Volumetric and refractive properties of binary mixtures containing 1,3-dioxolane and isomeric chlorobutanes

The relation between refractive index deviations and excess volumes for binary mixtures formed by a cyclic ether and a haloalkane has been tested using several methods: refractive index mixing rules and equations of state. Refractive index deviations, excess volumes and molar refractions have been calculated from experimental data of refractive indices and densities at two temperatures 298.15 and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions. Refractive indices were compared with those predicted by several mixing rules. Excess volumes have also been correlated using several cubic equations of state and finally a relation between parameter b from equations of state and molar refraction has been provided.     

Glass-state amorphous salt solids formed by freeze-drying of amines and hydroxy carboxylic acids: effect of hydrogen-bonding and electrostatic interactions

We studied effect of molecular interactions on the physical properties of binary freeze-dried solids and frozen aqueous solutions using model chemicals containing various functional groups (amino, carboxyl, hydroxyl). Thermal analysis of frozen solutions containing alkyl diamines and hydroxy di- or tricarboxylic acids showed thermal transitions (T(g)': glass transition of maximally freeze-concentrated phase) at temperatures higher than those of the individual solutes. A binary frozen solution containing 80 mM 1,3-diamino-2-hydroxypropane (single-solute T(g)'<-60 degrees C) and 120 mM citric acid (single-solute T(g)': -55.0 degrees C) made the transition at -30.8 degrees C. The molecular weight of the solutes had smaller effects on the transition temperatures of the frozen mixture component solutions. Lyophilization of some high T(g)' mixture frozen solutions (e.g., 1,3-diamino-2-hydroxypropane and citric acid) resulted in cake-structure amorphous solids with glass transition temperatures (T(g)) higher than those of the individual components. Networking of intense hydrogen-bondings and electrostatic interactions between the heterogeneous molecules through the multiple functional groups was suggested to reduce the component mobility in the amorphous freeze-concentrated phase and the freeze-dried solids. Controlling the interactions should be a key to optimizing the physical properties of multi-component amorphous freeze-dried pharmaceutical formulations.     

Qualitative analysis of excess dielectric properties of binary mixtures, ternary mixtures and mixing dynamics measurement using surface plasmon resonance

The analysis of the excess dielectric properties for various binary mixtures and a ternary mixture is demonstrated using a surface plasmon resonance (SPR) sensor. Strong deviations from ideality are seen using SPR to monitor deviations in the dielectric properties following mixing. Binary mixtures with similar refractive index were measured: hexanes/isopropanol, n-heptanes/propanol, 1-acetoxy-2-methoxyethane/2-methoxyethanol, butanol/dipropylamine, hexanes/ethylacetate, and ethylacetate/isopropanol binary mixtures. The ternary mixture was composed of 60 different proportions of hexanes, isopropanol, and ethylacetate. Using SPR, mixing dynamics is easily accessible. The mixing of hexanes and isopropanol in static solution was monitored.     

苯乙烯与邻、间、对-二甲苯二元混合液的分子间相互作用

The densities (ρ), ultrasonic speeds (v), and refractive indices (n) of binary mixtures of styrene (STY)with m-, o-, or p-xylene, including those of their pure liquids, were measured over the entire composition range at the temperatures 298.15, 303.15, 308.15, and 313.15 K. The excess volumes (VE), deviations in isentropic compressibilities(△ks), acoustic impedances (△Z), and refractive indices (△n) were calculated from the experimental data. Partial molar volumes (V0φ,2) and partial molar isentropic compressibilities (K0φ,2) of xylenes in styrene have also been calculated. The derived functions, namely, VE, △ks, △Z, △n, V0φ,2, and K0φ,2 were used to have a better understanding of the intermolecular interactions occurring between the component molecules of the present liquid mixtures. The variations of these parameters suggest that the interactions between styrene and o-, m-, or p-xylene molecules follow the sequences: p-xylene＞o-xylene＞m-xylene. Apart from using density data for the calculation of VE, excess molar volumes were also estimated using refractive index data. Furthermore, several refractive index mixing rules have been used to estimate the refractive indices of the studied liquid mixtures theoretically. Overall, the computed and measured data were interpreted in terms of interactions between the mixing components.     

Volumetric and refractive properties of binary mixtures containing 1,4-dioxane and chloroalkanes

Refractive index deviations, excess volumes, and molar refractions of binary mixtures containing 1,4-dioxane and 1-chloropropane or isomeric chlorobutanes have been calculated from experimental data of refractive indices and densities at temperatures of 298.15 K and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions and a comprehensive discussion has been provided. Excess volumes have been also correlated using Peng–Robinson–Stryjek–Vera cubic equation of state and the relation between parameter b (covolume) from the equation of state and molar refraction has been verified. Refractive indices were compared with those predicted using the equation of state and several mixing rules.     

