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Coefficients de transport de particules browniennes en solution : approche expérimentale et modélisation.

Abstract : Self and mutual diffusion coefficients and conductivity are transport properties of ions in solution which can be determined experimentally, by analytical expressions or by Brownian dynamic simulations.
We have compared these methods for three electrolytes in aqueous solution: sodium tungstosilicate with or without added sodium sulfate, potassium and baryum cryptates chlorides and potassium chloride.
Square wave voltammetry permitted to measure self-diffusion coefficient of tungstosilicate ions. Impulsional RMN with field gradient permitted to measure the self-diffusion coefficient of cryptates. Conductivity was classically measured with a conductimetric cell.
The systems have been modelized and their properties simulated by Brownian dynamics whose principles have been explained. We show how it is possible to get the different transport coefficients, especially the mutual diffusion coefficient which was never calculated by these methods before.
We showed that the tungstosilicate ion was a good model of Brownian particle and determined a value for its self-diffusion coefficient at infinite dilution in aqueous solution. Cryptate ions are more difficult to modelize. The calculus of mutual diffusion coefficient by Brownian dynamic provided a correct result for the simple system potassium chloride and could be extended to more complex systems.
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Submitted on : Thursday, May 17, 2007 - 2:19:20 PM
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Thierry Olynyk. Coefficients de transport de particules browniennes en solution : approche expérimentale et modélisation.. Autre. Université Pierre et Marie Curie - Paris VI, 2001. Français. ⟨tel-00146787⟩

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