Thermodynamical study of the zinc selenate-cobalt selenate-water system at 25°C

Summary The solubility in the ZnSeO₄-CoSeO₄-H₂O system has been studied at 25°C. It has been established that the CoSeO₄·6H₂O monoclinic crystal structure is unstable and undergoes a change into a tetragonal structure due to the included zinc ions. Activity coefficients of the salt components in the saturated solutions and in the mixed crystal hexahydrates have been determined by the isopiestic method. G ^F of (Zn_xCo_1–x)SeO₄·6H₂O mixed crystals shows a negative deviation from ideality.

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Thermodynamische Untersuchung des Systems Zinkselenat-Kobaltselenat-Wasser bei 25°C

Zusammenfassung Die Löslichkeitsisotherme des Systems ZnSeO₄-CoSeO₄-H₂O wurde bei 25°C untersucht. Es wird festgestellt, daß das monokline CoSeO₄·6H₂O unstabil ist und in tetragonale Mischkristalle übergeht. Mittels der isopiestischen Methode wurden die Aktivitätskoeffizienten der Komponenten in den gesättigten Dreistofflösungen und Mischkristallen bestimmt. G ^F der Mischkristallbildung weist eine negative Abweichung vom idealen Zustand auf.

     

Interaction in the manganese sulfate-carbamide-sulfuric acid-water system at 25°C

Heterogeneous equilibria in the manganese-carbamide-sulfuric acid-water quaternary system at 25°C are studied using the solubility method. The concentration boundaries are determined for crystallization of the initial solid components, eutectic compositions of the ternary systems, and binary compounds formed in the carbamide-sulfuric acid-water and carbamide-manganese sulfate-water systems, as well as for new compounds simultaneously containing carbamide, manganese sulfate, and sulfuric acid at a 1: 4: 1 and 1: 2: 1 ratios.     

Interactions in the zinc bromide-carbamide-hydrobromic acid-water system at 25°C

Interactions in the ZnBr₂-CO(NH₂)₂-HBr-H₂O quaternary system at 25°C were studied using the solubility method. The crystallization regions of the initial eutonic compositions, constituent ternary systems, binary compounds of carbamide with zinc bromide and hydrobromic acid, and two new coordination compounds ZnBr₂ · 4CO(NH₂)₂ · HBr and ZnBr₂ · 2CO(NH₂)₂ · HBr were identified.     

Phase diagram of an iodine-potassium iodide-water-ethanol system at 25°C

Phase equilibriums are studied in the isothermal-isobaric sections of the phase diagram of a fourcomponent iodine-potassium iodide-water-ethanol system at 25°C and atmospheric pressure. The compositions of the solvent at which it exhibits the greatest ability to dissolve iodine are established. It is shown that in all the investigated sections, there is three-phase eutonic equilibrium with potassium iodide and crystalline iodine as the solid phases. It is revealed that in the sections containing 30 and 50% of ethanol, potassium iodide serves as the salting in agent for crystalline iodine, due to the formation of polyiodide complexes of various composition in the studied system.     

Activity coefficients for NaBr in ethanol-water mixtures at 25°C

Activity coefficients for NaBr in ethanol-water mixtures with 0, 20, 40, 60, 70, 80, 90 and 99.9 weight% of ethanol have been determined at 25°C from the emf measurements of the galvanic cells

Diffusion of levodopa in aqueous solutions of hydrochloric acid at 25 °C

Ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂ and D₂₁) measured by the Taylor dispersion method are reported for aqueous solutions of {levodopa (l-dopa) + HCl} solutions at 25 °C and HCl concentrations up to 0.100 mol · dm⁻³. The coupled diffusion of l-dopa (1) and HCl (2) is significant, as indicated by large negative cross-diffusion coefficients. D₂₁, for example, reaches values that are larger than D₁₁, the main coefficient of l-dopa. Combined Fick and Nernst–Planck equations are used to analyze the proton coupled diffusion of l-dopa and HCl in terms of the binding of H⁺ ions to l-dopa and ion migration in the electric field generated by l-dopa and HCl concentration gradients.     

A new determination of the structure of water at 25°C

The results of a new neutron diffraction experiment to measure the structure of water are presented. The data, measured at the McMaster Nuclear Reactor, are of a high quality and are analysed to yield the hydrogen-hydrogen pair correlation function using a subtraction procedure which has been used in previous experiments of this kind. This procedure circumvents the necessity of applying inelasticity corrections. The results are in good agreement with earlier work and serve to establish the general correctness of the subtraction procedure when used to determine hydrogen correlations. The data are further analysed to yield separate oxygen-hydrogen and oxygen-oxygen partial structure factors for liquid water. For the second part of the analysis an effective mass model of the dynamic scattering law is used, with the model parameter, the effective mass of the scattering particle, chosen by a least-squares fit to the measured differential cross sections. The final pair correlation functions are obtained using a maximum entropy analysis of the structure functions.     

