Coupling between tracer and mutual diffusion in electrolyte solutions (original) (raw)
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A few decades earlier, Kirkaldy and Lane proposed an indirect method of estimating the tracer and intrinsic diffusion coefficients in a ternary system (without showing experimental verification), which is otherwise impossible following the Kirkendall marker experiments. Subsequently, Manning proposed the relations between the tracer and intrinsic diffusion coefficients in the multicomponent system by extending the Onsager formalism (although could not be estimated by intersecting the diffusion couples). By solving these issues in this article, we have now proposed the equations and method for estimating these parameters in pseudo-ternary diffusion couples in which diffusion paths can be intersected in multicomponent space. We have chosen NiCoFeCr system for verification of this method because of the availability of good quality diffusion couple experiments and estimated tracer diffusion coefficients of all the components measured by the radiotracer method. An excellent match is foun...
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A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering functio...