy (S^S) and enthalpy (H^S). The measured and derived properties are used to probe the microscopic liquid structure of the bulk and surface of the aqueous amine solutions.     

Surface tension,density, and speed of sound for the ternary mixture {diethyl carbonate + p-xylene + decane}

This paper reports the results of a new experimental study of thermophysical properties for the ternary mixture of {diethyl carbonate + p-xylene + decane}. Surface tension has been measured at 298.15 K and, density and speed of sound have been measured in the temperature range T = (288.15 to 308.15) K. Excess molar volumes, excess isentropic compressibilities, and surface tension deviations, have been calculated from experimental data. Surface tension deviations have been correlated with Cibulka equation and Nagata and Tamura equation was used for the other excess properties. Good accuracy has been obtained. These excess magnitudes are discussed qualitatively in terms of the nature and type of intermolecular interactions of the components involved.     

Surface and bulk behavior of (dialkylsulfoxides + carbon tetrachloride) mixtures

Surface tensions, surface tension deviations, densities, and excess molar volumes of binary mixtures of carbon tetrachloride (CCl₄) with dimethylsulfoxide (DMSO), diethylsulfoxide (DESO), dipropylsulfoxide (DPSO), and dibutylsulfoxide (DBSO) have been determined over the entire composition range at (298.15 and 313.15) K. The results were fitted by the Redlich–Kister polynomial equation and the corresponding binary coefficients have been derived.The obtained excess quantities show that both charge-transfer complex formation between CCl₄ and dialkylsulfoxides (DASO) molecules and on the other hand sulfoxides’ chain length are crucial factors conditioning the excess thermodynamic properties of (CCl₄ + DASO) binary mixtures.     

Changes of Refractive Indices for the Ternary Mixture Acetone + Methanol + N-Hexane at 288.15 and 298.15 K

Abstract

The refractive indices of the ternary mixture acetone + methanol + n-hexane have been measured at 288.15 and 298.15 K and atmosphere in the whole composition diagram. Parameters of polynomial equations which represent the composition dependence of physical and derived property are gathered. the use of a multicomponent extension of Heller equation in order to predict excess molar volumes from refractive indices on mixing are tested against literature data, a comparative accuracy with currently available models being obtained.     

Excess properties of binary mixtures hexane,heptane, octane and nonane with benzene,toluene and ethylbenzene at T = 283.15 and 298.15 K

Densities, speeds of sound and the refractive indices of binary systems containing alkanes (hexane, heptane, octane and nonane) with aromatic compounds (benzene, toluene and ethylbenzene) at T = 283.15 and 298.15 K under atmospheric pressure were determined over the whole composition range. From the experimental results, the derived and excess properties (excess molar volumes, isentropic compressibility, excess molar isentropic compressibility and refractive index deviations) at T = 283.15 and 298.15 K were calculated and satisfactorily fitted to the Redlich–Kister equation.     

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.     

Refractive Indices, Viscosities, and Densities for L-Cysteine Hydrochloride Monohydrate + D-Sorbitol + Water, and Glycerol + D-Sorbitol + Water in the Temperature Range between T=303.15 K and T=323.15 K

Viscosities, refractive indices, and densities for ternary systems of (L-cysteine hydrochloride monohydrate [LCHCMH] + D-sorbitol + water) and (glycerol + D-sorbitol + water) and binary systems of ([LCHCMH] + water) and (D-sorbitol + water) have been measured at several temperatures (between T=303.15 K and T=323.15 K) and mass fractions (0.1 to 0.8) at atmospheric pressure. For these mixtures, the experimental values of density were correlated with an experimental equation and the experimental values of viscosity were correlated with the Jones-Dole equation.     

Refractive Indices, Densities and Excess Molar Volumes of Monoalcohols + Water

The refractive index, n _D , and density, ρ, of binary mixtures of monoalcohols + water, have been measured at a temperature of 298.15,K and atmospheric pressure. The variation of the refractive indices of these solutions has also been determined with temperature in the range T = (278.15 to 338.15) K and atmospheric pressure. A comparative study has been made of the refractive indices obtained experimentally and those calculated by means of the Lorentz-Lorenz [Theory of Electrons, Dover Phoenix (1952)] and Gladstone-Dale relations [Trans. R. Soc. London 148:887–902 (1858)]; in all cases, the Gladstone–Dale equation was seen to afford values similar to those obtained experimentally. Calculations have been made of the excess molar volumes, V ^E, and the molar refraction deviations, ΔR, of these mixtures and the differences between the experimental values for refractive index and those obtained by means of the Gladstone–Dale equation. Values of V ^E were compared with others in the literature. In all cases the V ^E values were negative, and in all cases, except in the methanol + water, ΔR showed a maximum for x = 0.8.     

