Acoustic non-linearity parameter B/A and related molecular properties of binary organic liquid mixtures

Acoustic non-linearity parameter B/A is calculated for binary mixtures using four different methods. The interactions in the liquid mixtures are explained on the basis of excess non-linearity parameter and excess adiabatic compressibility. Sehgal's relations for calculating molecular properties of pure liquids are extended to binary mixtures.     

Non-linearity parameter B/A of binary liquid mixtures at elevated pressures

When sound waves of high amplitude propagate, several non-linear effects occur. Ultrasonic studies in liquid mixtures provide valuable information about structure and interaction in such systems. The present investigation comprises of theoretical evaluation of the acoustic non-linearity parameter B/A of four binary liquid mixtures using Tong and Dong equation at high pressures and T=303.15 K. Thermodynamic method has also been used to calculate the non-linearity parameter after making certain approximations.     

Ultrasonic study on organic liquid and binary organic liquid mixtures by using Schaaffs＇ collision factor theory

Based on Schaaff's collision factor theory (CFT) in liquids, the equations for nonlinear ultrasonic parameters in both organic liquid and binary organic liquid mixtures are deduced. The nonlinear ultrasonic parameters, including pressure coefficient, temperature coefficients of ultrasonic velocity, and nonlinear acoustic parameter B/A in both organic liquid and binary organic liquid mixtures, are evaluated for comparison with the measured results and data from other sources. The equations show that the coefficient of ultrasonic velocity and nonlinear acoustic parameter B/A are closely related to molecular interactions. These nonlinear ultrasonic parameters reflect some information of internal structure and outside status of the medium or mixtures. From the exponent of repulsive forces of the molecules, several thermodynamic parameters, pressure and temperature of the medium, the nonlinear ultrasonic parameters and ultrasonic nature of the medium can be evaluated. When evaluating and studying nonlinear acoustic parameter B/A of binary organic liquid mixtures, there is no need to know the nonlinear acoustic parameter B/A of the components. Obviously, the equation reveals the connection between the nonlinear ultrasonic nature and internal structure and outside status of the mixtures more directly and distinctly than traditional mixture law for B/A, e.g. Apfel's and Sehgal's laws for liquid binary mixtures.     

A brief study on the mixture rules of the acoustic non-linearity parameter B/A in binary biological mixtures

Using the improved thermodynamic method, the acoustic non-linearity parameter B/A of binary biological mixtures — such as pig blood, sheep blood and bovine blood — is measured in order to test the mixture rules proposed by Apfel and Sehgal. The results show that the B/A values of the above-mentioned blood decrease with an increasing volume fraction of water. The B/A value varies linearly with the volume fraction of protein. It is also shown that, treated as a binary mixture, the blood obeys the trend that the B/A value varies with the volume of water. This is in agreement with the rules proposed by Apfel and Sehgal. However, the measured B/A value is not exactly equal to that of the mixture rules.     

Nonlinear ultrasonic nature of organic liquid and organic liquid mixture

Based on Jacobson's molecular free length theory in liquids and the relationship between ultrasonic velocity and the molecular free length in organic liquids, this paper deduces the equations for pressure coefficient and temperature coefficient of ultrasonic velocity and nonlinear acoustic parameter B/A in both of organic liquid and organic liquid binary mixtures. These nonlinear acoustic parameters are evaluated against the measured results and data from other sources. The equations reveal the connections between the nonlinear acoustic parameters and some internal structural of the medium or mixtures e.g. the sizes of molecule, several thermodynamic physical parameters and outside status e.g. condition of pressure and temperature of the liquid or liquid mixture. With the equations the nonlinear acoustic parameter B/A of organic liquid binary mixtures, which is impossible to know without the nonlinear acoustic parameter B/A of the tow components before, can be calculated based on the structural and physical parameters of organic liquid and organic liquid binary mixtures.     

