Acoustic Study of Solvent Coordination in the Hydration Shells of Potassium Iodide

The isentropic compressibilities of aqueous solutions of potassium iodide, from dilute to almost saturated, were determined at 288 to 308 K based on precise measurements of the speed of ultrasound. Using proper correlations, the hydration numbers (h) were calculated as well as the molar volume and compressibility parameters of the hydrated complexes (V _h , β _h V _h ) of water in the hydration shell (V _1h , β_1h V _1h), and of the cavity containing stochiometric mixtures of K⁺ and I⁻ ions (V _2h, β_2h V _2h). It is revealed that under the studied conditions, the obtained values of h and β _h V _h are independent of temperature whereas the molar compressibility of the hydration shell β _h V _h) is independent of concentration. The electrostatic field of the ions is shown to influence the temperature dependence of the molar volume of water in the hydration shell more substantially than a change of pressure alone influences the temperature dependence of the molar volume of pure water.     

Solvation of the Electrolytic Components of Seawater

A new modification of the adiabatic compressibility method of investigating solvation in solutions is presented and applied to the analysis of the following structurally-related characteristics of hydrated complexes of seawater electrolytes (NaCl, KCl, MgCl₂, CaCl₂, Na₂SO₄, MgSO₄) at different concentrations (0.1 to 5.0 mol⋅kg⁻¹) and temperatures (278.15 to 308.15 K): solvation numbers (h) and their dependences on concentration, volumes of stoichiometric mixtures of ions without their hydration shells (V _2h ), compressibilities (β _1h ) and molar volumes of water in their solvation shells (V _1h ), their dependences on concentration and temperature, etc.     

Definition of Hydration Parameters in the Region of Maximal Solvent Density

The approach to the definition of hydration numbers using the ultraacoustic method is critically discussed. Leaning upon a correct thermodynamic analysis, limited validity is shown of the main equation used in the publication of Onori over a wide range of state parameters. It is revealed that the mentioned equation is true only in the region of maximum solvent density. For this range of conditions, hydration numbers, the compressibility of hydration formations, molar volume and compressibility of water in hydration shells, molar volume and compressibility of stoichiometric mixtures of ions of NaCl are calculated based upon the experimental data of density and speed of ultrasound in solutions.     

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。     

Density and compressibility measurements of a highly viscous polyelectrolyte solution: a study on aqueous solutions of sodium hyaluronate

The density of a highly viscous polyelectrolyte solution was measured using both pycnometers and oscillating-tube densimeters in parallel to elucidate the difficulties inevitably involved when an oscillating tube is employed for density measurements of viscous liquids. It was confirmed that the oscillating-tube densimeter gives too high values for viscous liquids, and the deviation increases with the increase in the viscosity of liquids. The analysis of adiabatic compressibilities of sodium hyaluronate (NaHy) solutions, as estimated from density and ultrasound velocity data of the same solution, suggests that the disaccharide unit of the NaHy chain is less hydrated than the sum of its component monosaccharide residues. Received: 2 September 1998 Accepted in revised form: 29 September 1998     

Conductance of Electrolyte Solutions

The present article deals with methods and results of conductance studies with special reference to nonaqueous solvents, e.g. ethanol, dioxane, dimethylformamide, acetonitrile, nitromethane, and acetone, in some cases mixed with water, as well as NH₃, SO₂, I₂, etc. On the basis of a model in which the ions are represented as charged spheres and the solvent as a homogeneous isotropic medium, the conductance theory can (at least for low electrolyte concentrations) give a more or less complete representation of the problem. A new statistical treatment of the transport problem confirms important results of this representation. The present state of the investigation is finally outlined in a review of recent publications.     

An Application of Percolation Theory to the Electrolyte Penetration through Porous Water-Swollen Cellulose Triacetate Membrane

Permeability coefficients P of KCl through porous cellulose triacetate (CTA) membranes were measured as a function of the water volume fraction V_W and diffusion coefficients D were determined using solubility parameters K and a membrane thickness d from the relationship of P = KD/d. D increased with an increase in V_W. D especially increases abruptly around V_W = 0.5, which corresponds to 2% triethylene glycol (TEG) content. The percolation theory was applied to the experimental results under the conditions D_A = D (V_W = 1) = 1.8 × 10⁻⁵ cm² s⁻¹, D_B = D(V_W = 0) = 1.8 × 10⁻⁸ cm² s⁻¹, coordination number (Z) = 2.5, 3, 3.5, and 4, and packing fraction f = 1.0. A good fit was obtained at Z = 3.5 because the experimental and calculated results also shifted at the same V_W below V_W = 0.5. It is suggested that a phase inversion, that is, change of a discontinuous water phase to a continuous water phase, occurs around V_W = 0.5. Above V_W = 0.5, the experimental results agree well with the calculated line for Z = 3 or Z = 2.5 which means that the coordination numbers decrease with an increase in water content. It is thought that V_W is overestimated because it is hard to completely wipe off the excess water quickly from the membrane surface. Z = 3.5 means that a pore can connect in 3.5 directions.     

