Deviation In Isentropic Compressibility Research Articles

Comment on the paper of Naushad Anwar Riyazuddeen and Shama Yasmeen entitled “Volumetric, compressibility and viscosity studies of binary mixtures of [EMIM][NTf2] with ethylacetate/methanol at (298.15–323.15) K”: A critical discussion on the application PFP model and isentropic compressibility analysis

Abstract The excess isentropic compressibilities of binary mixtures of 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide with ethyl acetate or methanol and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide with dimethyl sulfoxide or methanol were calculated based on thermodynamically rigorous ideal mixing rule. For the discussed mixtures, great differences between excess values of isentropic compressibilities and isentropic compressibility deviations from a simple mole fraction average of pure components isentropic compressibilities are observed. The usability and correctness of the Prigogine-Flory-Patterson (PFP) model for mixtures under test is discussed as well, because in constructing the PFP theory, hydrogen bonds and interactions of strong electrostatic nature are excluded [Fluid Phase Equilib. 233 (2005) 157].

Cibulka correlation for ternary excess/deviation properties of {[C2mim][EtSO4] (x1) + acetic or propionic acid (x2) + acetonitrile (x3)} systems at different temperatures

In this perspective, the main intention is to reveal the possible intra and inter molecular interactions between ternary ionic liquid systems. The excess molar volume (V123E), isentropic compressibility (ks) and deviation in isentropic compressibility (Δks123) were determined for two ternary liquid mixtures of {[C2mim][EtSO4] (x1)+acetic or propionic acid (x2)+acetonitrile (x3)} at different temperatures (293.15, 298.15, 303.15, 308.15 and 313.15)K and at p=1×105Pa with the aid of the experimental density (ρ) and speed of sound (u) measurements. The calculated ternary excess volume and deviation in isentropic compressibility results were correlated by using the Cibulka equation with the aid of Redlich–Kister parameters obtained from literature corresponding binary systems. Furthermore, the measured thermodynamic properties are discussed in terms of molecular interactions between component molecules in liquid mixtures.

Investigation of molecular interactions in binary mixtures (dichloromethane + aliphatic alcohols) at T = (298.15 to 308.15) K: Experimental, ERAS analyses and COSMO-RS predictions

Densities ρ, and ultrasonic velocities, u of binary mixtures of pure dichloromethane (DCM) with methanol (Me-OH), ethanol (Et-OH), propan-1-ol (Pr-OH) and butan-1-ol (Bu-OH) including those of their binary liquids were measured at (298.15, 303.15 and 308.15) K. From the experimental data the excess molar volume, VmE, deviation in isentropic compressibility, Δks, deviation in specific acoustic impedance, ΔZ, deviation in intermolecular free length, ΔLf, and deviation in ultrasonic velocity, Δu were calculated. The experimental excess molar volume values were correlated with theoretical values derived from extended real association solution model (ERAS). The σ-profile of dichloromethane and aliphatic alcohols were computed with conductor-like screening model (COSMO-RS) and are interpreted to show the possible interactions between the mixing components.

Volumetric, compressibility and viscosity studies of binary mixtures of [EMIM][NTf2] with ethylacetate/methanol at (298.15–323.15) K

Densities, speeds of sound and viscosities of pure and binary mixtures 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([EMIM][NTf2])+ethyl acetate/methanol have been measured experimentally over the entire composition range and at six temperatures from 298.15K to 323.15K, at pressure 0.1MPa using Anton Paar Density and Sound velocity meter DSA 5000M and, Lovis microviscometer 2000M. From these experimental data, the excess molar volumes (VE), viscosity deviations (∆η) and isentropic compressibility deviations (∆κs) have been evaluated. The VE values are negative for [EMIM][NTf2]+ethyl acetate system upto x1=0.90 and positive above this x1 value at all temperatures of study. However, the VE values are negative for [EMIM][NTf2]+methanol system at entire mole fraction range and at all temperatures. The VE values in both studied systems decrease with increase in temperature. The ∆η and ∆κs are found to be negative over the entire range of mole fraction and decrease with increasing temperature in both binary systems. The computed data of VE, ∆η and ∆κs have been correlated with Redlich-Kister polynomial equation. The measured and computed data have been interpreted in terms of ion-dipole, ion-ion and dipole-dipole interactions and structural effects between like and unlike molecules upon mixing. The experimental data of VE have also been used to examine the applicability of Prigogine–Flory–Patterson (PFP) theory in predicting the VE of the binary mixtures. The minimum and maximum percent deviations of experimental and calculated by PFP VE values are 0.017 and 3.01 for [EMIM][NTf2]+ethyl acetate and 1.19 and 2.10 for [EMIM][NTf2]+methanol systems, respectively.

