Volumetric Properties and Refractive Indices for Binary Mixtures of 1-Propyronitrile-3-hexylimidazolium Bromide + Ethanol at Temperatures from 293.15 to 323.15 K

Densities and refractive indices have been measured for binary mixtures of 1-propyronitrile-3-hexylimidazolium bromide + ethanol in the temperature range 293.15–323.15 K. From the experimental data the excess molar volume V ^E, refractive index deviation Δn _D, and the coefficient of thermal expansion α were calculated and fitted to fifth- and third-order Redlich–Kister type equations, respectively. Using the measured densities, the apparent molar volumes (V _ϕ ), limiting apparent molar volumes (V_f⁰V_{\phi}^{0}) and limiting apparent molar expansivities (E_f ⁰E_{\phi} ^{0}) were also determined and the details are discussed.     

二元体系C6H6-DMF在293.15 K下的体积性质

利用Anton Paar DMA4500振动管密度计, 测量了293.15 K时二元体系C6H6-DMF(苯-N,N-二甲基甲酰胺)溶液的密度, 利用最小二乘法确立了溶液密度与组成的函数关系. 利用密度数据分别计算了二元体系中C6H6和DMF的表观摩尔体积, 并利用非线性最小二乘拟合法, 分别拟合得到了优化的C6H6和DMF的表观摩尔体积和摩尔分数的函数关系, 以及C6H6和DMF的表观摩尔体积和质量分数的函数关系. 通过对函数关系的极限运算得到了C6H6和DMF的标准偏摩尔体积和摩尔体积. 此外, 还计算了不同组分下体系的超额摩尔体积, 数据可用四参数Redlich-Kister方程很好地关联拟合, 得到方程系数及体系的超额摩尔体积极值位置.     

二元体系C6H5CH3-DMF在293.15 K时的体积性质

利用Anton Paar DMA4500振动管密度计测量了293.15 K时二元体系甲苯-N,N-二甲基甲酰胺(C6H5CH3-DMF)在C6H5CH3(摩尔分数0~1)中的溶液密度, 利用最小二乘法关联了溶液密度与组成的函数关系, 关联精度为±0.005 kg/m3. 通过密度数据分别计算了二元体系中C6H5CH3和DMF的表观摩尔体积, 并利用非线性最小二乘拟合法, 分别拟合得到了优化的C6H5CH3和DMF的表观摩尔体积和摩尔分数的函数关系, 以及C6H5CH3和DMF的表观摩尔体积和质量分数的函数关系. 通过对函数关系的极限运算得到了C6H5CH3和DMF的极限偏摩尔体积、标准偏摩尔体积和摩尔体积. 还计算了不同组分下体系的超额摩尔体积, 数据可用四参数Redlich-Kister方程关联拟合得到方程系数. 计算关联了C6H5CH3和DMF的超额偏摩尔体积与摩尔分数的关系. 由三参数多项式极限法得到组分的极限超额偏摩尔体积值与Redlich-Kister系数法得到的值在误差范围内一致.     

Volumetric Properties of the Ternary System Dimethyl Carbonate + Butyl Methacrylate + Allyl Methacrylate and Its Binary Butyl Methacrylate + Allyl Methacrylate at 293.15 K and p=101.325 kPa

Densities of the ternary system dimethyl carbonate + butyl methacrylate + allyl methacrylate and its binary subsystem butyl methacrylate + allyl methacrylate have been measured in the whole composition range, at 293.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densimeter. The calculated excess molar volumes of the binary system are positive and were correlated with the Redlich?CKister equation and with a series of Legendre polynomials. Several models were used to correlate ternary behavior from the excess molar volume data of their constituent binaries and found to fit the data equally well. The best fit was based on a direct approach, without information on the component binary systems.     

Densimetric Studies of Binary Solutions Involving H2O or D2O as a Solute in Dimethylsulfoxide at Temperatures from (293.15 to 328.15) K and Atmospheric Pressure

Densities of H₂O and D₂O solutions in dimethylsulfoxide, with solute mole fractions ranging up to 0.037, were measured with an uncertainty of 1.5×10^?5?g?cm^?3 at eight temperatures between 293.15 and 328.15?K (with a step of 5?K) under atmospheric pressure using a sealed vibrating-tube densimeter. Apparent molar volumes and isobaric expansibilities (down to infinite dilution) of water isotopologues, as well as excess molar volumes of both solutes and solutions as a whole, were calculated. The temperature-dependent behavior of H₂O??D₂O solute isotope effects on the studied molar volumetric characteristics was interpreted by taking into account the structural and related interaction peculiarities of the dissolving medium in question.     

