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  • Author: A. Klemm x
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Diffusion and ionic conduction in pure 1:1 molten salts is described by an incomplete-disso­ciation model comprising neutral diatomic molecules and monoatomic ions. The internal mobility b+- and the self-diffusion coefficients D+ and D- are given in terms of the six inter­particle friction coefficients and the degree of dissociation. By an approximation it is possible to derive from experimental D+ and D- values an apparent degree of dissociation which ranges from 0.93 for NaCl to 0.51 for TlCl and decreases with temperature.

A change with concentration in the height of the first peak of the pair distribution function g+ - of a salt in a mixture of molten salts indicates a change in the degree of association of that salt. It is shown that the changes in association observed this way from MD-simulations of binary mixtures of charge symmetric salts with a common anion are qualitatively consistent (i) with the requirements for the occurrence of the crossing of mobility isotherms (Chemla effect) and (ii) with the ideal law of mass action

Abstract

The internal mobilities of additive binary molten salt systems are given in terms of correlation functions of mean ionic velocities. For isotopic systems the expressions obtained are expanded in terms of the relative difference of the masses of the two cationic or anionic species involved.

In the simulation of liquids by the periodic cube model the pressure can be evaluated by adding up the forces exerted by the particles on one side of a plane on the particles on the other side of the plane, or by an application of the virial theorem. The pressure also occurs in some relations between velocity-velocity- and force-position-autocorrelation functions.

Flüssiges Quecksilber wird bei Elektroendosmose-Versuchen in Glasapparaturen zur Kathode überführt. Die elektrokinetische Beweglichkeit ist α=2,5·10-3 cm2/Vs. Eine Analyse des Vorganges zeigt, daß der Effekt im wesentlichen darauf beruht, daß die Leitungselektronen bei der diffusen Reflexion an der Wand ihre Driftgeschwindigkeit verlieren, und daß deshalb in Wandnähe die an den Ionen angreifende Feldkraft die Elektronenreibungskraft überwiegt.

Beweglichkeitskoeffizienten bzw. Beweglichkeiten eignen sich zur Darstellung der Teilchen-Transporteigenschaften von isothermen Elektrolyten, wenn eine der Komponenten des Elektrolyten als Bezugssystem von Natur aus prädestiniert ist. Fehlt eine solche Komponente, so ist die Darstellung durch Reibungskoeffizienten vorzuziehen. Eine frühere Berechnung der Selbstdiffusion in reinen Salzen mit zusammengesetzten Bewegungseinheiten (unter Vernachlässigung der „Austauschdiffusion“) wird verbessert.

Abstract

Quasi-Darkén Relations. In binary mixtures with the self­friction coefficients r11 and r22 and the inter-friction coefficient r12, interpolations of the type 2 f (r12) = f (r11) + f (r22) cor­respound to Quasi-Darkén relations, If f = In, the Darkén relation is obtained.