Fluorides thermodynamic

The successful generation, by precipitation out of liquid anhydrous HF, of fluorides thermodynamically unstable with respect to loss of elemental F2, gave a forceful reminder of the remarkable stability of that solvent towards oxidation. Soon after the preparation of AgFa, in attempts to find evidence for cationic derivatives (e.g. [AgF2] ), it was discovered (see Ref. 98) that even divalent silver, as a cation, Ag + (solvated by HF), had the capability to oxidize Xe. This made chemical sense, since a cation, having an electron deficit, should have higher electronegativity than a related oxidation-state in a neutral or anionic species. Indeed, this had three important consequences. 

The physical properties of the halogen fluorides are given in Table 1. Calculated thermodynamic properties can be found in Reference 24. 

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

Table 1. Physical and Thermodynamic Properties of Helium-Group Gas Fluorides, Oxofluorides, and Oxides...

Preparation of Plutonium Metal from Fluorides. Plutonium fluoride, PuF or PuF, is reduced to the metal with calcium (31). Although the reactions of Ca with both fluorides are exothermic, iodine is added to provide additional heat. The thermodynamics of the process have been described (133). The purity of production-grade Pu metal by this method is ca 99.87 wt % (134). Metal of greater than 99.99 wt % purity can be produced by electrorefining, which is appHcable for Pu alloys as well as to purify Pu metal. The electrorefining has been conducted at 740°C in a NaCl—KCl electrolyte containing PuCl [13569-62-5], PuF, or PuF. Processing was done routinely on a 4-kg Pu batch basis (135). 

Electrolysis. Electrowinning of zirconium has long been considered as an alternative to the KroU process, and at one time zirconium was produced electrolyticaHy in a prototype production cell (70). Electrolysis of an aH-chloride molten-salt system is inefficient because of the stabiUty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the stabiUty of in solution, decreasing the concentration of lower valence zirconium ions, and results in much higher current efficiencies. The chloride—electrolyte systems and electrolysis approaches are reviewed in References 71 and 72. The recovery of zirconium metal by electrolysis of aqueous solutions in not thermodynamically feasible, although efforts in this direction persist. 

Thermodynamic data show that the stabilities of the caesium chloride-metal chloride complexes are greater than the conesponding sodium and potassium compounds, and tire fluorides form complexes more readily tlrair the chlorides, in the solid state. It would seem that tire stabilities of these compounds would transfer into tire liquid state. In fact, it has been possible to account for the heats of formation of molten salt mixtures by the assumption that molten complex salts contain complex as well as simple anions, so tlrat tire heat of formation of the liquid mixtures is tire mole fraction weighted product of the pure components and the complex. For example, in the CsCl-ZrCU system the heat of formation is given on each side of tire complex compound composition, the mole fraction of the compound... 

Clough, P.N. et al., 1987, Thermodynamics of Mixing and Final State of a Mixture formed by the Dilution of Anhydrous Hydrogen Fluoride with Most Air, Safety and Reliability Directorate, UKAEA, Wigshaw Lane, Culcheth, Warrington, Cheshire, England, WA3 4NE, SRD R 396. 

Vanderzee, C. E. and W. W. Rodenburg, 1970, Gas Imperfections and Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride, Journal of Chemical Thermodynamics, Vol. 2, pp. 461-478,. 

The anomalous iodoacetamide-fluoride reaction violates this rule, in that a less stable -halonium complex (18) must be involved, which then opens to (19) in the Markownikoff sense. This has been rationalized in the following way estimates of nonbonded destabilizing interactions in the possible products suggest that the actual product (16) is more stable than the alternative 6)5-fluoro-5a-iodo compound, so the reaction may be subject to a measure of thermodynamic control in the final attack of fluoride ion on the iodonium intermediate. To permit this, the a- and -iodonium complexes would have to exist in equilibrium with the original olefin, product formation being determined by a relatively high rate of attack upon the minor proportion of the less stable )9-iodonium ion. 

The synthesis of tantalum and niobium fluoride compounds is, above all, related to the fluorination of metals or oxides. Table 3 presents a thermodynamic analysis of fluorination processes at ambient temperature as performed by Rakov [51, 52]. It is obvious that the fluorination of both metals and oxides of niobium and tantalum can take place even at low temperatures, whereas fluorination using ammonium fluoride and ammonium hydrofluoride can be performed only at higher temperatures. 

Three conceptual steps can be discerned in the definition of the ionic structure of fluoride melts containing tantalum or niobium. Based on the very first thermodynamic calculations and melting diagram analysis, it was initially believed that the coordination numbers of tantalum and niobium, in a molten system containing alkali metal fluorides, increase up to 8. 

Nevertheless, the system, composed of chain fragments of oxyfluoroniobate complexes, is thermodynamically less stable. Dipole properties of fragments of a certain length are re-orientated so as to be linked into typical infinite chains. There is no doubt that the fragment re-orientation and linking process initiates the partial reduction of niobium to Nb4+ and the oxidation of fluoride to elementary fluorine. The process scheme can be presented as follows ... 

Thermodynamic data associated with the solid plutonium fluorides and oxyfluorides at 298 K. 

Complexes with the Fluoride Ion. For the compilation of stability constants (Table IV) of complexes with F , we have used, when needed, thermodynamic parameters (K, AH) pertaining to the dissociation of hydrofluoric acid as given by Smith and Martell (77) or extrapolated from their selection. 

Variations in the proportions of the different components of product mixtures are observed in reactions that involve anhydrous HF31-80-82-84-85 and in pyridinium poly(hydrogen fluoride).86 These variations can also be explained in terms of kinetic and thermodynamic control. Thus, less stable, but more rapidly formed, dianhydrides isomerize under thermodynamic conditions to give more-stable products. It has also been noted that the starting isomeric forms of the ketose influence the kinetic outcome of the reaction.119... 

These reactions proceed at lower temperature (250-750°C) than those based on the methyl-radical mechanism reviewed above. The halogen reaction mechanism is still controversial and the optimum precursor species are yet to be determined.P9] To proceed, the reactions must be highly favored thermodynamically. This is achieved when the reaction products are solid carbon and stable gaseous fluorides or chlorides (HF, HCl, SFg). 

The reason why this reaction produces fluorine is that MnF4 is thermodynamically unstable. Therefore, if the very strong Lewis acid SbF5 removes two fluoride ions from MnF62, the result is MnF4, and it decomposes to produce fluorine and MnF3. 

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