Excess Molar Volumes VE Research Articles

Density, viscosity, excess molar volume and viscosity deviation for [chloroform (1) + methanol (3)] binary system and [chloroform (1) + di-isopropylether (2) + methanol (3)] ternary system at 298.15 K

Abstract Densities ρ and viscosity η of the [chloroform (1) + methanol(3)] binary system and [chloroform (1) + di-isopropyaelther (DIPE) (2) + methanol (3)] ternary system have been measured at 298.15 K and a pressure of 960 hPa using an Anton Paar DMA 500 stavigmeter. Excess molar volumes VE and viscosity deviation Δη were calculated. The excess molar volume and viscosity deviation for binary system were fitted to a Redlich-Kister type equation and the ternary excess molar volumes VE and viscosity deviation Δη were correlated by a Redlich-Kister and Nagata and Tamura type equation. Also, the ternary excess molar volume and viscosity deviation Y 123 E were predicted using the Radojkovic equation. From the results we obtained conclusions about the molecular interactions in binary and ternary mixtures.

Excess molar volume and viscosity deviation for binary mixtures of γ-butyrolactone with dimethyl sulfoxide

The densities of binary liquid mixtures of dimethyl sulfoxide and γ-butyrolactone at (293.15, 298.15, 303.15 and 313.15)K and viscosity at T=298.15K have been measured at atmospheric pressure over the entire range of concentration. From these data the excess molar volumes VE at (293.15, 298.15, 303.15 and 313.15)K and the viscosity deviation, the excess entropy, and the excess Gibbs energy of activation for viscous flow at T=298.15K have been determined. These data were mathematically represented by the Redlich-Kister polynomial. Partial and apparent molar volumes have been calculated for better understanding of the interactions in the binary systems. The obtained data indicate the lack of specific interactions between unlike molecules, which seem to be a little weaker as compared to the interactions in pure solvents.

Excess molar volumes and viscosity behaviour of binary mixtures of aniline/or N,N-dimethylaniline with imidazolium ionic liquids having triflate or bistriflamide anion

In this study, densities and viscosities of four binary systems {aniline/N,N-dimethylaniline+1-butyl-3-methylimidazolium triflate ([bmim][OTf])} and {aniline/N,N-dimethylaniline+1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf2])} were measured at atmospheric pressure and within the temperature range T=(288.15 to 333.15)K. Excess molar volumes VE, viscosity deviations Δη and excess molar Gibbs energies of activation of viscous flow ∆G∗E were calculated and the results were fitted to a Redlich-Kister polynomial equation. Also, enthalpic and entropic parts of the ∆G∗E function were determined, at the same composition, for three studied systems that exhibit complete miscibility, since {aniline+[bmim][OTf]} is a partially miscible system. Considering the calculated thermodynamic properties, molecular interactions in the investigated binary systems were analysed and are discussed.

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.

Surface tension and density of mixtures of m-xylene + n-alkane at 293.15 K: Analysis under the extended Langmuir and Shereshefsky models

Surface tension (σ) and density (ρ) for {m-xylene+n-pentane, hexane, heptane and octane} at the temperature 293.15K and pressure 1.013bar have been determined as a function of mole fraction. In order to analyze the surface tension behavior, the extended Langmuir (EL) and Shereshefsky models were used and parameters of the models were obtained for these mixtures. The standard Gibbs energy of adsorption (-ΔG∘) was calculated using both models. The free energy change of replacing one mole of solute with one mole of solvent in surface region (ΔGS) and the excess number of molecular layers of solute in the surface region were calculated using Shereshefsky model. The magnitude of ΔGS and (-ΔG∘) was discussed in terms of nature and type of intermolecular interactions in binary mixtures. The Redlich-Kister polynomial equation was fitted to each of the experimental surface tension deviation (δσ) and excess molar volume (vE) results. Using the resulting polynomial equations, the surface tension deviations and the excess molar volumes (δσ, vE) were calculated over the entire composition range.

