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Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide

Abstract

Present interest centred around molten salts can be explained by their possible use in the field of nuclear energy, in particular as a support for fuels and also as reprocessing agents. It seemed of interest to consider the molten salt as a solvent and to study partition phenomena with a second phase stable at high temperatures. The salt chosen is a ternary eutectic of alkali nitrates and the second phase is a solution of tri-butyl phosphate in a liquid silicone. The working temperature is fixed at 150 deg. C. We have studied first of all the stability of the two phases and their mutual solubilities at this temperature. It has been shown that the two solvents are immiscible and stable. We have also described the extraction by the silicone solution of various products in solution in the salt phase, and have determined the partition coefficients and the formulae of the extracted molecules. It has been possible to calculate the partition coefficients of the following ions extracted as nitrates: Li{sup +}, Na{sup +}, K{sup +}, Sr{sup 2+}, Ca{sup 2+}, Ba{sup 2+}, Hg{sup 2+} whose partition coefficients are very low: Mg{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Zn{sup 2+} whose extraction yields are  More>>
Authors:
Hertzog, D [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Jul 01, 1964
Product Type:
Technical Report
Report Number:
CEA-R-2628
Resource Relation:
Other Information: 9 refs
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CATIONS; CHELATING AGENTS; COBALT CHLORIDES; COBALT COMPLEXES; COBALT NITRATES; CYANIDES; EUTECTICS; EXTRACTION; LITHIUM NITRATES; MAGNESIUM; MOLTEN SALTS; PARTITION; POTASSIUM NITRATES; SILICONES; SODIUM NITRATES; SOLUTIONS; TBP
OSTI ID:
20650645
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France); Ministere de l'Education Nationale, Institut National des Sciences et Techniques Nucleaires (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR05R2628090258
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
48 pages
Announcement Date:
Nov 28, 2005

Citation Formats

Hertzog, D. Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide. France: N. p., 1964. Web.
Hertzog, D. Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide. France.
Hertzog, D. 1964. "Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide." France.
@misc{etde_20650645,
title = {Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide}
author = {Hertzog, D}
abstractNote = {Present interest centred around molten salts can be explained by their possible use in the field of nuclear energy, in particular as a support for fuels and also as reprocessing agents. It seemed of interest to consider the molten salt as a solvent and to study partition phenomena with a second phase stable at high temperatures. The salt chosen is a ternary eutectic of alkali nitrates and the second phase is a solution of tri-butyl phosphate in a liquid silicone. The working temperature is fixed at 150 deg. C. We have studied first of all the stability of the two phases and their mutual solubilities at this temperature. It has been shown that the two solvents are immiscible and stable. We have also described the extraction by the silicone solution of various products in solution in the salt phase, and have determined the partition coefficients and the formulae of the extracted molecules. It has been possible to calculate the partition coefficients of the following ions extracted as nitrates: Li{sup +}, Na{sup +}, K{sup +}, Sr{sup 2+}, Ca{sup 2+}, Ba{sup 2+}, Hg{sup 2+} whose partition coefficients are very low: Mg{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Zn{sup 2+} whose extraction yields are greater than 50 per cent; finally Ce{sup 3+}, La{sup 3+}, UO{sub 2}{sup 2+}, highly extracted. Also the following anions have been extracted in the form of alkali salts: F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, IO{sub 3}{sup -}, CN{sup -}, SO{sub 4}{sup -}, C{sub 2}O{sub 4}{sup -}, NO{sub 2}{sup -}. Amongst these, only the halogens have non-negligible partition coefficients. In certain particular cases we have been able to study the influence of complex formation on the extraction phenomena. Two applications are described: - The separation of two products by complex formation and extraction (separation of magnesium from cobalt, nickel and zinc); - The calculation of the equilibrium constant of a complex by measurement of the variation in the partition coefficient of the ion complexed. The equilibrium constants for the reactions: (I) Co{sup 2+} + CN{sup -} {yields} CoCN{sup +} (II) Co{sup 2+} + Cl{sup -}{yields} CoCl{sup +} have been determined: K{sub 1} 10{sup -4}, K{sub 2} = 0.16. (author) [French] L'interet actuel porte aux sels fondus s'explique par leur emploi possible clans le domaine de l'energie nucleaire, en particulier comme supports de combustibles et comme agents de reprocessing. II nous a paru interessant de considerer un sel fondu comme un solvant et d'y etudier les phenomenes de partage avec une seconde phase stable a haute temperature. Le sel choisi est un eutectique ternaire de nitrates alcalins et la seconde phase est une solution de phosphate de tributyle dans un silicone liquide. La temperature de travail est fixee a 150 deg. C. Nous avons etudie en premier lieu la stabilite des deux phases et leurs solubilites respectives a cette temperature. On a demontre que les deux solvants sont immiscibles et stables. D'autre part nous avons decrit l'extraction par la solution de silicone de differents corps en solution dans la phase sel, determine les coefficients de partage et les formules des molecules extraites. Il nous a ete possible de calculer les coefficients de partage des cations suivants extraits sous la forme nitrates: Li{sup +}, Na{sup +}, K{sup +}, Sr{sup 2+}, Ca{sup 2+}, Ba{sup 2+}, Hg{sup 2+} dont les coefficients de partage sont tres faibles: Mg{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Zn{sup 2+}, dont les rendements d'extraction sont superieurs a 50 pour cent; enfin Ce{sup 3+}, La{sup 3+}, UO{sub 2}{sup 2+}, tres extraits. De meme les anions suivants ont ete extraits sous forme de sels alcalins: F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, IO{sub 3}{sup -}, CN{sup -}, SO{sub 4}{sup -}, C{sub 2}O{sub 4}{sup -}, NO{sub 2}{sup -}. Parmi ceux-ci seuls les halogenes ont des coefficients de partage non negligeables. Dans certains cas particuliers, nous avons pu etudier l'influence de la formation de complexes sur les phenomenes d'extraction. Deux applications ont ete decrites: - La separation de deux corps par complexation et extraction (separation du magnesium du cobalt, nickel et zinc), - Le calcul de la constante d'equilibre d'un complexe par mesure de la variation du coefficient de partage de l'ion complexe. Les constantes d'equilibre des reactions: (I) Co{sup 2+} + CN{sup -} {yields} CoCN{sup +} (II) Co{sup 2+} + Cl{sup -}{yields} CoCl{sup +} ont ete determinees soit K{sub 1} = 10{sup -4}, K{sub 2} = 0.16. (auteur)}
place = {France}
year = {1964}
month = {Jul}
}