Excess molar properties of ternary system (ethanol + water + 1,3-dimethylimidazolium methylsulphate) and its binary mixtures at several temperatures

The density, dynamic viscosity, and refractive index of the ternary system (ethanol + water + 1,3-dimethylimidazolium methylsulphate) at T = 298.15 K and of its binary systems 1,3-dimethylimidazolium methylsulphate with ethanol and with water at several temperatures T = (298.15, 313.15, and 328.15) K and at 0.1 MPa have been measured over the whole composition range. From these physical properties, excess molar volumes, viscosity deviations, refractive index deviations, and excess free energy of activation for the binary systems at the above mentioned temperatures, were calculated and fitted to the Redlich–Kister equation to determine the fitting parameters and the root-mean-square deviations. For the ternary system, the excess properties were calculated and fitted to Cibulka, Singh et al., and Nagata and Sakura equations. The ternary excess properties were predicted from binary contributions using geometrical solution models.     

Refractive Indices of the Ternary Mixtures Butanol + <Emphasis Type="Italic">n</Emphasis>-Hexane + 1-Chlorobutane

Refractive indices for the ternary mixtures formed by each one of the isomers of butanol (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol), with n-hexane and 1-chlorobutane, have been measured at 298.15 K. From these data the refractive index deviations were calculated and fitted by Cibulka’s equation, and the refractive index deviations were related to the corresponding excess volumes of the mixtures. Furthermore, several mixing rules were used to predict both refractive indices and excess volumes of the ternary mixtures from their densities or refractive indices. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Isavuconazole: Thermodynamic Evaluation of Processes Sublimation,Dissolution and Partition in Pharmaceutically Relevant Media

A temperature dependence of saturated vapor pressure of isavuconazole (IVZ), an antimycotic drug, was found by using the method of inert gas-carrier transfer and the thermodynamic functions of sublimation were calculated at a temperature of 298.15 K. The value of the compound standard molar enthalpy of sublimation was found to be 138.1 ± 0.5 kJ·mol⁻¹. The IVZ thermophysical properties—melting point and enthalpy—equaled 302.7 K and 29.9 kJ mol⁻¹, respectively. The isothermal saturation method was used to determine the drug solubility in seven pharmaceutically relevant solvents within the temperature range from 293.15 to 313.15 K. The IVZ solubility in the studied solvents increased in the following order: buffer pH 7.4, buffer pH 2.0, buffer pH 1.2, hexane, 1-octanol, 1-propanol, ethanol. Depending on the solvent chemical nature, the compound solubility varied from 6.7 × 10⁻⁶ to 0.3 mol·L⁻¹. The Hansen s approach was used for evaluating and analyzing the solubility data of drug. The results show that this model well-described intermolecular interactions in the solutions studied. It was established that in comparison with the van’t Hoff model, the modified Apelblat one ensured the best correlation with the experimental solubility data of the studied drug. The activity coefficients at infinite dilution and dissolution excess thermodynamic functions of IVZ were calculated in each of the solvents. Temperature dependences of the compound partition coefficients were obtained in a binary 1-octanol/buffer pH 7.4 system and the transfer thermodynamic functions were calculated. The drug distribution from the aqueous solution to the organic medium was found to be spontaneous and entropy-driven.     

Thermophysical properties of the binary mixtures (1,8-cineole + 1-alkanol) at T = (298.15 and 313.15) K and at atmospheric pressure

This work presents the measurements of the density, speed of sound, refractive index and enthalpy of binary mixtures containing {1,8-cineole + 1-alkanol (ethanol, 1-propanol, 1-butanol, and 1-pentanol)} at two temperatures (298.15 and 313.15) K and atmospheric pressure. The determination of excess molar volume, speed of sound deviation, refractive index deviation, molar refraction, molar refraction deviation, excess isentropic compressibility, and excess molar enthalpy are also given. Redlich–Kister equation was used to fit these derivate properties. The experimental data of the constituent binaries were analysed to discuss the nature and strengths of intermolecular interactions. Eventually some models, SAFT and PC-SAFT for density, Free Length and Collision Factor for speed of sound, Gladstone-Dale Arago-Biot for refractive index, and UNIFAC for excess molar enthalpy, among others, were successfully applied.     

