Thermodynamic properties of the mixture [x1,3-dioxane+(1-x) 1,4-dioxane] at the temperature 298.15 K

Excess enthalpies, excess heat capacities, excess volumes and sound velocities of the mixture of dioxane isomers, 1,3-dioxane and 1,4-dioxane, were measured. One of the isomers, 1,4-dioxane is considered as non-polar liquid and the other as polar liquid. Excess enthalpies are positive and small, less than 55 J mol^-1. Excess heat capacities are also very small and the curve is W-shaped, and the values are from 0.03 to -0.08 J mol^-1 K^-1. Excess volumes and excess isentropic compressibilities are small and positive, and less than 0.03 cm³ mol^-1 and 0.8 TPa^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermodynamic excess functions of methanol + piperidine at 298.15 K

Vapour pressures of methanol + piperidine at 298.15, 308.15, and 318.15 K were measured by a static method. Excess enthalpies and densities of the same mixtures at 298.15 K were also determined with an isothermal dilution calorimeter and a pyknometer. The excess functions were evaluated from these results; the values for mole fraction x = 0.5 at 298.15 K are: G^{E = ?834.1 Jmol?1}, H^{E = ?3159.1 Jmol?1}, TS^{E = ?2325.0 Jmol?1}, V^{E = ?1.26 cm3mol?1}.     

Solution thermodynamics and preferential solvation of triclocarban in {1,4-dioxane (1) + water (2)} mixtures at 298.15 K

The equilibrium solubility and preferential solvation of triclocarban in {1,4-dioxane (1) + water (2)} mixtures at 298.15 K was reported. Mole fraction solubility varies continuously from 2.85 × 10^–9 in neat water to 2.39 × 10^–3 in neat 1,4-dioxane. Solubility behaviour was adequately correlated by means of the Jouyban-Acree model. Based on the inverse Kirkwood-Buff integrals, preferential solvation parameters were calculated. Triclocarban is preferentially solvated by water in water-rich mixtures (0.00 < x₁ < 0.18) and also in 1,4-dioxane-rich mixtures (0.78 < x₁ < 1.00) but preferentially solvated by 1,4-dioxane in mixtures with similar solvent compositions.     

The solvation of L-serine in mixtures of water with some aprotic solvents at 298.15 K

The integral enthalpies of solution Δ_sol H ^m of L-serine in mixtures of water with acetonitrile, 1,4-dioxane, dimethylsulfoxide (DMSO), and acetone were measured by solution calorimetry at organic component concentrations up to 0.31 mole fractions. The standard enthalpies of solution (Δ_sol H°), transfer (Δ_tr H°), and solvation (Δ_solv H°) of L-serine from water into mixed solvents were calculated. The dependences of Δ_sol H°, Δ_solv H°, and Δ_tr H° on the composition of aqueous-organic solvents contained extrema. The calculated enthalpy coefficients of pair interactions of the amino acid with cosolvent molecules were positive and increased in the series acetonitrile, 1,4-dioxane, DMSO, acetone. The results obtained were interpreted from the point of view of various types of interactions in solutions and the influence of the nature of organic solvents on the thermochemical characteristics of solutions.     

The enthalpies of solution and solvation of glycine in mixed water-formamide solvents at 298.15 K

The enthalpies of solution (ΔH _sol ^o ) of glycine in aqueous formamide, N-methylformamide, N,N-dimethylformamide, and N,N-diethylformamide were determined by calorimetry at 298.15 K over the concentration range x ₂=0–0.3 mole fractions. The enthalpies of glycine solvation (ΔH _solv ^o ) and transfer from water to mixed solvents (ΔH _tr ^o ) were calculated. The ΔH _sol ^o =f(x ₂) dependences for glycine in water-N-and water-N,N-substituted amide mixtures had extrema and, in water-formamide mixtures, this dependence was a smooth function, whose values changed in the opposite direction. The enthalpy coefficients of pair glycine-amide interactions were calculated. The interrelation between the enthalpy characteristics of solution, transfer, and solvation of glycine and the structure and physicochemical characteristics of solvents, on the one hand, and the composition of mixtures, on the other, was revealed.     

