Molar Volumes Of Binary Mixtures Research Articles

Experimental and computational insight in molecular interactions of imidazolium based deep eutectic solvent with selected alcohols (C1 and C2)

The experimental thermophysical properties (densities (ρ), speed of sound (u) and refractive (nD) indices) of binary mixtures containing 1:3 mol ratio of [1-butyl-3-dimethylimidazolium chloride to ethylene glycol] [BMIM]Cl: EG], deep eutectic solvent (DES), with selected alcohols (methanol and ethanol) were measured. The measurements of the binary mixtures and the pure solvents were conducted at temperatures ranging from (293.15 to 313.15) K in the interval of 5 K and at ambient pressure using an Anton Paar densitometer. Thermodynamic properties such as excess molar volumes (VmE), intermolecular free length (Lf), isentropic compressibilities (ks), deviation in isentropic compressibilities (Δks) and deviation in refractive indices (ΔnD) were computed from the measured data of physical properties. These excess thermodynamic properties are utilized to investigate the intermolecular interactions occurring between imidazolium DES and methanol or ethanol. Geometry optimization calculations were undertaken using Density Functional Theory (DFT) to model the structure of DES with a 1:1 mol ratio employing the B3LYP-D3 functional and a basis set of 6–31G++**. The DFT results revealed that the interaction energies within the DES in the presence of solvent favoured the formation of the complex. Furthermore, interrogation of the optimized structures at molecular level showed that the interactions were mediated by the electrostatic ionic bonding with the co-solvent playing a significant role in solubility. The excess molar volumes of binary mixtures were correlated using the Lorentz-Lorenz equation, and the densities and refractive indices were predicted using the Lorentz-Lorenz equation. The interaction energies and electrostatic interactions between the different solvents were predicted using quantum mechanics. The experimental data was found to be in good agreement with the theoretical data for the measured properties as well as the computational predictions of the stability of the systems.

Densities and Excess Molar Volumes of Binary Mixtures Constituted by 2,5-Dimethylfuran + Octane, Nonane, Decane, or Dodecane from 293.15 to 353.15 K

Densities and Excess Molar Volumes of Binary Mixtures Constituted by 2,5-Dimethylfuran + Octane, Nonane, Decane, or Dodecane from 293.15 to 353.15 K

Flash point and excess molar volumes of binary mixtures containing d-limonene and alcohol compounds from propanol to dodecanol

D-limonene is a monoterpene naturally found in citrus peels, especially lemons and oranges, and is responsible for their strong odour. D-Limonene has specific properties that enable its use in various industrial segments such as foods, perfumes, beverages, cosmetics, pharmaceuticals, detergents, soaps, insecticides, disinfectants, fine chemicals, as a biodegradable solvent, and so on. Among the ways in which limonene can be used, the mixture of d-limonene with alcohol compounds has a great application potential, since alcoholic extracts of citrus essential oils have high solubility in aqueous solutions, reducing the occurrence of oxidation reactions as well as increasing the aromatic resistance of the mixture. However, studies on the thermodynamic properties of alcohol compounds and terpenes mixtures are still scarce. Thus, in this study, the density (ρ) and excess molar volume data (VmE) of seven binary mixtures of d-limonene with 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol and 1-dodecanol were determined at 298.15 K and throughout the whole mole fraction range. The flash point (FP) of these same mixtures was also determined from the 0.0 to 1.0 mol fraction range. The FP experimental values were compared to FP values calculated using Liaw’s approach and the activity coefficient models UNIQUAC, NRTL, UNIFAC and Ideal, with an average deviation of (0.55, 0.57, 1.43 and 4.02) K, respectively. The interaction parameters of the models UNIQUAC and NRTL were thus shown to be well adjusted and provide a better description of the FP behaviour than the ideal and UNIFAC models, as expected. The excess molar volumes calculated with use of density determination were all positive, indicating that the molecule interactions in the mixtures are weaker than those in the pure components causing an expansion of excess molar volume (>0). This behaviour was also corroborated by the activity coefficients calculated.