Volumetric and viscometric properties of binary and ternary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate, monoethanolamine and water

Densities and viscosities of binary {[Bmim][BF4]+H2O}, {[Bmim][BF4]+MEA}, (MEA+H2O) and ternary mixtures {[Bmim][BF4]+MEA+H2O} were measured at T=(293.15–333.15)K. The volumetric and viscometric properties, such as excess molar volume VE, viscosity deviation Δη, and excess Gibbs energy of activation of viscous flow ΔG∗E for all mixtures, and apparent molar volume, excess partial molar volume and Grunberg-Nissan interaction parameter G12 for binary mixtures, were deduced from experimental results, and the intermolecular interactions in solutions were also analysed. The excess molar volumes were correlated using the Redlich-Kister polynomial equation for binary mixtures, and Singh et al. equation for the ternary mixture with corresponding binary parameters. The viscosities of binary and ternary solutions were respectively fitted by Jouyban-Acree equation and its extended equation at each measurement temperature, the correlated values are in good agreement with the corresponding experimental data.

Thermodynamic and spectroscopic interpretation of molecular interactions of nicotine + alcohol binary mixtures

Density ρ, viscosity η and refractive index nD have been experimentally measured for four binary mixtures nicotine+1-butanol, nicotine+2-butanol, nicotine+1,2-propanediol and nicotine+1,3-propanediol over the temperature range T=(293.15–323.15)K with temperature step 5K and at atmospheric pressure. Excess molar volumes VE, viscosity deviations Δη, deviations in refractive index ΔnD, excess Gibbs free energy of activation of viscous flow ΔG∗E, thermal expansion coefficients α, excess thermal expansion coefficients αE, partial molar volumes V‾i, excess partial molar volumes V‾iE and it’s values at infinite dilutions V‾iE,∞ were calculated from experimental data and used to analyze non-ideal behavior of mixtures. Fourier-transform infrared analysis of binary mixtures and corresponding pure components was performed at 298.15K in order to gain insight into the molecular structure of mixtures and possible intermolecular interactions. Performed infra-red analysis confirms the presence of hydrogen bonding between unlike compounds, except for the system nicotine+1-butanol. Here, the non-ideal behavior of mixtures is contributed to strong intermolecular interaction or in the case of nicotine+1-butanol due to geometrical packing or dispersion forces of different species.

Thermophysical and thermoacoustical properties of acetophenone with ethyl butyrate at temperatures of 303.15, 313.15, and 323.15 K

Densities, viscosities, and ultrasonic velocities of the binary mixtures of acetophenone with ethyl butyrate were measured over the entire mole fractions at 303.15, 313.15, and 323.15 K. From these experimental results, excess molar volume VE, viscosity deviation Δη, deviations in isentropic compressibility Δκs, excess intermolecular free length ΔLf, and excess Gibbs free energy ΔG*E were calculated. The viscosity values were fit to the models of Krishnan–Laddha and McAllister. The thermophysical properties under study were fit to the Jouyban–Acree model. The excess values were correlated using Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. It was found that in all cases, the data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution.

Physicochemical properties of binary mixtures of 1,1,3,3-tetramethylguanidine imidazolide ionic liquid with water and alcohols

In this work, densities and viscosities of aqueous solution of 1,1,3,3-tetramethylguanidine imidazolide ([TMG]IM) ionic liquid were measured at temperatures from T=(293.15 to 313.15)K. Volumetric properties including excess molar volumes VE, apparent molar volumes, partial molar volumes, and excess partial molar volumes were calculated from the experimental density. Viscosity deviations Δη, Gibbs energy and excess Gibbs energy of activation for viscous flow were deduced from the viscosity. Moreover, electrical conductivities κ and refractive indices of binary mixtures of [TMG]IM with water and alcohols were determined at 298.15K. The results show that VE values of {[TMG]IM (1)+water (2)} mixture are negative over the whole composition range, while Δη and refractive index deviations ΔnD values exhibit positive deviations, indicating that the hydrogen bonding interaction between [TMG]IM and water is dominant. The absolute values of VE and Δη of the mixture decrease with the increasing temperature. The VE, Δη, and ΔnD can be fitted by the Redlich–Kister equation with satisfactory results. The concentration-dependent κ of the studied systems are fitted to Casteel–Amis equation, showing that the κ values of {[TMG]IM (1)+water (2)} mixture are much higher than those of {[TMG]IM (1)+ethanol (2)} mixture.

