肌醇在碱金属氯化物溶液中的体积性质

使用精密数字密度计测定了298.15和308.15 K肌醇在不同浓度的LiCl-H2O、NaCl-H2O或KCl-H2O溶液中的密度, 计算了肌醇的表观摩尔体积Vφ和极限偏摩尔体积Vθφ , 得到了其由纯水溶剂转移至混合溶剂中的迁移偏摩尔体积⊿trsVθ椎 .结果表明, LiCl, NaCl和KCl在溶液中对肌醇的体积性质影响显著, 极限偏摩尔体积Vθφ和极限迁移偏摩尔体积⊿trsVθφ都随盐浓度的增大而增加;温度对肌醇的极限偏摩尔体积和极限迁移偏摩尔体积只有轻微影响. 从分子-离子间的相互作用角度对实验结果进行了讨论.     

Decomposition Kinetics of Alkali Metal Gallams in Hydroxide Aqueous Solutions

The decomposition kinetics of alkali metal gallams in LiGa-LiOH, NaGa-NaOH, KGa-KOH, LiGa-NaOH, LiGa-KOH, and KGa-NaOH systems in the 40-80°C range was studied. The rate constant and current density of decomposition were determined. The rate equation of gallam decomposition under the given experimental conditions was obtained.     

Electrochemical Behavior of Lithium in Aqueous Solutions of Alkali Metal Hydroxides

Published data on the interaction of lithium with aqueous solutions of alkali metal hydroxides are discussed. The behavior of lithium in aqueous solutions of LiOH and KOH was studied experimentally.     

Solvent and Solute Effects on Electrokinetic Potentials at Interfaces between Air and Aqueous or Formamide Solutions of Alkali Metal Chlorides and Sodium Alkyl Sulfates

Electrokinetic flow in a hydrophilic capillary of a model direct emulsion consisting of a polar liquid (water or formamide) containing an alkali metal chloride or sodium alkyl sulfate and air is studied. The interfacial electrokinetic potentials are determined.     

Specific Features of Positron Annihilation in Aqueous Solutions of Alkali Metal Halides

The positron annihilation process was experimentally studied in aqueous solutions of NaF, NaCl, NaBr, and NaI over a wide concentration range. Different annihilation channels and their contribution to the overall process depending on the nature and concentration of halide ions were identified. A model was proposed, which assumes that positrons and halide ions form complexes having different lifetimes. Calculations in terms of the model showed a good fit to the experiment; the probabilities of formation of different positron and positronium states and their lifetimes were evaluated.     

Dielectric Properties and Structure of Aqueous Decaoxyethylene p-Isononylphenyl Ether Solutions

The static permittivity _s of aqueous decaoxyethylene p-isononylphenyl ether (NOP-10 grade) solutions is measured at surfactant concentrations of 1.14 and 4.97 wt % within 275–351 K temperature range; at concentrations of 9.96, 20, and 30 wt %, within 275–313 K range. Data on _s are analyzed, using the models of dilute disperse systems of oil–water type containing spherical particles, oblate and prolate spheroids. At 30, 20, and 9.96 wt % NOP-10 content, fragments of hexagonal mesophase are still retained in the isotropic phase near the interface, where there is a certain orientation of micelles acquiring the shape of prolate spheroids instead of cylindrical micelles. Upon heating up to 313 K, micelles are disoriented and their shape changes in prolate spheroid spherical micelle oblate spheroid sequence. With a further rise in water content, the fragments of lamellar mesophase appear in the isotropic phase at 4.97 and 1.14 wt % NOP-10 near the melting points of these solutions. They can exist with equal probability as the regions where either spherical micelles are located in the nodes of cubic lattice or oblate spheroidal micelles are distributed at random. As the temperature approaches the cloud point of dilute solutions, the randomly oriented oblate spheriodal micelles tend to acquire the disc-like shape.     

Changes in the IR Spectra of Aqueous Solutions of Alkali Metal Chlorides during Crystallization

The IR spectra of aqueous solutions of sodium chloride and rubidium chloride with the same concentration of 0.1 M upon freezing are studied in the middle IR region. The changes that occur in the absorption bands of the bending ν₂, compound ν₂ + ν_L, and stretching (ν₁, 2ν₂, and ν₃) vibrations of water molecules with gradual crystallization of the solutions are studied. The obtained spectra of crystallized solutions are compared to the IR spectrum of ice Ih. Analysis allows conclusions about the structure of the investigated frozen crystallized solutions.     

