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1.
Densities of aqueous solutions of sodium bromide at the molalities (0.09855, 0.49997, and 1.0001)mol · kg  1were determined at 1 K temperature intervals fromT =  278.15 K to T =  338.15 K. The densities were used in the evaluation of the apparent molar volumes, the cubic expansion coefficients, the apparent molar expansibilities and the second derivatives of the volume with respect to temperature. Properties of sodium bromide solutions which were determined in volumetric and calorimetric measurements are discussed and compared.  相似文献   

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Isoentropy compressibilities of aqueous magnesium chloride and sulfate were determined based on precision measurements of ultrasound velocity, density, and isobaric heat capacity at low to high concentrations at 278.15–323.15 K. The hydration numbers h and the molar parameters of volume and compressibility were calculated based on thermodynamically correct equations for hydration complexes (V h , β h V h ), water in the hydration shell (V 1h , β1h V 1h ), and the void containing a stoichiometric mixture of ions (V 2h , β2h V 2h ). The h and β h V h values were found to be independent of temperature; the molar compressibility of the hydration sphere (β1h V 1h ) and the stoichiometric mixture of ions without a hydration shell (β2h V 2h ) were independent of the concentration under the stated conditions. The effect of the electrostatic field of ions on the temperature dependence of the molar volume of water in the hydration sphere was more significant than the effect of pressure on the temperature dependence of the molar volume of bulk water. This is attributed to changes in the dielectric constant of water in the vicinity of the electrolyte ions.  相似文献   

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Present paper reports density, relative viscosity and refractive index of sodium salt of 1-heptanesulfonic acid and 1-octanesulfonic acid at 29°C. Density data has been fitted to Masson empirical relation and limiting apparent molar volumes were evaluated. Viscosity A and B coefficients characterizing ion-ion and ion-solvent interactions have been evaluated by fitting viscosity data in Jone-Doles equation. Experimental and calculated properties support the strong ion-solvent interactions in solution.  相似文献   

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Apparent molar volumes Vφ and apparent molar heat capacities Cp,φ were determined for aqueous solutions of d-lactose · H2O at molalities (0.01 to 0.34) mol · kg−1 at temperatures (278.15 to 393.15) K, and at the pressure 0.35 MPa. Our Vφ values were calculated from densities obtained using a vibrating tube densimeter, and our Cp,φ values were obtained using a twin fixed-cell, power-compensation, differential-output, temperature-scanning calorimeter. Our results for d-lactose(aq) and for d-lactcose · H2O were fitted to functions of m and T and compared with the literature results for aqueous d-glucose and d-galactose solutions. Infinite dilution partial molar volumes V2 and heat capacities Cp,2 are given over the range of temperatures.  相似文献   

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Apparent molar heat capacities Cp, φand apparent molar volumesVφ 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 (Vφ, T, m) and (Cp, φ,T , m) results. Infinite dilution partial molar volumes V2oand heat capacities Cp,2owere obtained over the range of temperatures by extrapolation of these surfaces to m =  0.  相似文献   

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Relative densities of CaCl 2 (aq) with 0.22ml(mol-kg–1)6.150 were measured with vibrating- tube densimeters between 25 and 250°C and near 70 and 400 bars. Apparent molar volumes V calculated from the measured density differences were represented with the Pitzer ioninteraction treatment, with appropriate expressions chosen for the temperature and pressure dependence of the virial coefficients of the model. It was found that the partial molar volume at infinite dilution V o , and the second and third virial coefficients B V and C V , were necessary to represent V near the estimated experimental uncertainty. The ionic-strength dependent (1)v term in the B V coefficient was included in the fit. The representation for V has been integrated with respect to pressure to establish the pressure dependence of excess free energies over the temperature range studied. The volumetric data indicate that the logarithm of the mean ionic activity coefficient, ln ±(CaCl 2 ), increases by a maximum of 0.3 at 400 bars, 250°C, and 6 mol-kg–1 as compared with its value at saturation pressure.  相似文献   