Correlations between Moelwyn–Hughes parameter, available volume and intermolecular free-lengths in liquid systems

Thermo-acoustical parameters of liquid mixtures viz., Acetone, Methyl Iodide and Acetone + Methyl Iodide have been evaluated at different temperatures in terms of the coefficient of volume expansion, on the assumption that the Moelwyn–Hughes parameter has been utilized to establish some simple relations between the lattice Gruneisen parameter, Beyer's non-linearity parameter, the Anderson–Gruneisen parameter and the Sharma constant. A relationship among the isobaric, isothermal and isochoric microscopic (lattice) Gruneisen parameters have been studied and analysed in the case of liquid mixtures. The Sharma's parameter S₀ remains invariant with the temperature over a wide range of temperatures and retains its characteristics value i.e., 1.11 ± 0.01 as observed in case of liquid systems. The present treatment has the distinct advantage of calculating available volume (V_a) and intermolecular free-length (L_f) through Moelwyn–Hughes parameter mainly. Analysis of such type is not found so far in literature.     

A comparative study of non-linearity parameter for binary liquid mixtures

The present investigation comprises of theoretical evaluation of acoustic non-linearity parameter,B/A for equimolar binary mixtures, viz. chlorobenzene or 1-chloronaphthalene with a series of normal alkanes (n-C_n,n = 6, 8, 10, 12, 14, 16), and with a series of highly branched alkanes (br-C_n,n = 6, 8, 12, 16), viz. 2,2-dimethylbutane (br-C₆), 2,2,4-trimethylpentane (br-C₈), 2,2,4,6,6-pentamethylheptane (br-C₁₂) and 2,2,4,4,6,8,8-heptamethylnonane (br-C₁₆). Tong and Dong method, thermoacoustical method, Hartmann relation and Ballou relation have been employed to evaluateB/A. A comparative study ofB/A values obtained from the aforementioned methods has been made. The results are discussed on the basis of structural orientations of normal and branched alkanes.     

含气泡液体中声传播的解析解及其强非线性声特性

声波在含气泡的液体中传播时,气泡的受迫振动会引起强的声散射,并且由于振动的非线性,使得气泡产生的次级波不仅含有基频成分,而且还会有高次谐波。本文从理论上描述了气泡个数随尺并给出了含气泡液体的等效非线性声参数Ｂ／Ａ的计算公式理论与已有的实验观测符合较好,文中对含气泡水的声速和声衰减等特性也进行了讨论。     

Excess properties of Lennard-Jones binary mixtures from computer simulation and theory

Monte Carlo simulation and theory are used to calculate the excess thermodynamic properties of binary mixtures of spherical Lennard-Jones molecules. We study the excess functions of three binary mixtures characterized by the following size and dispersive energy ratios: (1) (σ₂₂/σ₁₁)³ = 2 and ?₂₂/?₁₁ = 2; (2) (σ₂₂/σ₁₁)³ = 1 and ?₂₂/?₁₁ = 1/2 and (3) (σ₂₂/σ₁₁)³ = 1/2 and ?₂₂/?₁₁ = 2. In all cases, the unlike size parameter, σ₁₂, is kept constant and equal to the value given by the Lorentz combining rule (σ₁₂ = (σ₁₁ + σ₂₂)/2). However, different unlike dispersive energy parameter values are considered through the following combining rules: (a) ?₁₂ = (?₁₁?₂₂)^1/2 (Berthelot rule); (b) ?₁₂ = ?₁₁ (association); and (c) ?₁₂ = ?₂₂ (solvation). The pressure and temperature dependence of the excess volume and excess enthalpy is studied using the NpT Monte Carlo simulation technique for all the systems considered. Additionally, the simplest conformal solution theory is used to check the adequacy of this approach in predicting the excess properties in a wide range of thermodynamic conditions and variety of binary mixtures. In particular, we have applied the van der Waals one-fluid theory to describe Lennard-Jones binary mixtures through the use of the Johnson et al. [1993, Molec. Phys., 78, 591] Helmholtz free energy. Agreement between simulation results and theoretical predictions is excellent in all cases and thermodynamic conditions considered. This work confirms the applicability of the van der Waals one-fluid theory in predicting excess thermodynamic properties of mixtures of spherical molecules. Furthermore, since binary mixtures of spherical Lennard-Jones molecules constitute the reference fluid to be used in perturbation theories for complex fluids, such as the statistical association fluid theory (SAFT), this work shows clearly the applicability of the conformal solution theory within the framework of SAFT for predicting excess functions.     