Mixing properties of binary mixtures presenting azeotropes at several temperatures

Experimental densities, speeds of sound, and refractive indices of the binary mixtures presenting azeotropes of (ethanol with hexane or heptane or 2-butanone) and (2-propanol with 2-butanone or ethylacetate or cyclohexane) were determined from T = (293.15 to 303.15) K. Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems were calculated. A function of the mole fraction and temperature polynomial equation was used to fit these quantities. The standard deviations between experimental and calculated values are shown.     

Physical properties of the ternary system (ethanol + water + 1-butyl-3-methylimidazolium methylsulphate) and its binary mixtures at several temperatures

In this paper, we report experimental densities, dynamic viscosities, and refractive indices and their derived properties of the ternary system (1-butyl-3-methylimidazolium methylsulphate + ethanol + water) at T = 298.15 K and of its binary systems 1-butyl-3-methylimidazolium methylsulphate with ethanol and with water at several temperatures T = (298.15, 313.15, 328.15) K. These physical properties have been measured over the whole composition range and at 0.1 MPa. Excess molar volumes, viscosity deviations, and excess free energy of activation for the binary systems at the abovementioned temperatures, were calculated and fitted to the Redlich–Kister equation to determine the fitting parameters and the root-mean-square deviations and for the ternary systems were calculated and fitted to Cibulka, Singh et al., and Nagata and Sakura equations. The ternary excess properties were predicted from binary contributions using geometrical solution models. Refractive indices were measured from T = 298.15 K over the whole composition range for the binary and ternary systems. The results were used to calculate deviations in the refractive index.     

Densities, refractive indices and speeds of sound of the ternary mixtures (dimethyl carbonate + methanol + ethanol) and (dimethyl carbonate + methanol + 1-propanol) at T=298.15 K

Density, refractive index and speed of sound at T=298.15 K and atmospheric pressure have been measured over the entire composition range for (dimethyl carbonate (DMC) + methanol + ethanol) and (DMC + methanol + 1-propanol). Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems have been calculated. The calculated quantities are further fitted to the Cibulka equation to estimate the ternary fitting parameters. Standard deviations from the regression lines are shown.     

Effect of the temperature on the physical properties of pure 1-propyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide and characterization of its binary mixtures with alcohols

In this paper, physical properties of a high purity sample of the ionic liquid 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [PMim][NTf₂], and its binary mixtures with methanol, ethanol, 1-propanol, and 2-propanol were measured at atmospheric pressure. The temperature dependence of density, refractive index and speed of sound (293.15 to 343.15) K and dynamic viscosity (298.15 to 343.15) K were studied at atmospheric pressure by conventional techniques for the pure ionic liquid. For its mixtures with alcohols, density, speed of sound, and refractive index were measured at T = 298.15 K over the whole composition range. The thermal expansion coefficient of the [PMim][NTf₂] was calculated from the experimental results using an empirical equation, and values of the excess molar volume, excess refractive index, and excess molar isentropic compressibility for the binary systems at the above mentioned temperature, were calculated and fitted to the Redlich–Kister equation. The heat capacity of the pure ionic liquid at T = 298.15 K was determined using DSC.     

Hydrogen Bonding and Polymorphism of Amino Alcohol Salts with Quinaldinate: Structural Study