Studies on the interactional behaviour of binary liquid mixtures of tripropylene glycol monomethyl ether and butyl amines at different temperatures

In the present study densities, ρ, and speeds of sound u, have been measured for the binary mixtures of tripropylene glycol monomethyl ether with butyl amine, dibutyl amine, and tributyl amine across the entire composition range at temperatures T = (288.15, 293.15, 298.15, 303.15, 308.15) K and experimental pressure p = 0.1 MPa. Experimental densities and speeds of sound data has been used to determine excess molar volumes, isentropic compressibility, molar isentropic compressibility KS,m and its excess counterpart excess molar isentropic compressibility. Deviations in intermolecular free length and deviations in acoustic impedance have also been determined. Further we have also calculated the partial molar volumes for binary mixtures at different temperatures. The variation of these determined parameters with temperature and composition has been discussed with a view to understand molecular interactions present in the binary liquid mixtures of alkoxypropanol and butyl amines. The experimental data has also been fitted with Jouyban-Acree model.

Experimental and modeling study of diisopropyl ether and 2-alkanol; PC-SAFT model and free volume theory

In the present study, with the aim to discover the governing interactions in binary mixtures containing diisopropyl ether and short-range 2-alkanol (from 2-propanol to 2-hexanol), experimental values of density and viscosity at temperature range 293.15 K–323.15 K were reported. From these data, values of excess molar volume, partial molar volume, and viscosity deviation for mentioned systems were calculated. Findings show that strong interactions occur among unlike molecules while increasing in the carbon chain length of 2-alkanol, reinforces the interactions. Also, the perturbed-chain SAFT (PC-SAFT) equation of state was implemented to study the density and partial molar volume of binary mixtures. Combination of this model with Free Volume Theory was applied for prediction of binary viscosities. Maximum deviation in AAD for density correlation regarding PC-SAFT model was 1.21%, and for viscosity calculation was 2.19%.

Partial Molar Volumes and Spectral Studies on Binary Mixtures of p-Chloroacetophenone with Aniline and N-Alkyl Anilines

Ultrasonic velocities (u), viscosities (η) and densities (ρ) were measured for the binary mixtures of p-chloroacetophenone with aniline, N-methylaniline and N,N-dimethylaniline over the whole range of composition at different temperatures (303.15 K to 318.15 K) and at atmospheric pressure 0.1 MPa. Excess molar volume (VE), deviation in viscosity (Δη) and deviation in isentropic compressibility (Δks) have been calculated and fitted to Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. The analyzed viscosity data of binary liquid mixtures were used to test the Grunberg-Nissan, Katti-Chaudari and Hind semi-empirical equations. The FTIR spectral study supports the experimental data to explain the molecular interactions between unlike molecules. Partial molar volumes of binary mixtures were evaluated for better understanding of intermolecular interactions of the above binary mixtures.

Prediction of excess molar volumes of binary mixtures by Prigogine-Flory-Patterson (PFP) and extended real association solution (ERAS) models

In this paper, the Prigogine?Flory?Patterson (PFP) theoretical model and the extended real association solution (ERAS) model for the prediction of the excess molar volumes of 17 binary sets of alcohols (methanol, ethanol, propan-1-ol, butan-1-ol, butan-2-ol and pentan-1-ol) with benzene, chlorobenzene, acetonitrile, hexan-1-amine and n-heptane were tested at 298.15 K and atmospheric pressure. The binary sets contained 333 experimental data points for 11 different compounds. The ERAS model demonstrated better correlative characteristics for binary mixtures comparing to PFP model. The ERAS model is successfully applied on all binary systems except ethanol + benzene and propan-1-ol + benzene. PFP model gave less satisfactory results for all systems except butan-1-ol + hexan-1-amine, for which obtained results were acceptable.

