Values Of Excess Molar Volume Research Articles

Densities and volumetric properties of pyridine with 2-dimethylaminoethanol and 2-diethylaminoethanol at temperatures from 293.15 to 313.15 K

ABSTRACT The densities ρ of binary mixtures of 2-(dimethylamino)ethanol and 2-diethylaminoethanol with pyridine were measured over the entire concentration range at 293.15, 303.15 and 313.15 K. The values of excess molar volume, V m E , apparent molar volume, V φ , DMAE and V φ , DEAE ; partial molar volumes, V ˉ m , 1 and V ˉ m , 2 , excess partial molar volumes, V ˉ m , 1 E and V ˉ m , 2 E have been computed using the experimental observations. The partial molar volumes, V ˉ m , 1 o and V ˉ m , 2 o ; excess partial molar volumes, V ˉ m , 1 oE and V ˉ m , 2 oE at infinite dilution were also calculated. The variations of these parameters as a function of composition and temperature are discussed in terms of the intermolecular interactions in the studied binary mixtures.

Thermodynamic properties of {glycerol (1) + tert-butanol (2)} mixtures at temperatures from 278 K to 323 K and pressures up to 100 MPa

In the present study the densities at atmospheric pressure and the compression coefficients of a binary liquid mixture {glycerol (1) + tert-butanol (2)} were measured within the temperature range from 278.15 K to 323.15 K (278.15, 288.15, 288.15, 308.15 and 323.15) and pressures up to 100 MPa (10, 25, 50, 75 and 100). Due to the limited solubility of tert-butanol in glycerol and the transition of the mixture to the solid phase the measurements at 278.15 K and 100 MPa were carried out up tox2 = 0.45 (x2 is the mole fraction of tert–butanol). The excess molar volumes, molar isothermal compression, molar isobaric thermal expansion, isochoric coefficient of thermal pressure mixtures, as well as the partial molar volumes of the mixture components, including their limit values, were calculated. The excess molar volume values at 323.15 K (the only temperature at which the compression was measured over the entire composition range) were found to be negative. The partial molar volume of glycerol (GL) at 323.15 K was characterized by the presence of a baric inversion region. The limiting partial molar volume of GL was shown to decrease in its own environment as the pressure rose and to increase in the TBA environment. The molar isothermal compression of the mixture varied depending on the composition without extremes, and the partial molar isothermal compression of GL had negative values. The molar isobaric thermal expansion of the mixture in the area of small tert-butanol (TBA) additives changed slightly at low temperatures and pressures and the increase in both the pressure and the temperature led to dispersion of their concentration dependences. The isochoric coefficient of thermal pressure decreased with an increase in x2, forming a small plateau at small TBA additions. The results obtained were discussed from the perspective of solute–solvent and solute–solute interactions.

Excess Volume for Acetylene Tetrachloride with Pyridine, Methoxybenzene, 2-Butanone and 1,4-Dioxane at 298.15K

A dilatometric measurement have been carried out for getting excess volumes, VE, in the liquid state for  mixtures of acetylene tetrachloride (CHCl2CHCl2), with pyridine (C5H5N), methoxybenzene (C6H5O  CH3), 2-butanone (CH3COC2H5) and 1,4-dioxane (1,4-C4H8O2) at 298.15K and under atmospheric  pressure. The values of excess molar volume, VE, are negative in sign for all the mixtures over whole  composition range. Obtained data have been fitted by Redlich-Kister type polynomial smoothing  equation. The results are discussed in the light of molecular interactions occurred between components in  the liquid state. 

Density, Viscosity, and Refractive Index of a Choline Chloride + d-(−)-Fructose Deep Eutectic Solvent + Water Mixture at Different Temperatures: An Experimental Study and Thermodynamic Modeling

In the present study, first, the deep eutectic solvent (DES) of choline chloride + d-(−)-fructose was prepared using the heating method. Then, its physical properties including density, viscosity, and refractive index were experimentally measured at temperatures in the range of 283.15–343.15 K and a full composition range of DES at atmospheric pressure (83.09 kPa). The values of these three properties decrease with an increase in temperature, while the mole fraction has a nonlinear effect on these properties. For the density and refractive index, an increase in the mole fraction of DES to 0.3 causes a sharp increase in these physical properties, while from 0.3 to 1, this increase occurs slowly. For viscosity, increasing the mole fraction of DES has little effect at first, but at high mole fractions of DES, a sharp increase in viscosity occurs. In addition, the sharp change in the viscosity of DES depends on the temperature so that at low temperatures, this phenomenon occurs faster. So, adding water to DES will tailor the viscosity of the mixture to facilitate its applications. A polynomial equation was used to describe the density and refractive index as a function of temperature and mole fraction. Experimental viscosity was fitted to the Vogel–Tammann–Fulcher (VTF) equation. Using the measured data, in sequence, the values of excess molar volume (VmEx), viscosity deviation (Δη), and refractive index deviation (ΔnD) were calculated. The Redlich–Kister polynomial equation, finally, was used to correlate the values of VmEx, Δη, and ΔnD.

