The Possible Presence of Triple Ions in Electrolyte Solutions of Low Dielectric Permittivity

The cause of the appearance of a minimum in the molar electrical conductivity in many electrolyte solutions with increasing electrolyte concentration, in solvents of low dielectric permittivity, is reviewed. Tentative explanations include the formation of triple ions or, alternatively, changes in the electrical polarization of the solutions due to the presence of electrolyte ion pairs. Theoretical models for linear triple ions and apolar dimers are examined. Experimental evidence favors the polarization hypothesis over triple ions; the presence of a maximum in the dielectric permittivity with increasing electrolyte concentration is consistent with the presence of an equilibrium between ion pairs, AB, and their dimers, A₂B₂, at higher concentrations.     

Numerical Calculation of Permittivity and Dielectric Loss of Aqueous KF Solution Depending on State Parameters

Based on the analytical expressions for permittivity ε₁(ω) and dielectric loss ε₂(ω) are obtained by the kinetic equation method, the frequency spectra of these coefficients are analyzed for an aqueous KF solution in a wide variation range of the density ρ, the concentration C, and the temperature T. With a certain choice of the solution model, the potential interaction energy Φab(|r|), and the radial distribution function g_ab(|r|) of a- and b-type ions, ε₁(ω) and ε₂(ω) of an aqueous KF solution are numerically calculated depending on ρ, C, T, and ω.     

Numerically Calculating the Concentration and Temperature Dependences of the Electrical Conductivity of Aqueous Electrolyte Solutions

Russian Journal of Physical Chemistry A - Kinetic equations are used to find analytical expressions for dynamic electrical conductivity $$sigma (omega )$$ and electroelasticity modulus $$ {in}...     

Super-High-Frequency Permittivity and Relaxation of Aqueous Solutions of Aluminum Chloride

The super-high-frequency dielectric properties of aqueous solutions of aluminum chloride were measured at five frequencies (13–25 GHz) at 298 K. The static permittivities and the times and other parameters of dielectric relaxation of the solutions were calculated. The concentration dependences of the hydration properties of the solutions within various concentration ranges were studied.     

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.     

Structure of Aqueous Electrolyte Solutions by X-ray Diffraction

Cadmium nitrate and cesium chloride solutions were studied in a wide concentration range by the X-ray diffraction method. The structure of aqueous solutions of the electrolytes is similar to the structure of solid phases that crystallize from them.     

Solubility Calculations of Methane and Ethane in Aqueous Electrolyte Solutions

Journal of Solution Chemistry - Accurate calculation of light hydrocarbon solubilities in aqueous electrolyte solutions is critical for petroleum and geochemical applications. However, very few...     

电解质水溶液结构研究进展及前景*

叙述盐湖中主要离子Li⁺ 、Na⁺ 、K⁺ 、Mg²⁺ 、Ca²⁺ 、Cl^- 、SO^2-₄ 、NO^-₃ 的水溶液和纯水的结构, 简单介绍了主要的研究方法, 分析讨论了溶液结构研究的现状和发展前景。     

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.     

Cationic and Anionic Effects on the Glass Transition Temperature for Aqueous Electrolyte Solutions

Glass-forming composition regions of aqueous CH₃COOM (M = Li, Na, K, Rb, Cs, and Tl), CF₃COOM (M = Li, Na, K, Rb, and Cs), and Et₄NX (Et₄ = C₂H₅, X = OH, CH₃COO, Cl, Br, NO₃, and SCN) solutions are reported as a function of water concentration R (R = moles of water per moles of salt). Glass transition temperatures (T _g) were measured by a simple differential thermal analysis (DTA) method with a cooling rate of about 600 K-min^–1. The T _g of all solutions decrease with increasing R (decreasing salt concentration). It is found that T _g at the same R value decrease in the order Na⁺ > Li⁺ > K⁺ > Rb⁺ > Cs⁺ in all glass-forming composition regions of the alkali acetate salt and alkali trifluoroacetate salt solutions. T _g for Et₄NX solutions decrease in the order CH₃COO^– ~OH^– > Cl^– > Br^– > NO ₃ ^– > SCN^–. The effects of the cation and anion on the glass-forming behavior in these aqueous solutions are discussed.     

Structure at the Free Surface of Water and Aqueous Electrolyte Solutions

Abstract

During the past 20 years or so one of the regions of conspicuous growth in the field of physical chemistry has been the study of the structure and behaviour of water and aqueous solutions. There are practical reasons, for example technical and biological, for this interest, but it is also true that the complexity of water as a liquid provides its own motive to the rcsearch worker. It is unlikely that we would spend so much time in the study of water if it were as simple a liquid as Argon. However, strange though the behaviour of liquid water is, it is probably not as strange as it has sometimes been thought to be. The thermal “anomalies” of water and the abnormal “Poly-water” Seem rather likely to fade out of the scientific scene, as have other stimulating but nonviable scientific myths.     

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.     

Quasi-thermodynamics of Viscous Flow of Electrolyte Solutions in Aqueous, Non-aqueous and Mixed Aqueous Solvents

Viscosity B-coefficients for cesium chloride and lithium sulfate in methanol + water mixtures at 25 and 35 °C are reported. A general treatment of the quasi-thermodynamics of viscous flow of electrolyte solutions is described. ΔG ₃ ^Θ (1→1′), the contribution made to the Gibbs energy of activation of the solution by the influence of the solute on the solvent, is a function of solute–solvent interactions only; but, ΔH ₃ ^Θ (1→1′) and ΔS ₃ ^Θ (1→1′) also reflect the solvent–solvent interactions. In aqueous solution all alkali-metal ions except Li⁺ are sterically unsaturated, having solvent co-ordination numbers n<n _max, the maximum allowed sterically. Such complexes exchange molecules with the solvent more readily than saturated ones and have energy–reaction co-ordinate diagrams in forms that explain the negative B or ΔG ₃ ^Θ (1→1′) values found in aqueous solution. Saturated complexes are the norm in non-aqueous solvents, and the ΔG ₃ ^Θ (1→1′) values are determined mainly by the secondary solvation. Behavior in mixed solvents reflects the transition from aqueous to non-aqueous behavior across the range of solvent composition.     