Excess enthalpies of water+1,4-dioxane at 278.15, 298.15, 318.15 and 338.15 K

The excess molar enthalpies of (1–x)water+x1,4-dioxane have been measured at four different temperatures. All the mixtures showed negative enthalpies in the range of low mole fraction but positive ones in the range of high mole fraction of 1,4-dioxane. Excess enthalpies were increased with increasing temperature except those of at 278.15 K. Partial molar enthalpies have maximum around x=0.13 and minimum around x=0.75. Three different behaviors for the concentration dependence of partial molar enthalpies were observed for all temperature. Theoretical calculations of molecular interactions of three characteristic concentrations were carried out using the molecular orbital method.     

Excess molar volumes and excess viscosities of the n-pentanol-cumene-1,4-dioxane system at 298.15 K

Densities and viscosities were determined for the n-pentanol-cumene-1,4-dioxane system at 298.15 K. From the experimental results, molar excess volumes and excess viscosities were calculated. Different expressions exist in the literature to predict these excess properties from the binary data. The empirical correlation of Cibulka is shown to be the best for this system.     

Quantum-chemical simulation of glycine specific solvation in the solvents water-1,4-dioxane and water-2-propanol

Structural and energy characteristics of the solvatocomplexes of glycine molecular and anionic forms with the components of the solvents water-dioxane and water-2-propanol were calculated by the HF/6–31G method. The results of calculation were compared with kinetic data on the glycine reactions with 3-nitrobenzenesulfonyl chloride and benzoyl chloride that allowed to understand the difference in the effect of composition of these binary solvents on the rate of N-acylation of α-aminoacids.     

Thermochemistry of dissolution,solvation, and hydrogen bonding of anilines in proton-acceptor organic solvents at 298.15 K

Enthalpies of dissolution at infinite dilution (298.15 K) of aniline, N-methylaniline, and N,N-dimethylaniline in a series of proton-acceptor solvents of different classes of compounds have been measured. The solvation enthalpies have been determined, and its relationship with the anilines structure has been analyzed. Enthalpy of hydrogen bonding in the complexes of aniline (1: 2) and N-methylaniline (1: 1) with the solvents has been calculated. In the case of aniline complexes, negative cooperativity of hydrogen bonding has been revealed, the effect enhancing with increasing the solvent proton-acceptor ability.     

Proton solvation in the sulfuric acid-water-1,4-dioxane system

The dependence of the optical density on the composition of the solution in the range of 0–60%, 1,4-dioxane in 10% aqueous solution of H₂SO₄ was obtained by FMIR IR spectroscopy. It was shown that in the solutions studied, the proton is in the form of the two simplest stable solvates: H₅O₂ ⁺ and H₂OHD⁺ ions, where D is the 1,4-dioxane molecule. The equilibrium concentrations of the proton solvates were estimated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 298–301, February, 1990.     

Model calculations of limiting electrical conductivity values for hydrogen ions in various solvents at 298.15 K

A method for model calculations of λ _H+^∞ in various solvents was suggested. Its effectiveness was estimated by calculations of these values in 14 solvents with different chemical structures and physical parameters. Most often, close agreement between the calculated values and literature experimental data was obtained.     

Ternary excess molar enthalpies for the mixtures of methanol and ethanol with tetrahydropyran or 1,4-dioxane at 298.15 K

Ternary excess molar enthalpies, H_m^E, at 298.15 K and atmospheric pressure measured by using a flow microcalorimeter are reported for the (methanol+ethanol+tetrahydropyran) and (methanol+ethanol+1,4-dioxane) mixtures. The pseudobinary excess molar enthalpies for all the systems are found to be positive over the entire range of compositions. The experimental results are correlated with a polynomial equation to estimate the coefficients and standard errors. The results have been compared with those calculated from a UNIQUAC associated solution model in terms of the self-association of alcohols as well as solvation between unlike alcohols and alcohols with tetrahydropyran or 1,4-dioxane. The association constants, solvation constants and optimally fitted binary parameters obtained solely from the pertinent binary correlation predict the ternary excess molar enthalpies with an excellent accuracy.     