Excess molar volumes and isentropic compressibilities of binary liquid mixtures containing n-alkanes at 298.15 K

Excess molar volumes (V ^E) and deviation in isentropic compressibilities (Δβ _s) have been investigated from the density ρ and speed of sound u measurements of six binary liquid mixtures containing n-alkanes over the entire range of composition at 298.15 K. Excess molar volume exhibits inversion in sign in one binary mixture, i.e., n-heptane + n-hexane. Remaining five binary mixtures, n-heptane + toluene, cyclohexane + n-heptane, cyclohexane + n-hexane, toluene + n-hexane and n-decane + n-hexane show negative excess molar volumes over the whole composition range. However, the large negative values of excess molar volume becomes domainant in toluene + n-hexane mixture. Deviation in isentropic compressibility is negative over the whole range of composition in the case of all the six binary mixtures. Existence of specific intermolecular interactions in the mixtures has been analyzed in terms of excess molar volume and deviation in isentropic compressibility.     

Volumetric, acoustic and spectroscopic studies for binary mixtures of ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) with alkoxyalkanols at T = (288.15 to 318.15) K

Densities and speeds of sound have been measured for the binary mixtures of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF₆] with ethylene glycol monoethyl ether (EGMEE), diethylene glycol monoethyl ether (Di-EGMEE), triethylene glycol monoethyl ether (Tri-EGMEE) over the whole composition range at atmospheric pressure. Experimental densities have been used to estimate excess molar volumes, V^E. Changes in isentropic compressibility, Δκ_s have been estimated by using experimental speed of sound and density values. Excess properties were fitted to the Redlich-Kister polynomial equation to obtain the binary coefficients and the standard errors. The molecular scale interactions between ionic liquid and alkoxyalkanols have been investigated through ¹H NMR spectroscopy. NMR chemical shifts for hydroxyl group of alkoxyalkanols and their deviations show hydrogen bonding interactions of varying strengths between ionic liquid and alkoxyalkanol in their binary mixtures.     

Comparison of Lattice-Fluid Binary Parameters For Mixtures and Block Copolymers

The aim of this report is to discuss the method of determination of lattice-fluid binary interaction parameters by comparing well characterized immiscible blends and block copolymers of poly(methyl methacrylate) (PMMA) and poly(??caprolactone) (PCL). Experimental pressure-volume-temperature (PVT) data in the liquid state were correlated with the Sanchez—Lacombe (SL) equation of state with the scaling parameters for mixtures and copolymers obtained through combination rules of the characteristic parameters for the pure homopolymers. The lattice-fluid binary parameters for energy and volume were higher than those of block copolymers implying that the copolymers were more compatible due to the chemical links between the blocks. Therefore, a common parameter cannot account for both homopolymer blend and block copolymer phase behaviors based on current theory. As we were able to adjust all data of the mixtures with a single set of lattice-binary parameters and all data of the block copolymers with another single set we can conclude that both parameters did not depend on the composition for this system. This characteristic, plus the fact that the additivity law of specific volumes can be suitably applied for this system, allowed us to model the behavior of the immiscible blend with the SL equation of state. In addition, a discussion on the relationship between lattice-fluid binary parameters and the Flory–Huggins interaction parameter obtained from Leibler's theory is presented.     

Dielectric studies of some binary liquid mixtures using microwave cavity techniques

The excess parameter studies in the microwave frequency region (X-band) on complex dielectric permittivity for the binary mixtures are reported. The methods employed are fixed cavity perturbation technique and adjustable plunger cavity technique. Also Gopalakrishna method is used to calculate the relaxation time of the polar solute in a non-polar solvent. The samples under study are acetonitrile, chlorobenzene, dimethyl formamide, carbon tetrachloride and benzene.     