Properties for binary mixtures of (acetamide + KSCN) eutectic ionic liquid with ethanol at several temperatures

Density, viscosity and conductivity were determined for the binary mixture of (acetamide+KSCN) eutectic ionic liquid with ethanol at T=(298.15, 303.15, 308.15, 313.15, 318.15)K and atmospheric pressure. The density, viscosity values decrease with the increase of temperature while the conductivity values increase over the whole concentration range. The density and viscosity values decrease monotonically with the increase of the mole content of ethanol. From the experimental values, excess molar volumes VE and viscosity deviations Δη for the binary mixture were calculated and VE and Δη were both well fitted by a third order Redlich–Kister equation. With the increase mole fraction of ethanol, the conductivity values of the mixture increase gradually first and then decrease dramatically, and the highest conductivity values appear at 0.8562mol fraction of ethanol. The relationship between the conductivity and the mole fraction of ethanol can be well described by a Castell–Amis equation. The interactions with ethanol molecular and ions of (acetamide+KSCN) ionic liquid were discussed by FTIR spectra.

Densities, viscosities, and excess properties of binary mixtures of two imidazolide anion functionalized ionic liquids with water at T = (293.15 to 313.15) K

Densities and viscosities of binary mixtures of 8-hydrogen-1,8-diazabicyclo[5,4,0]-undec-7-enium imidazolide ([HDBU]IM) and 8-butyl-1,8-diazabicyclo[5,4,0]-undec-7-enium imidazolide ([BDBU]IM) ionic liquids (ILs) with water were measured at temperatures from T=(293.15 to 313.15)K. Excess molar volumes VE and viscosity deviations Δη of the mixtures were calculated to study the intermolecular interactions and structural factors between ILs and water. The results show that the VE values of the two mixtures are negative over the whole composition range, while the Δη values have positive deviations, indicating that the hydrogen bonding interactions between IL and water are dominant in the mixtures. Moreover, the absolute values of VE (|VE|) of {[HDBU]IM (1)+H2O (2)} system are larger than those of {[BDBU]IM (1)+H2O (2)} system at the same condition, indicating that the hydrogen bonding interactions between [HDBU]IM and water are stronger than those between [BDBU]IM and water. Both |VE| and Δη values of the mixtures decrease with the increasing temperature, resulting from the decreasing the hydrogen bonding interactions between IL and water. Other derived properties of the studied systems, such as the apparent molar volumes, partial molar volumes, excess partial molar volumes, Gibbs free energy of activation for viscous flow, and excess Gibbs free energy of activation for viscous flow were also calculated from the experimental values.

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.

Experimental Investigation of Interactions and Thermodynamic Properties of Poly(ethylene glycol) 200/400 + Dimethyl Adipate/Dimethyl Phthalate Binary Mixtures

Density ρ, viscosity η, and refractive index nD have been experimentally measured for four binary mixtures dimethyl adipate + poly(ethylene glycol) 200, dimethyl adipate + poly(ethylene glycol) 400, dimethyl phthalate + poly(ethylene glycol) 200, and dimethyl phthalate + poly(ethylene glycol) 400 in the temperature range T = (288.15 to 323.15) K with a temperature step of 5 K and at atmospheric pressure. Excess molar volumes VE, viscosity deviations Δη, and deviations of refractive index ΔnD were calculated from experimental data and fitted using Redlich–Kister polynomial. Fourier-transform infrared analysis of binary mixtures and corresponding pure components was performed at 298.15 K in order to gain insight into the molecular structure of mixtures and possible intra- and intermolecular interactions. Performed IR analysis confirms an absence of intermolecular interactions between unlike compounds. Consequently, the nonideal behavior of mixtures is contributed to geometrical packing or dispersion forces ...

