Measurements of densities,viscosities, speeds of sound and relative permittivities and excess molar volumes,excess isentropic compressibilities and deviations in relative permittivities and molar polarizations for dibutyl ether + benzene, + toluene and + p-xylene at different temperatures

The densities ρ, dynamic viscosities η, speeds of sound u, and relative permittivities ε_r, for (dibutyl ether + benzene, or toluene, or p-xylene) have been measured at different temperatures over the whole composition range and at atmospheric pressure. The mixture viscosities have been correlated with semi empirical equations. Calculations of the speed of sound based on Nomoto’s equation have been found to be close to experimental values for the three mixtures and at two temperatures. Excess functions such as excess molar volumes V_m^E, excess isentropic compressibilities κ_s^E, deviations in relative permittivities δε_r, and molar polarizations δP_m were calculated and fitted to Redlich–Kister type equations.     

Excess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 303.15 K

Excess molar volumes (V^E) and ultrasonic studies at T = 303.15 K and atmospheric pressure have been measured over the whole composition range for the binary mixtures of N-methyl-2-pyrrolidone (NMP) with ketones. The ketones studied in the present investigation include methyl ethyl ketone (MEK), diethylketone (DEK), methyl propyl ketone (MPK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The V^E values were measured using a dilatometer and were negative over the entire mole fraction range for NMP with MEK, DEK, MPK, and MIBK and were positive for NMP with CH. The ultrasonic sound velocities for the above systems were measured with a single crystal interferometer at a frequency of 3 MHz. The sound velocity (u) results have been used to calculate isentropic compressibility (K_s) and deviation in isentropic compressibility (ΔK_s) over the entire range of volume fraction. The sound velocity results have been predicted in terms of free length theory (FLT), collision factor theory (CFT), and Nomoto relation. The results reveal that all the theories gave a satisfactory estimate of the sound velocity. The deviation values of the isentropic compressibilities (ΔK_s) were negative over the entire range of volume fraction in all the binary liquid mixtures except in the binary system NMP with CH, where we observed positive ΔK_s values. The results are interpreted on possible molecular interactions between components.     

Thermodynamic properties of (tetradecane + benzene, + toluene, + chlorobenzene, + bromobenzene, + anisole) binary mixtures at T = (298.15, 303.15, and 308.15) K

Density ρ, viscosity η, and refractive index n_D, values for (tetradecane + benzene, + toluene, + chlorobenzene, + bromobenzene, + anisole) binary mixtures over the entire range of mole fraction have been measured at temperatures (298.15, 303.15, and 308.15) K at atmospheric pressure. The speed of sound u has been measured at T = 298.15 K only. Using these data, excess molar volume V^E, deviations in viscosity Δη, Lorentz–Lorenz molar refraction ΔR, speed of sound Δu, and isentropic compressibility Δk_s have been calculated. These results have been fitted to the Redlich and Kister polynomial equation to estimate the binary interaction parameters and standard deviations. Excess molar volumes have exhibited both positive and negative trends in many mixtures, depending upon the nature of the second component of the mixture. For the (tetradecane + chlorobenzene) binary mixture, an incipient inversion has been observed. Calculated thermodynamic quantities have been discussed in terms of intermolecular interactions between mixing components.     

Thermodynamic investigation of methyl salicylate/1-pentanol binary system in the temperature range from 278.15 K to 303.15 K

Densities (ρ), speeds of sound (u), isentropic compressibilities (k_s), refractive indices (n_D), and surface tensions (σ) of binary mixtures of methyl salicylate (MSL) with 1-pentanol (PEN) have been measured over the entire composition range at the temperatures of 278.15 K, 288.15 K, and 303.15 K. The excess molar volumes (V^E), excess surface tensions (σ^E), deviations in speed of sound (Δu), deviations in isentropic compressibility (Δk_s), and deviations in molar refraction (ΔR) have been calculated. The excess thermodynamic properties V^E, σ^E, Δu, Δk_s, and ΔR were fitted to the Redlich–Kister polynomial equation and the A_k coefficients as well as the standard deviations (d) between the calculated and experimental values have been derived. The surface tension (σ) values have been further used for the calculation of the surface entropy (S^S) and the surface enthalpy (H^S) per unit surface area. The lyophobicity (β) and the surface mole fraction $(x_2^{\text{S}})$ of the surfactant component PEN have been also derived using the extended Langmuir model. The results provide information on the molecular interactions between the unlike molecules that take place at the surface and the bulk.     

