Apparent molar volumes and apparent molar heat capacities of aqueous solutions ofα- andβ-cyclodextrins at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

Apparent molar heat capacities C_{p, φ}and apparent molar volumesV_φ were determined for aqueous solutions of α - and β -cyclodextrins at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa. The molalities investigated ranged from 0.008 mol · kg ^− 1to 0.12 mol · kg ^− 1forα -cyclodextrin and from 0.004 mol · kg ^− 1to 0.014 mol · kg ^− 1for β -cyclodextrin. We used a vibrating-tube densimeter (DMA 512P, Anton PAAR, Austria) to determine the densities and volumetric properties. Heat capacities were obtained using a twin fixed-cell, power-compensation, differential-output, temperature-scanning calorimeter (NanoDSC 6100, Calorimetry Sciences Corporation, Spanish Fork, UT, USA). Equations were fit by regression to our experimental (V_φ, T, m) and (C_{p, φ},T , m) results. Infinite dilution partial molar volumes V₂^oand heat capacities C_p,2^owere obtained over the range of temperatures by extrapolation of these surfaces to m =  0.     

Apparent molar and partial molar volumes of aqueous ceric ammonium nitrate solutions at 20, 25, 30, and 35°C

Present paper reports the measured densities (ρ) and refractive indices (n _D) of aqueous solutions of ceric ammonium nitrate (CAN) at 20, 25, 30, and 35°C in different concentrations of solution. Apparent molar volumes (φ_v) have been calculated from the density data at different temperatures and fitted to Massons relation to get limiting partial molar volumes (? _v ⁰ ) of CAN. Refractive index data were fitted to linear dependence over concentration of solutions and values of constant K and n _D ⁰ for different temperatures were evaluated. Specific refractions (R _D) of solutions were calculated from the refractive index and density data. Concentration and temperature effects on experimental and derived properties have been discussed in terms of structural interactions.     

Partial molar volume and partial molar compressibility of four homologous α-amino acids in aqueous sodium fluoride solutions at different temperatures

Density and ultrasonic speed of four amino acids (glycine, l-alanine, l-valine, and l-leucine) in aqueous sodium fluoride solutions {(0.1 to 0.5) M} have been measured at T = (308.15, 313.15, and 318.15) K. Apparent molar volumes (V_φ), partial molar volumes $\left(V_{\phi }^0\right)$, transfer volumes $\left(\mathrm{\Delta }{V}_{\phi }^0\right)$ and hydration number (n_H) are evaluated using density data. Adiabatic compressibility (β_s), change (Δβ_s), and relative change in compressibility (Δβ_s/β₀), apparent molar compressibility (K_φ), partial molar compressibility $\left(K_{\phi }^0\right)$, transfer compressibility $\left(\mathrm{\Delta }{K}_{\phi }^0\right)$, and hydration number (n_H) have been calculated using ultrasonic speed data. The linear correlation of $V_{\phi }^0\text{,}\mathrm{\Delta }{V}_{\phi }^0\text{,}{K}_{\phi }^0$ and $\mathrm{\Delta }{K}_{\phi }^0$ for a homologous series of amino acids have been used utilised to calculate the contribution of charged end groups (${\text{NH}}_3^{+}$, COO^?), CH₂ group and other alkyl chain of the amino acids. The analysis shows that the ion–ion interactions are much stronger than ion–hydrophobic interactions over the entire concentration range of sodium fluoride. It is observed that sodium fluoride has a strong dehydration effect on amino acids.     

Isothermal vapor–liquid equilibrium at 333.15 K and excess molar volumes and refractive indices at 298.15 K for the mixtures of di-methyl carbonate,ethanol and 2,2,4-trimethylpentane

Isothermal vapor–liquid equilibrium data at 333.15 K are measured for the binary system ethanol + 2,2,4-trimethylpentane and for ternary system di-methyl carbonate (DMC) + ethanol + 2,2,4-trimethylpentane by using headspace gas chromatography. The experimental binary and ternary vapor–liquid equilibrium data were correlated with different activity coefficient models. Excess volume and deviations in molar refractivity data are also reported for the binary systems DMC + ethanol and DMC + 2,2,4-trimethylpentane and the ternary system DMC + ethanol + 2,2,4-trimethylpentane at 298.15 K. These data were correlated with the Redlich-Kister equation for the binary systems and the Cibulka equation for the ternary system, respectively. The ternary excess volume and deviations in molar refractivity data were also compared with estimated values from the binary contribution models of Tsao–Smith, Kohler, Rastogi and Radojkovi?.     