Thermodynamic and spectroscopic properties of binary mixtures of n-butylammonium butanoate ionic liquid with alcohols at T = (293.15–313.15) K

In this work, density and speed of sound of binary mixtures of {n-butylammonium butanoate ionic liquid (N4Bu)+alcohols (methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol)} have been measured as a function of composition at T=(293.15–313.15)K and atmospheric pressure. The results were used to calculate the excess molar volume, VmE, and deviation in isentropic compressibility, ΔκS, and correlated to the Redlich-Kister polynomial equation. N4Bu was synthesized by the method of acid-base neutralization reaction using n-butylamine and butanoic acid, and characterized using 1H NMR, 13C NMR and FTIR spectroscopy techniques. For all systems studied, the values of excess molar volumes and deviations in isentropic compressibility were negative over the entire composition range. The results obtained were discussed in terms of structural effects and intermolecular interactions between like and unlike molecules.

Volumetric, acoustic and optical properties for binary mixtures of nitroethane with chloroalkane at temperatures between 298.15 K and 318.15 K. Comparison with theories

In a continuation from a previous work, experimental densities, speeds of sound, and refractive indices data, for eight binary liquid mixtures of nitroethane with 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1-chlorobutane and 1-chloropentane were measured in the temperature range of (298.15–318.15) K and at atmospheric pressure. From the measured data the derived properties, such as the excess molar volumes, the isentropic compressibility, the deviations in isentropic compressibility, the deviations in refractive indices, the molar refractions and the deviations in molar refractions data have been calculated. The excess properties of the binary mixtures were correlated by the Redlich–Kister type polynomials using a robust regression along the gnostic influence function. Speed of sound and isentropic compressibility data have been compared with calculated values from Jacobson free length theory (FLT), Nomoto's relation (NR), Zhang Junjie's relation (JR), Van Deal's ideal mixing relation (IMR), Impedance dependence relation (IDR) and Schaaff's collision factor theory (CFT). The ability of different theoretical (n,ρ) mixing rules (Lorentz–Lorenz, Gladstone–Dale, Arago–Biot, Edwards and Eykman) to predict the refractive indices was evaluated. The experimental and calculated results are discussed in terms of molecular interactions and structural effects between components of mixtures.

A study of the molecular interactions between ammonium-based ionic liquids and N,N-dimethylacetamide

In this work, we report the molecular interactions of different cation alkyl chain lengths with same anion of ammonium-based ionic liquids (ILs) such as tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) with N,N-dimethylacetamide (DMA) through thermophysical properties with varying the compositions of ILs at different temperatures from 25 to 40°C under atmospheric pressure. Experimental densities (ρ), ultrasonic sound velocities (u), viscosities (η) and refractive indices (nD) of binary mixtures of ILs with DMA are measured over the wide composition range. The excess molar volumes (VE), deviation in isentropic compressibilities (Δκs), deviation in viscosities (Δη) and deviation in refractive indices (ΔnD) are calculated from experimental values and are correlated by Redlich-Kister polynomial equations. Consequently, VE values show that negative for small cation alkyl chain length of ammonium-based ILs as compared to large cation alkyl chain length of ILs. We have observed the strength of intermolecular interactions such as hydrogen bonding, ion-ion pair interactions and induced dipole interactions between the ions of ammonium-based ILs with DMA from obtained data. Thermophysical properties, however, possessed by these binary systems are exceedingly promising and predictable that these systems will find applications in chemical industry.

Refractive index, speed of sound, FT-IR and computational study of intermolecular interaction between binary mixtures of 1,8-cineole with o-, m- and p-cresol at 303.15, 308.15 and 313.15 K