Thermodynamics of (1-alkanol + linear monoether) systems

Densities, ρ, and speeds of sound, u, of systems formed by 1-heptanol, or 1-octanol, or 1-decanol and dibutylether have been measured at a temperature of (293.15, 298.15, and 303.15) K and atmospheric pressure using a vibrating tube densimeter and sound analyser Anton Paar model DSA-5000. The ρ and u values were used to calculate excess molar volumes, V^E, and deviations from the ideal behaviour of the thermal expansion coefficient, Δα_p and of the isentropic compressibilities, Δκ_S. The available database on molar excess enthalpies, H^E, and V^E for (1-alkanol + linear monoether) systems was used to investigate interactional and structural effects in such mixtures. The enthalpy of the OH?O bonds is lower for methanol solutions, and for the remainder systems, it is practically independent of the mixture compounds. The V^E variation with the chain length of the 1-alkanol points out the existence of structural effects for systems including longer 1-alkanols. The ERAS model is applied to the studied mixtures. ERAS represents quite accurately H^E and V^E data using parameters which consistently depend on the molecular structure.     

Densities,speeds of sound,and refractive indices of the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K

Density, ρ, speed of sound, u, and refractive index, n_D, at 298.15 K and atmospheric pressure have been measured over the entire composition range for (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) systems. Excess molar volumes, V^E, isentropic compressibility, κ_s, isentropic compressibility deviations, Δκ_s, and changes of refractive index on mixing, Δn_D, for the above systems, have been calculated from experimental data and fitted to Cibulka, Singh et al., and Nagata and Sakura equations, standard deviations from the regression lines are shown. Geometrical solution models, Tsao and Smith, Kholer, Jacob and Fitzner, Rastogi et al. were also applied to predict ternary properties from binary contributions.     

Volumetric and ultrasonic behaviour of binary mixtures of 1-nonanol with o-cresol,m-cresol,p-cresol and anisole at T = (293.15 and 313.15) K

Densities, ρ, and speeds of sound, u, of binary liquid mixtures of 1-nonanol with o-cresol, m-cresol, p-cresol and anisole have been measured over the entire range of composition at T = (293.15 and 313.15) K and at atmospheric pressure. Using these data, the excess molar volume, V^E, molar free volume, V_f, parameters related to space-filling ability, V_f/V, non-linearity parameters, B/A, isentropic compressibility, κ_S, molar isentropic compressibility, K_S,m, deviation of molar isentropic compressibility, $K_{S\text{,}m}^E$, deviations of the speed of sound, u^D, and limiting excess partial molar volume, ${\overline{V}}_{m\text{,}i}^{E\text{,}0}$, and isentropic compressibility, ${\overline{K}}_{m\text{,}i}^{E\text{,}0}$, have been calculated. The calculated excess and deviation functions have been fitted to the Redlich–Kister polynomial equations and the results analyzed in terms of molecular interactions and structural effects.     

Volumetric study of (2-methoxyethanol + tetrahydrofuran + cyclohexane) at T=298.15 K

The excess molar volumes V_m^E at T=298.15 have been determined in the whole composition domain for (2-methoxyethanol + tetrahydrofuran + cyclohexane) and for the parent binary mixtures. Data on V_m^E are also reported for (2-ethoxyethanol + cyclohexane). All binaries showed positive V_m^E values, small for (methoxyethanol + tetrahydrofuran) and large for the other ones. The ternary V_m^E surface is always positive and exhibits a smooth trend with a maximum corresponding to the binary (2-methoxyethanol + cyclohexane). The capabilities of various models of either predicting or reproducing the ternary data have been compared. The behaviour of V_m^E and of the excess apparent molar volume of the components is discussed in both binary and ternary mixtures. The results suggest that hydrogen bonding decreases with alcohol dilution and increases with the tetrahydrofuran content in the ternary solutions.     