Three amino alcohols, 3-amino-1-propanol (abbreviated as 3a1pOH), 2-amino-1-butanol (2a1bOH), and 2-amino-2-methyl-1-propanol (2a2m1pOH), were reacted with quinoline-2-carboxylic acid, known as quinaldinic acid. This combination yielded three salts, (3a1pOHH)quin (1, 3a1pOHH⁺ = protonated 3-amino-1-propanol, quin⁻ = anion of quinaldinic acid), (2a1bOHH)quin (2, 2a1bOHH⁺ = protonated 2-amino-1-butanol), and (2a2m1pOHH)quin (3, 2a2m1pOHH⁺ = protonated 2-amino-2-methyl-1-propanol). The 2-amino-1-butanol and 2-amino-2-methyl-1-propanol systems produced two polymorphs each, labeled 2a/2b and 3a/3b, respectively. The compounds were characterized by X-ray structure analysis on single-crystal. The crystal structures of all consisted of protonated amino alcohols with NH₃⁺ moiety and quinaldinate anions with carboxylate moiety. The used amino alcohols contained one OH and one NH₂ functional group, both prone to participate in hydrogen bonding. Therefore, similar connectivity patterns were expected. This proved to be true to some extent as all structures contained the NH₃⁺∙∙∙⁻OOC heterosynthon. Nevertheless, different hydrogen bonding and π∙∙∙π stacking interactions were observed, leading to distinct connectivity motifs. The largest difference in hydrogen bonding occurred between polymorphs 3a and 3b, as they had only one heterosynton in common.     

Excess Molar Volumes,Viscosity Deviations and Isentropic Compressibility of Binary Mixtures Containing 1,3-Dioxolane and Monoalcohols at 303.15 K

The excess molar volume (V ^E), viscosity deviations (Δη) and Gibbs excess energy of activation for viscous flow (G^∗E) have been investigated from density (ρ) and viscosity (η) measurements of eight binary mixtures of 1,3-dioxolane with methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, and i-amyl alcohol over the entire range of mole fractions at 303.15 K. The viscosity data have been correlated with the Grunberg and Nissan equation. Furthermore, excess isentropic compressibilities (K_S^E) have been calculated from ultrasonic speed measurements of these binary mixtures at 303.15 K. The deviations have been fitted by a Redlich–Kister equation and the results are discussed in terms of molecular interactions and structural effects. The excess properties are found to be either negative or positive depending on the molecular interactions and the nature of the liquid mixtures. The systems studied exhibit very strong cross association through hydrogen bonding.     

The properties of aqueous solutions of some short chain cosurfactants used for radical polymerization of vinyl acetate

 The refractive index and excess molar volume, of the following short hydrocarbon chain co-surfactants were studied: ethylene glycol, ethylene glycol monomethyl ether, ethanol, n-, i-propanol, acrylic acid, ethyl monomethylmaleate and acrylamide. The refractive indexes of the aqueous solutions of these compounds vary nonlinearly with composition. The maximum variation of refractive indexes occurs up to a cosurfactant/water molar ratio equal to 1 5. The fluorescence probe method was successfully used to evidence the structure modifications of the alcohol–water mixtures. The intensity ratio of pyrene fluorescence vibrational bands varies nonlinearly with the composition of the systems; in case of 1-propanol, the sudden decrease of the ratio is similar to that of micellar solutions, so that a critical concentration of association can be determined at a 0.88 water mole fraction. It was shown, in good agreement with data in literature, that the compounds mentioned penetrate into the cluster structure of water and associate. At concentrations higher than critical, restructuring of aqueous solutions continues and structures of bicontinuous or w/o type may arise. The excess volume of the first six compounds is negative owing to the restructuring just mentioned. Vinyl acetate may penetrate in the struc-tures of binary systems to form homogeneous systems. The number of homogeneous systems decreases in the sequence: ethanol, i-propanol, acrylic acid, n-propanol, the mono-methylether of ethyleneglycol, methyl monomaleate. The vinyl acetate over cosurfactant molar ratio of limiting homogeneous systems varies in inverse sequence at the same monomer/water ratio. After radical polymerization of VAc in homogeneous samples transparent systems were obtained only when the polymer was solubilized in cosurfactant water mixtures. Received: 16 July 1996 Accepted: 14 January 1997     

Molar Volume, Molar Refraction, and Isentropic Compressibility Changes of Mixing at 25°C for the System Ethanol + Methanol + Dibutyl Ether

The densities, refractive indexes, and sound velocities for mixtures of ethanol + methanol + dibutyl ether at 25°C and atmospheric pressure, were determined and used to calculate molar volumes, molar refractions, and isentropic compressibilities. The excess molar volumes and the deviations of molar refractions and isentropic compressibilities from mole fraction and volume fraction averages, respectively, of these properties of the pure components were satisfactorily correlated with the composition data by means of the Redlich–Kister polynomial.     

