Volumetric,Acoustic and Refractive Index for the Binary System (Butyric acid + Hexanoic acid) at Different Temperatures

In this paper density, sound velocity, and refractive index for the binary system (butyric acid + hexanoic acid) were measured over the entire composition range and at 5 K intervals in the temperature range 293.15–313.15 K. The excess molar volumes, isentropic compressibilities, excess isentropic compressibilities, deviation in refractive indices, molar refractions, and deviation in molar refractions were calculated by using the experimental densities, sound velocities, and refractive indices, respectively. The Redlich–Kister equation was used to fit the excess molar volume, excess isentropic compressibility, deviation in refractive index and deviation in molar refraction data. The Lorentz–Lorenz approximation was used to correlate the excess molar volume from the deviation in refractive index and also to predict the density from refractive index or the refractive index from density of the binary mixtures. Four sound velocity mixing rules were tested and the best model for the systems studied in this work was the Berryman mixing rule. The thermodynamic properties are discussed in terms of intermolecular interactions between the components of the mixtures.     

Volumetric and refractive properties of binary mixtures containing 1,3-dioxolane and isomeric chlorobutanes

The relation between refractive index deviations and excess volumes for binary mixtures formed by a cyclic ether and a haloalkane has been tested using several methods: refractive index mixing rules and equations of state. Refractive index deviations, excess volumes and molar refractions have been calculated from experimental data of refractive indices and densities at two temperatures 298.15 and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions. Refractive indices were compared with those predicted by several mixing rules. Excess volumes have also been correlated using several cubic equations of state and finally a relation between parameter b from equations of state and molar refraction has been provided.     

Study of some volumetric and refractive properties of {PEG 300 (1) + ethanol (2)} mixtures at several temperatures

Molar volumes and excess molar volumes were investigated from measured density values for {PEG 300 (1) + ethanol (2)} binary mixtures at temperatures from 278.15 to 313.15 K. Both systems exhibit negative excess volumes probably due to increased interactions like hydrogen bonding and/or large differences in molar volumes of the components. Volume thermal expansion coefficients were also calculated for both binary mixtures and pure solvents. Refractive indices were also determined for all these non-aqueous mixtures and neat solvents at all temperatures. Furthermore, the Jouyban–Acree model was used for density, molar volume and refractive index correlations of the studied mixtures at different temperatures. The mean relative deviations between experimental and back-calculated density, molar volume and refractive index data were 0.07%, 0.99% and 0.01%, respectively.     

Derived Properties of Binary Mixtures Containing (Acetone or Methanol) + Hydroxil Compounds

Abstract

This work reports values of the density, refractive index and speed of sound of the binary mixtures acetone or methanol with (2-methyl, 1-propanol, 3-methyl, 1-butanol, 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol) at 298.15 K and atmosphere, as a function of the mole fraction. From the experimental values, the corresponding excess and derived magnitudes were computed (excess molar volumes, changes of refractive index on mixing and changes of isentropic compressibility on mixing), variable-degree polynomials being fitted to the results. Only expansive trend was observed for those mixtures enclosing branched alcohols. The influence of the hydroxil group in the nonideal behaviour of these mixtures were analyzed in terms of the partial molar excess volumes.     

Temperature dependence of thermophysical properties of octane+1-butanol system

The aim of this work is to complete our studies on physical properties of binary mixtures of alkane+1-alkanols. This work reports densities, refractive indices, speeds of sound and isentropic compressibilities of the mixture octane + 1-butanol at different temperatures, from 288.15 to 308.15 K. From the experimental values, the corresponding excess and deviation values were computed (excess molar volumes, changes of refractive index on mixing, changes of speed of sound on mixing and changes of isentropic compressibilities on mixing). The results were fitted to variable-degree polynomials. Excess molar volumes were compared with the predictions of Nitta-Chao Group Contribution Model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Densities,excess molar volumes,and refractive indices of 1,1,2,2-tetrachloroethane and 1-alkanols binary mixtures

Densities, excess molar volumes, refractive indices, and changes in refractive index on mixing for 1,1,2,2-tetrachloroethane + 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-decanol have been determined at T = (293.15 and 303.15) K. The excess molar volumes and changes in refractive index have been fitted to Redlich–Kister polynomials. The effect of the chain length of the 1-alkanol on the excess molar volume and the change in the refractive index of its mixtures with 1,1,2,2-tetrachloroethane was discussed. In addition, the refractive indices were compared with calculated values using mixing rules proposed by several authors, and a very good agreement was obtained.     