Densities and Excess Molar Volumes of Alkane (Heptane, Octane, Nonane, or Decane) + Thiophene from T=293.15 to 313.15 K

Densities of four binary systems composed of an alkane (heptane, octane, nonane, or decane) and thiophene were measured at temperatures from 293.15 to 313.15?K at atmospheric pressure (0.7?atm). Measurements were made covering the full range of compositions for all systems studied and for the pure compounds by using a vibrating-tube densimeter (VTD). Excess molar volumes have been obtained from these experimental results and were fitted to a Redlich?CKister type expansion. The excess molar volumes exhibit positive deviations from ideal behavior for all of the binary systems studied here.     

Volumetric Properties of (Difurylmethane + Alkan-1-ol) Binary Mixtures at 298.15 K

Densities (ρ)of the binary systems of {difurylmethane + (ethanol or propan-1-ol or butan-1-ol or pentan-1-ol or hexan-1-ol)} have been measured with an Anton Paar DMA 4500 vibrating-tube densimeter over the entire composition range at 298.15,K and atmospheric pressure. Excess molar volumes (V _m ^E ) of each binary system were determined and correlated by the Redlich-Kister equation. Limiting (V _i ^E,∞) and excess partial molar volumes (V _i ^E ) of components of each binary system have been calculated to provide insight into the intermolecular interactions present and the packing efficiencies. The results have been discussed in terms of specific intermolecular interactions, dispersive forces and structural effects.     

Excess properties and spectroscopic studies of binary system 1,4-butanediol + water at T = (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K

Density and dynamic viscosity data were measured over the whole concentration range for the binary system 1,4-butanediol (1) + water (2) at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K as a function of composition under atmospheric pressure. Based on density and dynamic viscosity data, excess molar density (ρ^E), dynamic viscosity deviation (Δν) and excess molar volume (V_m^E) were calculated. From the dynamic viscosity data, excess Gibbs energies (ΔG*^E), Gibbs free energy of activation of viscous flow (ΔG*), enthalpy of activation for viscous flow (ΔH*) and entropy of activation for viscous flow (ΔS*) were also calculated. The ρ^E, V_m^E, Δν and ΔG*^E values were correlated by a Redlich?Kister-type function to obtain the coefficients and to estimate the standard deviations between the experimental and calculated quantities. Based on FTIR and UV spectral results, the intermolecular interaction of 1,4-butanediol with H₂O was discussed.     

Volumetric Properties of Binary Mixtures of Glycerol + <Emphasis Type="Italic">tert</Emphasis>-Butanol over the Temperature Range 293.15 to 348.15 K at Atmospheric Pressure

Densities of glycerol (1) + tert-butanol (2) mixtures were measured over the temperature range 293.15 to 348.15 K at atmospheric pressure, over the entire composition range, with a vibrating tube densimeter. Excess molar volumes, apparent and partial molar volumes of glycerol and tert-butanol, thermal isobaric expansivities of the mixture and partial molar expansivities of the components were calculated. The excess molar volumes of the mixtures are negative at all temperatures, and deviations from ideality increase with increasing temperature. Excess molar volumes were fitted to the Redlich–Kister equation. Partial molar volumes of glycerol decrease with increasing tert-butanol concentration. The temperature dependence of the partial molar volumes of glycerol is characterized by an inversion at x ₂≈0.7. “Negative expansion” of the limiting partial volumes of glycerol was observed.     

Densities and Volumetric Properties of Binary Mixtures of Formamide with 1-Butanol, 2-Butanol, 1,3-Butanediol and 1,4-Butanediol at Temperatures between 293.15 and 318.15 K

The densities of binary mixtures of formamide (FA) with 1-butanol, 2-butanol, 1,3-butanediol, and 1,4-butanediol, including those of the pure liquids, over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, V _m ^E, partial molar volumes, and , at infinite dilution, and excess partial molar volumes, and , at infinite dilution were calculated. The variation of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interactions in these mixtures. The partial molar expansivities, and , at infinite dilution and excess partial molar expansivities, and , at infinite dilution were also calculated. The V _m ^E values were found to be positive for all the mixtures at each temperature studied, except for FA + 1-butanol which exhibits a sigmoid trend wherein V _m ^E values change sign from positive to negative as the concentration of FA in the mixture is increased. The V _m ^E values for these mixtures follow the order: 1-butanol < 2-butanol < 1,3-butanediol < 1,4-butanediol. It is observed that the V _m ^E values depend upon the number and position of hydroxyl groups in these alkanol molecules.     