Solubility in the magnesium chlorate-carbamide-water system at 50°C

The solubility of phases in the magnesium chlorate-carbamide-water system was studied by the isothermal solubility method at 50°C. The crystallization branches of carbamide, magnesium chlorate hexahydrate, Mg(ClO₃)₂ · 6CO(NH₂)₂, Mg(ClO₃)₂ · 4CO(NH₂)₂ · 2H₂O, and Mg(ClO₃)₂ · 2CO(NH₂)₂ · 4H₂O were revealed in the phase diagram.     

Corrected values of osmotic and activity coefficients of aqueous NaTcO4 and HTcO4 at 25°C

Published isopiestic molalities for aqueous NaTcO₄ and HTcO₄ solutions at 25°C have been reexamined. Our calculations indicate that published smoothed values of the osmotic coefficients and mean molal activity coefficients _± of NaTcO₄ are substantially in error, by up to 100% for and 300% for _±. Published smoothed values of and _± for HTcO₄ solutions are in somewhat better agreement with the input data, but the reported are sometimes higher and sometimes lower than experimental values, by up to 6%. Consequently, we have reanalyzed isopiestic data for these two systems, and find that errors arose in representing the data mathematically. We report parameters for an extended form of the specific ion interaction equations and for Pitzer's equations, and corrected values of and _± are tabulated for aqueous NaTcO₄ and HTcO₄.     

Phase equilibria in the fluorosilicic acid-o-phenylenediamine-water system at 25°C: The crystal structure of o-phenylenediammonium hexafluorosilicate

The interactions in the H₂SiF₆-o-phenylenediamine-H₂O (FSA-PDA-H₂O) system at 25°C is studied using the isothermal solubility method. The solid phases existing in the system are o-PDA (0-23.70 wt % H₂SiF₆) and hexafluorosilicate formulated as (o-PDAH₂)SiF₆ (23.70–44.60 wt % H₂SiF₆). The structure for the latter is solved in single-crystal X-ray diffraction experiments. In the ionic structure of the complex, o-PDAH ₂ ²⁺ cations and SiF ₆ ² anions are linked through H-bonds NH-F((N-F 2.865(2)-2.967(2) Å) into a two-dimensional net. The Si-F bond lengths are 1.6709(12)-1.6958(12) Å.     

Solid-liquid phase equilibria in the fullerenol-d-CuCl2-H2O system at 25°C

Solubility in the ternary fullerenol-d-CuCl₂-H₂O system at 25°C is studied by means of isothermal saturation in ampoules. It is established that the diagram consists of two branches corresponding to the crystallization of fullerenol-d crystallohydrate and copper(II) chloride dihydrate and contains a single non-variant eutonic point corresponding to the reciprocal saturation with both solid phases. The salting-in effect on the crystallization branch of CuCl₂ · 2H₂O and the salting-out effect on the crystallization branch of fullerenol-d is revealed.     

Effect of pressure on the solubility of naphthalene in water at 25°C

Solubility of naphthalene in water was measured at 25°C and pressures up to 200 MPa. The solubility decreased with increasing pressure. From the pressure coefficient of the solubility, the volume change V accompanying the dissolution was estimated as 13.8±0.4 cm ³ -mol ^–1 . Further we estimated the volume change V _CH accompanying hydrophobic hydration as –0.1±0.6 cm ³ -mol ^–1 using the V value, the molar volume of crystalline naphthalene, and the partial molar volume of naphthalene in n-heptane. This V _CH is much larger (i.e., less negative) than that for hydrophobic hydration of alkyl-chain compounds and suggests that the hydration structure of naphthalene differs from that of alkyl-chain compounds.     

The Effects of Cosolvents on the Complexation of α-Cyclodextrin with Alkylated Substances. Calorimetric Studies at 25 °C

The formation of complexes of -cyclodextrin with 1,2-alkanediols, ,-alkanediols and some cycloalkanols has been studied calorimetrically at 25 °C in water, in 7 mol kg^-1 aqueous urea and in 3 mol kg^-1 aqueous glucose. When a complex is formed, calorimetry enables the calculation of both the enthalpy and the association constant, from which the free energy and the entropy of the process can be obtained. The forces involved in the association process are discussed in the light of the signs and values of the thermodynamic parameters obtained. The effect of the variation of the aqueous medium on the hydration of the interacting substances and the consequent changes in the association parameters have been investigated. As respect to water, complexes are less stable in urea and more stable in glucose. The analysis of the data shows that this is the result of a different enthalpy-entropy balance in the two solvent media. Deaquation of the interacting substances plays a major role in determining the stability of the inclusion complexes.     

Voltammetric Analysis of Iodide and Diffusion Coefficients Between 25 and 85°C

The oxidation wave of iodide in 0.075 mol-L^–1 H₂SO₄ was analyzed at 25, 40, 55, 70, and 85°C. The reversibility of the I₂/I^– system was checked using logarithmic transforms, half-wave potentials, and by studying I ^–1 = f(^–1/2). The limiting currents obtained enabled us to determine the diffusion coefficient of I^– using Newman's equation. These experimental results were compared with Nernst's limiting values. The Stokes–Einstein equation is not verified. Hydration numbers for I^– at different temperatures were established. An empirical equation is proposed to predict the evolution of diffusion coefficients in a sulfuric acid medium with temperature.     