Volumetric properties of {PEG 200 (or 300) (1) + water (2)} mixtures at several temperatures and correlation with the Jouyban–Acree model

Molar volumes and excess molar volumes were investigated from density values for {PEG 200 (1) + water (2)} and {PEG 300 (1) + water (2)} binary mixtures at temperatures from 278.15 to 313.15 K. Both systems exhibit negative excess volumes probably due to increased interactions such as hydrogen bonding and/or large differences in molar volumes of components. Volume thermal expansion coefficients were also calculated for both binary mixtures and pure solvents. The Jouyban–Acree model was used for density and molar volume correlations of the studied mixtures at different temperatures. The mean relative deviations between experimental and calculated density data were 0.02% and 0.04%, for aqueous mixtures of PEG 200 and PEG 300, respectively; whereas the corresponding values for molar volume data were 1.76% and 2.72%.     

Refractive indices and molar refractions of binary mixtures formed by some cyclic ethers and isomeric chlorobutanes

Refractive indices of binary mixtures formed by a cyclic ether (tetrahydrofuran or tetrahydropyran) and each of the isomeric chlorobutanes (1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 2-chloro-2-methylpropane) have been measured at two temperatures, 298.15?K and 313.15?K. From experimental data, refractive index deviations and molar refractions have been calculated. Furthermore, several common mixing rules have been used to predict refractive indices of the mixtures from their experimental densities reported previously.     

Measurement and Modeling of Phase Equilibrium,Volumetric Properties and Molar Refractivity of 2-Methylpropan-2-ol + Ethane-1,2-diol

2-Methylpropan-2-ol, an important fine chemical, may be dehydrated during extractive distillation with glycols as entrainer. Experimental isobaric phase equilibrium studies were carried out on binary mixtures of 2-methylpropan-2-ol with ethane-1,2-diol, as an entrainer, at the local atmospheric pressure of 94.99 kPa and at sub-atmospheric pressures of 19.99, 39.99, 59.99, 78.79 kPa using a Sweitoslawski-type ebulliometer. The Wilson and NRTL activity coefficient models were used to correlate the experimental results and the binary interaction parameters were obtained using the Generalized Reduced Gradient optimization technique. UNIFAC was also used to predict the deviations in bubble temperatures. Moreover, the variation in density, refractive index values and other derived properties (excess molar volumes, partial molar volumes and deviations in molar refractivity) were explored at 303.15, 313.15, 323.15 and 333.15 K to understand the shift of equilibrium with the variation in the mixture composition for the conformational state of the molecules. The Redlich–Kister polynomial equation was used to correlate the excess molar volumes and deviations from molar refractivity. Different theoretical mixing rules (Lorentz–Lorenz, Wiener, Heller, Gladstone–Dale and Arago–Biot) are investigated and reported in terms of average percentage deviation. Furthermore, the Prigogine–Flory–Patterson theory was used to predict the trend of the dependence of excess molar volumes on composition for the present system.     

Influence of temperature on microdomain organization of mixed cationic-zwitterionic lipidic monolayers at the air-water interface

The thermodynamic behavior of mixed DOTAP-DPPC monolayers at the air-water interface has been investigated in the temperature range from 15 to 45 degrees C, covering the temperature interval where the thermotropic phase transition of DPPC, from solid-like to liquid-like, takes place. Based on the regular solution theory, the miscibility of the two lipids in the mixed monolayer was evaluated in terms of the excess Gibbs free energy of mixing DeltaG(ex), activity coefficients f(1) and f(2) and interaction parameter omega between the two lipids. The mixed DOTAP-DPPC film was found to have positive deviations from ideality at low DOTAP mole fractions, indicating a phase-separated binary mixture. This effect depends on the temperature and is largely conditioned by the structural chain conformation of the DPPC lipid monolayer. The thermodynamic parameters associated to the stability and the miscibility of these two lipids in a monolayer structure have been discussed in the light of the phase diagram of the DOTAP-DPPC aqueous mixtures obtained from differential scanning calorimetry measurements. The correlation between the temperature behavior of DOTAP-DPPC monolayers and their bulk aqueous mixtures has been briefly discussed.     

Low pressure vapor–liquid equilibrium in ethanol + congener mixtures using the Wong–Sandler mixing rule

Phase equilibrium in binary ethanol mixtures found in alcoholic beverage production has been analyzed using a cubic equation of state (EoS) and suitable mixing and combining rules. The main objective of the study is the accurate modeling of the congener concentration in the vapor phase (substances different from ethanol), considered to be an important enological parameter in the alcohol industry. The Peng–Robinson (PR) equation of state has been used and the Wong–Sandler (WS) mixing rules, that include a model for the excess Gibbs free energy, have been incorporated into the equation of state constants. In the Wong–Sandler mixing rules the van Laar (VL) model for the excess Gibbs energy has been used. This combination of equations of state, mixing rules and combining rules are commonly applied to high pressure phase equilibrium and have not yet been treated in a systematic way to complex low pressure ethanol mixtures as done in this work. Nine binary ethanol + congener mixtures have been considered for analysis. Comparison with available literature data is done and the accuracy of the calculations is discussed, concluding that the model used is accurate enough for engineering applications.     