Excess properties of binary mixtures hexane,heptane, octane and nonane with benzene,toluene and ethylbenzene at T = 283.15 and 298.15 K

Densities, speeds of sound and the refractive indices of binary systems containing alkanes (hexane, heptane, octane and nonane) with aromatic compounds (benzene, toluene and ethylbenzene) at T = 283.15 and 298.15 K under atmospheric pressure were determined over the whole composition range. From the experimental results, the derived and excess properties (excess molar volumes, isentropic compressibility, excess molar isentropic compressibility and refractive index deviations) at T = 283.15 and 298.15 K were calculated and satisfactorily fitted to the Redlich–Kister equation.     

Dielectric Relaxation Study of Liquids Having Chloro Group with Associated Liquids. I. Chlorobenzene with Methanol, Ethanol, and 1-Propanol

The complex permittivity for chlorobenzene–alcohol binary mixtures have been determined over the frequency range of 10 MHz to 20 GHz, at 15, 25, 35, and 45°C, using the time-domain reflectometry (TDR) method for 11 concentrations of each chlorobenzene–alcohol system. The alcohols used were methanol, ethanol, and 1-propanol. The values of static dielectric constant, relaxation time, the corresponding excess properties, the Redlich–Kister coefficients up to the third order, the Kirkwood correlation factor, and thermodynamic parameters of the mixtures have been determined. The excess permittivity is found to be negative for chlorobenzene–methanol and chlorobenzene–ethanol, whereas it is positive in the 1-propanol rich region. The excess inverse relaxation time is negative for all the systems studied here. The Kirkwood effective correlation factor increases with an increasing in the molecular size of the alcohol, but decreases with increasing temperature.     

Viscosity,density, and speed of sound of methylcyclopentane with primary and secondary alcohols at T = (293.15, 298.15, and 303.15) K

Viscosities, densities, and speed of sound have been measured over the whole composition range for (methylcyclopentane with ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, and 2-pentanol) at T = (293.15, 298.15, and 303.15) K and atmospheric pressure along with the properties of the pure components. Excess molar volumes, isentropic compressibility, deviations in isentropic compressibility, and viscosity deviations for the binary systems at the above-mentioned temperatures were calculated and fitted to Redlich–Kister equation to determine the fitting parameters and the root-mean square deviations. UNIQUAC equation was used to correlate the experimental data. Dynamic viscosities of the binary mixtures have been predicted using UNIFAC-VISCO and ASOG-VISCO methods.     

Physico-chemical and excess properties of the binary mixtures of methylcyclohexane + ethanol, + propan-1-ol, + propan-2-ol, + butan-1-ol, + 2-methyl-1-propanol,or 3-methyl-1-butanol at T = (298.15, 303.15, and 308.15) K

Physico-chemical properties viz., density, viscosity, and refractive index at temperatures = (298.15, 303.15, and 308.15) K and the speed of sound at T = 298.15 K are measured for the binary mixtures of methylcyclohexane with ethanol, propan1-ol, propan-2-ol, butan-1-ol, 2-methyl-1-propanol, and 3-methyl-1-butanol over the entire range of mixture composition. From these data, excess molar volume, deviations in viscosity, molar refraction, speed of sound, and isentropic compressibility have been calculated. These results are fitted to the polynomial equation to derive the coefficients and standard errors. The experimental and calculated quantities are used to study the nature of mixing behaviours between the mixture components.     