Isentropic expansion and related thermodynamic properties of non-ionic amphiphile-water mixtures

A concise thermodynamic formalism is developed for the molar isentropic thermal expansion, ES,m = ( partial differential Vm/ partial differential T)(Sm,x), and the ideal and excess quantities for the molar, apparent molar and partial molar isentropic expansions of binary liquid mixtures. Ultrasound speeds were determined by means of the pulse-echo-overlap method in aqueous mixtures of 2-methylpropan-2-ol at 298.15 K over the entire composition range. These data complement selected extensive literature data on density, isobaric heat capacity and ultrasound speed for 9 amphiphile (methanol, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-2-ol, ethane-1,2-diol, 2-methoxyethanol, 2-ethoxyethanol or 2-butoxyethanol)-water binary systems, which form the basis of tables listing molar and excess molar isobaric expansions and heat capacities, and molar and excess molar isentropic compressions and expansions at 298.15 K and at 65 fixed mole fractions spanning the entire composition range and fine-grained in the water-rich region. The dependence on composition of these 9 systems is graphically depicted for the excess molar isobaric and isentropic expansions and for the excess partial molar isobaric and isentropic expansions of the amphiphile. The analysis shows that isentropic thermal expansion properties give a much stronger response to amphiphile-water molecular interactions than do their isobaric counterparts. Depending on the pair property-system, the maximum excess molar isentropic value is generally twenty- to a hundred-fold greater than the corresponding maximum isobaric value, and occurs at a lower mole fraction of the amphiphile. Values at infinite dilution of the 9 amphiphiles in water are given for the excess partial molar isobaric heat capacity, isentropic compression, isobaric expansion and isentropic expansion. These values are interpreted in terms of the changes occurring when amphiphile molecules cluster into an oligomeric form. Present results are discussed from theoretical and experimental thermodynamic viewpoints. It is concluded that isentropic thermal expansion properties constitute a new distinct resource for revealing particular features and trends in complex mixing processes, and that analyses using these new properties compare favourably with conventional approaches.     

Thermodynamic Properties of Alkanediols+Acetates at 298.15 K

In this work we present experimental values of the density, refractive index, speed of sound, isentropic compressibility and liquid-liquid equilibria of the binary mixtures (methyl acetate, ethyl acetate, propyl acetate, and butyl acetate) with (1,2-ethanediol, 1,2-propanediol, or 1,3-propanediol) at 298.15 K and atmospheric pressure, as a function of mole fraction. From the experimental values, the corresponding excess and deviation values were computed (excess molar volumes, changes of refractive index on mixing, and changes of isentropic compressibility), variable-degree polynomials being fitted to the results. The validity of different estimation methods for predicting the experimental values of physical properties was tested. The limiting partial excess molar volume of the components in each binary mixture was determined by means of predetermined Redlich-Kister parameters. Group contribution method (UNIFAC-Dortmund) was applied in order to compare their capability in predicting the experimental equilibria values. This revised version was published online in July 2006 with corrections to the Cover Date.     

苯乙烯与邻、间、对-二甲苯二元混合液的分子间相互作用

The densities (ρ), ultrasonic speeds (v), and refractive indices (n) of binary mixtures of styrene (STY)with m-, o-, or p-xylene, including those of their pure liquids, were measured over the entire composition range at the temperatures 298.15, 303.15, 308.15, and 313.15 K. The excess volumes (VE), deviations in isentropic compressibilities(△ks), acoustic impedances (△Z), and refractive indices (△n) were calculated from the experimental data. Partial molar volumes (V0φ,2) and partial molar isentropic compressibilities (K0φ,2) of xylenes in styrene have also been calculated. The derived functions, namely, VE, △ks, △Z, △n, V0φ,2, and K0φ,2 were used to have a better understanding of the intermolecular interactions occurring between the component molecules of the present liquid mixtures. The variations of these parameters suggest that the interactions between styrene and o-, m-, or p-xylene molecules follow the sequences: p-xylene＞o-xylene＞m-xylene. Apart from using density data for the calculation of VE, excess molar volumes were also estimated using refractive index data. Furthermore, several refractive index mixing rules have been used to estimate the refractive indices of the studied liquid mixtures theoretically. Overall, the computed and measured data were interpreted in terms of interactions between the mixing components.     