Thermodynamic Properties of Aqueous Solution of 2-Isopropoxyethanol at 25°C

Excess enthalpy, excess isobaric heat capacity, density, and speed of sound for aqueous 2-isopropoxyethanol solutions were measured at 25°C. The density was also measured at 20°C. The excess enthalpy was –800 J-mol^–1 at the minimum (mole fraction alcohol, x = 0.2), showing that the hydrogen bonds formed between unlike molecules are stronger than those in both pure liquid states. The excess volume also was large and negative, more than –1.2 cm³-mol^–1 at the minimum (x = 0.35). Excess isentropic and isothermal compressibilities are extremely negative. These results suggest that breaking the hydrogen bond network in water and forming the stronger hydrogen bonds between unlike molecules reduces the volume of the solution and makes the solution less compressible. The excess isobaric heat capacity is positive and large, up to 10 J-K^–1-mol^–1 and shows anomalous behavior in the neighborhood of x = 0.15.     

Pressure and isotope effects on the proton jump of the hydroxide ion at 25°C

The limiting molar conductances Λ⁰ of potassium deuteroxide KOD in D₂O and potassium hydroxide KOH in H₂O were determined at 25°C as a function of pressure to disclose the difference in the proton-jump mechanism between an OH^? (OD^?) and a H₃O⁺ (D₃O⁺) ion. The excess conductance of the OD^? ion in D₂O λ _E ^O (OD ^-), as estimated by the equation $$\lambda _E^O (OD^ - ) = \Lambda ^O (KOD/D_2 O) - \Lambda ^O (KCl/D_2 O)$$ increases a little with pressure as well as the excess conductance of the OH^? ion in H₂O $$\lambda _E^O (OH^ - ) = \Lambda ^O (KOH/H_2 O) - \Lambda ^O (KCl/H_2 O)$$ However, their rates of increase with pressure are much smaller than those of the excess deuteron and proton conductances, λ _E ^O (D ⁺) and λ _E ^O (H ⁺). With respect to the isotope effect on the excess conductance, λ _E ^O (OH ^-)/λ _E ^O (D ⁺) decreases with presure as in the case of λ _E ^O (H ⁺)/λ _E ^O (D ⁺), but the value of λ _E ^O (OH ^-)/λ _E ^O (OD ^-) itself is much larger than that of λ _E ^O (H ⁺)/λ _E ^O (D ⁺) at each pressure. These results are ascribed to the difference in the pre-rotation of water molecules, which is brought about by the difference in the intial orientation of the rotating water molecule adjacent to the OH^? (OD^?) or the H₃O⁺ (D₃O⁺) ion.     

Excess enthalpies of aqueous solutions of small peptides at 25°C

Heats of dilution of aqueous solutions of the following di-and tripeptides were determined at 25°C over a wide concentration range: -alanyl-glycine, -alanyl--alanine, DL--alanyl-glycine, glycyl-DL--alanine, L--alanyl-L-alanine, DL--alanyl-DL--alanine, DL--alanyl-DL-valine, DL--alanyl--alanine, glycyl--aminobutyric acid, glycyl-L-leucine and DL--alanyl-glycylglycine. The excess enthalpies H^ex and partial molar relative enthalpies L₂ were calculated and enthalpy coefficients of intermolecular interaction were analysed using the additivity principle of Savage and Wood. The concentration dependence of the enthalpic characteristics of peptide-peptide interactions is discussed based on of their hydrophobicity and hydrophilicity. The three-stage model of peptide association is described using enthalpic coefficients of intermolecular interactions.     

Solubility equilibria in the system Cd(II)-2-mercaptopropionic acid at 25°C

The solubility equilibria between Cd(II) and 2-mercaptoproprionic acid in 3.0 M NaClO₄ at 25°C have been studied by e.m.f. The e.m.f. measurement with both glass and Cd(Hg) electrodes in the range 2.5 < pH < 4.8 were made in solutions where a solid phase coexists with soluble complexes Cd_qA_p. Free ligand and metal ion concentrations were calculated in order to determine the solubility product of CdA (eqn 5). From the values of the formation constants for the soluble complexes and the solubility product, the solubility constants k_spq have been computed. A general equation for the redissolution of the precipitate is proposed and a set of equilibrium constants is given.     

Dependence of the volume characteristics and viscosity of solutions of methanol-octane-naphthalene on composition at 25°C

The limiting solubility of naphthalene in a mixture of methanol-octane at 25°C is determined via isothermal saturation. The kinematic viscosity of a mixture of methanol-octane-naphthalene is measured at 25°C. Data on the density of triple mixtures of methanol-octane-naphthalene, used to calculate the partial and apparent molar volumes of naphthalene, are obtained with a high degree of accuracy. The obtained results are discussed in terms of the interactions that occur in solution.