Excess molar volumes and ultrasonic studies of dimethylsulphoxide with ketones at T = 303.15 K

Excess molar volumes (V^E) and ultrasonic sound velocities at T = 303.15 K and ambient pressure have been measured as a function of composition for the binary liquid mixtures of dimethylsulphoxide (DMSO) with ketones. The ketones studied in the present investigation include ethyl methyl ketone (EMK), diethylketone (DEK), methyl propyl ketone (MPK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The V^E values were measured using a dilatometer and were positive over the entire mole fraction range for all systems except in the binary system DMSO with EMK where the V^E exhibits an inversion in sign. The experimental V^E values have been correlated using Redlich–Kister and Hwang et al. equations. The ultrasonic sound velocities for the above systems have been measured with a single crystal interferometer at a frequency of 3 MHz. The sound velocity (u) data have been used to calculate isentropic compressibility (K_s) and deviation in isentropic compressibility (ΔK_s) over the entire range of volume fraction. The sound velocity data have been predicted in terms of free length theory (FLT), collision factor theory (CFT), and Nomoto relation. The results reveal that all the theories gave a satisfactory estimate of the sound velocity. The deviations in values of isentropic compressibility (ΔK_s) were negative over the entire range of volume fraction in all the binary liquid mixtures. The results are interpreted with respect to possible molecular interactions between components.     

Study of densities,viscosities, and speeds of sound of binary liquid mixtures of butan-1-ol with n-alkanes (C6, C8, and C10) at T = (298.15, 303.15, and 308.15) K

The densities (ρ) and speeds of sound (u) have been measured over the whole composition range for (butan-1-ol with hexane, or octane, or decane) at T = (298.15, 303.15, and 308.15) K and atmospheric pressure along with the properties of the pure components. Viscosities (η) of these binary mixtures have also been measured over the entire composition range at T = 298.15 K. Experimental values of density, viscosity and speed of sound have been used to evaluate excess properties viz. excess molar volumes (V^E), deviation in viscosity (Δη), deviation in speeds of sound (Δu), deviation in isentropic compressibility (Δκ_s) and excess Gibbs free energy of activation of viscous flow (ΔG^1E). The excess properties have been correlated using the Redlich–Kister polynomial equation. The sign and magnitude of these excess properties have been used to interpret the results in terms of intermolecular interactions and structural effects. The viscosity data have also been correlated by Grunberg and Nissan, Tamura–Kurata, and Hind correlation equations.     

Excess molar enthalpies and excess molar heat capacities of (2-butanone + cyclohexane,or methylcyclohexane,or benzene,or toluene,or chlorobenzene,or cyclohexanone) atT = 298.15 K

Excess molar enthalpies of (2- butanone  +  cyclohexane, or methylcyclohexane, or toluene, or chlorobenzene, or cyclohexanone) and excess molar heat capacities of (2- butanone  +  benzene, or toluene, or chlorobenzene, or cyclohexanone) were measured atT =  298.15 K. Aliphatic systems were endothermic and the chlorobenzene system was exothermic. On the other hand, the toluene system changed sign to be S-shaped similar to the benzene system reported by Kiyohara et al. The values of excess molar enthalpies of the present mixtures were slightly larger than the corresponding mixtures of cyclohexanone already reported. Excess molar heat capacities of aromatic systems were characteristically S-shaped for the mixture containing aromatics. The values of the present mixtures were less than the corresponding mixtures of cyclohexanone. The mixture (2-butanone  +  cyclohexanone) was endothermic forH_m^E and negative for C_p,m^E.     

Thermodynamic and optical studies of some ethylene glycol ethers in aqueous solutions at T = 298.15 K

Experimental results of density (ρ), speed of sound (u), and refractive index (n_D) have been obtained for aqueous solutions of ethylene glycol monomethyl ether (EGMME), ethylene glycol monoethyl ether (EGMEE), diethylene glycol monomethyl ether (DEGMME), and diethylene glycol monoethyl ether (DEGMEE) over the entire concentration range at T = 298.15 K. From these measurements, the derived parameters, apparent molar volume of solute (?_V), excess molar volume (V^E), isentropic compressibility of solution (β_S), apparent molar isentropic compressibility of solute (?_KS), deviation in isentropic compressibility (Δβ_S), molar refraction [R]_1,2 and deviation in refractive index of solution (Δn_D) have been calculated. The Redlich–Kister equation has been fitted to the calculated values of V^E, Δβ_S and Δn_D for the solution. The results obtained are interpreted in terms of hydrogen bonding and various interactions among solute and solvent molecules.     