Binary mixtures containing OMIM PF6: density,speed of sound,refractive index and LLE with hexane,heptane and 2-propanol at several temperatures

Experimental densities, speeds of sound and refractive indices of the binary mixtures OMIM PF₆ (1-methyl-3-octylimidazolium hexafluorophosphate) with hexane, heptane, and 2-propanol were determined at T = 293.15, 298.15, and 303.15 K. Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems were performed. The liquid–liquid equilibrium data of these binary mixtures were carried out experimentally and the NRTL and UNIQUAC correlative equations were applied.     

Density,speed of sound,and refractive index measurements for the binary systems (butanoic acid + propanoic acid,or 2-methyl-propanoic acid) at T = (293.15 to 313.15) K

Density, speed of sound, and refractive index for the binary systems (butanoic acid + propanoic acid, or 2-methyl-propanoic acid) were measured over the whole composition range and at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K. The excess molar volumes, isentropic compressibilities, excess isentropic compressibilities, molar refractions, and deviation in refractive indices were also calculated by using the experimental densities, speed of sound, and refractive indices data, respectively. The Redlich–Kister smoothing polynomial equation was used to fit the excess molar volume, excess isentropic compressibility and deviation in refractive index data. The thermodynamic properties have been discussed in terms of intermolecular interactions between the components of the mixtures.     

Densities,excess molar volumes,and refractive indices of 1,1,2,2-tetrabromoethane and 1-alkanols binary mixtures

Densities, excess molar volumes, refractive indices, and changes in refractive index on mixing for (1,1,2,2-tetrabromoethane + 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-decanol) have been determined at T = 293.15 K and at T = 303.15 K. The excess molar volumes and changes in refractive index have been fitted to Redlich–Kister polynomials. The effect of the chain length of the 1-alkanol on the excess molar volume and the change in the refractive index of its mixtures with 1,1,2,2-tetrabromoethane are discussed. In addition, the refractive indices are compared with calculated values using mixing rules proposed by several authors, and a good agreement is obtained.     

Thermodynamic properties of the mixture benzene+cyclohexane+2-methyl-2-butanol at the temperature 298.15 K: excess molar volumes prediction by application of cubic equations of state

Excess molar volumes, changes of refractive indices, and changes of isentropic compressibilities of the ternary mixture benzene (1)+cyclohexane (2)+2-methyl-2-butanol (3), and the corresponding binary mixtures benzene (1)+2-methyl-2-butanol (3), and cyclohexane (2)+2-methyl-2-butanol (3) have been evaluated from density, refractive index, and speed of sound measurements at 298.15 K, and atmosphere. These derived properties of binary, and ternary mixtures were fitted to Redlich–Kister, and Nagata equations, respectively, the correlation parameters being gathered. In spite of the high non-ideality observed, the excess molar volumes were satisfactorily predicted by means of cubic equations of state with simple mixing rules.     

Physical properties and their corresponding changes of mixing for the ternary mixture acetone + n-hexane + water at 298.15 K

Experimental density and the refractive index of the ternary mixture acetone + n-hexane + water, and their binary systems were experimentally measured and correlated at 298.15 K and atmospheric pressure. A maximum in refractive indices has been observed for the acetone + water system while the excess molar volume and the molar refraction change are all negative. For the mixture acetone + n-hexane, the excess molar volume is always positive and the molar refraction change of mixing showed a S-shaped dependence on acetone composition. The excess molar volumes and molar refraction changes of mixing were correlated using the Redlich-Kister expression and Cibulka equation. The coefficients and standard deviation between the experimental and fitted values were estimated. Good agreement between both results was obtained.     

