Excess Isentropic Compressibility κsE Research Articles

Density, Viscosity, Refractive Index, Speed of Sound, Molar Volume, Isobaric Thermal Compressibility, Excess Gibbs Activation for Fluid Flow, and Isentropic Compressibility of Binary Mixtures of Methanol with Anisole and with Toluene at 298.15 K and 0.1 MPa

Density, viscosity, refractive index, and ultrasonic velocity were measured for the pure materials anisole, methanol, and toluene, and for the binary mixtures: methanol—anisole and methanol—toluene. Excess molar volume VE, isobaric thermal compressibility α, excess Gibbs activation energy for fluid flow ΔGE*, and excess isentropic compressibility κSE were calculated from the measured quantities. For both binary mixtures VE and κSE were <0 while Δn > 0 and ΔGE* > 0 over the entire mole fraction composition range. Anisole mixtures exhibited more negative values for VE and κSE while more positive values were displayed for Δn and ΔGE* compared to toluene mixtures. For Δη, negative values were observed at low alcohol concentrations but positive values at high alcohol concentrations for both systems.

Acoustic, volumetric and FTIR study of binary liquid mixtures of 2-methyl cyclohexanone with amides

Densities, speeds of sound, and viscosities at various temperatures were determined for the systems: 2-methylcyclohexanone (2-MCYH) + formamide (F), N-methylformamide (NMF) and N, N-dimethylformamide (DMF). From the experimental results, Excess molar volume VmE, Excess isentropic compressibility κsE, deviation in viscosity Δη and excess Gibbs energy of activation of viscous flow G*E, Excess partial molar properties at infinite dilution V¯m,1°E, V¯m,2°E, K¯s,m,1°E and K¯s,m,2°E were calculated. There is evidence of complex formation between unlike molecules. FT-IR properties have been carried out to study the specific interaction, such as the formation of the hydrogen bond between unlike molecules in the binary liquid mixtures, a good agreement is observed among the excess parameters and FT-IR spectroscopic properties.

Physicochemical investigations of polyethylene glycols with N, N dimethylacetamide

The densitiesρ and ultrasonic speeds u for the binary mixture of polyethylene glycol (PEG 200) and poly ethylene glycol 400 (PEG 400) with N, N dimethylacetamide (DMA) are measured over the entire mole fraction range and at temperatures 303.15, 313.15, and 323.15 K. From the experimental data, and excess molar volume, VmE, excess ultrasonic speed uE, excess isentropic compressibility κsE, Excess intermolecular free length LfE, excess acoustic impedance ZE and excess molar isentropic compressibility Ks,mE are evaluated. The partial molar properties and their excess properties are also determined. The solute-solvent interactions are also analyzed using FTIR spectra, recorded at the room temperature.

Acoustic, volumetric and spectral studies of binary liquid mixtures of aliphatic dialkylamine and 2-alkanols at different temperatures

This article reports experimental densities ρ and speeds of sound (u) for the binary mixtures of di-n-butylamine and diisopropylamine with 2-butanol and 2-pentanol at a temperature range of (293.15–308.15) K with a temperature step of 5 K over entire composition range and at atmospheric pressure. Various thermodynamic parameters have been calculated using experimental data of densities and speeds of sound. The different parameters calculated are excess molar volume VmE, excess isentropic compressibilities κsE, deviations in speed of sound uD, apparent molar volumes Vϕ, partial molar volumes V¯m, excess partial molar volumes V¯mE excess intermolecular free lengths LfE and excess acoustic impedance ZE. These parameters have been analysed in terms of nature and extent of intermolecular interactions. Effects of temperature, chain length and branching on intermolecular interactions have also been examined. Apart from this, FT-IR spectroscopy technique has also used to find more support for the results obtained from the calculated thermodynamic parameters. All the calculated properties have been correlated using Redlich-Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard deviations.