Binary mixtures of {1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][triflate]) + alcohols} at high-pressure: A thermodynamic, spectroscopic and correlation approach

The density of binary mixtures of {1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][triflate]) + alcohols} has been measured at temperatures from (298.15 to 308.15) K and pressures from (0.1 to 40) MPa. The effect of temperature and pressure on density and calculated excess molar volumes, partial molar volumes, apparent molar volumes and partial molar volumes at infinite dilution was analyzed. The experimental density results were correlated by using the Tait-Tammann equation to deduce isothermal compressibility and isobaric expansivity. In addition to the thermodynamic study, some spectroscopic properties (H-NMR, C-NMR and FT-IR) were presented to elucidate some possible molecular interactions between the components under study. Furthermore, the Extended Real Associated Solution Model (ERAS Model) was applied to correlate the values of excess molar volume.

Optimization of Thermo-Physical Properties For The Binary System Of Acetone–Water At 303.15-318.15 K By Response Surface Quadratic Model

Thermo bodily residences of binary liquid combos are very beneficial in biotechnology, pharmaceutical, chemical and petroleum refining industries for improved favoured products from diverse raw materials. The physical property data on mixed solvents are important for the theoretical and applied areas of research and are frequently used in many chemical and industrial processes such as design of new process and process equipment (fluid flow, mass transfer or heat transfer calculation) and designing of bioreactor/fermenter. The objective of the current paper is to determine the density, viscosity, ultrasonic velocity, refractive index and surface tension of acetone (1) + water (2) at temperatures of 303.15K to 318.15K for the complete composition degrees and atmospheric pressure. These experimental values were used to calculate the respective excess homes in conjunction with a few acoustic properties. The experimental facts and excess residences have been used to calculate the interacting coefficients and well known deviations from different existing models. Also the new model equations have been evolved with the aid of the use of Design Expert application for density, viscosity, ultrasonic velocity, refractive indices and surface tension. Experimental consequences have been analysed on the premise of molecular interactions among element molecules with the assistance of FT-IR spectrum. Acetone-water binary structures of the prevailing observer have positive values of excess molar volumes and deviations in isentropic compressibility over whole composition range and at all temperatures which suggests sturdy interactions among the components of binary mixtures. Thermodynamic observations of acetone and water mixtures were made. Negative viscosity deviation of acetone-water combinations suggests robust dipole-dipole interactions within the device. Fourier remodel infrared spectroscopy also indicates the sturdy interaction made at 3589 cm-1 and based on the response surface method outcomes, more interplay takes area at zero. Five and zero six moles of acetone and water combination and the consequences are conformed with reference to the R2 cost (0.89). Excess molar extent and isentropic compressibility were decided and kinds of interactions have been discussed primarily based on the derived properties.

Volumetric properties of binary mixtures of glycerol + alkanols (C1-C4): Experimental study and application of the Peng–Robinson–Stryjek–Vera equation of state

Volumetric properties for binary mixtures of (glycerol + methanol, or + ethanol, or + 1-propanol, or + 2-propanol, or + 1-butanol) have been determined as a function of composition using experimental data of density at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K and p = 92.3 kPa. The density measurements have been determined by using a vibrating-tube densimeter. The density values enabled the determination of the thermal expansion coefficient and the excess molar volume. The values of excess molar volume were correlated by a Redlich-Kister polynomial and by the Peng-Robinson-Stryjek-Vera equation of state (PRSV EOS). These values were also used in the estimation of the partial molar volumes, excess partial molar volumes and apparent molar volumes. Three different methods were used to determine the partial molar volumes at infinite dilution. For all studied systems, the values of excess molar volumes were negative over the entire composition range and suggest predominance of chemical and structural effects.

