Solubility of Noble Gases in Molten Fluorides. II. In the Lif–NaF–LF Eutectic Mixtures

Blander, M.; Grimes, W.R.; Smith, N. V.; Watson, G.M.

doi:10.1021/j150577a033

Cited by 97 publications

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“…Previous workers (26)(27)(28)(29) have used values of surface or interfacial tension to calculate the free energy of cavity formation in connection with solubilities in various kinds of system. Two obvious difficulties which arise with the application of such methods concern the possible variation of the free energy of cavity formation with curvature of the cavity surface, and the suitable choice of the effective surface of the cavity.…”

Section: Discussionmentioning

confidence: 99%

A surface tension approach to the salting-out of nonpolar nonelectrolytes

Aveyard¹

1982

Can. J. Chem.

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ROBERT AVEYARD. Can. J. Chem. 60, 1317Chem. 60, (1982. A simple approach is developed for the salting-out of nonpolar molecules by strongly solvated salts. The standard free energy of transfer of solute from pure solvent to salt solution, and hence the salting coefficient, k, is calculated in terms of the surface tension increment caused by the addition of salt to the solvent. In its simplest form the method gives k in terms of the molar volumes of solvent and solute, and the osmotic coefficient of the salt solution. It is more successful in the prediction of k than the McDevit and Long theory, and it also has advantages over the more complex scaled particle theory of salt effects. In addition to a range of nonpolar solutes, the salt effects on some alcohols are also considered but application to polar solutes generally requires a knowledge of experimentally determined surface tension increments which are not widely available. The correct order of magnitude for the temperature coefficient of k at room temperature for some alkanes and H, in water is given, although minima ink as a function of temperature, which have sometimes been observed, are not reproduced.ROBERT AVEYARD. Can. J. Chem. 60, 1317Chem. 60, (1982. On a mis au point une methode simple de relargage des mol6cules non polaires par les sels fortement solvatb. On a calcule 1'6nergie libre standard de transfert du solute a partir du solvant pur jusqu'l une solution saline, et par consequent le coefficient de salinite, k, en fonction de I'incrdment de la tension de surface provoque par I'addition de sel au solvant. Dans saforme la plus simple, la mdthode permet d'obtenir k en fonction des volumes molaires de solvant et de solute et du coefficient d'osmose de la solution saline. Elle a plus de succks dans la prevision de k que la theorie de McDevit et Long et elle a certains avantages sur la theorie plus complexe de la particule a l'8chelle des effets de sel. En plus d'une variitk de solutes non polaires, on a igalement considere les effets de sel sur certains alcools; toutefois son application des solutes polaires requiert generalement une connaissance des increments de la tension de surface d6termin6s exp6rimentalement et ces incrdments ne sont generalement pas disponibles. On donne l'ordre de grandeur reel du coefficient de temperature de k a la temperature ambiante pour quelques alcanes et I'hydrogkne dans I'eau bien que les minima observes quelque fois pour k en fonction de la temperature ne soient pas reproduits.[Traduit par le journal]

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Section: Discussionmentioning

confidence: 99%

A surface tension approach to the salting-out of nonpolar nonelectrolytes

Aveyard¹

1982

Can. J. Chem.

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“…The 6% of U+S was probably due to uranyl chloride present in the as-received salt, which analyzed 92% U+4. All gases were dried by passing through 1 liter of calcium sulfate at flow rate less than 0.1 cu. ft./hr.…”

Section: Methodsmentioning

confidence: 99%

“…was measured by the technique developed at Oak Ridge (1). Chlorine was sparged into a stainless steel tank containing 500 cc.…”

Section: E Q U I L I B R I U M Studiesmentioning

confidence: 99%

“…The equilibrium of reaction (1) was studied by sparging pure chlorine gas into a fused salt melt containing 2 t I I I 1 0. I u wt.…”