Densities,viscosities, speed of sound,and IR spectroscopic studies of binary mixtures of tert-butyl acetate with benzene,methylbenzene, and ethylbenzene at T = (298.15 and 308.15) K

Densities, viscosities, speed of sound, and IR spectroscopy of binary mixtures of tert-butyl acetate (TBA) with benzene, methylbenzene, and ethylbenzene have been measured over the entire range of composition, at (298.15 and 308.15) K and at atmospheric pressure. From the experimental values of density, viscosity, speed of sound, and IR spectroscopy; excess molar volumes V^E, deviations in viscosity Δη, deviations in isentropic compressibility Δκ_s and stretching frequency ν have been calculated. The excess molar volumes and deviations in isentropic compressibility are positive for the binaries studied over the whole composition, while deviations in viscosities are negative for the binary mixtures. The excess molar volumes, deviations in viscosity, and deviations in isentropic compressibility have been fitted to the Redlich–Kister polynomial equation. The Jouyban–Acree model is used to correlate the experimental values of density, viscosity, and speed of sound.     

Thermodynamics of proton dissociations from aqueous l-methionine at temperatures from (278.15 to 393.15) K,molalities from (0.0125 to 1.0) mol · kg−1, and at the pressure 0.35 MPa: Apparent molar heat capacities and apparent molar volumes of l-methionine,methioninium chloride,and sodium methioninate

We have measured the densities of aqueous solutions of l-methionine, l-methionine plus equimolal HCl, and l-methionine plus equimolal NaOH at temperatures 278.15 ⩽ T/K ⩽ 368.15, at molalities 0.0125 ⩽ m/mol · kg⁻¹ ⩽ 1.0 as solubilities allowed, and at p = 0.35 MPa using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15 ⩽ T/K ⩽ 393.15 and at the same m and p using a twin fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes V_ϕ and the heat capacities to calculate apparent molar heat capacities C_p,ϕ for these solutions. We used our results and values from the literature for V_ϕ(T, m) and C_p,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change Δ_rC_p,m(T, m) for ionization of water to calculate parameters for Δ_rC_p,m(T, m) for the two proton dissociations from protonated aqueous cationic l-methionine. We integrated these results in an iterative algorithm using Young’s Rule to account for the effects of speciation and chemical relaxation on V_ϕ(T, m) and C_p,ϕ(T, m). This procedure yielded parameters for V_ϕ(T, m) and C_p,ϕ(T, m) for methioninium chloride {H₂Met⁺Cl⁻(aq)} and for sodium methioninate {Na⁺Met⁻(aq)} which successfully modeled our observed results. Values are given for Δ_rC_p,m, Δ_rH_m, pQ_a, Δ_rS_m, and Δ_rV_m for the first and second proton dissociations from protonated aqueous l-methionine as functions of T and m.     

The excess molar enthalpies of (N-methyl-2-pyrrolidinone + mono-, or di-, or trichlorobenzene) atT = 298.15 K

Excess molar enthalpies H_m^EatT =  298.15 K are reported for (N -methyl-2-pyrrolidinone  +  chlorobenzene, or 1,2-dichlorobenzene, or 1,3-dichlorobenzene, or 1,2,4,-trichlorobenzene). The values ofH_m^E were obtained by using the flow calorimetric method. All the mixtures, over the whole composition range, are formed exothermically. The H_m^Eresults are discussed in terms of the NRTL and UNIQUAC models.     

