用定标粒子理论研究不同温度下2-甲基-2-丙醇与腈二元液相混合物的超额热力学参数和超音速度理论估值(英文)

Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. From these experimental data, the excess available volume, E a V , excess free volume, E f V , excess isothermal compressibility, E T β , excess thermal expansion coefficient, E α , and excess internal pressure, E i π , are calculated. The variation of these properties with composition and temperature are discussed in terms of molecular interactions between unlike molecules of the mixtures. It is found that the values of E a V , E f V , E T β and E α are positive and those of E i π are negative for all the mixtures at each temperature studied, indicating the presence of weak interactions between 2M2P and AN/PN/BN molecules. The variations of E a V , E f V , E T β , E α and E i π values with composition indicate that the interactions in these mixtures follow the order: ANPNBN, i.e., the 2M2P-nitrile interaction decreases with the increase of alkyl chain length in these nitrile molecules. In addition, the theoretical ultrasonic velocity is calculated using the scaled particle theory and compared with the experimental values.     

Study of intermolecular interactions in binary mixtures of methyl acrylate with benzene and methyl substituted benzenes at different temperatures: An experimental and theoretical approach

The ultrasonic speeds, u and viscosities, η of the binary mixtures of methyl acrylate with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene over the whole mole fraction range were measured at six different temperatures and at atmospheric pressure. From the experimental data, the excess isentropic compressibility, K_S^E, excess ultrasonic speed, u^E, excess molar isentropic compressibility, K_s,m^E, excess specific impedance, Z^Eand deviations in viscosity, Δηhave been calculated. The partial molar isentropic compressions, K_s,m,1 and K_s,m,2, and excess partial molar isentropic compressions, ${\mathop K\limits^{ - E}}$_s,m,1 and ${\mathop K\limits^{ - E}}$_s,m,2 over the whole composition range, partial molar isentropic compressions, and , and excess partial molar isentropic compressions, $\mathop K\limits^{ - \hat E} $_s,m,1 and $\mathop K\limits^{ - \hat E} $_s,m,2 of the components at infinite dilution have also been calculated. The results specified the existence of weak interactions between unlike molecules, and these interactions follow the order: benzene > toluene > p-xylene > m-xylene > o-xylene > mesitylene. The magnitude of interactions was found to be dependent on the number and position of the methyl groups in these aromatic hydrocarbons.     

Density, ultrasonic velocity, viscosity and their excess parameters of the binary mixtures of N,N-dimethylaniline+1-alkanols (C3-C5), +2-alkanols (C3-C4), +2-methyl-1-propanol, +2-methyl-2-propanol at 303.15K

The density, ultrasonic velocity of sound and viscosity of binary mixtures of N,N-dimethyl aniline (N,NDMA) with 1-propanol, +2-propanol, +1-butanol, +2-butanol, +1-pentanol, +2-methyl-1-propanol, +2-methyl-2-propanol were measured at 303.15 K. These experimental data have been used to calculate excess volume V ^E , excess ultrasonic speeds u ^E , excess intermolecular free length L _f ^E , excess acoustic impedance Z ^E , excess isentropic compressibility κ _s ^E , deviation in viscosity Δη and excess Gibbs free energy of activation of viscous flow (G* ^E ). The values of L _f ^E and κ _s ^E are negative over the wide range of composition for all the binary mixtures, while the values of Z ^E are positive. These results have been used to discuss the nature of interaction between unlike molecules in terms of hydrogen bonding, dipole-dipole interaction, proton-acceptor interaction and dispersive forces. The viscosity data have been correlated using three equations: Grunberg and Nissan, Katti & Chaudhri and Hind et al. The excess/deviations were fitted by a Redlich-Kister equation and the results were analyzed in terms of specific interactions present in these mixtures.     

Densities,ultrasonic speeds,refractive indices,and COSMO analysis for binary mixtures of dichloromethane with acetone and dimethylsulfoxide at T = (298.15, 303.15, and 308.15) K

Experimental densities (ρ), ultrasonic speeds (u), and refractive indices (n_D) of binary mixtures of dichloromethane (DCM) with acetone (ACT) and dimethylsulfoxide (DMSO) were measured over the whole composition range at T?=?298.15, 303.15, and 308.15?K. From the experimental data, excess molar volume (V^E), deviations in isentropic compressibility (Δk_s), deviations in intermolecular free length (ΔL_f), deviations in refractive index (Δn_D), and deviations in ultrasonic speed (Δu) were calculated. Moreover, the Benson–Kiyohara theory was applied to the binary mixtures to obtain the theoretical Δk_s values. The COSMO calculations depending on density functional theory were utilized to estimate the σ-profiles for the DCM, ACT, and DMSO. The interpreted σ-profile trends were found supportive with the experimental findings. Applicability of different empirical and semi-empirical relations of refractive index data were tested against the measured results, and good agreement has been obtained. The possible results of intermolecular molecular interactions among mixture components were interpreted.     