Refractive indexes (nD) and speed of sound (u) have been experimentally measured for binary mixtures of 1,8-cineole+o-, m- and p-cresol at entire composition range at 303.15, 308.15 and 313.15K at atmospheric pressure. The deviation in refractive index (∆nD), molar refraction (Rm) and deviation in molar refraction (∆Rm) has been calculated using experimentally measured values of the refractive index. Similarly, from the measured values of speed of sound (u), some of its related properties like deviation in speed of sound (∆u), isentropic compressibility (ks), deviation in isentropic compressibility (∆ks), acoustic impedance (z), deviation in acoustic impedance (∆z) have been calculated. The partial molar isentropic compressibility K−s,m,io, excess partial molar isentropic compressibility K−s,m,io,E, apparent molar isentropic compressibility (Ks,m,Φ,i) have been also calculated. The values of apparent molar isentropic compressibility (Ks,m,Φ,i) have been fitted with the Redlich-Rosenberg-Mayer equation to get limiting apparent molar isentropic compressibility (Kos,m,Φ,i) and Sk and Bk empirical parameter values. All these calculated results were fitted with the Redlich-Kister polynomial equation. The FT-IR spectra of pure and their binary mixtures are also studied. The geometrically optimization, harmonic vibrational wave numbers, bond characteristics and single point energy has been theoretically calculated using density functional theory (DFT-B3LYP) method with 6-31+G(d,p) basis sets for pure components and their binary mixtures. Positive values of ∆nD, ∆u, ∆z and negative values of ∆Rm, ∆ks and K−s,m,io,E support for the presence of strong intermolecular interactions between components of these binary mixtures.

Interaction of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide with methanol/dimethyl sulfoxide at (298.15, 303.15, 308.15, 313.15, 318.15 and 323.15) K: Measurements and correlations of thermophysical properties

Densities, speeds of sound and viscosities of 1-butyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)imide+methanol/dimethylsulfoxide mixtures have been measured experimentally over the entire composition range and at six temperatures, 298.15, 303.15, 308.15, 313.15, 318.15 and 323.15K, under 0.1MPa pressure using Anton Paar density and sound velocity meter DSA 5000M and Lovis microviscometer 2000M. From these experimental data, the excess molar volumes, VE, isentropic compressibility deviations, ∆κs and the viscosity deviations, ∆η have been evaluated. The computed data have been adequately fitted to the Redlich–Kister polynomial equation. The measured and computed data have been interpreted in terms of ion–dipole interactions and structural effects between like and unlike molecules upon mixing. The VE results have been correlated to the Prigogine–Flory–Patterson (PFP) theory. The experimental and PFP correlated values are quite close to each other.

Interaction of 1-Butyl-3-methylimidazolium Trifluoromethanesulfonate with Ethyl Acetate/1-Butanol: Thermophysical Properties

Densities, speeds of sound and viscosities of pure and the binary mixtures of [BMIM][CF3SO3] + ethyl acetate or 1-butanol have been measured over the entire range of mole fractions at T = (298.15–323.15) K and at 0.1 MPa pressure using an Anton Paar density and sound velocity meter DSA 5000M and a Lovis microviscometer 2000M. The excess molar volumes (VE), viscosity deviations (Δη) and the isentropic compressibility deviations (ΔκS) have been calculated using the experimental data. The variations in VE, Δη and ΔκS with changes in mole fraction and temperature have been interpreted in terms of ion–dipole interactions and structural effects on mixing of IL and solvents. The Redlich–Kister equation has been fitted to the VE, Δη and ΔκS values using a multi-parametric nonlinear regression method. The PFP theory has been applied to correlate the excess molar volumes. The experimental and PFP correlated values of VE are found to be quite close to each other.

Synthesis, characterization and thermophysical properties of ionic liquid N-methyl-N-(2′,3′-epoxypropyl)-2-oxopyrrolidinium chloride and its binary mixtures with water or ethanol at different temperatures

A novel ionic liquid, namely, N-methyl-N-(2′,3′-epoxypropyl)-2-oxopyrrolidinium chloride [Epmpyr]+[Cl]− was synthesized and characterized by different techniques such as NMR (1H and 13C), FTIR, and elemental analysis. The water content of the ionic liquid was checked by Karl Fisher titration. Further, the density, ρ, and speed of sound, u, were measured for the above ionic liquid and the corresponding binary systems with water or ethanol at different temperatures ranging from (293.15 to 313.15) K. The derived thermodynamic properties for instance excess molar volumes, VmE isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were investigated from the density and speed of sound data, respectively. It is noted that density and speed of sound of the ionic liquid and its binary mixtures were decreased with increase in temperature, whereas excess molar volume, isentropic compressibility, and deviation in isentropic compressibility values increased. Derived properties such as excess molar volumes, and deviation in isentropic compressibility data were fitted to the Redlich-Kister polynomial equation. The measured and calculated data were interpreted in terms of intermolecular interfaces and structural effects between similar and dissimilar molecules upon mixing.