Viscous synergy and antagonism,excess molar volume,isoentropic compressibility and excess molar refraction of ternary mixtures containing tetrahydrofuran,methanol and six membered cyclic compounds at 298.15 K

The densities (ρ), viscosities (η), sound speeds (u) and refractive indices (n _D) of seven ternary mixtures of cyclic ether (tetrahydrofuran), methanoland cyclic compounds; benzene, toluene, chlorobenzene, nitrobenzene, anisole, cyclohexane and cyclohexanone are determined over the entire range of composition at 298.15?K. From the experimental observations, viscosity deviation (Δη), the viscous synergy and antagonism, synergic and antagonic index are derived by the equations developed by Kalentunc-Gencer and Peleg [G. Kalentunc-Gencer and M. Peleg, J. Texture Stud. 17, 61 (1986)] and Howell [N.K. Howell, Presented at the Proceedings of the Seventh International Conference, Wales, 1993], respectively. Excess molar volume (V ^E), excess isoentropic compressibility (ΔK _S) and excess molar refraction (ΔR) have been calculated from the experimentally measured density, sound speed and refractive index values. The excess Gibb's free energy of activation (ΔG ^E) has also been calculated. The results are discussed and interpreted in terms of molecular package and specific interaction predominated by hydrogen bonding.     

Excess molar enthalpy for methanol,ethanol, 1-propanol, 1-butanol + <Emphasis Type="Italic">n</Emphasis>-butylamine mixtures at 288.15 and 308.15 K at atmospheric pressure

Experimental data of excess molar enthalpy (H _m^E) of binary liquid mixtures containing (methanol or ethanol or 1-propanol, or 1-butanol) + n-butylamine mixtures have been determined as a function of composition at temperatures 288.15 and 308.15 K, at atmospheric pressure, using a modified 1455 PARR mixture calorimeter. The H _m^E values are negative for both systems over the whole composition range. The applicability of the ERAS Model to correlate H _m^E of mixtures studied is tested, and the agreement between experimental and theoretical results is satisfactory. The model results are discussed in terms of the cross-association interactions with temperature variation as well as in terms of the variation of the carbon chain in the alcohols presents in the mixtures.     

Isothermal vapor–liquid equilibrium at 333.15 K,excess molar volumes and refractive indices at 298.15 K for mixtures of tert-amyl methyl ether + ethanol + 2,2,4-trimethylpentane

Isothermal vapor–liquid equilibrium data at 333.15 K are measured for the binary system tert-amyl methyl ether + ethanol and tert-amyl methyl ether + 2,2,4-trimethylpentane and for ternary system tert-amyl methyl ether + ethanol + 2,2,4-trimethylpentane by using headspace gas chromatography. The experimental vapor–liquid equilibrium data were correlated with G^E models (Margules, van Laar, Wilson, NRTL, UNIQUAC) equations. The excess volume and deviations in molar refractivity data are also reported for the same binary and ternary systems at 298.15 K. These data were correlated with the Redlich–Kister equation for the binary systems and the Cibulka equation for the ternary system, respectively. The experimental ternary excess volume and deviations in molar refractivity data, were also compared with the estimated values from the binary contribution models of Tsao–Smith, Kohler, Rastogi and Radojkovi?.     

Limiting partial molar volumes at 298.15 K of some open chain and cyclic organic compounds in 1—octanol

Partial molar volumes at 298.15 K in 1—octanol have been determined for some hydrocarbons, ethers, ketones, and water from density measurements carried out with a vibrating-tube density meter.In the transfer process from the pure liquid state to the infinitely dilute solution in 1—octanol, a slight shrinkage is generally observed for solutes showing density values lower than that of the solvent. On the contrary, for solutes with higher density values, a weak expansion is produced.Comparisons are made among the partial molar volumes of organic solutes in 1—octanol, in water, and in other organic solvents. The case of water as a solute in 1—octanol and in many other organic liquids is carefully considered. In non-polar solvents the value of the limiting partial molar volume of water is always larger in respect to the value of the molar volume of pure water, but in polar solvents the contrary occurs. An explanation of this phenomenon is provided and a rationale is given to the value of the limiting partial molar volume of water in 1—octanol and to the trend exhibited by the partial molar volume of water in the 1—octanol/water mixture as water concentration is increased.     