乙酸丁酯-芳香烃混合液中声速和超额等熵压缩系数的测定

Speed of sound data for butyl acetate＋benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressibilities （ Ks^E ） were computed from speed of sound and density data, derived from molar excess volume data. The Ks^E values were analyzed by using graph theoretical approach. The Ks^E values evaluated by graph theory compared reasonably well with their corresponding experimental values. The Ks^E data were also expressed in terms of Redlich-Kister polynomial equation to derive the coefficients and the standard deviation.     

308.15 K时N,N-二甲基甲酰胺中咪唑啉酮衍生物们的热动力学性质(英文)

Density,ultrasonic velocity and viscosity of imidazolinone derivatives are studied in dimethyl formamide(DMF) at 308.15 K.From the experimental data,various acoustical parameters,such as specific impedance Z,isentropic compressibilityκs,Rao's molar sound function Rm,van der Waals constant b,relaxation strength r,intermolecular free length Lf,internal pressureπ,solvation number Sn,relative association RA,etc.are evaluated,which helps in understanding the molecular interactions occurring in these solutions.     

Mixing properties of isopropyl acetate+aromatic hydrocarbons at 298.15 K: Density,refractive index and isentropic compressibility

We present new experimental data of density, refractive index and speed of sound for the binaries of isopropyl acetate+(toluene, ethylbenzene, p-xylene, mesitylene, isopropylbenzene, butylbenzene, isobutylbenzene, or t-butylbenzene) at T=298.15 K. and standard conditions, and the corresponding computed derived magnitudes (change of isentropic compressibility, change of refractive index on mixing, and excess molar volume). The mixtures show a clear expansive tendency for the highest molar weight compounds and the steric hindrance role of the aromatic chemicals being analyzed to the light of the non-ideality on mixing. A good agreement among experimental data and the values estimated by theoretical procedures was obtained.     

Excess volumes, densities, speeds of sound and viscosities of binary systems of diisopropyl ether and acetates at 303.15 K

Excess volumes, speeds of sound and viscosities at 303.15 K for the binary mixtures of diisopropyl ether (DIPE) + methyl acetate (MA) + ethyl acetate (EA) butyl acetate (BA) and + isoamyl acetate (IAA) were measured as a function of mole fraction over the entire range of composition. Insentropic compressibilities were computed from speed of sound and density data. Densities were obtained from experimental excess volume data. Speeds of sounds were evaluated using Jacobson free length theory and Schaaffs collision factor theory. The viscosity data were analyzed on the basis of corresponding states approach and Grunberg and Nissan treatment. The experimental results on excess volume, deviations in isentropic compressibility and in viscosity were discussed in terms of molecular interactions between unlike molecules.     

Physicochemical Properties of Mixtures of Morama Seed Oil With Alkanols and Alkyl Acetates at 298.15 K Atmospheric Pressure

Densities, ρ, ultrasonic speed, u, and dynamic viscosities, η, of mixtures of morama, Tylosema esculentum, seed oil with 1‐propanol, 1‐butanol, methyl acetate, and ethyl acetate were determined over the entire composition range at 298.15 K and atmospheric pressure. Excess molar volumes, , excess molar‐free volumes , deviations in isentropic compressibility, Δκ_s, deviations in ultrasonic speed, Δu, deviations in dynamic viscosity, Δη, and the excess free energy of activation of viscous flow, ΔG*^E, were calculated and correlated using the Redlich–Kister equation for each of the (morama seed oil + 1‐propanol or 1‐butanol or methyl acetate or ethyl acetate) mixtures. The results obtained were discussed in terms of possible dipole–dipole intermolecular interactions and structural effects.     

