Application of Kirkwood-Buff theory to electrolyte solutions. III. Activity coefficients of aqueous NaCl between 273.15 and 573.15 K

Using a theory recently developed for the interpretation of activity coefficients of 1:1 electrolytes up to high concentrations in aqueous solution at 25°C, we have analysed available data for aqueous sodium chloride solutions up to saturation in the temperature range 273.15–573.15 K. The approach, which is based on Kirkwood-Buff theory and uses the truncated Poisson-Boltzmann equation to obtain the required information about the various ion-ion radial distributions, is able to fit the results to high accuracy with minimum of parameters, viz, three, of which one is the distance of closest approach, the other two relate to ion-solvent interactions and/or higher order terms in the ion-ion interaction.     

Interactions between terminally substituted amino acids in an aqueous and a non-aqueous environment. Enthalpic interaction coefficients in water and in N,N-dimethylformamide at 25°C

Enthalpies of dilution of the N-acetyl amides of glycine, L-alanine, L-valine, L-leucine, and L-phenylalanine, dissolved in N,N-dimethylformamide (DMF) as a solvent have been measured at 25°C. The results obtained have been analyzed to give the enthalpic interaction (or virial) coefficients of the solutes and these are compared with information previously obtained in aqueous systems. There are marked differences in the interaction properties in the two solvents and, while the additivity approach of Savage and Wood is applicable to the solutes in water it is not suitable for representing the interactions in DMF. A correlation is presented between the enthalpic second virial coefficients in DMF and the propensity of side-chains to be in proximity in globular proteins.     

The Pharmaceutical Use of Captisol®: Some Surprising Observations

The purpose of this paper is to share some recent observations on the pharmaceuticaluses and properties of Captisol^® or SBE_7M--CD in controlled porosity osmotic pump tablets (CP-OPT) and the underlying mechanism/sthat lead to apparent zero-order drug release pattern. It would have been simple toattribute the apparent zero-order release mechanism/s of poorly water-soluble drugsfrom CP-OPTs and pellets utilizing Captisol^®as both a solubilizing andosmotic agent, to purely osmotic and diffusional components. However, the mechanismmay be more related to a counterbalancing of physical properties as the concentration of Captisol^®changes within the matrix. Specifically, the initial concentration of Captisol^®within a core is 0.3–0.4M. When this drops to lower values an osmotic pressure drop occurs across the membrane. Therefore, drug release should not follow apparent zero-order kinetics if all the drug is solubilized. However, as the viscosity within the tablet also drops, the apparent diffusion coefficient of both Captisol^® and drug increases. Therefore, it appears that there is an initial resistance (hydraulic pressure) to fluid flow from the tablet through the rate-limiting microporous membrane. This resistance decreases so that even as osmotic pressure and concentration differences drop with time, counterbalancing faster release occurs. Osmotic driving force appears to be the most important initial driving force but a diffusional component becomes more significant with time.     

Osmotic Coefficients of Aqueous Solutions of Some Poly(oxyethylene) Glycols at the Freezing Point of Solution

Summary. The freezing temperatures of dilute aqueous solutions of some poly(oxyethylene) glycols (PEG, HO–(CH₂CH₂O) _n –H, n varying from 4 to 117) were measured over a solute to solvent mass ratio from 0.0100 to 0.3900. The second and third osmotic virial coefficient (A ₂₂ and A ₂₂₂) of poly(oxyethylene) glycols in aqueous solution were determined. The molecular weight dependence of the second virial coefficient can be described by a simple relation A ₂₂=2×10^–5 M _n ^1.86, and the third virial coefficient is A ₂₂₂=0.038A ₂₂ ². The activity coefficients of the solute were calculated using the Gibbs-Duhem equation as applied by Bjerrum. From the osmotic and activity coefficients the excess Gibbs energies of solution, as well as the respective partial molar functions of solute and solvent and the virial pair interaction coefficients for the excess Gibbs energies were estimated. The second and the third osmotic virial coefficients are correlated with the Mc-Millan-Mayer virial coefficients.     

N–N2 state to state vibrational-relaxation and dissociation rates based on quasiclassical calculations

Interpolation formulas are presented to reproduce the rate coefficients for vibrational–translational energy exchange and dissociation for the N + N₂ collision process. The original data have been obtained by quasiclassical method in a detailed way, including the effect of molecular rotation. The fitting procedure results are compared with original data and the related error is evaluated. Comparison with global experimental dissociation results is also presented.     

Bestimmung der Aktivitätskoeffizienten im chromatographischen Modell „binärer Lösungen“

An explanation is given for the two possible ways of determination of the activity coefficients of solutes, when applying a new thermodynamic model of adsorption and partition chromatography, i. e. the binary solutions model.

     

定标粒子理论计算非水溶液的盐效应常数

本文应用定标粒子理论计算了非电解质溶质在盐(NaI、或KI)和环丁砜组成的非水电解质溶液中溶解度的盐效应常数。硬球作用项采用Masterton-Lee的方法。软球作用项采用胡英等的径向分布函数处理方法, 并考虑进了偶极-偶极、偶极-诱导偶极、电荷-偶极和电荷-诱导偶极等相互作用。分子的硬球直径σ和能量参数∈/k由经验方程计算。由理论值和实验结果比较得出: 当σ_2取0.563 nm、离子半径取电子密度标度时, 理论值与实验值符合得较好。     

Long-range dispersion coefficients for like centrosymmetric linear molecules and an application to H2-H2

The real spherical tensor theory of long-range intermolecular coefficients developed in previous papers is applied to derive explicit formulae for the first three dispersion coefficients for like centrosymmetric linear molecules. The expansion of angle-dependent coefficients in associated Legendre polynomials allows one to identify the isotropic and anisotropic components of the dispersion interaction in terms of London dispersion constants, the treatment of higher coefficients being simplified by the coupling of the elementary (l, l′)-polarizations to resultant angular momenta L_A and L_B onto each molecule. The contributions from all coupling schemes are given explicitly for C₆, C₈, C₁₀, and numerical results are presented for H₂-H₂ using two-term reduced spectra values from the Kaiserlautern group.     

Thermodynamics of multicomponent electrolyte solutions: Aqueous mixtures of two salts from among NaCl,KCl, NaH2PO4, and KH2PO4 at 25° C

Five of the six possible aqueous two-salt mixtures from among NaCl, KCl, NaH₂PO₄,and KH₂PO₄ have been studied by the isopiestic method at 25°C. The sixth mixture, NaCl–KCl, has been studied previously. The deviations from ideal mixing behavior are described by a series of coefficients which were found by regression analysis. The coefficients were used to calculate the excess Gibbs energies of mixing for equal ionic strength fractions of each salt and the trace activity coefficient of each salt at an ionic strength of 2 mode-kg^–1. The cross-square mixing rule is obeyed within experimental uncertainty for the excess Gibbs energies of mixing.     

Existence and Uniqueness of Solutions to Time-delays Stochastic Fractional Differential Equations with Non-Lipschitz Coefficients

In this paper, we consider the existence and uniqueness of solutions to time-varying delays stochastic fractional differential equations (SFDEs) with non-Lipschitz coefficients. By using fractional calculus and stochastic analysis, we can obtain the existence result of solutions for stochastic fractional differential equations.