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The apparent molar volume of urea ? in aqueous solution in the range T = 273–323 K and m = 1–10 (molality) depends linearly on m 1/2. An equation for ?(m, T) was derived. The partial molar characteristics of urea ? 2 and water ? 1 (volume, dilatability, and temperature coefficients of volumes) were calculated. The ?(T) dependences have characteristic points (extrema, inflection points), shifted to the region of lower temperatures for dilute solutions. The ? 1(T) dependences for 2m and 4m of the urea solution retain the characteristics of the Y 1(T) of pure water. In these solutions, the proper structure of water is preserved.  相似文献   

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Journal of Solid State Electrochemistry - The 3d-cation-substituted perovskites Sr2MnNbO6 − δ, Sr2Cr0.5Mn0.5NbO6 − δ and...  相似文献   

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The densities of H2O, D2O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10–6 g cm–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V 2 ) and the isotope effects in V 2 and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H2O, D2O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility.  相似文献   

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Precise density and sound velocity measurements have been carried out for aqueous solutions of PPG725 in the absence and presence of (0.2 and 0.5) mol · kg−1 amino acids: alanine, glycine, serine and proline, and also for aqueous solutions of these amino acids in the absence and presence of 0.01 w/w PPG725 at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K. From the experimental density and sound velocity values, the apparent molar volume and isentropic compressibility have been obtained and extrapolated to infinite dilution. The infinite dilution apparent molar properties for transfer of PPG from water to aqueous amino acids solutions and also those for transfer of amino acids from water to aqueous PPG solutions have been studied. Temperature dependency of the infinite dilution apparent molar volume was utilised to determine structure-breaker or structure-maker effects of the solutes. Hydration numbers of the amino acids in the investigated aqueous solutions have been evaluated from the volumetric and compressibility properties. All results are discussed based on the salting-out aptitude of the amino acids (hydrophilic + hydrophobic) interactions and (hydrophobic + hydrophobic) interactions occurred between PPG and the investigated amino acids.  相似文献   

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Conductivities of concentrated solutions of lithium chloride in glycerol were measured for concentrations ranging from 0.005 to 1.5 mol.dm?3. The conductivity dependencies were analysed successively using the Debye–Huckel–Onsager limiting law (DHO) at very low concentrations, the Fuoss equation of 1978 up to 0.1 mol.dm?3, the Casteel–Amis empirical equation and the quasi-lattice model (QLM) at moderate and higher concentrations. The molar conductivities at infinite dilution, obtained using DHO and QLM were quite different from each other, because the salt forms contact pairs which were underestimated in the Λ f(C1/3) in QLM, as it may well be proved by Raman spectroscopy. Besides, the value of Madelung constant suggests that LiCl crystallises face centred cubic (FCC) at higher concentrations. On the basis of Raman spectroscopy analysis of previous lithium salts, we assume that the dissociation coefficient varies slightly with concentration and fraction of paired ion constant, the QLM equation is applied successfully in the concentration range used in this study. The temperature dependency of conductivity was also described using the Vogel–Tamman–Fulcher (VTF) empirical equation where the Arrhenius type was found. The results also suggest that as NaCl, LiCl can be considered as a structure maker electrolyte.  相似文献   

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Densities, viscosities, and refractive indices of aqueous solutions of hydroxylamine hydrochloride containing 0.05, 0.10, and 0.15 mol/dm3 NaCl, KCl, and NH4Cl were measured at different concentrations of hydroxylamine hydrochloride at 30°C. Viscosity coefficients A and B representing ion-ion and ion-solvent interactions were determined from Jones-Dole equation. Experimental properties and viscosity coefficients have been interpreted in terms of ion-ion and ion-solvent interactions. Ion-solvent interactions were found to be dominating over the ion-ion interactions in studied systems.  相似文献   

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