Excess molar volumes, excess thermal expansion coefficients and isentropic compressibility deviations for binary mixtures of benzyl alcohol + (1-butanol, 2-butanol, 2-methyl-1-butanol and tert-butanol) at T = (298.15-328.15) K and ambient pressure

ABSTRACTIn the present paper, we report the density (ρ) and ultrasonic speed (u) of four binary mixtures of benzyl alcohol with 1-butanol, 2-butanol, 2-methyl-1-butanol and tert-butanol over the temperature range 298.15–328.15 K and ambient pressure, covering the entire composition range, expressed by the mole fraction (x1) of benzyl alcohol. The experimental data on density and ultrasonic speed were used to calculate the excess molar volumes, , deviations in isentropic compressibility, , excess thermal expansion coefficients, , excess partial molar volumes, , and excess partial molar volumes at infinite dilution, . The results obtained were used to investigate the nature and strength of intermolecular interactions in these mixtures. The calculated quantities , and are well correlated with the Redlich–Kister equation.

Influence of alkyl group on interactions between carboxylic acid and acetonitrile at different temperatures

In this paper, the influence of alkyl group as well as temperature on interactions between carboxylic acid and acetonitrile were examined using thermodynamics technique. The carboxylic acid used in this study was acetic acid and propionic acid. To explore the utility of carboxylic acid and acetonitrile, we have carried out the interaction studies of carboxylic acid with acetonitrile using density, ρ, and sound velocity, u, measurements of acetic acid, propionic acid, acetonitrile, and their binary systems {acetic acid or propionic acid (x1)+acetonitrile (x2)} as function of temperature. The excess molar volumes, VmE, isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were calculated from thermophysical properties, respectively which provide information about the intermolecular interactions as well as the influence alkyl group and temperatures that occurs between carboxylic acid and acetonitrile mixtures. The Redlich–Kister polynomial equation was used to fit the thermodynamics properties to test the experimental data. These results are useful for describing the intermolecular interactions; developing structure–property correlation and molecular modeling that exist between the carboxylic acid and acetonitrile mixtures.

Physico-Chemical Properties of Binary Liquid Mixtures of n-Hexane + Acrylic Esters (C4, C5, C6, C7) at Different Temperatures

Densities ρ, ultrasonic speeds u, and refractive indices n for pure n-hexane, methylacrylate (MA), ethylacrylate (EA), ethylmethacrylate (EMA), butylacrylate (BA), and of their 36 binary mixtures over the entire composition range were measured at 298.15, 303.15, 308.15, and 313.15 K. Using these data, the excess molar volumes, VE, deviations in isentropic compressibilities, Δks, deviations in molar refractions, ΔRm, and deviations in internal pressure, ΔPi, were calculated for the mixtures at given temperatures. Apparent molar volumes, Vϕ,2, and apparent molar compressibilities, Kϕ,2, of acrylic esters in n-hexane were also calculated. Partial molar volumes, , and partial molar isentropic compressibilities, , at infinite dilution were estimated. Moreover, the optical property and partial molar refraction, , of the systems at infinite dilution were examined. The variations of these parameters and of the optical property suggest that the strength of interactions in these mixtures follow the sequence: MA < EA < EMA < BA.

Volumetric, Viscometric, Acoustic and IR Spectroscopic Studies of Binary Mixtures of Tert-butyl Acetate with Isopropylbenzene, Isobutylbenzene and Methoxybenzene 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 isopropylbenzene, isobutylbenzene, methoxybenzene 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 the excess molar volumes (VE), deviations in viscosity (Δη) and deviation in isentropic compressibility (Δks) and stretching frequency () have been calculated. The excess molar volumes and deviations in isentropic compressibility with tBA are positive for the mixtures of isobutylbenzene and methoxybenzene with tBA and, negative for isopropylbenzene with tBA while deviations in viscosities are negative for the binary mixtures of isobutylbenzene, methoxybenzene and positive for isopropylbenzene. The excess molar volumes, deviations in viscosity and, deviations in isentropic compressibility have been fitted to the Redlich-Kister polynomial equation.