Properties of pure 1,1,3,3-tetramethylguanidine imidazole ionic liquid and its binary mixtures with alcohols at T = (293.15 to 313.15) K

Densities and viscosities of the pure ionic liquid 1,1,3,3-tetramethylguanidine imidazole ([TMG]IM) and its binary mixtures with methanol, ethanol, 1-propanol, and 1-butanol were measured at temperatures from T=(293.15 to 313.15)K. The thermal expansion coefficient, molecular volume, standard entropy, and lattice energy of [TMG]IM were obtained from the experimental density value. The temperature dependence of the viscosity of [TMG]IM was fitted to the fluidity equation. Excess molar volumes VE and viscosity deviations Δη of the binary mixtures were calculated and fitted to the Redlich–Kister equation with satisfactory results. The result shows that the VE values of the binary mixtures are negative over the whole composition range, while Δη values have an S-shape deviation. Temperature has little effect on the VE of the systems, but it has significant effect on the Δη. Furthermore, the absolute values of VE for {[TMG]IM (1)+alcohol (2)} systems at the same temperature decrease with increasing carbon alkyl chain of the primary alcohol. Other derived properties, such as the apparent molar volumes, partial molar volumes, excess partial molar volumes, Gibbs free energy of activation for viscous flow, and excess Gibbs free energy of activation for viscous flow of the above-mentioned systems were also calculated.

Densities, Viscosities, and Refractive Indices of the Ternary Mixture Dimethyladipate + 2-Butanone + 1-Butanol at T = (288.15 to 323.15) K

Excess molar volumes VE, refractive index deviations ΔnD, and viscosity deviations Δη of the ternary dimethyladipate + 2-butanone + 1-butanol and binary 2-butanone + 1-butanol systems are determined from the measured densities ρ, refractive indices nD, and viscosities η. Viscosities and viscosity deviations of the binary dimethyladipate + 2-butanone system are also presented. Measurements are carried out at eight temperatures from (288.15 to 323.15) K and at an ambient pressure of 0.1 MPa. Instruments from Anton Paar were utilized: a digital vibrating tube densimeter type DMA 5000, RXA 156 refractometer, and SVM 3000/G2 digital Stabinger viscometer. Excess properties of the binary system were fitted to the Redlich–Kister polynomial equation, whereas for the ternary system, the Nagata–Tamura equation was applied. To try to comprehend the nature of the interactions between compounds that cause nonideal behavior in mixtures, FT-IR spectra of the binary constituents were collected at T = 298.15 K. VE data of ...

Density and viscometric study of binary liquid mixtures of morpholine with some aromatic hydrocarbons at temperatures 303.15, 308.15 and 313.15 K

The experimental data of densities and viscosities of the binary mixtures of morpholine with benzene, toluene, m-xylene and mesitylene have been reported over the whole composition range at (303.15 to 313.15)K at normal atmospheric pressure. Experimental data on density and viscosity have been used to derive excess properties like excess molar volumes VE, viscosity deviations (Δη) and Gibbs energy of activation for viscous flow (GE) as a function of composition. The experimental viscosity data have been correlated with the two body empirical equations like Grunberg–Nissan, Dolezalek–Schulze, Tamura–Kurata, Katti–Chaudhri and three body McAllister's equation. Interaction parameters D12, G12, T12, and Wvis/RT have been calculated. The experimental determined values of VE, Δη and GE were fitted to the Redlich–Kister-type polynomial equation. The variation of these properties with composition and temperature of the binary mixtures are discussed in terms of intermolecular interactions between unlike molecules.

Physicochemical Properties for the Binary Systems of Ionic Liquids [Cnmim]Cl + N,N-Dimethylformamide

Density ρ, refractive index nD, and viscosity η for ionic liquids [Cnmim]Cl (Cnmim = 1-alkyl-3-methylimidazolium; n = 2, 4, 6, 8 for ethyl, butyl, hetyl, and octyl) + N,N-dimethylformamide (DMF) binary systems have been investigated at atmospheric pressure from 288.15 K to 318.15 K. The molar excess Gibbs energy ΔG*E, volumetric properties including excess molar volume VE, and apparent molar volume Vφ,i have been calculated from the experimental data. Furthermore, the refractive index and viscosity deviations (ΔnD, Δη) from the ideal behavior have been obtained and well fitted to the Redlich–Kister equation. Our results show that DMF can effectively adjust the physicochemical properties of 1-alkyl-3-methylimidazolium ionic liquids.