Temperature-dependent aggregation of bio-surfactants in aqueous solutions of galactose and lactose: Volumetric and viscometric approach

Modulation in the aggregation behavior of bio-surfactants(bile salts), sodium cholate(NaC) and sodium deoxycholate(NaDC) in aqueous solutions of carbohydrates(galactose and lactose) have been investigated by measuring the density(ρ), speed of sound(u) and viscosity(η) of the mixtures at different temperatures293.15, 298.15, 303.15, 308.15 and 313.15 K. The density and speed of sound data have been used to calculate various volumetric and compressibility parameters such as apparent molar volume(V_φ), isentropic compressibility(κ_s), apparent molar adiabatic compression(κ_(s, φ)) to get a better insight into the micellization mechanism of bile salts. Further, the viscosity data have been studied in the light of relative viscosity(η_r) and viscous relaxation time(τ). Some derived parameters such as free volume(V_f), internal pressure(πi) and molar cohesive energy(MCE) of Na C and Na DC in aqueous solution of saccharides have also been calculated from viscosity data in conjunction with density and speed of sound values. All the calculated and derived parameters provide qualitative information regarding the nature of interactions i.e. solute–solute, solute–solvent and solvent–solvent in the solution.     

Viscometric and FTIR studies of molecular interactions in 2-propanol+hydrocarbons mixtures at 298.15 and 308.15 K

The deviation in viscosity was coupled with respective excess molar volume data to study the molecular interaction in binary mixtures with one associated component. This approach was applied to the experimentally measured viscosity and excess molar volume data of the 2-propanol+hydrocarbons at 298.15 K and 308.15 K. It was suggested that depolymerization power of aromatic hydrocarbon toward 2-propanol as well as strength of intermolecular interactions (electron-donor-acceptor type) between monomer of 2-propanol and aromatics depend on π-electron density of the aromatic hydrocarbon. These interactions were further confirmed by FTIR spectroscopy. The viscosity of these binary mixtures was best predicted by Gruenberg-Nissan correlation among the four correlations applied.     

Thermodynamics of molecular interactions in binary mixtures containing associated liquids

Experimentally measured data of excess molar volumes and enthalpies at 308.15 K for binary mixtures of formamide with 1-butanol or 2-methyl-1-propanol were fitted to the Redlich-Kister polynomial equation. Thermodynamics of molecular interaction in these mixtures was discussed using Prigogine-Flory-Patterson theory, Treszczanowicz-Benson association model and Graph theoretical approach. Extent of inter-molecular H-bonding in formamide and butanol in their binary mixtures was also reflected in their molar enthalpy of association of H-bonding Δh _H ⁰ and association constant K _H calculated from Treszczanowicz-Benson association model. All the three theories predict the excess property data reasonably well.     

Mixing properties of propyl acetate+aromatic hydrocarbons at 298.15 K

We present experimental data of speed of sound, refractive index on mixing and density for the binaries of propyl acetate+(toluene, ethylbenzene, p-xylene, isopropylbenzene, butylbenzene, isobutylbenzene, mesitylene, or t-butylbenzene) at T=298.15 K and 1 atm, and the corresponding computed derived magnitudes (change of isentropic compressibility, change of refractive index on mixing, and excess molar volume). The mixtures show a clear expansive tendency for the highest molar weight compounds, and the steric hindrance role of the aromatic chemicals was analyzed to the light of the non ideality on mixing. Values of physical properties were compared with the results obtained by theoretical estimation procedures.     

Speed of sound and isentropic compressibility of organic solvents + sunflower oil mixtures at 298.15 K

The speed of sound in binary liquid mixtures of organic solvents with sunflower oil was measured over the entire range of concentrations at 298.15 K. The solvents considered were: n-hexane, n-heptane, n-octane, n-nonane, ethanol, 1-propanol, 2-propanol, 1-butanol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and vinyl acetate. The speed of sound data were used to calculate isentropic compressibilities and excess isentropic compressibilities. The excess isentropic compressibilities vs. concentrations were correlated using Redlich-Kister polynomials. Speed of sound determinations in the mixtures were predicted using two mixing rules proposed in the literature, and values were compared with experimental data. In all cases, SD between predicted and experimental data were less than 3.5%.     

Molar volume and ultrasonic studies of europium soaps in mixed organic solvents

The ultrasonic velocity and density measurements of europium soaps in a mixture of benzene and methanol (3:2, vol/vol) were used to evaluate various acoustic parameters and molar volume and to determine the critical micelle concentration. The results showed that the ultrasonic velocity, specific acoustic impedance, molar sound velocity, and molar compressibility increase, and intermolecular free length, adiabatic Compressibility, and relative association decrease with increasing concentration and chainlength of the soap. The results were interpreted in terms of soap-solvent interaction.     

Acoustic behavior of calcium soap solutions

The results of ultrasonic velocity for calcium soap solutions show that the adiabatic compressibility, intermolecular free length and solvation number decrease while the specific acoustic impedence, apparent molal compressibility, apparent molal volume and molar sound velocity increase with increasing soap concentration. The ultrasonic results are in agreement with the conductance measurements and confirm that calcium soaps behave as weak electrolytes in solutions.     