Volumetric properties of (an organic compound + di-n-butyl ether) atT = 298.15 K

Excess molar volumes V_m^Eof {di- n -butyl ether (DBE)  +  a monofunctional organic compound} have been determined atT =  298.15 K over the whole composition range by means of a vibrating-tube densimeter. TheV_m^E values were either positive (propylamine, or butylamine, or acetone, or tetrahydrofuran  +  DBE) or negative (methanol, or butanol, or diethyl ether, or cyclopentanone, or acetonitrile  +  DBE). Markedly asymmetric V_m^Ecurves were displayed by (DBE  +  methanol) and (DBE  +  acetonitrile). Partial molar volumes __ V_m^oat infinite dilution in DBE, both from this work and the literature, were analysed in terms of an additivity scheme, and the group contributions thus obtained were discussed and compared with analogous results in water. DBE revealed a greater capability of distinguishing between polar and non-polar solutes, as well as in discriminating differently shaped molecules (unbranched, branched, cyclic). The limiting slopes of apparent excess molar volumes are evaluated and briefly discussed in terms of solute–solute and solute–solvent interactions.     

Excess molar enthalpies and excess molar volumes of (1,3-dimethyl-2-imidazolidinone + an aromatic hydrocarbon) atT = 298.15 K

Excess molar enthalpies H_m^Eand excess molar volumesV_m^E of (1,3-dimethyl-2-imidazolidinone  +  benzene, or methylbenzene, or 1,2-dimethylbenzene, or 1,3-dimethylbenzene, or 1,4-dimethylbenzene, or 1,3,5-trimethylbenzene, or ethylbenzene) over the whole range of compositions have been measured at T =  298.15 K. The excess molar enthalpy values were positive for five of the seven systems studied and the excess molar volume values were negative for six of the seven systems studied. The excess enthalpy ranged from a maximum of 435 J · mol ^− 1for (1,3-dimethyl-2-imidazoline  +  1,3,5-trimethylbenzene) to a minimum of  − 308 J · mol ^− 1for (1,3-dimethyl-2-imidazoline  +  benzene). The excess molar volume values ranged from a maximum of 0.95cm³mol ^− 1 for (1,3-dimethyl-2-imidazoline  +  ethylbenzene) and a minimum of  − 1.41 cm³mol ^− 1for (1,3-dimethyl-2-imidazoline  +  methylbenzene). The Redlich–Kister polynomial was used to correlate both the excess molar enthalpy and the excess molar volume data and the NRTL and UNIQUAC models were used to correlate the enthalpy of mixing data. The NRTL equation was found to be more suitable than the UNIQUAC equation for these systems. The results are discussed in terms of the polarizability of the aromatic compound and the effect of methyl substituents on the benzene ring.     

Thermodynamics of proton dissociations from aqueous alanine at temperatures from (278.15 to 393.15) K,molalities from (0.0075 to 1.0) mol · kg−1, and at the pressure 0.35 MPa: Apparent molar heat capacities and apparent molar volumes of alanine,alaninium chloride,and sodium alaninate

We have measured the densities of aqueous solutions of alanine, alanine plus equimolal HCl, and alanine plus equimolal NaOH at temperatures 278.15 ⩽ T/K ⩽ 368.15, at molalities 0.0075 ⩽ m/mol · kg⁻¹ ⩽ 1.0, and at the pressure p = 0.35 MPa using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15 ⩽ T/K ⩽ 393.15 and at the same m and p using a twin fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes V_ϕ and the heat capacities to calculate apparent molar heat capacities C_p,ϕ for these solutions. We used our results and values from the literature for V_ϕ(T, m) and C_p,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change Δ_rC_p,m(T, m) for ionization of water to calculate parameters for Δ_rC_p,m(T, m) for the two proton dissociations from protonated aqueous cationic alanine. We integrated these results in an iterative algorithm using Young’s Rule to account for the effects of speciation and chemical relaxation on V_ϕ(T, m) and C_p,ϕ(T, m). This procedure yielded parameters for V_ϕ(T, m) and C_p,ϕ(T, m) for alaninium chloride {H₂Ala⁺Cl⁻(aq)} and for sodium alaninate {Na⁺Ala⁻(aq)} which successfully modeled our observed results. Values are given for Δ_rC_p,m, Δ_rH_m, pQ_a, Δ_rS_m, and Δ_rV_m for the first and second proton dissociations from protonated aqueous alanine as functions of T and m.