Volumetric properties of piperidine + 1-alkanol binary liquid mixtures experimental results and application of Prigogine–Flory–Patterson theory

Densities of binary liquid mixtures of piperidine with methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol and1-octanol have been measured at 293.15, 298.15, 308.15 and 313.15K and at atmospheric pressure, over the entire range of composition, with a vibrating u-tube densimeter. Density data were used to calculate the excess molar volumes VE. All the mixtures exhibit large and negative VE value over the whole mole fraction range indicating strong interactions between unlike molecules. These interactions increase with increasing alkanol chain length and are far stronger for piperidine+methanol system. Temperature effect on VE is insignificant. Experimental VE values were fitted with the Redlich–Kister equation. Partial molar volumes at infinite dilution were also determined. Finally, the applicability of the Prigogine–Flory–Patterson theory was tested and discussed.

Thermophysical and Spectroscopic Studies of Pure 1-Butyl-3-methylimidazolium Tetrafluoroborate and Its Aqueous Mixtures

Intermolecular interactions in the aqueous mixtures of the room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), have been studied. The thermophysical properties: density ρ, speed of sound u, specific conductivity κ and refractive index nD have been measured over the whole composition range at different temperatures (293.15–323.15 K) and are discussed. The results from thermophysical measurements are explained with the help of spectroscopy. In order to interpret the nature of molecular interactions occurring between [BMIM][BF4] and water molecules, as well as to identify the moieties in which interactions are taking place, 1H, 13C NMR and FT-IR spectra of the solutions have been studied. Excess molar volume VE, excess molar isentropic compressibility \( K_{S}^{\text{E}} \), partial molar excess volume \( V_{i}^{\text{E}} \), partial molar excess isentropic compressibility \( K_{S,i}^{\text{E}} \), deviation in specific conductivity ∆κ, and deviation in refractive index ∆R have also been determined and analyzed to have a better understanding of the interactions taking place between the different components. Additionally, the excess ultrasonic speed uE and excess isentropic compressibility \( k_{S}^{\text{E}} \), in terms of volume fractions, have been calculated and analyzed. It has been observed that temperature has a significant effect on the thermophysical properties of the studied system. Spectroscopic measurements confirm the disruption of ion-pair interactions of [BMIM][BF4] and hydrogen-bonded network of water in the aqueous mixture of [BMIM][BF4].

Refractive Indices Measurement and Correlation for Selected Binary Systems of Various Polarities at 25 °C

New refractive indices at 25 °C were measured and are reported here for 19 binary mixtures of pentan-3-one+1,2-dichloroethane, +1,3-dichloropropane, +1,4-dichlorobutane, +trichloromethane, +1,1,1-trichloroethane, +1,1,2,2-tetrachloroethane; cyclopentanone+1-chlorobutane, +1,1,2,2-tetrachloroethane; cyclohexanone+1,1,2,2-tetrachloroethane; 5-chloro-2-pentanone+n-hexane, +toluene, +ethylbenzene; nitromethane+trichloromethane; and nitromethane or nitroethane, +1,2-dichloroethane, +1,3-dichloropropane, +1,4-dichlorobutane. The experimental refractive index deviations from linear mixing behavior have been evaluated and correlated consistently with the 3-parameter Redlich–Kister equation with good results. The molar refraction was also examined for the systems including pentan-3-one, cyclopentanone, cyclohexanone and 5-chloro-2-pentanone for which densities and excess molar volumes are available from previous works. Different theoretical (n, ρ) mixing rules were tested for these systems. The excess Gibbs energy G E and excess enthalpy H E values were considered together with the excess molar volumes V E, excess refractive indexes $$ n_{\text{D}}^{\text{E}} $$ , molar refraction R and excess molar refractions R E on mixing in the discussion of the influence of the alkyl chain length or of the nature of the second component in the mixture in terms of molecular interactions.