Some Physical Properties of Binary Liquid Systems: (2-Butanone + n-Propionic Acid or n-Butyric Acid)

Abstract

Density, viscosity and surface tension of two binary liquid systems: 2-butanone + n-propionic acid, 2-butanone + n-butyric acid have been determined at 20, 30 and 40°C, over the whole compositional range. The excess values of molar volume, viscosity, Gibbs free energy for the activation of flow and surface tension were evaluated. These excess values were fitted to a Redlich-Kister type of equation. The Grunberg-Nissan parameter, d, was also calculated. The binary viscosity data were fitted to the models of McAllister, Heric, Auslander and Teja and Rice. Surface tension data were fitted to the models of Zihao and Jufu, Rice and Teja, and an empirical two-constant model proposed in this study.     

Densities, Refractive Indexes, and Excess Properties of Mixing of the n-Hexanol + Ethanenitrile + Dichloromethane Ternary System at 25°C

Excess molar volumes and excess refractive indexes of the n-hexanol + ethanenitrile + dichloromethane system and the three corresponding binary mixtures have been determined at 25°C, by measuring densities and refractive indexes. Different expressions exist in the literature to predict these excess properties from binary data. The empirical correlation of Cibulka is shown to be the best in this system. An estimation of excess molar volumes is also evaluated using a modified Heller equation, which depends on the refractive indexes of the mixtures. Comparison of the predictions by different methods with the experimental values of the physical properties has been made.     

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.     

Surface tension and density of binary mixtures of monoalcohols,water and acetonitrile: equation of correlation of the surface tension

Measurements of the surface tension (σ) and density (ρ) of binary mixtures of monoalcohols, water and acetonitrile at 298.15 K and at atmospheric pressure, as a function of mole fraction (x) have been made. The experimental values of the deviation of surface tension and the excess of molar volume (Δσ, V ^E) have been correlated by the Redlich–Kister equation. An empirical correlation equation is presented for the study of the surface tension of these mixtures, and comparisons are made of the experimental values of surface tension versus those obtained with the correlation equation and with other models of correlation. Finally, with the purpose of corroborating the validity of the correlation equation, the latter is applied to other reference binary mixtures.     

Thermodynamic properties of dimethyl phthalate + vinyl acetate, diethyl phthalate + vinyl acetate or bromocyclohexane, and dibutyl phthalate + vinyl acetate or 1,2-dichlorobenzene at T = 298.15–308.15 K

Thermodynamic properties (densities and viscosities) of binary mixtures of diethyl phthalate (DEP) + bromocyclohexane, dibutyl phthalate (DBP) + 1,2-dichlorobenzene, and vinyl acetate (1) + dimethyl phthalate (DMP) (2), + diethyl phthalate (2), or + dibutyl phthalate (2) were measured over the whole range of mole fractions at atmospheric pressure and different temperatures (T = 298.15 K to 308.15 K). For these mixtures, their excess molar volumes (V ^E) and viscosity deviations (Δη) were calculated from the experimental data. These results were correlated with the Redlich-Kister polynomial equation to derive the coefficients and standard errors.     

Excess Molar Volume and Viscosity of Isobutyric Acid + Water Binary Mixtures Near and Far Away from the Critical Temperature

The excess molar volume V^E, shear viscosity deviation Δη and excess Gibbs energy of activation ΔG^∗E of viscous flow have been investigated by using density (ρ) and shear viscosity (η) measurements for isobutyric acid + water (IBA+W) mixtures over the entire range of mole fractions at five different temperatures, both near and close to the critical temperature (2.055K ≤ (T−T_c)≤ 13.055K). The results were also fitted with the Redlich–Kister equation. This system exhibited very large negative values of V^E and very large positive values of Δη due to increased hydrogen bonding interactions and correlation length between unlike molecules in the critical region and to very large differences between the molar volumes of the pure components at low temperatures. The activation parameters ΔH^∗ and ΔS^∗ have been also calculated and show that the critical region has an important effect on the volumetric properties.     

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.     

Reaction rates for O + HD → OH + D and O + HD → OD + H

We have calculated reaction rates for the reactions O + HD → OH + D and O + DH → OD + H using improved canonical variational transition state theory and least-action ground-state transmission coefficients with an ab initio potential energy surface. The kinetic isotope effects are in good agreement with experiment. The optimized tunneling paths and properties of the variational transition states and the rate enhancement for vibrationally excited reactants are also presented and compared with those for the isotopically unsubstituted reaction O + H₂ → OH + H. The thermal reactions at low and room temperature are predicted to occur by tunneling at extended configurations, i.e., to initiate early on the reaction path and to avoid the saddle point regions. Tunneling also dominates the low and room temperature reactions for excited vibrational states, but in these cases the results are not as sensitive to the nature of the tunneling path. Overbarrier mechanisms dominate for both thermal and excited-vibrational state reactions for T > 600 K. For the excited-state reaction (with initial vibrational quantum number n > 0) a transition state switch occurs for T > 1000 K for the O + HD(n = 1) → OD + H case and for T > 1500 K for the O + DH(n = 1) → OD + H reaction, and this may be a general phenomenon for excited-state reactions at higher temperature. In the present case the switch occurs from an early variational transition state where the vibrationally adiabatic approximation is expected to be valid to a tighter variational transition state where nonadiabatic effects are probably important and should be included.     

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.