RETRACTED ARTICLE: Density, viscosity and speed of sound of benzaldehyde with benzene at 303.15, 308.15, and 313.15 K

The values of density, viscosity and speed of sound for the binary liquid mixture of Benzaldehyde with Benzene were measured over the entire range of composition at 303.15, 308.15, and 313.15 K. These values are used to calculate the excess molar volume (VE), deviation in viscosity (Δη), deviation in speed of sound (ΔU), deviation in isentropic compressibility (Δβs), excess internal pressure (Δπ), excess intermolecular free length (ΔLf), excess free volume (VEf) and excess acoustic impedance (ΔZ). McAllister’s three-body interaction model is used for correlating Kinematic Viscosity of binary mixtures. The excess values were correlated using the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The thermophysical properties (density, viscosity, and speed of sound) under the study were fit to the Jouyban–Acree model.

Volumetric, ultrasonic and spectroscopic (FT-IR) studies for the binary mixtures of imidazolium based ILs with 1,2-propanediol

Volumetric and ultrasonic properties of ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C4mim][NTf2] and 1-butyl-3-methylimidazolium methylsulfate [C4mim][C1OSO3] with 1,2-propanediol (1,2-PD) have been investigated using density, ρ speed of sound, u measurements over the entire composition range at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K. The density values were used to calculate excess molar volume, VmE whereas speed of sound results have been used to calculate deviation in isentropic compressibility, ΔκS. Excess properties have been fitted to the Redlich-Kister polynomial equation to obtain the binary coefficients and the standard deviations. Spectroscopic technique like Fourier transform infrared (FT-IR) has been utilized for analyzing molecular level interaction prevailing between the binary mixtures. FT-IR technique has been used to scrutinize the –OH interactions between the binary mixtures and the influence on the structural variations in the ionic liquid. The excess properties and spectroscopic data have been analyzed in terms of the effect of temperature and the change of the anion of ionic liquid.

Excess molar volume and isentropic compressibility of monoethanolamine in aqueous system at temperatures from 298.15 to 318.15 K

ABSTRACTDensities and sound velocities for aqueous monoethanolamine (MEA) system are reported over the entire composition range at different temperatures (298.15, 303.15, 313.15 and 318.15 K). These experimental data have been further used in calculating the excess molar volume, partial molar volumes, isobaric thermal expansion coefficients and the deviation in isentropic compressibility. The excess molar volumes data were fitted to the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The partial molar volume at infinite dilution of both water in MEA and MEA in water and have been determined using two different methods. Knowledge of the above properties of these mixtures is a basis for understanding some of the molecular interactions in these systems. From the analysis of the results, the type of interactions between the MEA and water is discussed in terms of the number and size of the alkyl groups attached to the nitrogen atom of MEA.

Effect of the Alkyl Chain Length of the Cation on the Interactions between Water and Ammonium-Based Ionic Liquids: Experimental and COSMO-RS Studies

To improve the understanding of the molecular interactions of water with tetraalkyl ammonium-based ionic liquids (ILs) such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, thermophysical properties such as density (ρ), speed of sound (u), viscosity (η) and refractive index (nD) were measured and a computational study using COSMO-RS was performed. The derived properties such as excess volumes (VE), deviation in isentropic compressibilities (Δκs), deviation in viscosities (Δη), and deviation in refractive indices (ΔnD) under the same experimental conditions for these systems were also estimated. The observed VE and Δκs values are negative over the entire composition of ILs at all investigated temperatures, whereas Δη and ΔnD values are positive under the same experimental conditions. These results reveal that the ammonium-based ILs significantly affect the intermolecular interactions between the solvent molecules. The computati...

Excess thermodynamic and spectroscopic study of ternary mixtures containing N-methylcyclohexylamine, bromobenzene, and 1-alkanols at 303.15 K

Excess volume and sound speed data for three ternary mixtures, containing N-methylcyclohexylamine and bromobenzene as common components and 1-alkanols such as 1-propanol, 1-butanol, and 1-pentanol as third component, were measured at 303.15 K over the entire composition range. The experimental speeds of sound were used to compute isentropic compressibility and deviation in isentropic compressibility. The excess volume data of all mixtures were compared with data obtained from predictive expressions due to Redlich–Kister, Kohler, Tsao–Smith, and Hwang et al.’s equations. Further, the experimental results were analyzed in terms of molecular interactions between component molecules with FT-IR spectrum. Excess volume and speed of sound measured at 303.15 K for three ternary mixtures containing N-methylcyclohexylamine (1), bromobenzene (2), and 1-alcohols (3). Results were used to calculate derived thermodynamic properties and analyzed in terms of intermolecular interactions between component molecules.