Section: E Q U I L I B R I U M Studiesmentioning

confidence: 99%

“…However, while the removal of uranium was a relatively slow process, the fraction of the uranium present as U + 4 appeared to equilibrate with greater speed. All the samples taken at a particular temperature showed the same U + 4 fraction (usually to within 1%) and permitted determination of the equilibrium constant of reaction (1) by the method outlined in the Appendix. The results shown in Figure 1 can be expressed by…”

Section: E Q U I L I B R I U M Studiesmentioning

confidence: 99%

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Reaction of chlorine and uranium tetrachloride in the fused lithium chloride‐potassium chloride eutectic

Olander

Camahort

1966

AIChE Journal

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The rates of the reaction of chlorine gas with uranium tetrachloride dissolved in the lithium chloride-potassium chloride eutectic have been studied in a wetted-rod contactor. The reaction was studied a t temperatures from 400" to 7OO0C., uranium tetrachloride concentrations of 1 to 3 wt. %, and chlorine partial pressures of 0.25 to 1 atm. The production of uranium hexachloride appears to be limited by the equilibrium of the reaction U C 4 (solution) + Clz (g) = uc16 (solution) a t the.interface and by U + 4 diffusion in the liquid phase.High-temperature nonaqueous reprocessing of spent fuel from nuclear reactors has received considerable attention in recent years, and in some instances can conipete favorably with the standard aqueous methods. In a typical volatility process, separation of uranium and plutonium from fission products and cladding materials is effected by producing the volatile hexahalide of the heavy elements by contact with the halogen gas. The halides of the fission product metals are generally not appreciably volatile and remain behind (8).While considerable thermochemical information on high-temperature metal-halogen systems has been accumulated, very little is known about the kinetics of these reactions in fused salts. The overall rate of conversion of a lower to a higher halide depends upon the interaction of the appropriate chemical and physical equilibria and the diffusional and chemical rates. The only pertinent work in this area is the fluoride volatility study by workers at the Argonne National Laboratory ( 5 ) in which a uranium tetrafluoride-sodium fluoride-zirconium tetrafluoride melt was sprayed into a quiescent atmosphere of fluorine gas. Two possible rate controlling steps were considered: the diffusion of uranium tetrafluoride in the fused salt to the interface, and transfer by diffusion-convection of the product uranium hexafluoride from the interface to the bulk gas phase. Both of these mechanisms predicted essentially complete removal of uranium from the salt, but the observed removal never exceeded 30%. It was concluded that the rate was limited by chemical kinetics.The,*fluoride volatility reaction is the most interesting from Ian application standpoint, but the corrosion and toxicity problems require elaborate safety precautions. Conse uently, the analogous chlorine system was chosen since c x lorine is somewhat more manageable than fluorine.The purpose of this study was to investigate the diffusional and chemical rate phenomenon associated with the reaction:The reaction was carried out between gaseous chlorine and uranium tetrachloride dissolved in the fused eutectic lithium chloride-potassium chloride mixture ( 59 mole % lithium chloride). The eutectic melts at 350°C. and experiments were carried out in the range of 400" to 700°C. At these temperatures the pure hexachloride is volatile and, depending upon the conditions of the reaction, may appear either as a gaseous or a dissolved species. E Q U I L I B R I U M STUDIESTo assist in interpreting the kinetic data, the solub...

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Salzschmelzen und ihre Verwendung als Reaktionsmedien

Sundermeyer

1965

Angewandte Chemie

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Solubility of Noble Gases in Molten Fluorides. II. In the Lif–NaF–LF Eutectic Mixtures

Cited by 97 publications

References 0 publications

A surface tension approach to the salting-out of nonpolar nonelectrolytes

A surface tension approach to the salting-out of nonpolar nonelectrolytes

Reaction of chlorine and uranium tetrachloride in the fused lithium chloride‐potassium chloride eutectic

Salzschmelzen und ihre Verwendung als Reaktionsmedien

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