The Solubility of Boric Acid in Electrolyte Solutions

The solubility of boric acid [B] in LiCl, NaCl, KCl, RbCl, and CsCl was determined as a function of ionic strength (0–6 mol ⋅ kg⁻¹) at 25 ^∘C. The results were examined using the Pitzer equation

强电解质溶液粘度的研究

研究对强电解质溶液粘度的影响因素,18种强电解溶液在不同温度和不同浓度下的粘度测定结果显示,强电解质溶液的粘度和离子强度、温度倒数分别成指数关系,符合经验公式:lnη=lna+b/T+kl,且粘度和电解质的电荷强度、离子半径等相关.     

电解质溶液中牛血清白蛋白分子相互作用的动态光散射研究

溶液中粒子斥与吸引作用力,这种依赖关系可以通过作用参数λ来的扩散系数对浓度的依赖关系主要取决于粒子在溶液中所占的体积分数和粒子间的排表示。本研究利用动态光散射技术测量了不同离子强度下牛血清白蛋白分子的扩散系数,求出了相应条件下的λ值。结果表明,在低离子强度下,λ是正值,蛋白质分子间的作用以排斥力为主,随着离子强度的逐渐增大,λ变为负值,蛋白质分子间的作用以吸引力为主,当离子强度大于0．5mol／L的时候,蛋白质开始发生聚集。利用DLVO理论的两体硬球相互作用模型解释了蛋白质分子间相互作用的变化规律：随着离子强度的增加,静电斥力被屏蔽,范德华分子作用力起主要作用。根据值与离子强度变化的相关性,回归出了蛋白质参数：在实验条件下,蛋白质所带的有效电荷Zr=-9．0e、Hamaker常量AH=2．8kBT。实验结果表明：动态光散射技术可以有效地用来研究蛋白质分子间的相互作用。     

Calculation of the osmotic and activity coefficients of seawater at 25°C

The equation of Reilly, Wood, and Robinson was used to predict the osmotic coefficient of seawater and of its concentrates at molal ionic strengths of 0.5 to 6.0 at 25°C. The results agree closely with experimental data at ionic strengths below 5. The average difference in osmotic coefficients over the entire concentration range is 0.0014. The only serious discrepancy is at an ionic strength of 6, where a difference of 0.0068 is found. The accuracy of the predictions of osmotic coefficients prompted the calculation of the activity coefficients of NaCl, Na₂SO₄, MgCl₂, MgSO₄, KCl, and K₂SO₄ in the mixture. The calculated activity coefficients of NaCl and Na₂SO₄ agree within experimental error with previous measurements. This agreement demonstrates the prediction of activity and osmotic coefficients for complex mixtures.     

Compressibility and thermal expansion coefficients of nanocomposites with amorphous and crystalline polymer matrix

Clay-containing polymeric nanocomposites (CPNC) with polystyrene (PS) or polyamide-6 (PA-6) matrix were studied within T = 300-600 K and P = 0.1-190 MPa. From the Pressure-Volume-Temperature (PVT) data the derivatives: compressibility, κ, and thermal expansion coefficient, α, were computed as functions of T, P and clay content, w. Dependence of these coefficients on P and T were significantly different for the amorphous PS than for the semi-crystalline PA-6. In the PS plots of κ and αvs.T the presence of secondary transitions, T_β/T_g ≈ 0.9 ± 0.1 and T_c/T_g = 1.2 ± 0.1, were detected and the clay effect at low T was prominent, affecting the physical aging. The isobaric values of α = α(T) were characterized by nearly T-independent values in the glassy and molten phase, connected by a large transitory region stretching from the ambient pressure values of T_g to T_c; this region was even more prominent in κ = κ(T). The derivative properties of PA-6 based CPNC were distinctly different. Here, the isobaric κ = κ(T) followed the same dependence on both sides of the melting zone, while the isobaric α = α(T) dependencies were dramatically different for the solid and molten phase; at T < T_mα linearly increased with T, after melting its value sharply decreased, and then at T > T_m (depending on w and P) either increased or decreased with T. Interpretation of the behavior in the melt and glass is based on the Simha-Somcynsky (S-S) cell-hole theory while that of the semicrystalline state on the Midha-Nanda-Simha-Jain (MNSJ) cell theory. In spite of the nonequilibrium conditions below the main transition point, T_g or T_m, the theories well predict the observed dependencies.     

Osmotic Coefficients and Activity Coefficients of Nonaqueous Electrolyte Solutions. Part 2. Lithium Perchlorate in the Aprotic Solvents Acetone, Acetonitrile, Dimethoxyethane, and Dimethylcarbonate

Vapor pressure lowering by the addition of lithium perchlorate to the aprotic solvents acetone (0.02–0.6 m), acetonitrile (0.05–1.2 m), dimethoxyethane (0.02–0.4 m), and dimethylcarbonate (0.03–1.8 m) was measured at 25°C with high precision. The experimental data for the corresponding osmotic coefficients are compared to those obtained from the Pitzer equations and chemical model calculations. Mean activity coefficients are derived from the osmotic coefficients.     