VOLUMETRIC AND VISCOMETRIC DETERMINATION OF BINARY LIQUID MIXTURES OF 2-ETHOXYETHANOL AND AMYL ACETATE AT TEMPERATURES OF (298.15 AND 303.15) K

Densities and viscosities have been determined at temperatures of (298.15 and 303.15) K for binary liquid mixtures of 2-ethoxyethanol with amyl acetate over the entire range of solvent composition. From the experimentally determined values, excess molar volume, VE, excess viscosity, ηE and excess Gibbs free energy of activation of viscous flow, G*E have been calculated. These calculated excess thermodynamic functions were fitted to Redlich-Kister polynomial equation to obtain the fitting coefficients and standard deviations. The values of excess molar volume, VE were negative and that of the excess viscosities, ηE were found to be positive, while excess Gibbs free energy of activation of viscous flow, ΔG*E were negative over the whole range of solvent composition for the binary systems at the studied temperatures. The behavior of these excess functions with composition of the mixtures have been discussed in respect of molecular interactions between the components of liquid systems. The mixture viscosities were correlated using empirical relations like Grunberg-Nissan, Frenkel, Hind, Wijk and Kendall-Monroe model equations. Comparison of these interaction parameters have been engaged to explain the intermolecular interactions between the alkoxy alcohol and the ester.

Volumetric and compressibility studies on aqueous mixtures of deep eutectic solvents based on choline chloride and carboxylic acids at different temperatures: Experimental, theoretical and computational approach

Deep eutectic solvents (DESs) constitute a new class of green solvents, the studies on which are going at a fast pace. The binary mixtures of DESs with water are attracting a great deal of interest for various industrial applications owing to their unique properties not exhibited by the neat components. Therefore, thermodynamic properties of DESs-water mixtures should be explored to better understand the prevailing intermolecular interactions for enhancing the application arena of such binary mixtures. Herein, the density (ρ) and speed of sound (u) of binary mixtures of DESs (choline chloride: acetic acid; 1: 2; and choline chloride: L-(+)-lactic acid; 1: 2) with water has been measured over whole composition range at different temperatures (T = 298.15 to 313.15 K) and atmospheric pressure. The values of various thermodynamic parameters have been derived and discussed in terms of the varying extent of intermolecular interactions governed by the components of DESs. The negative values of excess molar volumes (VmE) are ascribed to the stronger hydrogen bond interactions and efficient molecular packing in the binary mixtures over repulsive interactions. The VmE values have been analyzed using Prigogine-Flory-Patterson (PFP) theory, which satisfactorily explained the volumetric behaviour of the binary mixtures. Density functional theory (DFT) calculations have been made to support the variation in VmE and the underlying interactions prevailing between the components. Further, isentropic compressibility (ks) and excess isentropic compressibility (ksE) have been evaluated from the speed of sound data. It is expected that such studies will be beneficial from the academic as well as industrial point of view considering the increasing utilization of DESs for various applications.

Thermodynamic and spectroscopic properties of binary {1-Ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) + alcohols} mixtures at T = (298.15 to 308.15) K and p = (0.1 to 40) MPa: Experimental study and modelling

In this study, densities for binary mixtures of {1-Ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) + alcohols} have been measured at temperatures from T = (298.15 to 308.15) K and pressures from p = (0.1 to 40) MPa. These results have been used to calculate the excess molar volumes, partial molar volumes, apparent molar volumes and partial molar volumes at infinite dilution. The experimental density data were correlated by using the Tait-Tammann equation to obtain isothermal compressibility and isobaric expansion. Moreover, the values of excess molar volume were used to test the applicability of the Extended Real Associated Solution Model (ERAS Model). In order to elucidate possible structural phenomena, spectroscopic properties (H-NMR, C-NMR and FT-IR) were combined with the thermodynamic results trying to understand the molecular interactions among the unlike components present in the studied systems.

Binary mixtures of 2-methyl cyclohexanone with various functional groups (Thermodynamic and acoustic properties)

In the binary mixtures of 2-methylcyclohexanone with various functional groups (3-methyl aniline, 4-methoxy benzyl alcohol, 4-hydroxy benzoic acid and isobutyric acid) the densities, and speeds of sound including those of pure liquids, were measured over the entire composition range at different temperatures (303.15, 308.15 and 313.15) K and atmospheric pressure 0.1 MPa. Using these experimentally determined data, the excess values of molar volume, isentropic compressibility of the studied binary mixtures and partial molar volumes, partial molar isentropic compressibilities of these pure components at infinite dilution were calculated. The results are discussed both in terms of free volume and proton donor–acceptor interactions between the unlike molecules.