The study of partial and excess molar volumes for binary mixtures of nitrobenzene and benzaldehyde with xylene isomers from T = (298.15 to 318.15) K and P = 0.087 MPa

Based on density measurements, partial and excess molar volumes for binary mixtures of nitrobenzene and benzaldehyde with three isomers of xylene have been measured. The whole range of composition and temperatures from T=(298.15 to 318.15)K at ambient pressure 0.087MPa, has been considered. The excess molar volumes were negative and decreased by increasing temperature for all mixtures which are explained based on intermolecular interactions. Excess molar volumes for solutions including nitrobenzene were absolutely larger than benzaldehyde binary mixtures. The partial and excess molar volumes for each component have been appraised and reported. The excess molar volumes have been successfully fitted to Redlich–Kister equation.

Solubility, density and excess molar volume of binary mixtures of aromatic compounds and common ionic liquids at T = 283.15 K and atmospheric pressure

In this work, the solubility of aromatic compounds (benzene, or toluene, or ethylbenzene, or o-xylene, or m-xylene, or p-xylene) in several ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, or 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, or 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, or 1-propyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, or 1-ethyl-3-methylpyridinium ethylsulfate, or 1-hexyl-3-methylimidazolium dicyanamide) was experimentally determined at T = 283.15 K and atmospheric pressure. Moreover, density of the above-mentioned mixtures was also measured over the miscible region at the same temperature. This physical property was used to calculate the corresponding excess molar volume, which was fitted to the Redlich–Kister equation.

Density and Viscosity of Ionic Liquid Binary Mixtures of 1-n-Butyl-3-methylimidazolium Tetrafluoroborate with Acetonitrile, N,N-Dimethylacetamide, Methanol, and N-Methyl-2-pyrrolidone

In this study, thermodynamic properties of the binary mixtures of ionic liquid with an organic compound, as potential solvent systems in pharmaceutical industry applications, are studied. The densities and viscosities of the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) with acetonitrile, N,N-dimethylacetamide, methanol, and N-methyl-2-pyrrolidone were measured at atmospheric pressure over the [C4mim][BF4] mole fraction range from 0.1 to 0.9 and at temperatures from 303.15 to 333.15 K at intervals of 10 K. The densities were measured using a vibrating-tube digital density meter and the viscosities were measured using a capillary viscometer. The excess molar volumes (VE) and viscosity deviations (Δη) were calculated from densities and viscosities of mixture, respectively, and fitted to the Redlich–Kister polynomial. The optimally fitted parameters are also determined and the correlation results are in satisfactory agreement with the experimental data. In addition, the excess molar volumes of binary mixtures of ionic liquid with different organic compounds are compared and discussed using the Hansen solubility parameter.

Excess molar volume of binary mixtures containing an oxygenate

Increasing fuel demand, environmental concern, and occasional oil crises brought the use of oxygenated compounds as fuel additives to improve octane/cetane rating of fuel. These oxygenates are the oxygen containing compounds such as ethers, alcohol, and esters of vegetable oils. In order to study the interactions of oxygenate with gasoline components, excess molar volumes (VmE) for 2-propanol + benzene or toluene or xylenes mixtures were reported. The VmE values, for an equimolar composition, follow the sequence: benzene > m-xylene > p-xylene > toluene > o-xylene. The excess volume data were interpreted in terms of a Graph-theoretical approach and the Prigogine–Flory–Patterson theory. While the Graph-theoretical approach yielded information about the state of aggregation of pure components as well as of the mixtures, the PFP theory correctly predicts the values as well as the sign and shape of curves for benzene containing mixtures but for other systems, predicted values were smaller for x1 < 0.4 and higher thereafter than the corresponding experimental values. Partial molar volumes, excess partial molar volumes, and apparent molar volumes of 2-propanol and aromatic hydrocarbons were also calculated from VmE data and interpreted qualitatively.