Modelling the phase equilibria of multicomponent mixtures containing CO2, alkanes,water, and/or alcohols using the quadrupolar CPA equation of state

ABSTRACT

In this work, a quadrupolar cubic plus association (qCPA) equation of state is evaluated for its ability to predict the phase equilibria of multicomponent mixtures containing CO₂ and alkanes, alcohols, and/or water. A single binary interaction parameter is employed in qCPA for all binary combinations. All parameters are based solely on pure fluid or binary mixture data and multicomponent data are used only to evaluate the predictions. The performance of qCPA is, for all mixtures, compared to CPA where CO₂ is considered to be either non-associating (inert), solvating or self-associating. In the latter two approaches, an additional adjustable parameter is employed for binary pairs of CO₂ and an associating compound. The results show that the predictions with qCPA are very similar to the best performing CPA approaches, even though the model uses fewer adjustable binary parameters. The predictions with qCPA and the best CPA approaches are typically satisfactory and predict the general behaviour of the systems. As expected, qCPA and CPA with solvation or association typically performs better than inert CPA for two- and three phase vapour–liquid and vapour–liquid–liquid equilibria. However, inert CPA yields the best results of all the models for the prediction of dew point pressures.     

Excess thermodynamic properties of mixtures of Lennard-Jones liquids

The results of Monte Carlo calculations in the isothermal-isobaric ensemble are reported for a series of binary mixtures of Lennard-Jones liquids at zero pressure and a temperature of 115·8 K. In the case of equimolar mixtures comparison is made with the predictions of several recently developed theories of liquid mixtures. Particularly good results for excess Gibbs free energy and enthalpy are obtained from the variational theory of Mansoori and Leland and for excess volume from the one-fluid version of the so-called van der Waals model.     

Ultrasonic velocity, density, viscosity and their excess parameters of the binary mixtures of tetrahydrofuran with methanol and o-cresol at varying temperatures

The ultrasonic velocity, density and viscosity of binary mixtures of tetrahydrofuran (THF) with methanol and o-cresol were measured at 293, 303 and 313 K over the entire range of composition. Using these experimental data, various thermo-acoustic parameters such as deviation in isentropic compressibility Δκ_s, excess molar volume , viscosity deviation Δη and excess Gibb’s free energy of activation for viscous flow ΔG^∗E have been calculated and fitted to Redlich-Kister polynomial equation. The deviation/excess parameter were plotted against the mole fraction of THF over the whole composition range. The observed negative and positive values of deviation/excess thermo-acoustic parameters were explained on the basis of the intermolecular interactions present in these mixtures. Since methanol is less acidic than o-cresol, the removal of proton from methanol is less likely than the removal of proton from o-cresol which is more acidic than methanol. Hence the intermolecular interaction in the mixture of THF with o-cresol is found to be stronger than mixture of THF with methanol, which is reflected from the observed positive and negative values of excess thermo-acoustic parameters. Thus it may be concluded that THF + o-cresol mixture exhibits strong intermolecular interaction. However, dispersive forces are responsible for THF + methanol mixture due to weak interaction. Further, Nomoto, Junjie, CFT and Flory’s theory were applied for evaluating the ultrasonic velocity theoretically. The theoretical evaluation of ultrasonic velocity based on molecular models in liquid mixtures has been used to correlate with the experimental findings and to know the thermodynamics of the mixtures. The comparison of theoretical and experimental results provides better understanding about the validity of the various thermodynamic, empirical, semi empirical and statistical theories.     

Densities, excess molar volumes, and viscosities of the binary and ternary mixtures of {diethylcarbonate (1) + p-chloroacetophenone (2) + 1-hexanol (3)} at 303.15 K for the liquid region and at ambient pressure

Densities ρ, dynamic viscosities η, of the ternary mixture (diethylcarbonate + p-chloroacetophenone + 1-hexanol) and the involved binary mixtures (diethylcarbonate + p-chloroacetophenone), (diethylcarbonate + 1-hexanol), and (p-chloroacetophenone + 1-hexanol) have been measured over the whole composition range at 303.15 K for the liquid region and at ambient pressure. The data obtained are used to calculate excess molar volumes V_m^E, excess partial molar volumes V¯_m,i^E, limiting excess partial molar volumes V¯_m,i^E,∞, and viscosity deviations Δη, of the binary and ternary mixtures. The data of excess molar volumes of the binary systems were fitted to the Redlich–Kister equation while for the ternary system the Cibulka equation was used. The McAllister's four body, and Kalidas and Laddha interaction models are used to correlate the kinematic viscosities of binary and ternary mixtures, respectively, to determine the fitting parameters and the standard deviations. The experimental data of the constitute binaries and ternary are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Dielectric permittivity, density, viscosity and refractive index of binary mixtures of anisole with methanol and 1-propanol at different temperatures