Thermodynamic Properties of Alkanediols+Acetates at 298.15 K

In this work we present experimental values of the density, refractive index, speed of sound, isentropic compressibility and liquid-liquid equilibria of the binary mixtures (methyl acetate, ethyl acetate, propyl acetate, and butyl acetate) with (1,2-ethanediol, 1,2-propanediol, or 1,3-propanediol) at 298.15 K and atmospheric pressure, as a function of mole fraction. From the experimental values, the corresponding excess and deviation values were computed (excess molar volumes, changes of refractive index on mixing, and changes of isentropic compressibility), variable-degree polynomials being fitted to the results. The validity of different estimation methods for predicting the experimental values of physical properties was tested. The limiting partial excess molar volume of the components in each binary mixture was determined by means of predetermined Redlich-Kister parameters. Group contribution method (UNIFAC-Dortmund) was applied in order to compare their capability in predicting the experimental equilibria values. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preferential solvation of methocarbamol in aqueous binary co-solvent mixtures at 298.15 K

The preferential solvation parameters of methocarbamol in dioxane + water, ethanol + water, methanol + water and propylene glycol + water mixtures are derived from their thermodynamic properties by using the inverse Kirkwood–Buff integrals (IKBI) method. This drug is sensitive to solvation effects, being the preferential solvation parameter δx_1,3, negative in water-rich and co-solvent-rich mixtures, but positive in mixtures with similar proportions of solvents, except in methanol + water mixtures, where positive values are found in all the methanol-rich mixtures. It is conjecturable that the hydrophobic hydration around the non-polar groups in water-rich mixtures plays a relevant role. Otherwise, in mixtures of similar solvent compositions, the drug is mainly solvated by co-solvent, probably due to the basic behaviour of the co-solvents; whereas, in co-solvent-rich mixtures, the preferential solvation by water could be due to the acidic behaviour of water. Nevertheless, the specific solute–solvent interactions present in the different binary systems remain unclear.     

The thermodynamic properties and solvation of lithium halides in N-methylpyrrolidone at 298.15 K

The heat capacity and density of solutions of lithium chloride, bromide, and iodide in N-methylpyrrolidone (I) were determined by calorimetry and densimetry techniques. The standard partial molar heat capacities and volumes ( $\overline {C^\circ _{p2} } $ and $\overline {V^\circ _2 } $ ) of lithium halides in I were calculated. The $\overline {C^\circ _{pi} } $ and $\overline {V^\circ _i } $ values for halogen and lithium ions in I were determined. The coordination numbers of the Li⁺, Cl^?, Br^?, and I^? ions in solutions in I at 298.15 K were calculated.     

NaCl在CH~3OH-H~2O混合溶剂中活度系数的测定(298.15K)

用电动势法测定了298.15K时,由Na^+和Cl^-离子选择电极组成的电池在NaCl-CH~3OH-H~2O混合体系中的电动势,用扩展的Debye-huckel方程和Pitzer方程关联不同溶剂组成下电动势的实验值,得到电池的标准电动势能和NaCl 在混合溶剂中的活度系数.将Pitzer-Simonson方程应用于含离子缔合体系.求出NaCl 在混合溶剂中的缔合常数,结果表明NaCl在甲醇含量为60%时,可能已有离子对生成     

Enthalpies of dilution and homotactic enthalpic interaction coefficients of THF and 1,4-dioxane at 298.15 k

Enthalpies of dilution at 298.15 K of aqueous solutions of THF and 1,4-dioxane have been determined using flow microcalorimetry. The results obtained were used to determine the homotactic enthalpic interaction coefficients that characterize pair interactions of THF and 1,4-dioxane in aqueous solution. These are briefly discussed from the point of view of intermolecular interaction between the hydrated solute species.     

Solubility and preferential solvation of acetaminophen in methanol + water mixtures at 298.15 K

The equilibrium solubility of acetaminophen in methanol + water binary mixtures at 298.15 K was determined and correlated with the Jouyban–Acree model. Preferential solvation parameters by methanol (δx_1,3) were derived from their thermodynamic solution properties by means of the inverse Kirkwood–Buff integrals method. δx_1,3 values are negative in water-rich mixtures but positive in compositions from 0.32 in mole fraction of methanol to pure methanol. It is conjecturable that in the former case, the hydrophobic hydration around non-polar groups plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behavior of this cosolvent.