Density, viscosity and ultrasonic velocity study: Binary mixtures of 3-bromoanisole and methanol at different temperatures

The values of density, viscosity and ultrasonic velocity at three different temperatures (303.15, 313.15 and 323.15 K) of the prepared binary mixture solutions with different compositions of 3-bromoanisole (3-BA) and methanol (MeOH) are experimentally determined and presented. Moreover, the excess values of molar volume, viscosity and ultrasonic velocity have been determined. These determined excess properties are fitted to the Redlich-Kister equation. Deviations from the linearity are found in the experimentally measured parameters with variation in mixture composition and are interpreted in terms of molecular interaction. Moreover, thermodynamic properties are evaluated to understand the dynamic behavior of the system.

Thermodynamic study of binary mixture of 2-butanol + monoethanolamine at different temperatures; PC-SAFT and ERAS models

In this paper, to study the possible intermolecular interactions in the binary mixtures 2-butanol with monoethanolamine, values of density were measured at temperatures 293.15 to 323.15 K and atmospheric pressure (P = 0.0815 MPa). From experimental densities, values of excess molar volume, VmE thermal expansion coefficient, α excess thermal expansion coefficient, αE and isothermal coefficient of excess molar enthalpy, (∂HmE/∂P)T, x were calculated. Excess molar volume is negative for the mentioned binary mixture over the whole range of concentration and becomes more negative with the increase in the temperature. ERAS model with the six adjustable parameters was used to correlate the excess molar volumes at different temperatures. Agreement between experimental data and predicted values through this model was reasonable at all temperatures. The maximum standard deviation for the mentioned binary mixture was 1%. Also, PC-SAFT model with one adjustable parameter and different schemes (2B, 3B, 4C) was applied to correlate the binary densities. A comparison among the performance of three approaches shows that the scheme 3B-2B at 293.15 K with the average absolute deviation (AAD) 1.63% has the best agreement with experimental data. When the PC-SAFT model with the prediction ability (p = 0) was implemented, the minimum of AAD increased to 4.66%.

Thermophysical properties of ternary liquid mixture of diisopropyl ether (1) + ethanol (2) + n-heptane (3): Measurement and correlation

Densities (ρ), speeds of sound (u) and refractive indices (n) of system containing diisopropyl ether, ethanol and n-heptane were measured at temperature 298.15 K to 318.15 K and at pressure 0.1 MPa. The values of excess molar volume (VmE), deviation in speed of sound (Δu), deviation in refractive index (Δn), excess isentropic compressibility (κsE), excess intermolecular free length (LfE), and excess available volume (VaE) of the system were calculated using measured data of densities, speeds of sound and refractive indices. The VmE values were fitted to the Singh, Cibulka and Nagata equations. Several analytical models like Rastogi model, Kohler model, Tsao-Smith model, Radojkovic model and Jacob-Fitzner model were applied to estimate VmE values. The values of Δu, κsE, LfE, VaE and Δn were also fitted to the Singh equation. Different correlations and models were applied for estimation of speed of sound and refractive index values.

Volumetric Behaviour of Binary Mixtures of Diethyl Ether + (C1 – C4) Alkoxyethanols at Different Temperatures

Densities of pure liquids and binary mixtures of diethyl ether (DEE) with 2-alkoxyethanols (2- methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol) have been determined over the entire range of solvent compositions at (293.15, 298.15 and 303.15) K. Excess molar volumes (VM E ) have been calculated from the density data and were fitted into the Redlich-Kister type polynomial equation to obtain the fitting parameters Ai. The values of excess molar volumes, vm E were negative in regions of low diethyl ether (DEE) composition and small positive values were observed in regions of high diethyl ether (DEE) compositions in all the systems studied. VM E values were also found to decrease with increase in temperature and increase in chain length of the 2-alkoxyethanols. The above trends were attributed to the combined effects of disruption and formation of hydrogen bonds between like molecules of 2- alkoxyethanols and unlike molecules of diethyl ether (DEE), respectively.