Volumetric,ultrasonic and viscometric studies of binary liquid mixures of N-ethylaniline + chlorobenzene, + Bromobeneze, + 1, 2-dichlorobenzene + 1, 3-dichlorobenzene+1, 2, 4-trichlorobenzene at 303.15 and 308.15K

We measured densities (ρ), ultrasonic speeds (u) and viscosities (η) for binary binary mixtures of N-ethylaniline (N-EA) with chlorobenzene (CB), bromobenzene (BB), 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB), and 1,2,4-trichlorobenzene (1,2,4-TCB) and their pure liquids at 303.15 K and 308.15 K. These experimental data were used to calculate the excess volume (V ^E ), deviations in ultrasonic speeds (Δu), deviation in isentropic compressibility (Δ κ _s ), deviation in intermolecular free length (ΔL _f ), deviation in acoustic impedance (ΔZ), deviation in viscosity (Δη) and excess Gibbs free energy of activation of viscous flow (G* ^E ). The variations of these properties with composition of binary mixtures suggest loss of dipolar association, difference in size and shape of the component molecules, dipole-dipole interactions and hydrogen bonding between unlike molecules. The viscosity data were correlated with Grunberg and Nissan, Katti and Chaudhri, and Hind et al. equations and the results were compared with the experimental results. The excess parameters were fitted to the Redlich-Kister polynomial equation using multi parametric nonlinear regression analysis to derive the binary coefficients and to estimate the standard deviation.     

Orientation effect on sign and magnitude of excess thermodynamic functions of non electrolyte solutions at different temperatures (303.15 K, 308.15 K,and 313.15K)

Experimental values of the density and viscosity have been measured for binary mixtures of N-ethylaniline with isomeric butanols (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol) at 303.15, 308.15 and 313.15 K over the entire mole fraction range. These data, the excess molar volumes, and deviation viscosity for the binary systems at the above-mentioned temperatures were calculated and fitted to Redlich-Kister equation to determine the fitting parameters and the root-mean-square deviations. The excess molar volumes, deviation viscosity and excess Gibbs energy of activation of viscous flow have been analyzed in terms of acid-base interactions, hydrogen bond, and dipole-dipole interaction between unlike molecules. The results obtained for dynamic viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, Katti-Chaudhri, and Hind et al. equations.     

Investigation of Some Physicochemical Properties of Mixtures of Morama Seed Oil with (C6–C9) n-Alkanes at 298.15 and Atmospheric Pressure

Densities ρ, ultrasonic speeds u and dynamic viscosities η, of mixtures of morama, Tylosema esculentum, seed oil with n‐hexane, n‐heptane, n‐octane and n‐nonane were determined over the entire composition range at 298.15 K and atmospheric pressure. Excess molar volumes, , excess molar free volumes , deviations in isentropic compressibility, Δκ_s, deviations in ultrasonic speed, Δu, deviations in viscosity, Δη, and the excess free energy of activation of viscous flow, ΔG*^E, were calculated therefrom and correlated by the Redlich–Kister equation for each of the [morama seed oil + (n‐hexane or n‐heptane or n‐octane or n‐nonane)] mixtures. The results have been discussed in terms of possible intermolecular interactions and structural effects.     

Characterization of Water/Sucrose Laurate/n-Propanol/Allylbenzene Microemulsions

Water/n-propanol/sucrose laurate/allylbenzene micellar systems were formulated and applied in the isomerization of allylbenzene in the presence of heterogenized derivatives of some platinum group catalysts. The ratio (w/w) of n-propanol/surfactant studied herewith was 2/1. Temperature insensitive microemulsions were found. The microemulsions were characterized by the volumetric parameters, density, excess volume, ultrasonic velocity, and isentropic compressibility. The densities increase with increases in the water volume fraction. Excess volumes of the microemulsions decrease for water volume fractions below 0.2, level off for water volume fractions between 0.2 and 0.6 then increase for water volume fractions above 0.6. Excess volumes of the studied micellar systems increase with temperature. Isentropic compressibilities increase with temperature for water volume fractions below 0.8 and decrease for water volume fractions above 0.8. Structural transitions from water-in-oil to bicontinuous to oil-in-water occur along the microemulsion phase. The particle hydrodynamic diameter of the oil-in-water microemulsions at the 0.95 water volume fraction was found to decrease with temperature.