The Effect of a Background Electrolyte on the Viscosity of Aqueous Dodecyltrimethylammonium Bromide Solutions

Conductometry and viscometry have been employed to study the effect of a background electrolyte (KBr) taken in concentrations of 0.03 and 0.1 M on the critical micelle concentration of dodecyltrimethylammonium bromide (С₁₂ТАB) and the dependence of relative viscosity η/η₀ of С₁₂ТАB micellar solutions on the overall surfactant concentration. It has been found that, as a first approximation, each of these dependences may be represented as the sum of two linear portions. Concentrations c* of С₁₂ТАB micellar solutions, which correspond to the inflections between the two linear portions in the concentration curves of relative viscosity, have been determined. The Einstein equation η/η₀ = 1 + 2.5p (p is the volume fraction of the dispersed phase and 2.5 is a theoretical parameter that takes into account the spherical shape of the particles) has been transformed into a form corresponding to the concentration dependence of the relative viscosity on the overall surfactant concentration to make it applicable to the consideration of low-concentration systems, which are uncomplicated by intermicellar interaction. In particular, the applicability of the above equation for estimating micelle radii has been studied. It has been shown that the (η/η₀–1) = f(c/с₀₁–1) concentration dependences represented in bilogarithmic coordinates (c is the overall С₁₂ТАB concentration and c₀₁ is the critical micelle concentration) are linear in the absence of a significant intermicellar interaction and have slopes equal to unity. This fact may be considered as a criterion for the applicability of the Einstein equation to micellar solutions.     

聚合物电解质离子迁移数的测定方法

介绍了用于测定理想聚合物电解质中离子迁移数的三种比较常用的电化学方法,阐述了实际聚合物电解质输运性质和理想聚合物电解质输运性质之间的区别,并说明了实际聚合物电解质的离子迁移数的测定方法。     

The origin and development of the acidity function

The acidity function is a thermodynamic quantitative measure of acid strength for non-aqueous and concentrated aqueous Brønsted acids, with acid strength being defined as the extent to which the acid protonates a base of known basicity. The acidity function, which was developed, both theoretically and experimentally, by Louis P. Hammett of Columbia University during the 1930s, has proven useful in the area of physical organic chemistry where it has been used to correlate rates of acid-catalyzed reactions and to quantitate the acidity of superacids, acids with protonating abilities greater than pure sulfuric acid. All Brønsted acids can now be compared using a common measure. Karl Popper’s seminal idea of theory falsification does not apply here because of the many successful applications of the acidity function. Likewise, Thomas Kuhn’s idea of a paradigm shift does not apply here, even though the acidity function concept was revolutionary, because the acidity function is commensurate with classical concepts of acidity.     

Osmotic Coefficients and Activity Coefficients of Nonaqueous Electrolyte Solutions. Part 3. Tetraalkylammonium Bromides in Ethanol and 2-Propanol

Vapor pressure lowering by the addition of tetraethylammonium bromide (0.04 to 2.3 m), tetrapropylammonium bromide (0.04–2.7 m), tetrabutylammonium bromide (0.05–2.5 m), bispiperidinium bromide (0.04–0.7 m) to ethanol and tetrapropylammonium bromide (0.04–1.3 m) and tetrabutylammonium bromide (0.03–1.9 m) to 2-propanol was measured at 25°C with high precision. The experimental data of the corresponding osmotic coefficients are compared to those obtained by the use of Pitzer equations and chemical model calculations. Mean activity coefficients are derived from the osmotic coefficients.     

Osmotic and Activity Coefficients of Nonaqueous Electrolyte Solutions. 1. Lithium Perchlorate in the Protic Solvents Methanol, Ethanol, and 2-Propanol

Vapor pressure lowering by the addition of LiClO₄ to the protic solvents methanol (0.04–5.1 m), ethanol (0.03–1.5 m), and 2-propanol (0.05–1.5 m) was measured at 25°C with high precision. The experimental data of the corresponding osmotic coefficients are compared to those obtained by the use of Pitzer equations and chemical model calculations. Mean activity coefficients are derived from the osmotic coefficients.     

Volumetric,Viscosity and Self-Diffusion Coefficient Studies of [18-Crown-6:M]A Complexed Species in Water at 298.15 K

Density and viscosity measurements were made for aqueous solutions of electrolytes containing 18-crown-6 (18C6) at 298.15 K. A method is proposed to extract the volumetric and viscosity data of the [18C6:M]A complexed species in aqueous solutions from ternary mixtures using the thermodynamic equilibrium constant values at 298.15 K. The apparent molar volume of the [18C6:M]A complexed species have been estimated for these binary solutions. Further, the viscosity data thus obtained were subjected to analysis using the Jones-Dole equation to get viscosity A- and B-coefficients of complexed ions in water. The hydration number and molecular radius of the hydrated complexes in water have been estimated. It was observed that hydration of the complexed ion is strongly influenced by the charge density of the metal ions in the complexed state. The self-diffusion coefficient and correlation time values for the complexes in water were calculated using viscosity data, which indicated that diffusion of complexed species was faster than that of the host ligand 18C6 (D_3d structural entity) in water at 298.15 K. It was suggested that the ionic radii estimated in this work for large hydrophobic cations can be of use in studying electrostatic and hydrophobic interactions especially in aqueous solutions.