The pair distributions and the osmotic coefficient in binary electrolytes up to concentrations c 1 mol/l

Referring to the results of a previous paper dealing with the pair distributions in a fully ionized dilute hydrogen plasma it is concluded that the pair distributions in binary electrolytes up to concentrations c 1 mo1/1 take the form

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. Here (r) represents the screened Coulomb potential and V(^hs)(r) a hard sphere potential. The contact distances R of the hard sphere potentials are assumed to be equal for ions with the same sign of their charges, that means R₊₊ = R_-- = R, and to be smaller than R for ions of opposite charges, that means R_+- = qR, 0 < q < 1. With the help of these pair distributions the pressure of the ionic components and the osmotic coefficient are calculated. The numerical evaluation of the osmotic coefficient of hydrous electrolytes at T = 273 K shows that the above pair distributions explain the experimental data of all kinds of 1-1-valent electrolytes, even those of the tetra-alkylammonium halogenids, within a domain of very reasonable values of R and q. No necessity seems to exist for considering additional short range attractive forces. Furthermore, some numerical results for 2-2-valent electrolytes in water are given. It comes out that the osmotic coefficient of all 2-2-valent electrolytes with R 5 Å is larger than the limiting law in a certain domain of concentration.     

Stability analysis of a spherical electrostatic suspension in a liquid in the induction approximation

In [1] the image force was shown to impose additional conditions for the electrostatic suspension of a sphere without dynamic control of the electrode potential, and the dependence of the critical voltage between the electrodes on the sphere radius was derived experimentally. In this work, this dependence is found analytically by calculating electrical forces in the third-order approximation in shift of the sphere from equilibrium.     

The grand canonical ensemble Monte Carlo method applied to electrolyte solutions

A grand canonical ensemble Monte Carlo method is developed for application to electrolyte solutions.

The method proves to be of comparable accuracy and speed to the conventional NVT Monte Carlo method for electrolytes but has the added advantage of being able to fix the chemical potential. This latter point is vital for the study of surface phenomena. Application of the method to 1:1 and 2:2 primitive model electrolytes is made as is a comparison with the results of approximate statistical mechanical treatments.     

Saturation of nuclear forces in Brueckner theory

The basic equations in the Brueckner theory of nuclear matter are solved for a two-nucleon potential taken as a rectangular well with a rectangular repulsive sphere and the properties of the solutions are investigated for various dimensions of the repulsive sphere. The two-nucleon interaction is considered to be non-vanishing only if the nucleons are in theS-state. Under such assumptions a two nucleon potential always gives saturation, i.e. a minimum of the mean binding energy per nucleon, at a finite nuclear density. It is shown that the nuclear density and the mean binding energy decreases if the height or the width of the repulsive sphere increases. If the repulsive sphere is infinitely high a nucleus can exist as a bound state only if the width of this sphere is sufficiently small. The limit value for the width of the sphere is given. It is shown in the conclusion how the solution of the basic equations will change if the two-nucleon potential does not contain an infinite repulsive sphere, but only a very high one.     

Irreversible loss of adatoms on Ag electrodes during potential cycling determined from surface enhanced raman intensities

Surface enhanced Raman scattering of adsorbates (Ag⁰-Cl^?, H₂O and pyridine) on Ag electrodes in 1M KC1 and 1M KCl+0.05M pyridine electrolytes was monitored continuously with an optical multichannel analyzer system as the electrode potential was cycled over various ranges within nonfaradaic regions of the oxidation-reduction cycle. A systematic investigation was performed of the potential dependence of SERS of pyridine in 1M KX + 0.05M pyridine electrolytes, where X = F, Cl, Br and I. Since the surface coverage of the adsorbates is reversible with potential cycling within a potential range, it was possible to determine potential dependences of the irreversible loss in the SERS enhancement factor which occurs as the electrode potential is ramped toward the potential of zero charge (PZC). The results provide strong support for the role of adatoms on the electrode surface in the overall enhancement mechanism. There is evidence that the strongly bound adsorbates immobilize the adatoms at positive potentials but allow the adatoms to migrate and become lost at surface defects as the potential approaches the PZC where the adsorbates are less tightly bound.     

Large-Time Behavior of Solutions for the Boltzmann Equation with Hard potentials

We study the quantitative behavior of the solutions of the one-dimensional Boltzmann equation for hard potential models with Grad’s angular cutoff. Our results generalize those of [5] for hard sphere models. The main difference between hard sphere and hard potential models is in the exponent of the collision frequency . This gives rise to new wave phenomena, particularly the sub-exponential behavior of waves. Unlike the hard sphere models, the spectrum of the Fourier operator is non-analytic in η for hard potential models. Thus the complex analytic methods for inverting the Fourier transform are not applicable and we need to use the real analytic method in the estimates of the fluidlike waves. We devise a new weighted energy function to account for the sub-exponential behavior of waves.     