Refractive Index and Density Measurements for Selected Binary Protic‐Protic,Aprotic‐Aprotic,and Aprotic‐Protic Systems at Temperatures from 298.15 K to 308.15 K

The refractive indices (n) and the densities (ρ) of: (1) protic‐protic solvent mixtures (methanol‐ethanol, methanol‐porpanol, methanol‐butanol and ethanol‐water), (2) aprotic‐aprotic solvent mixtures (acetonitrile‐dimethylformamide, acetonitrile‐dimethylsulphoxide, and acetonitrile‐1,4‐dioxane) and (3) aprotic‐protic solvent mixtures (dimethylformamide, acetonitrile with water and some aliphatic alcohols) were measured experimentally at different temperatures (25, 30 and 35 °C). From the values of the measured refractive indices and densities, the excess refractive indices (n^E), molar refractions (R), atomic polarization (P_A), molar volumes (V), solvated radii (r) and polarizabilities (α) of the mixed solvents were calculated. The results show that the solvent‐solvent interaction reaches maximum value at a definite mole fraction (x) of each solvent depending on its nature. Also, the excess refractive indices, densities and atomic polarizations are found to decrease as the temperature increases. On the other hand, the molar volumes, solvated radii, molar refractions and polarizabilities are found to increase as the temperature increases.     

Density,excess molar volumes and refractive indices of β-pinene with o,m, p-xylene and toluene at 303.15, 308.15 and 313.15 K

Densities (ρ), excess molar volumes (V^E ), refractive indices (n_D ) and deviation in refractive (Δn_D ) indices on mixing for β-pinene with o-xylene, m-xylene, p-xylene and toluene have been determined at T?=?303.15, 308.15 and 313.15?K. The excess molar volume and deviation in refractive index have been fitted to Redlich–Kister polynomials. In addition, deviations in refractive indices were compared with the predictions of several mixing rules. Results obtained have been discussed in terms of intermolecular interactions.     

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.     

Densities,Refractive Indices and Excess Properties of N-<Emphasis Type="Italic">p</Emphasis>-Tolylbenzohydroxamic Acid in Dimethyl Sulfoxide at 298.15 to 313.15 K

Densities and refractive indices have been measured for N-p-tolylbenzohydroxamic acid (p-TBHA) in dimethyl sulfoxide (DMSO) as a function of concentration at (298.15, 303.15, 308.15, 313.15 and 318.15) K. The apparent molar volumes and partial molar volumes were obtained from these density data. The limited partial molar expansivities have been calculated from the temperature dependence of the limiting partial molar volume. The molar refractions were calculated from the experimental refractive index values for p-TBHA in DMSO. The excess volumes, deviations of the refractive indices, and molar refractions were also calculated. The results are discussed in terms of molecular interactions.     

Densities,Ultrasonic Speeds,Viscosities and Refractive Indices of Binary Mixtures of Benzene with Benzyl Alcohol,Benzonitrile, Benzoyl Chloride and Chlorobenzene at 303.15 K

Densities,ρ, ultrasonic speeds, u, viscosities,η, and refractive indices, n, of pure benzene, benzyl alcohol (BA), benzonitrile (BN), benzoyl chloride (BC), chlorobenzene (CB) and their thirty six binary mixtures, with benzene as common component, were measured at 303.15 K over the entire mole fraction range. From these experimental data the values of deviations in ultrasonic speed, △u, isentropic compressibility, △k_s,excess acoustic impedance, Z^E, deviation in viscosity, Dh, and excess Gibbs free energy of activation of viscous flow, G^*E, and partial molar isentropic compressibility, Kφ,2⁰ of BA, BN, BC and CB in benzene were computed. The variation of these derived functions with composition of the mixtures suggested the increased cohesion (molecular order) in the solution and that interaction (A-B)＞(A-A) or (B-B).Moreover, theoretical prediction of ultrasonic speed, viscosity and refractive index of all the four binary mixtures was made on the basis of empirical and semi-empirical relations by using the experimental values of the pure components. Comparison of theoretical results with the experimental values was made in order to assess the suitability of these relations in reproducing the experimental values of u, η and n. Also, molecular radii of pure liquids and the average molecular radii of binary mixtures were evaluated using the corresponding refractive indices of pure liquids and binary mixtures. The average molecular radii of binary mixtures were found to be additive with respect to mole fraction of the pure component.     

Refractive Indices of the Ternary Mixtures Butanol + <Emphasis Type="Italic">n</Emphasis>-Hexane + 1-Chlorobutane

Refractive indices for the ternary mixtures formed by each one of the isomers of butanol (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol), with n-hexane and 1-chlorobutane, have been measured at 298.15 K. From these data the refractive index deviations were calculated and fitted by Cibulka’s equation, and the refractive index deviations were related to the corresponding excess volumes of the mixtures. Furthermore, several mixing rules were used to predict both refractive indices and excess volumes of the ternary mixtures from their densities or refractive indices. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.