Thec logc contribution to the electrolyte conductance and Onsager's reciprocal relation

The differential equations and the boundary conditions for the nonequilibrium binary distribution function of an unsymmetrical binary electrolyte are derived from the Ebeling-Falkenhagen continuity equation. The connection between the Onsager reciprocal relation and the binary distribution functions is shown. Further, Feistel's result for thec logc contribution to the conductance is extended to unsymmetrical binary electrolytes. The reason for the difference between Feistel's and Chen'sc logc term is explained, and the significance of Onsager's reciprocal relation for the calculation ofc logc and higher-concentration contributions of the conductance is discussed.     

A simple scheme for calculating the energy levels and the spectra of molecular crystals

A simple matrix method for calculating the vibrational and electron energy levels and spectra in molecular crystals is proposed.     

Role of isoconversional methods in varying activation energies of solid-state kinetics: I. isothermal kinetic studies

Solid-state kinetics was developed from kinetic concepts for reactions in homogeneous phase systems, which has created considerable debate over issues such as variable activation energy. This behavior has been viewed by some as a violation of basic chemical kinetic principles. Variation in activation energy has been detected by isoconversional or ‘model-free’ calculation methods. The relationship between different calculation methods and the occurrence of variable activation energy was investigated in this work by employing model-fitting and isoconversional methods to analyze simulated isothermal data. In addition, these approaches were applied for sulfameter-dioxolane solvate desolvation data. We showed that variable activation energy is of two types—a true variation that results from the complex nature of the solid-state process and an artifactual one resulting from the use of some isoconversional methods.     

Diffusion coefficients from stopped-flow gas chromatography

Summary Mutual diffusion coefficients of two gases A and B can be determined in an empty gas chromatographic column by letting component B enter at an intermediate position of the column and continuously flow through a part only of it, as a carrier gas. The other component A is injected in a small amount instantaneously at the closed end of the column with the detector placed at the other end. By repeatedly stopping and then restoring after a short time the flow of B, narrow extra peaks are produced on the chromatographic elution curve, owing to diffusion of A into B. An equation is derived giving the area under the curve of each stop-peak as a function of time of the corresponding stop. Plotting the experimental data according to this equation permits the determination of the diffusion coefficient of A into B. Some results obtained by this method show negligible variations with changes in the experimental parameters.     

Schrödinger Equation Solutions for the Central Field Power Potential Energy I. V(r) = V 0(r/a 0)2ν−2, ν ≥ 1

The solution of a generalized non-relativistic Schrödinger equation with radial potential energy V(r)=V ₀(r/a ₀)^2–2 is presented. After reviewing the general properties of the radial ordinary differential equation, power series solutions are developed. The Green's function is constructed, its trace and the trace of its first iteration are calculated, and the ability of the traces to provide upper and lower bounds for the ground eigenvalue is examined. In addition, WKB-like solutions for the eigenvalues and eigenfunctions are derived. The approximation method yields valid eigenvalues for large quantum numbers (Rydberg states).     

固相热分解反应最可几机制的判断

固相热分解反应最可几机制的判断高永煜，邹文樵，冯仰婕（华东理工大学化学系上海２００２３７）关键词热分解，动力学方程，反应机制固相热分解反应机制的判断，是热分析动力学中令人感兴趣的领域。常用的方法是从含机制函数的非等温积分动力学方程出发，分别用Ｓｅｓｔ...     

Finite extensibility and orientational effects in rubbers. A physical interpretation of the ‘van der Waals equation’ for the elastic force

We propose a physical interpretation of the so-called van der Waals equation of state for rubbers, which gives a relation between the force and the deformation. On a phenomenological basis this equation takes the finite extensibility and a non-defined interaction into account. Here the fininte extensibility is discussed for the dilute case (no entanglements) and the highly entangled limit. The intramolecular interactions are described by orientational effects. The resulting equation of state for the force shows the same features as the van der Waals equation.Dedicated to Prof. H.-G. Kilian on the occasion of his 60th birthday.     

Vapor pressure measurement for water,methanol, ethanol,and their binary mixtures in the presence of an ionic liquid 1-ethyl-3-methylimidazolium dimethylphosphate

Vapor pressure data were measured for water, methanol and ethanol as well as their binary mixtures with an ionic liquid (IL) 1-ethyl-3-methylimidazolium dimethylphosphate ([EMIM][DMP]) at varying temperature and IL-content ranging from mass fraction of 0.10–0.70 by a quasi-static method. The vapor pressure data for the IL-containing binary systems were correlated using NRTL equation with average absolute relative deviation (ARD) within 0.0076, and the binary NRTL parameters was used for predicting the vapor pressure of the IL-containing ternary systems with reasonable accuracy. In addition, the infinite activity coefficients of solvents in [EMIM][DMP] and isobaric vapor–liquid equilibrium for IL-containing ternary systems at 101.325 kPa and mass fraction of IL being 0.5 were predicted with the regressed NRTL parameters. The results indicate that ionic liquid [EMIM][DMP] can depress the volatility of the solvents of water, methanol and ethanol but to a varying degree, leading to the variation of relative volatility of a solvent and even removal of azeotrope for water–ethanol mixture.     

Fast Marching Method for Calculating Reactive Trajectories for Chemical Reactions

We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical system of interest.     

On the Nonlocal Electron Kinetics in s- and p-Striations of DC Glow Discharge Plasmas: I. Electron Establishment in Striation-like Fields

The nonlocal behavior of the electrons in strongly modulated and period-averaged electric fields typical of s- and p-striations in neon glow discharge plasmas is investigated by numerically solving the axially inhomogeneous electron Boltzmann equation. A good agreement between the period lengths measured in the striations and those obtained from the spatially periodic electron relaxation in the period-averaged field of the striations is found confirming the close relation of both phenomena. The s- and p-striations represent the fundamental and first harmonics of the inherent periodic electron relaxation. Furthermore, starting from different boundary conditions the establishment of the velocity distribution function and of selected macroscopic quantities of the electrons into unique periodic states under the action of strongly modulated striation-like fields is investigated. It is shown that the same damping processes that cause in homogeneous fields a relaxation into homogeneous states lead to unique periodic states in strongly modulated fields.