Excess Molar Volume of Binary Mixtures of Tetrachloroethylene + Acetylacetone, + Acrylonitrile, + Anisole and + Tetrahydrofuran at 303.15 K

Excess Molar Volume of Binary Mixtures of Tetrachloroethylene + Acetylacetone, + Acrylonitrile, + Anisole and + Tetrahydrofuran at 303.15 K

Density, viscosity and excess molar volume of binary mixtures of tri-n-octylamine + diluents (n-heptane, n-octane, n-nonane, and n-decane) at various temperatures

Densities (ρ) and viscosities (η) for binary mixtures of tri-n-octylamine (TOA)+n-heptane, TOA+n-octane, TOA+n-nonane, and TOA+n-decane are determined at T (283.15, 293.15, and 303.15)K and atmospheric pressure. The excess molar volume is calculated from the density data and is correlated by a Redlich–Kister type equation. The excess molar volume is negative for all the four systems. The results show that the volume accommodation effect is predominant in these systems. The Grunberg & Nissan equation and Fang & He equation for binary mixtures are used to correlate the experimental viscosity data. The Fang & He equation gives an average absolute deviation (AAD%) of 0.8% for TOA with alkane mixtures, better than that of 3.8% given by the Grunberg & Nissan equation.

Volumetric and viscometric properties observed for the mixtures of DMF (N,N-dimethyl formamide) and other alcohols (butanol and 1-propanol)

In this study, we have observed binary mixtures properties for (a) N,N-dimethyl formamide (DMF) + butanol, and (b) DMF + 1-propanol at different temperatures. These are useful solvents because of their various types of applications. Densities, molar volume, excess molar volume, viscosity, and excess viscosity of two binary systems DMF + 1-propanol, and DMF + butanol have been measured at five different temperatures ranging from 303.15 to 323.15 K, respectively. The volumetric and viscometric behaviours of DMF + alcohols are shown as a function of mole fraction of DMF. The molar volume of binary mixtures has been changed according to the chain length of alcohols. For DMF + 1-propanol system, the excess viscosities are found to be negative throughout the entire range of concentration.

Vapor–Liquid Equilibrium, Excess Molar Enthalpies, and Excess Molar Volumes of Binary Mixtures Containing 2-Ethoxy-2-methylpropane or 2-Ethoxy-2-methylbutane and Acetonitrile or Propanenitrile

Vapor–liquid equilibrium (VLE), excess molar enthalpies (HE), and excess molar volumes (VE) provide complementary data for thermodynamic models. In this work, new data of binary mixtures of acetonitrile (ACN) or propanenitrile (PPN) with 2-ethoxy-2-methylpropane (ETBE) or 2-ethoxy-2-methylbutane (TAEE) are reported. Isothermal VLE data were measured by using a circulation still at 333 K for ETBE + ACN, at 343 K for TAEE + ACN, and at 363 K for TAEE + PPN. HE were measured by using a SETARAM C80 calorimeter equipped with a flow mixing cell at 298 K for all four binary systems. VE were measured by using an Anton Paar DMA 512P densimeter at 298 K for all four binary systems. HE data and measured VLE data, or literature VLE data for the binary system of ETBE and PPN, were used for the optimization of Wilson model parameters by using VLEFIT software. Redlich–Kister equation parameters were separately regressed for the VE data.

Density and surface tension of binary mixtures of 1-ethyl-3-methylimdazolium nitrate with alcohols

Abstract New experimental data of densities and surface tensions are presented for the binary mixtures of the ionic liquid 1-ethyl-3-methyl imidazolium nitrate ([EMIM]NO 3 ) with methanol and ethanol. Measurements were performed at 298.15 K and atmospheric pressure, covering the whole composition range. Excess molar volumes V E and the surface tension deviations δγ have been determined. For the excess molar volumes of binary mixture, there is a region of negative V E at low IL mole fraction, passing through a minimum and then V E increases and becomes positive, showing maximum at higher IL mole fraction. It is shown that the surface tension deviations δγ of [EMIM]NO 3 + methanol system are positive but those of [EMIM]NO 3 + ethanol system are negative over the entire mole fraction range.