Thermodynamic Studies of Molecular Interactions in Mixtures Containing Tetrahydropyran, 1,4-Dioxane, and Cyclic Ketones

The densities ρ, speeds of sound u, and molar heat capacities CP of tetrahydropyran or 1,4-dioxane (1) + cyclohexanone or cycloheptanone (2) mixtures at 293.15, 298.15, 303.15, and 308.15 K, and excess molar enthalpies, HE at 308.15 K and atmospheric pressure 0.1 MPa have been measured over the entire composition range. The excess molar volumes VE, excess isentropic compressibilities κSE, and excess heat capacities, CPE of the studied mixtures have been determined using the measured experimental data. The observed VE, κSE, HE, and CPE data have been tested in terms of graph theory. The analyses of VE data by graph theory suggest that while tetrahydropyran or 1,4-dioxane exists as a mixture of monomer and dimer; cyclohexanone or cycloheptanone exists as a mixture of open and cyclic dimer. Further, (1 + 2) mixtures are characterized by interactions between oxygen atom/s and hydrogen atom of tetrahydropyran or 1,4-dioxane with hydrogen atom/s and oxygen atom of cyclohexanone or cycloheptanone. The quantum mechanical calculations and analysis of IR spectral data of (1 + 2) mixtures also support this viewpoint. It has been observed that graph theory correctly predicts the VE, κSE, HE, and CpE data of the present mixtures.

Density, Speed of Sound, and Refractive Index Measurements for the Binary Mixture (1, 4-Dioxane + Isobutyric Acid) at T = (295.15, 298.15, 301.15, 304.15, 307.15, 310.15, and 313.15) K

Density, speed of sound, and refractive index for the binary mixture (1,4-dioxane (1) + isobutyric acid (2)) were measured over the whole composition range at temperatures T = (295.15, 298.15, 301.15, 304.15, 307.15, 310.15, and 313.15) K and at the atmospheric pressure. From the experimental data, excess molar volume VE, excess isentropic compressibility κSE, excess speed of sound cE, excess refractive index nE, molar refraction R, and deviation in molar refraction ΔR were calculated. These results have been fitted to the Redlich–Kister polynomial equation. The excess molar volume, excess isentropic compressibility, and deviation in molar refraction were found to be negative, whereas excess speed of sound and excess refractive index were found to be positive for all temperatures. The thermodynamic properties have been discussed in terms of nature of molecular interactions between the components of the mixture.

Thermodynamics of amine + ketone mixtures 3. Volumetric, speed of sound data and viscosity at (303.15 and 308.15 K) for the binary mixtures of N,N-dimethylaniline + propiophenone, + p-methylacetophenone, + p-chloroacetophenone

Densities ρ, viscosities η and ultrasonic sound speed u of pure propiophenone (PP), p-methylacetophenone (p-MeAP), p-chloroacetophenone (p-ClAP) and those of their binary mixtures prepared using N,N-dimethylaniline (N,N-DMA) as a common component, were measured at 303.15K and 308.15K over the entire composition range. These experimental data have been used to calculate excess volume VE, excess ultrasonic velocity uE, isentropic compressibility κs, intermolecular free length Lf, acoustic impedance Z, excess isentropic compressibility κsE, deviation in viscosity ∆η and excess Gibbs free energy of activation of viscous flow (G⁎E) were evaluated. The viscosity data have been correlated using three equations; Grunberg and Nissan, Katti and Chaudhri and Hind et al. The excess/deviations have been fitted by a Redlich–Kister equation and the results are discussed in terms of molecular interactions present in these mixtures.

Thermodynamic and Acoustic Properties of Binary Mixtures of Ethers. 2. Diisopropyl Ether with Arylamines at (303.15, 313.15, and 323.15) K and Application of ERAS Model to Aniline Mixtures with Diisopropyl Ether and Oxolane

Densities, ρ, and speeds of sound, u, of binary mixtures formed by aniline or N-methylaniline or N-ethylaniline with diisopropyl ether (DIPE) have been measured over the entire range of composition at a temperature of (303.15, 313.15, and 323.15) K and atmospheric pressure. The ρ and u values were used to calculate isentropic compressibilities, κS, excess molar volumes, VmE, and excess isentropic compressibilities κSE. The results have been used to investigate molecular interactions and structural effects in these mixtures. The speed of sound u in present mixtures has been estimated using several theoretical models to determine their relative predicting ability in terms of pure component properties. The ERAS model is applied to study VmE for DIPE−aniline and oxolane−aniline mixtures at (303.15, 313.15, and 323.15) K. The ERAS model represents qualitatively very large negative VmE data.