Static dielectric permittivity, density, viscosity, and refractive index of anisole (AN), methanol (MeOH), 1-propanol (1-PrOH) and binary mixtures of AN with MeOH and 1-PrOH at nine different concentrations, were measured at 303, 313 and 323 K temperatures. Measured properties of pure AN, MeOH and 1-PrOH were compared with literature values and they were found in good agreement. The investigation of binary mixtures showed a systematic change in static dielectric permittivity, density and viscosity with change in concentration of anisole in the mixture. Measured properties of liquid samples were used to calculate Kirkwood correlation factor and excess parameters such as excess dielectric permittivity, excess molar volume and excess viscosity. Determined parameters have been interpreted in terms of molecular interaction among the molecular species of the binary mixtures.     

Excess molar volumes, viscosities, and refractive indices for binary and ternary mixtures of {cyclohexanone (1) + N,N-dimethylacetamide (2) + N,N-diethylethanolamine (3)} at (298.15, 308.15, and 318.15) K

Densities ρ, viscosities η, and refractive indices n_D, of the binary and ternary mixtures formed by cyclohexanone + N,N-dimethylacetamide + N,N-diethylethanolamine were measured at (298.15, 308.15, and 318.15) K for the liquid region and at ambient pressure for the whole composition ranges. The excess molar volumes V_m^E, viscosity deviations Δη, and refractive index deviations Δn_D, were calculated from experimental densities and refractive indices. The excess molar volumes are positive over the mole fraction range for binary mixtures of cyclohexanone(1) + N,N-dimethylacetamide (2) and N,N-dimethylactamide (2) + N,N-diethylethanolamine (3) and increase with increasing temperatures from (298.15 to 318.15) K. The excess molar volumes of cyclohexanone (1) + N,N-diethylethanolamine (3) are S-shaped dependence on composition with negative values in the N,N-diethylethanolamine rich-region and positive values at the opposite extreme and increase with increasing temperatures from (298.15 to 318.15) K. The excess molar volumes are positive over the whole mole fraction ranges for the ternary mixtures at all temperatures. Viscosity deviations are negative over the mole fraction range for all binary and ternary mixtures and decrease with increasing temperatures from (298.15 to 318.15) K. Refractive index deviations are negative over the mole fraction range for all binary and ternary mixtures and increase with increasing temperatures from (298.15 to 318.15) K. The experimental data of constitute were correlated as a function of the mole fraction by using the Redlich–Kister equation for binary and , Cibulka, Jasinski and Malanowski , Singe et al., Pintos et al., Calvo et al., Kohler, and Jacob–Fitzner for ternary mixture, respectively. McAllister^'s three body, Hind, and Nissan–Grunberg models were used for correlating the kinematic and dynamic viscosity of binary mixtures. The experimental data of the constitute binaries are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Thermodynamic investigations of ternary o-toluidine + tetrahydropyran + N,N-dimethylformamide mixture and its binaries at 298.15, 303.15 and 308.15 K

The densities ρ, speed of sound u, data of o-toluidine (i) + tetrahydropyran (j) + N,N-dimethylformamide (k) and its {tetrahydropyran (j) + N,N-dimethylformamide (k); o-toluidine (i) + N,N-dimethylformamide (k)} binaries have been measured as a function of composition at 298.15, 303.15 and 308.15 K. The excess molar enthalpies, H^E data of same set of binary mixtures have also been measured over entire composition at 308.15 K. The densities and speeds of sound data of binary and ternary mixtures have been utilized to determine their excess molar volumes, V^E and excess isentropic compressibilities, κ_S^E. The observed thermodynamic properties of binary and ternary mixtures have been analyzed in terms of Graph theory. It has been observed that Graph theory correctly predicts the sign as well as magnitude of thermodynamic properties.