Experimental excess molar properties of binary mixtures of (3-amino-1-propanol + isobutanol, 2-propanol) at T = (293.15 to 333.15) K and modelling the excess molar volume by Prigogine–Flory–Patterson theory

Density and viscosity of binary mixtures of (x₁3-amino-1-propanol + x₂isobutanol) and (x₁3-amino-1-propanol + x₂2-propanol) were measured over the entire composition range and from temperatures (293.15 to 333.15) K at ambient pressure. The excess molar volumes and viscosity deviations were calculated and correlated by the Redlich–Kister (RK) equation. The thermal expansion coefficient and its excess value, isothermal coefficient of excess molar enthalpy, and excess partial molar volumes were determined by using the experimental values of density and are described as a function of composition and temperature. The excess molar volumes are negative over the entire mole fraction range for both mixtures and increase with increasing temperature. The excess molar volumes obtained were correlated by the Prigogine–Flory–Patterson (PFP) model. The viscosity deviations of the binary mixtures are negative over the entire composition range and decrease with increasing temperature.     

Effective Utilisation of Halophyte Biomass from Saline Soils for Biorefinering Processes

The salinity of European soil is increasing every year, causing severe economic damage (estimated 1–3 million hectares in the enlarged EU). This study uses the biomass of halophytes—tall fescue (grass) and hemp of the Białobrzeskie variety from saline soils—for bioenergy, second generation biofuels and designing new materials—fillers for polymer composites. In the bioethanol obtaining process, in the first stage, the grass and hemp biomass were pretreated with 1.5% NaOH. Before and after the treatment, the chemical composition was determined and the FTIR spectra and SEM pictures were taken. Then, the process of simultaneous saccharification and fermentation (SSF) was carried out. The concentration of ethanol for both the grass and hemp biomass was approx. 7 g·L⁻¹ (14 g·100 g⁻¹ of raw material). In addition, trials of obtaining green composites with halophyte biomass using polymers (PP) and biopolymers (PLA) as a matrix were performed. The mechanical properties of the composites (tensile and flexural tests) were determined. It was found that the addition of a compatibilizer improved the adhesion at the interface of PP composites with a hemp filler. In conclusion, the grass and hemp biomass were found to be an interesting and promising source to be used for bioethanol and biocomposites production. The use of annually renewable plant biomass from saline soils for biorefinering processes opens up opportunities for the development of a new value chains and new approaches to sustainable agriculture.     

Dynamic viscosities of binary mixtures of cycloalkanes with primary alcohols at T = (293.15, 298.15, and 303.15) K: New UNIFAC-VISCO interaction parameters

In this work, dynamic viscosities, densities, and speed of sound have been measured over the whole composition range and 0.1 MPa for the binary mixtures (cyclopentane and cyclohexane with ethanol, 1-propanol, and 1-butanol) at several temperatures (293.15, 298.15, 303.15) K along with the properties of the pure components. Excess molar volumes, molar isentropic compression, excess molar isentropic compression, and excess free energy of activation for the binary systems at the above mentioned temperatures, were calculated and fitted to the Redlich–Kister equation to determine the fitting parameters and the root-mean-square deviations. The UNIQUAC equation was used to correlate the experimental viscosity data. The UNIFAC-VISCO method and ASOG-VISCO method, based on contribution groups, were used to predict the dynamic viscosities of the binary mixtures. The interaction parameters of cycloalkanes with primary alcohol (CH_cy/-OH) have been determined for their application in the predictive UNIFAC-VISCO method.     

Physicochemical Properties of Binary Mixtures of the Protic Ionic Liquid Bis(2-hydroxyethyl)methylammonium Formate with Methanol,Ethanol, and 1-Propanol

Densities and viscosities were determined for binary mixtures containing the protic ionic liquid bis(2-hydroxyethyl)methylammonium formate [BHEMF] with methanol, ethanol, and 1-propanol at four different temperatures (293.15, 303.15, 313.15, and 323.15 K) and atmospheric pressure. Excess molar volume and viscosity deviations for the binary system were calculated. The calculated results were fitted to a Redlich-Kister equation to obtain the coefficients and estimate the standard deviations between the experimental and calculated quantities. The negative values of excess volume molar for these mixtures indicate that ion-dipole interactions and packing between ionic liquids and alcohols are present. The values of viscosity deviation are also negative over the whole composition range, and their values become less negative as the temperature increases.