Excess molar volumes of binary mixtures of aliphatic alcohols (C 1–C 5) with Nitromethane over the temperature range 293.15 to 308.15 K: Application of the ERAS model and cubic EOS

Densities were measured for the binary mixtures of methanol, ethanol, 1-propanol, 1-butanol with nitromethane at temperatures (293.15, 298.15, 303.15 and 308.15) K and for 1-pentanol with nitromethane at temperatures (303.15 and 308.15) K and atmospheric pressure. Densities were determined using a vibrating-tube densimeter. Excess molar volumes as a function of mole fraction were derived, and the computed results were fitted to the Redlich–Kister equation. Excess molar volumes of mixtures studied were consistently described by the ERAS model. Also The Peng–Robinson–Stryjek–Vera (PRSV) equation of state was applied, in combination with simple mixing rules.

Ultrasonic velocities, densities, and excess molar volumes of binary mixtures of N, N-dimethyl formamide with methyl acrylate, or ethyl acrylate, or butyl acrylate, or 2-ethyl hexyl acrylate at T = 308.15 K

Ultrasonic velocities, u, densities, ρ, of binary mixtures of N, N-dimethyl formamide (DMF) with methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), and 2-ethyl hexyl acrylate (EHA), including pure liquids, over the entire composition range have been measured at T = 308.15 K. Using the experimental results, the excess molar volume, V m E , partial molar volumes, V ¯ m , 1 , V ¯ m , 2 , and excess partial molar volumes, V ¯ m , 1 E , V ¯ m , 2 E have been calculated. Molecular interactions in the systems have been studied in the light of variation of excess values of calculated properties. The excess properties have been fitted to Redlich–Kister type polynomial and the corresponding standard deviations have been calculated. The positive values of V m E indicate the presence of dispersion forces between the DMF and acrylic ester molecules. Further theoretical values of sound velocity in the mixtures have been evaluated using various theories and have been compared with experimental sound velocities to verify the applicability of such theories to the systems studied. Theoretical ultrasonic velocity data have been used to study molecular interactions in the binary systems investigated.

Densities, refractive indices and excess molar volumes for binary mixtures of protic ionic liquids with methanol at T = 293.15 to 313.15 K

Densities and refractive indices for the binary mixtures involving four different Protic Ionic Liquids (PILs) namely (2-Hydroxyethanaminium formate [HEF] + methanol), (2-Hydroxyethanaminium acetate [HEA] + methanol), (2-Hydroxyethanaminium propionate [HEP] + methanol), and (2-Hydroxyethanaminium lactate [HEL] + methanol) have been measured at the temperature range from 293.15 to 313.15 K and at atmospheric pressure. The excess molar volumes V E , refractive index deviations Δ n D for these binary mixtures were calculated and correlated using Redlich–Kister equation. The coefficients of thermal expansion α, were also calculated from these experimental data. The values of V E are negative for the entire mole fraction range covered for all these binary mixtures and increased with temperature, whereas the values of Δ n D are positive and also increased with temperature. The measured refractive indices were compared with those predicted using the Lorentz–Lorenz, Gladstone–Dale, and Eykman equations and a satisfactory agreement was found for all the binary systems (PILs + methanol) studied in the present work.

Densities and Excess Molar Volumes of Binary Mixtures of Bis(2-hydroxyethyl)ammonium Acetate + Water and Monoethanolamine + Bis(2-hydroxyethyl)ammonium Acetate at Temperatures from (303.15 to 353.15) K

In the present work, binary mixtures of bis(2-hydroxyethyl)ammonium acetate + water and monoethanolamine + bis(2-hydroxyethyl)ammonium acetate were prepared with different compositions, and their densities were measured over the temperature range from (303.15 to 353.15) K. Excess molar volumes were calculated using the measured density values and correlated using a Redlich-Kister-type polynomial equation.