Aqueous solutions containing amino acids and peptides. Part 22 - free energetic and enthalpic virial coefficients at 25°C for some interactions of isofunctional amides

The excess free energies of aqueous solutions containing N-acetyl-L-prolinamide, N-acetyl-N-methyl-L-alaninamide and binary mixtures of these have been determined at 25°C from isopiestic measurements. The corresponding excess enthalpies for the last two systems have been obtained from enthalpy of dilution measurements. The results derived have been considered using the Savage-Wood group additivity principle, and it is shown that this works remarkably well although deviations are observed which are probably significant.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Density and Excess Molar Volume of the Protic Ionic Liquid Bis(2-hydroxyethyl)ammonium Acetate with Alcohols

Densities were determined for binary mixtures containing the protic ionic liquid bis(2-hydroxyethyl)ammonium acetate [BHEAA] and an alcohol (methanol, ethanol, and 1-propanol) at four different temperatures (293.15, 303.15, 313.15, and 323.15) K and ambient pressure. Coefficients of thermal expansion and excess molar volumes were calculated from the experimental densities. The excess molar volumes were fitted using the Redlich-Kister polynomial equation. Negative deviations from ideal behavior of the excess molar volume were observed for all systems investigated in this study. The results were interpreted in terms of ion-dipole interactions and structural factors of the ionic liquid and alcohol. It was observed that an increase of the alcohol carbon chain length led to lower interactions on mixing.     

Molecular interaction study of the diisopropyl ether-propionic acid mixture by spectroscopic and dielectric studies

FTIR and 13C NMR spectral studies have been carried out on diisopropyl ether-propionic acid binary mixture to probe the molecular interactions and stoichiometry of complexation. Density functional theory (DFT) calculations of vibrational frequencies of pure acid and ether-acid binary mixtures have also been performed. In addition, Kirkwood-correlation factors, excess permittivity and excess free energy of mixing have been obtained at various concentrations and at four different temperatures from the dielectric measurements. Excess permittivity is found to have positive deviation and excess free energy deviates negatively from ideal behaviour.     

Thermodynamic Characteristics of Phenacetin in Solid State and Saturated Solutions in Several Neat and Binary Solvents

The thermodynamic properties of phenacetin in solid state and in saturated conditions in neat and binary solvents were characterized based on differential scanning calorimetry and spectroscopic solubility measurements. The temperature-related heat capacity values measured for both the solid and melt states were provided and used for precise determination of the values for ideal solubility, fusion thermodynamic functions, and activity coefficients in the studied solutions. Factors affecting the accuracy of these values were discussed in terms of various models of specific heat capacity difference for phenacetin in crystal and super-cooled liquid states. It was concluded that different properties have varying sensitivity in relation to the accuracy of heat capacity values. The values of temperature-related excess solubility in aqueous binary mixtures were interpreted using the Jouyban–Acree solubility equation for aqueous binary mixtures of methanol, DMSO, DMF, 1,4-dioxane, and acetonitrile. All binary solvent systems studied exhibited strong positive non-ideal deviations from an algebraic rule of mixing. Additionally, an interesting co-solvency phenomenon was observed with phenacetin solubility in aqueous mixtures with acetonitrile or 1,4-dioxane. The remaining three solvents acted as strong co-solvents.     

Application of a generalized van der Waals equation of state to several nonpolar mixtures

A generalized van der Waals equation of state, applied recently (Nguyen Van Nhu and Kohler, 1995) to the calculation of excess properties and phase equilibria for the mixture methane + ethane, is now extended to several nonpolar binary mixtures.Improved mixing rules for the van der Waals attractive term and for the correction term are proposed. With these mixing rules, the equation gives good agreement for vapour-liquid and liquid-liquid equilibria over a large temperature range for 29 binary mixtures. The agreement of mixture volumes and cross second virial coefficients is also satisfactory.     

Volumetric,Acoustic and Refractive Index for the Binary System (Butyric acid + Hexanoic acid) at Different Temperatures

In this paper density, sound velocity, and refractive index for the binary system (butyric acid + hexanoic acid) were measured over the entire composition range and at 5 K intervals in the temperature range 293.15–313.15 K. The excess molar volumes, isentropic compressibilities, excess isentropic compressibilities, deviation in refractive indices, molar refractions, and deviation in molar refractions were calculated by using the experimental densities, sound velocities, and refractive indices, respectively. The Redlich–Kister equation was used to fit the excess molar volume, excess isentropic compressibility, deviation in refractive index and deviation in molar refraction data. The Lorentz–Lorenz approximation was used to correlate the excess molar volume from the deviation in refractive index and also to predict the density from refractive index or the refractive index from density of the binary mixtures. Four sound velocity mixing rules were tested and the best model for the systems studied in this work was the Berryman mixing rule. The thermodynamic properties are discussed in terms of intermolecular interactions between the components of the mixtures.     