Conductometry and Thermodynamics Study of Metal Dodecyl Sulfates in Aqueous Solution

The aggregation behavior of metal dodecyl sulfates (MDS), [Na¹⁺, Mg²⁺, Mn²⁺, Co²⁺, and Ni²⁺] in water has been studied by electrical conductivity (at 293.15–333.15 K) and surface tension methods (at 303.15 K). Critical micelle concentrations (CMCs), degree of counterion dissociation (β) evaluated from conductivity data. Using law of mass action model, the thermodynamic parameters viz. Gibbs energy (ΔG_m ⁰), enthalpy (ΔH_m ⁰), and entropy (ΔS_m ⁰) were evaluated. The enthalpy of micellization decreases strongly with increasing temperature. ΔG is always negative (thermodynamically favored process) and slightly temperature and counterion dependent. Gibbs energy and entropy exploit micellization as thermodynamic favorable process. The electrostatic repulsions between ionic head groups, which prevent the aggregation, are progressively screened as the ionic character decreases with the size of the counterion. The plots of differential conductivity, (dk/dc) _T,P , versus the total surfactant concentration enables us to determine the CMC values more precisely than the conventional method. Surfactants with strong condense counterion are adapted to rodlike micelle better than to a spherical micelle. The data are explained in terms of molecular characteristics of surfactants viz. degree of dissociation, polar head group size and counterion.     

Heats of Mixing of Aqueous Solutions of Alkali Metal Salts of Substituted Benzenesulfonic Acids

The enthalpy change on mixing aqueous solutions of substituted benzene sulfonic acids and their salts, with salts having a common cation or anion, were measured at constant total ionic strength and at 25°C. The results are qualitatively interpreted in terms of solute–water structural properties and the ion size effect. The heat effects of mixing solutions having common anions obey the sign rule of Young and Smith. In anion–common cation mixings at concentration of 0.5 mol-kg^–1 only exothermic heat effects were observed, whose magnitude increase with the increasing difference in size of the mixed anions. The magnitude of the mixing effect increased with the salt concentration in cation–common anion mixing processes, In anion–common cation mixings the enthalpy of mixing changes sign from negative to positive, indicating a predominantly endothermic effect as concentration increases.     

Dielectric Relaxation of Aqueous Trimethylamineoxide Solutions

Dielectric relaxation was examined for aqueous trimethylamineoxide (TMAO) solutions over a wide concentration (c) range. The dielectric relaxation of TMAO was described by a Debye-type function with a relaxation time of about 3 × 10^–11 s, with the strength proportional to c. The number of water molecules tightly hydrated to unprotonated TMAO was estimated to be two. Ab initio calculations predict the magnitudes of the dipoles for individual TMAO and TMAO tightly hydrated by two water molecules, to be 4.9 and 4.2 D, respectively. When the amount of HBr added was increased, dielectric spectra were described by two modes with relaxation times, about 3 × 10^–11 and the about 8 × 10^–10. The fast relaxation was assigned to the rotational mode of unprotonated TMAO tightly hydrated by two water molecules, and the slow mode to the rotational mode of dimers formed between a protonated and unprotonated TMAO due to hydrogen bonding.     

Relationship between Radioluminance and the Dielectric Properties of Aqueous Salt Solutions in the Millimeter-Wavelength Spectral Range

Russian Journal of Physical Chemistry A - A new approach is developed to studying aqueous solutions of salts based on their emission in the millimeter waves spectral range. Using a highly sensitive...     

Adsorption Properties of Metal Ions Using Alumina Nano-Particles in Aqueous and Alcoholic Solutions

Different metal ions in aqueous and alcoholic solutions were adsorbed on alumina nano-particles prepared by the sol-gel method. The flocculation of the alumina sol was induced by the addition of different metal ions in solution. The flocculation kinetics was obtained by monitoring the particle growth with time using dynamic light scattering. These experiments were carried out following two different methods: a) the multiple injection method which consist in adding small amounts of metal ions until the critical flocculation concentration was reached and b) single injection method where an amount of metal ions equal to the critical flocculation concentration is added all in one shot. The efficiency of metal adsorption was determined by Atomic Absorption Spectroscopy.     

Dielectric Study of Aqueous Solutions of Alanine and Phenylalanine

Dielectric relaxation measurements on aqueous solutions of alanine and phenylalanine were carried out using time domain reflectometry (TDR) at 25, 30, 35, and 40 °C in the frequency range from 10 MHz to 20 GHz. Aqueous solutions of alanine and phenylalanine are prepared for five different molar concentrations of the respective amino acid. For all the solutions considered, only one relaxation peak was observed in this frequency range. The relaxation peaks shift to lower frequency with an increase in alanine and phenylalanine molar concentration. The molar enthalpy of activation and molar entropy of activation show endothermic interactions.     