点电荷与介质球系统电势的计算和讨论

计算了点电荷与介质球系统的电势．指出点电荷与导体球、点电荷与无限大导体平面或介质分界平面均匀外电场中有导体球或介质球系统的电势都可由点电荷与介质球系统的电势给出。     

Charging of a conducting sphere moving in a weakly ionized gas under an arbitrarily oriented external uniform electric field

A charging conducting sphere moving in a weakly ionized gas is investigated. An external uniform electric field is applied with arbitrary orientation relative to the gas flow. The ion current is obtained analytically and investigated numerically in ballistic assumption. It is shown that charging regimes depend not only on the net charge of the sphere but also on the gas flow type, and the parameter ξ_± – the ratio of ion drift velocity far from the sphere to the gas velocity. The cases |ξ_±|<1 and |ξ_±|>1 yield two different charging regimes for Stokes and potential flows. For the potential flow, the ion current has been found analytically in continuous ξ_±-parameter space. The stationary charge of an isolated sphere is also calculated numerically as a function of α. It achieves maximum magnitudes in direct (α=0) and back (α=π) flows respectively.     

Solution of the Ornstein-Zernike equation for a soft-core Yukawa fluid. III. A restricted model for electrolytes and fused salts

A model for dense electrolytes and fused salts is proposed which incorporates both the known long-range asymptotic form for the direct correlation function and a parametric form for the total correlation function appropriate to a soft-core interaction potential. A special case extending the MSA for the restricted primitive model for electrolytes is discussed in some detail.Supported by ARGC grant No. B7715646R.     

Sticky hard sphere potential—Evaluation of the structure function of liquids

The direct correlation function as obtained by Baxter for a sticky hard sphere potential, which is significant improvement over that of the hard sphere potential, has been used in the evaluation of the structure function of aluminium and lead. The values obtained by the present method are in good agreement with experiment.     

Analysis of general multipolar images on dielectric layers for the calculation of DEP force

An axisymmetric field problem of a sphere and a multi-layered planer dielectric body is investigated based on the multipolar expansion method. First, the multipolar potential, produced by the sphere and expressed in the spherical coordinate system, is re-written in the cylindrical coordinate system as an integral of Bessel function. Then the field problem is solved with the boundary conditions at the planer interface of the dielectrics, and the obtained potential is written back to spherical harmonics, which can be regarded as “image multipoles” inside the dielectric body. The “images” influences back the “multipoles” on the sphere, and the field can be determined by solving these relations in self-consistent manner. DEP force exerted on the particle is calculated as the multipolar interaction, as well as the capacitance for the case involving a conducting sphere and a conducting plane.     

Determination of structure of weak scatterers from holographic images

For a weak scatterer a three dimensional Fourier transform of the image formed by a generalized hologram is shown to yield directly the Fourier transform of the scattering potential evaluated on the Ewald sphere. The entire scattering potential can be approximately determined if the object is illuminated from all directions in a series of experiments and if the scattering potential is essentially bandlimited to within a sphere of radius 4π/λ.     

Magnetohydrodynamics of a viscous spherical layer rotating in a strong potential field

An analytic solution is given for classical magnetohydrodynamic (MHD) problem of almost rigid-body rotation of a viscous, conducting spherical layer of liquid in an axisymmetric potential magnetic field. Large-scale flows bounded by rigid spheres are described for the first time in a new approximation. Two problems are solved: (1) in which both spheres are insulators and (2) in which the outer sphere is an insulator and the inner sphere a conductor. Axially symmetric flows and azimuthal magnetic fields are maintained by a slightly faster rotation of the inner sphere. The primary regeneration takes place in the boundary and shear MHD layers. The shear layers, described here for the first time, smooth out the large gradients at the boundaries of the MHD structures encompassed by them. There is essentially no azimuthal magnetic field inside these original structures, which are bounded by potential contours tangent to the spheres. An applied constant magnetic field creates a rigid MHD structure outside an axial cylinder tangent to the inner sphere. Inside the cylinder the rotation is faster and the meridional flux depends on height. A magnetic dipole forms a structure tangent to the outer equator. Outside the structure, the rotation is also rigid-body when both spheres are insulators. When a conducting sphere is present, the liquid rotates differentially everywhere, while near the axis and inside the MHD structure, it rotates even faster than the inner sphere. The last example of a general solution is a quadrupole magnetic field. In this case, two equatorially symmetric MHD structures are formed which rotate together with the inner sphere. Outside the structures, as in the most general case, the rotation is differential, the azimuthal magnetic field falls off as the first power of the applied field, and the meridional flux falls off as the square of the field in the first problem, and as the cube in the second. Zh. éksp. Teor. Fiz. 112, 2056–2078 (December 1997)     

类氢氖基态电离势随等离子体温度密度的变化

采用自洽场离子球模型,研究类氢氖基态1s的电离势随等离子体电子温度及电子密度的变化规律,计算得到基态电离势的百分偏移量随等离子体电子密度的变化关系,拟合结果表明两者的对数值满足很好的线性关系.该结果对计算等离子体电离态分布及光谱模拟具有一定意义.     