Microcalorimetric Investigations of K+- and Mg2+-Induced Polymerization of Actin at Temperatures from 293.15 K to 310.15 K

Microcalorimetric measurements of the polymerization of actin in the presence of 100 mM KCl and 2 mM MgCl₂were carried out with a Calvet MS-80 microcalorimeter at temperatures from 293.15 to 310.15 K. It was observed that the polymerization of actin was endothermic and the enthalpy change for actin polymerization was temperature-dependent. The enthalpy change ΔH^owas fitted to ΔH^o(kJ mol^-1)=434.0-1.16 (T/K) and the change in heat capacity ΔC_p ^ocalculated from ΔH^owas -1.16 kJ (mol K)^-1in the above range of temperatures. The direct calorimetry results showed that the enthalpy and entropy change for actin polymerization could not be obtained from measurements of the critical concentration and the only way to assess the enthalpy change for the polymerization of actin and similar reactions lies in the use of calorimetry. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermophysical Properties of Acetophenone with N,N-Dimethylethanolamine or with N,N-Diethylethanolamine at Temperatures of (303.15, 313.15 and 323.15) K and Pressure of 0.1 MPa

Densities, viscosities and refractive indices have been determined for mixtures of acetophenone with N,N-dimethylethanolamine or with N,N-diethylethanolamine over the entire composition range at temperatures of (303.15, 313.15 and 323.15) K. The viscosity values were fitted to the Krishnan-Laddha and McAllister models. The thermophysical properties under study were also fitted to the Jouyban-Acree model. The excess values were correlated using the Redlich-Kister polynomial equation. It was found that, in all cases, the obtained data were correlated very well by the corresponding models. The molecular interactions existing between the components are also discussed.     

The Relative Reduced Redlich–Kister Equations for Correlating Excess Properties of N,N-Dimethylacetamide + Water Binary Mixtures at Temperatures from 298.15 K to 318.15 K

Excess molar volumes, viscosity deviations, and isentropic compressibility changes in N,N-dimethylacetamide + water binary mixtures at (298.15, 308.15 and 318.15)?K were calculated from experimental density, viscosity and sound velocity results presented in previous work. Here these experimental values were used to test the applicability of the correlative reduced Redlich?CKister equation and the recently proposed Herráez equation, as well as their corresponding relative functions. Their correlation ability at different temperatures, and the use of different numbers of parameters, are discussed for the case of limited experimental data. The relative functions are important to reduce the effect of temperature and, consequently, to reveal the effects of different types of interactions. Values of the limiting excess partial molar volume at infinite dilution were deduced using different methods. Also, the activation parameters and partial molar Gibbs energy of activation of viscous flow were analyzed as functions of composition. Correlation between the two Arrhenius parameters of viscosity in all composition domains show the existence of two distinct behaviors, separated by a stabilized structure over a short range of mole fractions from (0.2?to?0.3) in N,N-dimethylacetamide. In this regard, a correlation equation recently proposed by Belda has also been applied to the present system for deriving molar volume properties, in order to assess the validity of the proposed equation,     

Densities and Volumetric Properties of Binary Mixtures of Tetrahydrofuran with Some Aromatic Hydrocarbons at Temperatures from 278.15 to 318.15 K

The densities, ρ, of binary mixtures of tetrahydrofuran (THF) with benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene, including those of the pure liquids, were measured over the entire composition range at the temperatures (278.15, 283.15, 288.15, 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, V _m ^E, partial molar volumes, _m,1 ^∘ and _m,2 ^∘, and excess partial molar volumes, _m,1 ^∘E and _m,2 ^∘E, at infinite dilution were calculated. The V _m ^E values were found to be negative over the whole composition range for all of the mixtures and at each temperature studied, except for THF + mesitylene, which exhibits a sigmoid trend wherein V _m ^E changes sign from negative to positive as the concentration of THF in the mixture is increased, indicating the presence of specific interactions between THF and aromatic hydrocarbon molecules. The extent of negative deviations in the V _m ^E values follows the order: benzene > toluene > p-xylene > m-xylene > o-xylene > mesitylene. It is observed that the V _m ^E values depend upon the number and position of the methyl groups in these aromatic hydrocarbons.     

Volumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran, 2-butanone,and ethylacetate from T = (293.15 to 313.15) K

Densities of binary liquid mixtures of N-ethylformamide (NEF) with tetrahydrofuran (THF), 2-butanone (B), and ethylacetate (EA) were measured at temperatures from (293.15 to 313.15) K and at atmospheric pressure over the whole composition range. Excess molar volumes, V^E, have been obtained from values of the experimental density and were fitted to the Redlich–Kister polynomial equation. The V^E values for all three mixtures are negative over the entire composition and temperature ranges. The V^E values become more negative as the temperature increases for all binary mixtures studied. Other volumetric properties, such as isobaric thermal expansion coefficients, partial molar volumes, apparent molar volumes, partial molar excess volumes and excess thermal expansions have been calculated.     

Volumetric and viscometric properties of aqueous solutions of N-(2-hydroxyethyl)morpholine at T = (293.15, 303.15, 313.15, 323.15, 333.15) K

Densities, ρ, and viscosities, η, of aqueous solutions of N-(2-hydroxyethyl)morpholine were measured over the entire composition range at T = (293.15, 303.15, 313.15, 323.15, 333.15) K and at atmospheric pressure. The excess molar volumes V^E and viscosity deviations η^E of aqueous solutions were calculated from the experimental results of density and viscosity measurements and fitted to the Redlich–Kister polynomial equation. Apparent molar volumes V?, partial molar volume at infinite dilution V^∞, and the thermal expansion coefficient α were also calculated. The V^E values were found to be negative over the entire composition range at all temperatures studied and become less negative with increasing temperature, whereas the viscosity data η^E exhibited positive deviations from ideal behaviour.     

Thermodynamic Properties of Binary Mixtures of Cyclohexanone with n-Alkanols (C1–C5) at 293.15 K

The excess molar volumes (V^E), excess surface tensions (σ^E), and deviations in molar refraction (R^E) and isentropic compressibility (k_s^E) of binary mixtures of cyclohexanone with methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol have been determined over the entire composition range at 293.15 K. The results were fitted by the Redlich–Kister polynomial equation and the corresponding binary coefficients A_k have been derived. The standard deviations between the calculated and the experimental excess properties have been determined. The results provide information on the interactions of the molecules in the pure liquids as well as in the binary mixtures.     

The Relative Reduced Redlich–Kister and Herráez Equations for Correlating Excess Properties of N,N-Dimethylacetamide + Formamide Binary Mixtures at Temperatures from 298.15 K to 318.15 K

Excess molar volumes and viscosity deviations in binary mixtures of N,N-dimethylacetamide with formamide at (298.15, 308.15 and 318.15) K were calculated from experimental density and viscosity data presented in previous work. The density and viscosity data as well as their corresponding derived functions were used to test the applicability of two correlative equations: the reduced Redlich?CKister equation and the recently proposed Herráez equation. Their correlation abilities at different temperatures, and the use of different numbers of parameters, are discussed for the case of limiting experimental data. These relative functions are important to reduce the effect of temperature and, consequently, to reveal the effects of different types of interactions. Correlation between the two Arrhenius parameters of viscosity over the composition domains shows the existence of two distinct behaviors.     

Liquid Densities and Excess Molar Volumes for Binary Systems (Ionic Liquids + Methanol or Water) at 298.15, 303.15 and 313.15 K,and at Atmospheric Pressure

Binary excess molar volumes, V _m ^E, have been evaluated from density measurements, using a vibrating tube densimeter over the entire composition range for binary liquid mixtures of ionic liquids 1-ethyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-butyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [BMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-methyl-3-octyl-imidazolium diethyleneglycol monomethylethersulphate [MOIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+methanol and [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+water at 298.15, 303.15 and 313.15 K. The V _m ^E values were found to be negative for all systems studied. The V _m ^E results are explained in terms of intermolecular interactions and packing effects. The experimental data were fitted by the Redlich-Kister polynomial.