Theoretical and experimental study of 1-butyl-3-methylimidazolium nitrate with 1-pentanol, 1-hexanol and 1-heptanol: COSMO-RS and structure factor

In this paper, some thermodynamic and structural properties of the binary mixtures containing [Bmim][NO3] and 1-alkanols (1-pentanol, 1-hexanol, and 1-heptanol) was studied using theoretical and experimental methods. Density and viscosity for the mixtures above were measured at temperatures (293.15 K to 323.15 K), and values of excess molar volumes, VmE and viscosity deviations Δη were calculated. For binary mixtures of [Bmim][NO3] with 1-octanol, 1-nonanol, and 1-decanol a miscibility gap was observed in the mole fraction regions between 0.1 and 0.9. Findings indicate that strong interactions occur in the binary solutions containing short-range 1-alkanol, and increasing the length of the alcohol causes the weakening of the intermolecular interactions. To obtain more information about the molecular structure of aforesaid mixtures, the conductor-like screening model for real solutions (COSMO-RS) method was applied, and the D parameter, the concentration-concentration structure factor, Scc(0), and the chemical short-range order parameter α′, were calculated for the binary mixtures.

A study of non-ideal mixtures of ethanol and the (1 choline chloride +2 ethylene glycol) deep eutectic solvent for their volumetric behaviour

In the present study, the volumetric behaviour of mixtures of (Ethaline + ethanol) was investigated for the first time. Ethaline, which is the mixture of choline chloride and ethylene glycol at a molar ratio of 1:2, is among the most well-known Deep Eutectic Solvents (DESs). Because of its rather low viscosities as compared to many DESs, it has gained the interest of researchers for use in different applications. In this work, isobaric densities of the mixtures of Ethaline + ethanol were measured and presented over the entire mixture concentration range within the temperature range of (293.15–333.15) K. Using the measured data, excess molar volumes of the mixtures were calculated and analysed. The negative values of excess molar volumes suggested the stronger interactions of hydrogen bonds in the mixture with respect to the pure states of its constituents. Additionally, partial molar volumes and excess partial molar volumes, as well as the corresponding values at infinite dilution, were calculated and analysed. It was found that both Ethaline and ethanol have the tendency to be solvated by the mutual unlike-molecule in the mixture, and this tendency is stronger for Ethaline. It is also suggested that within the established hydrogen bond networks in the mixture, the Ethaline pseudo-molecules are probably located at central positions, being mostly surrounded by ethanol molecules.

Excess Properties for the Binary System Diethylene Glycol Dibutyl Ether � Ethanol

This paper reports propertiesdata at 20, 25 and 30 0C and 1 atmosphere pressure for diethylene glycol dibutyl ether - ethanol system depending on concentration. The experimental values of density and viscosities of pure components and mixtures were correlated with temperature. The excess properties were determined from experimental data of densities and viscosities. These excess values were correlated to Hwang and Redlich-Kister equations. The value of excess molar volume for equimolar solution was compared with the values calculated from the Flory and Prigogine-Flory-Patterson theories.

Binary mixtures of 2-methylcyclohexanone with various functional groups (m-cresol, p-cresol and o-chlorophenol)

The densities , speeds of sound and viscosities including those of pure liquids, were measured for the binary mixtures of 2-methylcyclohexanone with various functional groups (m-cresol, p-cresol, and o-chlorophenol) over the entire composition range at different temperatures (303.15 - 318.15) K and atmospheric pressure 0.1MPa. Using this experimentally determined data, the values of excess molar volume, excess isentropic compressibility, partial molar volumes, partial molar isentropic compressibilities and deviation in viscosity of these components at infinite dilution were calculated. The results are discussed both in terms of acid-base interactions and the formation of π-π complexes between the, unlike molecules. Excess molar volume values have been analyzed with Prigogine- Flory-Patterson. Curves of excess molar volume ( V E ) with mole fraction for the binary mixtures of 2-methylcyclohexanone with p-cresol (■); m-cresol (▲) and (●)o-chlorophenol and at 303.15 K and (—) calculated with PFP theory using Parameters.

Densities and thermal expansions of (water + tetrahydrofuran) mixtures within the temperature range from (274.15 to 333.15) K at atmospheric pressure

The mixture {water (1) + tetrahydrofuran (2)} densities have been measured over the whole composition range at temperatures between (274.15 and 333.15 K) and atmospheric pressure using the vibration type densimeter. Values of excess molar volume and molar isobaric thermal expansion of the mixture as well as apparent/partial molar volumes (down at infinite dilution) for water and tetrahydrofuran (THF) have been calculated. It is shown that the formation of the water + THF mixture occurs with decreasing its volume under all the temperatures. Concentration dependences of partial molar volumes of water and THF are characterized by the presence of extreme regions. Standard (limiting) partial molar volumes of water and THF increase as the temperature is rising. Increase in both temperature and THF content influence on the value of molar isobaric expansion of the mixture in the same way.