Calculation of critical lines of hydrocarbon/water systems by extrapolating mixing rules fitted to subcritical equilibrium data

The phase behavior of water/hydrocarbon mixtures in a wide range of pressures is important for various applications ranging from reservoir engineering to environmental engineering. In this work, mutual solubility and critical loci of hydrocarbon/water systems are calculated using the Peng–Robinson–Stryjek–Vera cubic equation of state with four mixing rules: (1) van der Waals mixing rules with one binary interaction parameter (vdW-1), (2) van der Waals mixing rules with asymmetric composition dependent binary interaction parameter (vdW-A), (3) Wong–Sandler mixing rules (WS) and (4) second-order modified Huron–Vidal mixing rules (MHV2). It was found that the parameters obtained from correlating liquid–liquid equilibria using different mixing rules would lead to prediction of completely different forms of critical behavior. Unusual branches of critical loci were found with WS and MHV2 mixing rules. Therefore, equation of states models must be used with extreme caution when applied for predicting phase behavior over wide ranges of temperatures and pressures.     

Study of some volumetric and refractive properties of {PEG 300 (1) + ethanol (2)} mixtures at several temperatures

Molar volumes and excess molar volumes were investigated from measured density values for {PEG 300 (1) + ethanol (2)} binary mixtures at temperatures from 278.15 to 313.15 K. Both systems exhibit negative excess volumes probably due to increased interactions like hydrogen bonding and/or large differences in molar volumes of the components. Volume thermal expansion coefficients were also calculated for both binary mixtures and pure solvents. Refractive indices were also determined for all these non-aqueous mixtures and neat solvents at all temperatures. Furthermore, the Jouyban–Acree model was used for density, molar volume and refractive index correlations of the studied mixtures at different temperatures. The mean relative deviations between experimental and back-calculated density, molar volume and refractive index data were 0.07%, 0.99% and 0.01%, respectively.     

A local composition extension of the van der Waals mixing rule for PR cubic equation of state

New mixing rules (VWLC-I and II) capable of connecting van der Waals (VDW) to CEOS/A^E mixing rule models were developed. These models are able to incorporate the same multi-component mixture parameters obtained for the van der Waals and CEOS/A^E models simultaneously. The VWLC mixing rules directly incorporate local compositions into the cubic equations of state (CEOS). The energy parameters required for the local compositions are calculated from the CEOS parameters. The Peng–Robinson (PR) CEOS was used for this study. Binary interactions parameters were obtained by adjusting the vapor pressure of the binary mixture for several low and high-pressure systems. The predictive capabilities of the VWLC mixing rules were tested by vapor–liquid equilibria calculations for low and high-pressure multicomponent systems. The results were compared with the predictions of the VDW mixing rule and a Huron–Vidal (HV) kind of CEOS/A^E-NRTL mixing rule. The VWLC mixing rules are consistent models giving good results in a broad range of pressures and temperatures in binary and multicomponent mixtures. They compare favorably with the CEOS/A^E-NRTL mixing rule for low-pressure systems. In high-pressure ternary systems VWLC-I and II give good predictions, much better, in fact, than the CEOS/A^E-NRTL mixing rule.     

Study of Molecular Interactions in Binary Mixtures of Aniline with Carboxylic Acids at 293.15 K, 303.15 K and 313.15 K

Ultrasonic velocity, density, refractive index and viscosity of binary mixtures of aniline with acetic acid (AA) and propionic acid (PA) have been measured at 293.15, 303.15 and 313.15 K over the entire composition range. Further, the specific heat ratio, heat capacity, effective Debye temperature and pseudo-Gruensisen parameter and non-linearity parameter have been evaluated using ultrasonic absorption data. The deviation in isentropic compressibility, excess molar volume, excess intermolecular free length, deviation in molar refraction, deviation in viscosity, relaxation time, enthalpy, entropy and Gibbs energy of activation have been calculated from the experimental data and fitted with the Redlich-Kister polynomial equation. A comparative study has also been made between experimental and theoretically calculated values of densities using the HBT and Rackett density models. Mixing rules for the prediction of refractive index, e.g. Lorentz-Lorenz (L-L), Eykmen (Eyk), Weiner (W), Heller (H), Gladstone-Dale (G-D), Arago-Biot (A-B) and Newton (N) have been applied to these binary mixtures.