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Simulations par dynamique moléculaire de la solvatation et du comportement interfacial d'espèces hydrophobes.
Application à l'hypothèse TATB et à l'extraction liquide/liquide de cations par le CO2 supercritique.

Abstract : We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces.
The first part of the thesis deals with the TATB hypothesis according to which the AsΦ4+ (TA+) and BΦ4- (TB-) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on isovolumic spherical S+ and S- ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of "long range interactions" (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent.
In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO2, we report the behaviour of ions (Cs+, UO22+, Eu3+), of uncomplexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during demixing simulations which started from a perfectly mixed CO2 / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO2.
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https://tel.archives-ouvertes.fr/tel-00292205
Contributor : Rachel Schurhammer <>
Submitted on : Monday, June 30, 2008 - 4:22:23 PM
Last modification on : Thursday, April 23, 2020 - 2:26:35 PM
Long-term archiving on: : Friday, May 28, 2010 - 7:44:19 PM

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  • HAL Id : tel-00292205, version 1

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Schurhammer Rachel. Simulations par dynamique moléculaire de la solvatation et du comportement interfacial d'espèces hydrophobes.
Application à l'hypothèse TATB et à l'extraction liquide/liquide de cations par le CO2 supercritique.. Chimie. Université Louis Pasteur - Strasbourg I, 2001. Français. ⟨tel-00292205⟩

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