Speed of sound and isentropic compressibility of (1-butanol + n-hexane + 1-chlorobutane) and the constituent binary mixtures at the temperatures 298.15 K and 313.15 K

Densities ρ and speeds of sound u for {x1C4H10O +x2C6H14+ (1 −x1−x2)C4H9Cl }at T= 298.15 K and T= 313.15 K, and the constituent binary mixtures {xC6H14+ (1 −x)C4H9Cl} at T= 298.15 K and {xC4H10O + (1 −x)C6H14}, {xC4H10O + (1 −x)C4H9Cl}, and {xC6H14+ (1 −x)C4H9Cl} at T= 313.15 K have been measured. The isentropic compressibilities κS, the excess isentropic compressibilities κSE, and the speeds of sound deviations Δu have been calculated for both the binary and the ternary systems, from the experimental data. The isentropic compressibilities have been compared with calculated values from the free length theory (FLT) and collision factor theory (CFT).

Speeds of sound and isentropic compressibilities of (cyclohexanone + dichloromethane, or trichloromethane, or trichloroethene, or 1,2-dichloroethane) atT = 303.15 K

Measurements of speeds of sound u have been made in binary liquid mixtures of cyclohexanone (C6H10O) and dichloromethane (CH2Cl2), or trichloromethane (CHCl3), or trichloroethene (CHClCCl2), or 1,2-dichloroethane (CH2ClCH2Cl) at T= 303.15 K. The values of u have been used to calculate the apparent excess speeds of sound Δu and the isentropic compressibilities κSfor these mixtures. The excess isentropic compressibilitiesκSE have also been calculated from the values ofκS . The κSEproperty has been found to be negative throughout the entire composition range for mixtures of C6H10O andCH2Cl2 , or CHCl3, or CHClCCl2. For {xC6H10O + (1 −x)CH2ClCH2Cl },κSE has been found to be positive at low values of x and negative at higher values of x, with an inversion of sign occurring at x≈ 0.24. The values ofΔu and κSEhave been fitted to representative equations.

Ultrasonic speeds and isentropic compressibilities for (decan-1-ol + n-alkane) at 298.15 K

Ultrasonic speeds in decan-1-ol + n-pentane, + n-hexane, + n-octane, + n-decane, and + n-hexadecane at 298.15 K are reported. Particular attention was paid to measurements in the region of high dilution with respect to decan-1-ol. The present results, in conjunction with our earlier work on molar excess volumes for the same set of mixtures, give excess isentropic compressibilities κSE and the partial molar excess quantities KS,iE = −(∂ViE∂p)S. KS,1E of decan-1-ol at low mole fractions is discussed.

On the symmetry of the diffraction pattern obtained by the diffraction of light by ultrasonic waves : Mertens, R., Leroy, O., 28 (March 1973) 182–185

Isentropic compressibilities κS, excess isentropic compressibilities κSE and excess molar volumes VE have been determined from measurements of speeds of sound u and densities ρ on binary mixtures of propan-2-ol, butan-2-ol, pentan-2-ol, and octan-2-ol with cyclohexane and of butan-1-ol, pentan-1-ol, hexan-1-ol, and heptan-1-ol with methylcyclohexane at 303.15 K over the whole mole fraction range. The values of VE for all the eight mixtures are positive and the values of VE decrease with the number of carbon atoms in alkanol. The values of κSE for all four alkan-2-ol + cyclohexane systems are positive while in case of alkan-1-ol + methylcyclohexane systems, positive values of κSE for butan-1-ol + methylcyclohexane decrease to negative values for heptan-1-ol + methylcyclohexane. The change of sign occurs between pentan-1-ol and hexan-1-ol. The experimental speeds of sound have been analysed in terms of Schaaffs’ collision factor theory and Jacobson’s free length theory while the excess molar volumes of alkan-1-ols + cyclohexane, alkane-2-ols + cyclohexane and alkan-1-ols + methylcyclohexane have been analysed in terms of associated solution theory with a Flory equation of state contribution described by Treszczanowicz and Benson [Fluid Phase Equilib. 23 (1985) 117] and Heintz [Ber. Bunsen. Phys. Chem. 89 (1985) 172].