Representation of Electrical Conductances for Polyvalent Electrolytes by the Quint-Viallard Conductivity Equation. Part 1. Symmetrical 2:2 Type Electrolytes. Dilute Aqueous Solutions of Alkaline Earth Metal Sulfates and Transition Metal Sulfates

Literature values of the electrical conductivities of dilute aqueous solutions of alkaline metal sulfates (BeSO₄, MgSO₄, CaSO₄, SrSO₄) and of transition metal sulfates (MnSO₄, FeSO₄, CoSO₄, NiSO₄, CuSO₄, ZnSO₄, CdSO₄) were reexamined within the framework of the Quint-Viallard conductivity equations in order to obtain a uniform representation of conductivities. It was observed that the limiting conductances of electrolytes at infinite dilution are very similar irrespective of the applied conductivity equation, whereas the derived ion association equilibrium constants vary considerably. The ion association equilibrium constants are therefore of doubtful physical value and should be treated rather as just fitting parameters.     

Diffusion and Ion Association in Concentrated Solutions of Aqueous Lithium, Sodium, and Potassium Sulfates

Taylor dispersion is used to measure mutual diffusion coefficients for aqueous Li₂SO₄ solutions at concentrations from 0.09 to 2.62 mol-dm^-3 at 25°C. The Li₂SO₄ results and previously reported diffusion coefficients for aqueous Na₂SO₄ and K₂SO₄ are compared with predictions made by treating the limiting electrolyte diffusion coefficients as reference values and applying corrections for nonideal solution behavior, ionic hydration, and viscosity changes as the concentration is raised. Good agreement is obtained if the M⁺ + SO ₄ ^2- ? MSO ₄ ^- (M = Li, Na, K) association equilibria are included in the analysis. Extents of formation of the MSO ₄ ^- ion pairs are evaluated by fitting Pitzer's mixed electrolyte equations for aqueous M⁺–MSO ₄ ^- –SO ₄ ^2- ions to osmotic coefficient data. Diffusion coefficients for hypothetical solutions of the completely dissociated M₂SO₄ electrolytes are calculated to illustrate the effects of ion association on diffusion. Association of the M⁺ and SO ₄ ^2- ions increases the overall mobility and thermodynamic driving forces for their diffusion.     

Onium Sulfates and Hydrogen Sulfates: Products of Reactions of Sulfur(IV) Oxide with Aqueous Solutions of Alkylamines and Aniline

The reaction products formed in the SO₂–L–H₂O–O₂ systems (L is n-propylamine, n-butylamine, tert-butylamine, n-heptylamine, n-octylamine, aniline) were isolated and identified as “onium” salts [n-C₃H₇NH₃]₂SO₄, [n-C₄H₉NH₃]₂SO₄, [t-C₄H₉NH₃]₂SO₄, [n-C₇H₁₅NH₃]₃SO₄(HSO₄), [n-C₈H₁₇NH₃]₃SO₄(HSO₄), and [C₆H₅NH₃]₂SO₄. The products were characterized by elemental analysis, IR and Raman spectroscopy, mass spectrometry, and thermogravimetry.     

Effect of Alkali Metal Cations on the EDL Structure at a Gold Electrode in Alkali Solutions

Effect of the nature of cations of alkali metals on the EDL structure during adsorption of hydroxide ions at a gold electrode is considered. It is shown that the reason for such an effect can be the pulling of cations into the dense layer resulting from the formation of associates of cations and specifically adsorbed anions OH^–. Parameters that reflect this phenomenon are estimated quantitatively.     

The Effect of Water Addition on the Electrosurface Properties of Quartz in Solutions of Alkali Metal Bromides in Ethanol

Electrosurface properties (the -potential and surface conductivity) of quartz particles in water–ethanol solutions of CsBr, NaBr, and LiBr with concentrations C = 10^–5–10^–2 M are studied. The (log C) dependences plotted from the results of electrophoretic measurements with allowance made for the particle surface conductivity demonstrate that, when water content in the aforementioned solutions increases from 4 to 40 vol %, the -potential of quartz becomes more negative and the isoelectric point shifts toward higher electrolyte concentrations, which increase in the following series: CsBr < NaBr < LiBr. This shift of the isoelectric point is explained by a decrease in the specific interaction of the alkali metal cations with the quartz surface because of a rise in the degree of their hydration (supersolvation).     

Effect of Alkali Metal Cation on Copolymerization of Acrylamide with Salts of 2-Acrylamido-2-methylpropanesulfonic Acid in Aqueous Solutions

The kinetics of radical copolymerization of acrylamide with lithium, sodium, and potassium 2-acrylamido-2-methylpropanesulfonates in concentrated aqueous solutions in the presence of potassium persulfate as initiating agent at pH 9 and 50°C was studied by dilatometry.