Electrosurface Properties of Schungite III Particles in Aqueous Electrolyte Solutions

The kinetics of electrolyte extraction into water and the electrosurface properties (adsorption of potential-determining ions H⁺ and OH⁻ and ζ potential) of five fractions of schungite III (particle sizes of < 5, 50–100, 160–400, 400–1000, and 1600–2500 µm) are studied in aqueous NaCl, CaCl₂, and AlCl₃ solutions at different pH values. It is shown that, in water and NaCl and CaCl₂ solutions, the point of zero charge (PZC) of the particles with sizes of 50–100 and 160–400 µm is observed at pH 4.0 and is independent of the electrolyte concentration. The isoelectric point (IEP) for small (<5 µm) schungite III particles is observed at pH 2.8. The IEP position is independent of CaCl₂ concentration, but it shifts to pH 2.4 when NaCl concentration increases to 0.1 M. The disclosed differences in the PZC and IEP values may be caused by different compositions of particles of different fractions. In a 10⁻⁵ M AlCl₃ solution, schungite particles demonstrate three IEPs (pH 3.0, 4.5, and 7.4) due to different degrees of AlCl₃ hydrolysis at different pH values.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 450–457.Original Russian Text Copyright © 2005 by Aleinikov, Lorentsson, Chernoberezhskii.     

用Pitzer理论预测混合电解质溶液的偏摩尔体积

用Pitzer理论研究了混合电解质溶液的偏摩尔体积,建立了偏摩尔体积的预测方法,并利用所得电解质溶液的表观摩尔体积的Pitzer参数预测了HNO₃-UO₂(NO₃)₂-H₂O、KCl-Na₂SO₄-H₂O、NaCl-Na₂SO₄-H₂O、NaCl-CaCl₂-H₂O、KCl-CaCl₂-H₂O、KCl-MgCl₂-H₂O和KCl-NaBr-H₂O共7个系统4种类型的混合溶液的偏摩尔体积。     

A New Gibbs Energy Model for Obtaining Thermophysical Properties of Aqueous Electrolyte Solutions

In this paper, a new Gibbs energy model is proposed to study the thermophysical properties of aqueous electrolyte solutions at various temperatures. The proposed model assumes that the electrolytes completely dissociate in solution. The model also has two temperature-independent adjustable parameters that were regressed using experimental values of the mean ionic activity coefficients (MIAC) for 87 electrolyte solutions at 298.15 K. Results from the proposed model for the MIAC were compared with those obtained from the E-Wilson, E-NRTL, Pitzer and the E-UNIQUAC models, and the adjustable model parameters were used directly to predict the osmotic coefficients at this temperature. The results showed that the proposed model can accurately correlate the MIAC and predict the osmotic coefficients of the aqueous electrolyte solutions better on the average than the other models studied in this work at 298.15 K. Also, the proposed model was examined to study the osmotic coefficient and vapor pressure for a number of aqueous electrolyte solutions at high temperatures. It should be stated that in order to calculate the osmotic coefficients for the electrolyte solutions, the regressed values of parameters obtained for the vapor pressure at high temperatures were used directly. The results obtained for the osmotic coefficients and vapor pressures of electrolyte solutions indicate that good agreement is attained between the experimental data and the results of the proposed model. In order to unequivocally compare the results, the same experimental data and same minimization procedure were used for all of the studied models.     

Activity Coefficient Prediction for Binary and Ternary Aqueous Electrolyte Solutions at Different Temperatures and Concentrations

The mean spherical approximation (MSA) model, coupled with two hard sphere models, was used to predict the activity coefficients of mixtures of electrolyte solutions at different temperatures and concentrations. The models, namely the Ghotbi-Vera-MSA (GV-MSA) and Mansoori et al.-MSA (BMCSL-MSA), were directly used without introducing any new adjustable parameters for mixing of electrolyte solutions. In the correlation step, the anion diameters were considered to be constant, whereas the cation diameters were considered to be concentration dependent. The adjustable parameters were determined by fitting the models to the experimental mean ionic activity coefficients for single aqueous electrolytes at fixed temperature. The results showed that the studied models predict accurately the activity coefficients for single electrolyte aqueous solutions at different temperatures. In the systems of binary aqueous electrolyte solutions with a common anion, the GV-MSA model has slightly better accuracy in predicting the activity coefficients. Also, it was observed that the GV-MSA model can more accurately predict the activity coefficients for ternary electrolyte solutions with a common anion, especially at higher concentrations.     

MX—NX2和MX—NX3电解质水溶液的热力学研究

本文用Pitzer方程研究相同阴离子的非对称性混合电解质溶液的热力学性质,讨论了高次静电项(~Eθ_(ij)、~Eθ′_(ij))所产生的效应。引入混合参数(θ_(ij))和离子强度(Ⅰ)的关系式,估算了25℃时MX-NX_2和MX-NX_3电解质水溶液的Pitzer混合参数~Sθ_(ij)~(0)、~Sθ_(ij0~(1)和φ_(ij)k,其计算值和文献值吻合。     

Salting-in/Salting-out Mechanism of Carbon Dioxide in Aqueous Electrolyte Solutions

The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO₂ in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO₂ in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO₄ solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO₄ (0.012) should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO₄ is due to the strongly direct anion-CO₂ interaction. The inconsistency between Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.