Apparent molar volumes and compressibilities of electrolytes and ions in γ-butyrolactone

The densities of tetraphenylphosphonium bromide, sodium tetraphenylborate, lithium perchlorate, sodium perchlorate and lithium bromide in γ-butyrolactone at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and speed of sound at 298.15 K have been measured. From these data apparent molar volumes V_Φ at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and the apparent molar isentropic compressibility K_S,Φ, at T = 298.15 K of the salts have been determined. The apparent molar volumes and the apparent molar isentropic compressibilities were fitted to the Redlich, Rosenfeld and Mayer equation as well as to the Pitzer and Masson equations yielding infinite dilution data. The obtained limiting values have been used to estimate the ionic data of the standard partial molar volume and the standard partial isentropic compressibility in γ-butyrolactone solutions.     

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.     

Partial Molar Volumes and Partial Molar Isentropic Compressions of <Emphasis Type="Italic">γ</Emphasis>-Butyrolactone and <Emphasis Type="Italic">ε</Emphasis>-Caprolactone at Infinite Dilution in Water at Temperatures (278.15 to 318.15) K and at Atmospheric Pressure

Density and speed-of-sound values at T = (278.15, 283.15, 288.15, 293.15, 298.15, 308.15, and 318.15) K and at atmospheric pressure were measured, for dilute aqueous solutions of γ-butyrolactone and ε-caprolactone, using an Anton Paar DSA 5000 vibrating-tube densimeter and sound analyzer. A small but significant effect of hydrolysis was observed for aqueous ε-caprolactone and a procedure for eliminating its effect was proposed and employed. Values of the partial molar volume and isentropic compression at infinite dilution were obtained from this experimental data by suitable extrapolation procedures and compared with available data from the literature. The group contribution of the methylene group was evaluated and compared with that obtained for other classes of aqueous cyclic solutes.     

1-Butanol + hexylamine + n-heptane at temperature range (288.15–323.15 K): Experimental density data,excess molar volumes determination and modeling with cubic EOS

Densities ρ of the ternary system 1-butanol + hexylamine + n-heptane and binaries: 1-butanol + hexylamine and hexylamine + n-heptane within the temperature range (288.15–323.15 K) and atmospheric pressure are reported. Excess molar volumes V^E were calculated from the density data and fitted by the Redlich–Kister and Nagata and Tamura equations. The results are analyzed in terms of the molecular interactions between the components of mixtures.     

Densities and apparent molar volumes for aqueous solutions of HNO3−UO2(NO3)2 at 298.15 K

In order to obtain the exact information of atomic number density in the ternary system of HNO₃−UO₂(NO₃)₂−H₂O, the densities were measured with an Anton-Paar DMA60/602 digital density meter thermostated at 298.15±0.01 K. The apparent molal volumes for the systems were calculated from the experimental data. The present measured apparent molar volumes have been fitted to the Pitzer ion-interaction model, which provides an adequate representation of the experimental data for mixed aqueous electrolyte solutions up to 6.2 mol/kg ionic strength. This fit yields θ ^V , and ψ ^V , which are the first derivatives with respect to pressure of the mixing interaction parameters for the excess free energy. With the mixing parameters θ ^V , and ψ ^V , the densities and apparent molar volumes of the ternary system studied in this work can be calculated with good accuracy, as shown by the standard deviations.     

Synchrotron X-ray structures of cellulose I<Subscript>β</Subscript> and regenerated cellulose II at ambient temperature and 100 K

Synchrotron X-ray data have been collected to 1.4 Å resolution at the NE-CAT beam-line at the Advanced Photon Source from fibers of cellulose I_β and regenerated cellulose II (Fortisan) at ambient temperature and at 100 K in order to understand the effects of low temperature on cellulose more thoroughly. Crystal structures have been determined at each temperature. The unit cell of regenerated cellulose II contracted, with decreasing temperature, by 0.25%, 0.22% and 0.1% along the a, b, and c axes, respectively, whereas that of cellulose I_β contracted only in the direction of the a axis, by 0.9%. The value of 4.6×10^?5 K^?1 for the thermal expansion coefficient of cellulose I_β in the a axis direction can be explained by simple harmonic molecular oscillations and the lack of hydrogen-bonding in this direction. The molecular conformations of each allomorph are essential unchanged by cooling to 100 K. The room temperature crystal structure of regenerated cellulose II is essentially identical to the crystal structure of mercerized cellulose II.