Numerical study of a modified BBGY integral equation for the primitive model of an electrolyte solution

A modified Poisson-Boltzmann equation derived from the BBGY hierarchy of equations is solved numerically for the restricted primitive model of an electrolyte solution. Computations are carried out for 1 : 1 and 2 : 2 electrolytes, and results compared with 1 : 1 Monte Carlo data and results from the Poisson-Boltzmann extensions arising from the Kirkwood hierarchy. Satisfactory agreement with the Monte Carlo results are found in the 1 : 1 case, and the correct qualitative behaviour of thermodynamic properties obtained in the 2 : 2 case. At low concentrations in the 2 : 2 case the modified Poisson-Boltzmann equations from the Kirkwood and BBGY hierarchies predict the anomalous behaviour found in the thermodynamic properties of real electrolytes. The behaviour of the mean electrostatic potential changes from a damped exponential to a damped oscillatory form for 1·2 < κa < 1·3 (where κ is the Debye-Hückel constant and a is an ionic diameter) in the 1 : 1 case and at κa ～ 0·8 in the 2 : 2 case for the parameters considered.     

Ionic transport studies in hyperbranched polyurethane/clay nanocomposite gel polymer electrolytes

In the present work, we report a novel nanocomposite gel electrolytes based on intercalation of hyperbranched polyurethane (HBPU) into organically modified montmorillonite for application in Li-ion batteries. The nanocomposites have been prepared by solution intercalation technique with varying clay loading. The formation of partially exfoliated nanocomposites has been confirmed by X-ray diffraction. Nanocomposites were soaked with 1 M LiCO₄ in 1:1 (v/v) solution of propylene carbonate and diethyl carbonate to get the required gel electrolytes. AC impedance analysis shows that ionic conductivity increases with the increase of clay loading and attains the highest value of 8.3?×?10^?3 S/cm for 5 wt.% clay concentration. Surface morphology of the nanocomposite electrolytes has been examined by SEM analysis. Improvement of electrochemical properties, viz., electrochemical potential window and interfacial stability, is also observed in the clay-loaded HBPU samples.     

Critical adsorption of polyelectrolytes onto charged spherical colloids

The adsorption of a flexible polyelectrolyte in a salt solution onto an oppositely charged spherical surface is investigated. An analytical solution is derived, which is valid for any sphere radius and consistently recovers the result of a planar surface in the limit of large sphere radii, by substituting the Debye-Hückel potential via the Hulthén potential. Expressions for critical quantities such as the critical radius and the critical surface charge density are provide. A comparison of our theoretical results with experiments and computer simulations yields remarkable good agreement.     

Energy of a solid sphere under nonstationary oscillations

Analytical solution for spherically symmetric nonstationary oscillations of acoustic and elastic solid sphere is given. Time dependence of potential, kinetic and internal energy of a solid sphere is analyzed. The received results are of practical importance for a wide range of problems connected to testing of material dynamic strength parameters and to the problems of optimizing (minimizing) energy needed for fracture of solids.     

The investigation of electrochemical properties and ionic motion of functionalized copolymer electrolytes based on polysiloxane

The effect of EO side chain functionalization on the transport and electrochemical properties of polysiloxane electrolytes has been examined in this report. First, a study of the electrochemical stability of the electrolytes by linear sweep voltammetry shows that the polymer electrolytes have a negligible effect on the electrolyte stability windows. In addition, the parameters of cation mobility in polysiloxane electrolytes, such as ionic transference numbers and diffusion coefficients, were increased by increasing the lengths of the EO side chain. However, cation mobility in polymer structures is quite different compared to liquid-based systems and is probably suppressed, resulting in their polymer structure. Therefore, Positron Annihilation Lifetime Spectroscopy (PALS) was used to study the relationship between orthopositronium (o-Ps) lifetime, free volume radius, free volume of micro voids and EO side chain affection at different temperatures. Finally, a battery application with LiCoO₂ and LiFePO₄/polymer electrolyte/lithium metal electrode was monitored for its potential use in the future.     

Gas molecule-molecule interaction and the gas-surface scattering effect on the rarefied gas flow through a slit into a vacuum

The effect of the gas molecule-molecule interaction and the gas-surface scattering on the gas flow through a slit into a vacuum are investigated in a wide range of the gas rarefaction using the direct simulation Monte Carlo method. To study the gas molecule-molecule interaction influence, we used the variable hard sphere and variable soft sphere models defined for an inverse-power-law potential and the generalized hard sphere model defined for the 12–6 Lennard-Jones potential. The Maxwell, Cercignani-Lampis, and Epstein models were used to simulate the gas-surface scattering. This study demonstrates that the gas molecule-molecule interaction can have a significant influence on the rarefied gas flow through a slit, while the influence of the gas-surface scattering is negligibly small. The presented numerical results are in agreement with the corresponding experimental ones. The article is published in the original.