Uranium tetrafluoride

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Reduction of uranium tetrafluoride by magnesium metal has been described in detail (40,53). It is often referred to as the Ames process, since it was demonstrated at the Ames Laboratory in early 1942. The reaction is very exothermic and the reduction process is carried out in a sealed bomb due to... 

M. H. West, M. M. Maitinez, J. B. Nielson, D. C. Court, and Q. D. Appeit, Synthesis of Uranium Metal UsingEaser-InitiatedTeduction of Uranium Tetrafluoride by Calcium Metal, LA-12996-MS, Los Alamos National Laboiatoiy, N.M., 1995. 

Bismuth pentafluoride is an active fluorinating agent. It reacts explosively with water to form ozone, oxygen difluoride, and a voluminous chocolate-brown precipitate, possibly a hydrated bismuth(V) oxyfluoride. A similar brown precipitate is observed when the white soHd compound bismuth oxytrifluoride [66172-91 -6] BiOF, is hydrolyzed. Upon standing, the chocolate-brown precipitate slowly undergoes reduction to yield a white bismuth(Ill) compound. At room temperature BiF reacts vigorously with iodine or sulfur above 50°C it converts paraffin oil to fluorocarbons at 150°C it fluorinates uranium tetrafluoride to uranium pentafluoride and at 180°C it converts Br2 to bromine trifluoride, BrF, and bromine pentafluoride, BrF, and chlorine to chlorine fluoride, GIF. It apparently does not react with dry oxygen. 

The primar> uses for hydrogen fluoride in the United States arc in the manufacture of chlorofluorocarbons, aluminum fluoride, sodium aluminum fluoride (ciyolitc). md uranium tetrafluoride, and in petroleum alkylation. 

UO2 IS combined with hydrogen fluoride (I IF) to form uranium tetrafluoride (UF4). This can be accomplished by reacting the UO, with either gaseous or lic uid FIF. The UF4 is combined with gaseous fluorine to produce UF,., and is shipped to a facility for enrichment. 

In the usual high-vacuum apparatus I placed aluminum borohydride onto a sample of uranium tetrafluoride. I observed an immediate reaction, with formation of green crystals which could be moved about the vacuum apparatus. As it happened, on the very day I was performing the synthesis, we had a visit from Professor H. C. Urey, who was in charge of the overall study. He immediately asked us to increase our research effort and undertake to prepare uranium tetraborohydride on a relatively large scale, adequate for testing. 

One of the most important examples of the fluorination of oxides is the fluorination of uranium dioxide. Uranium tetrafluoride (UF4) is the intermediate compound which is reduced to uranium metal. The gaseous higher fluoride, uranium hexafluoride (UF6) is used for the separation of uranium isotopes to obtain enriched uranium (i.e., uranium containing a higher proportion of the isotope, U235, than natural uranium). 

The double fluoride, ammonium hexafluorovanadate ((NH4)3VF6), forms from the oxide at 210 to 250 °C, but decomposes at 600 to 700 °C to yield pure vanadium fluoride. Examples of metal fluorides obtainable through the double fluoride route include uranium tetrafluoride, beryllium difluoride and the rare earth fluorides ... 

Fluorides are nonhygroscopic, and their melting points are higher than those of the corresponding chlorides. Besides, the fluoride reduction reactions are considerably more exothermic. The prime examples of the use of fluorides as intermediates are the reduction of uranium tetrafluoride by calcium or magnesium the reduction of rare earth fluorides by calcium, reduction of beryllium fluoride by magnesium and the reduction of potassium tantalum double fluoride by sodium. 

Magnesium can be obtained in high purity at low cost. It is the preferred reducing agent whenever feasible. The reduction of uranium tetrafluoride by magnesium involves the reaction... 

The reduction of uranium tetrafluoride by calcium, in accordance with the reaction... 

Ames (1) A process for making uranium by reducing uranium tetrafluoride with calcium or magnesium. 

Excer A process for making uranium tetrafluoride by electrolytic reduction of a uranyl fluoride solution, precipitation of a uranium tetrafluoride hydrate, and ignition of this. 

Uses. Conversion of uranium tetrafluoride to uranium hexafluoride oxidizer in rocket fuel systems manufacture of various fluorides and fluorocarbons... 

Synonyms Soluble Uranyl nitrate, uranyl fluoride, uranium hexafluoride insoluble uranium dioxide, uranium tetrafluoride... 

Hawthorn, E., Shortis, L.R and Lloyd, J.E., Fluidised solids drying process for production of uranium tetrafluoride, Trans. Inst. Chem. Engrs., 38 (1960) 197-215. 

Metallic uranium can be prepared from its oxides or hahdes by reduction at high temperature. Uranium dioxide, UO2, or other oxides such as UO3 or UsOs may be reduced to uranium metal by heating with carbon, calcium or aluminum at high temperatures. Similarly, uranium tetrafluoride or other halides can be reduced to metal by heating with sodium, potassium, calcium, or magnesium at high temperatures. Alternatively, uranium tetrafluoride mixed with fused alkali chlorides is electrolyzed to generate uranium metal. 

Another preparative method involves converting triuranium octaoxide to uranyl nitrate, U02(N0s)2, by treatment with nitric acid. Uranyl nitrate then is decomposed to uranium trioxide, UO3, which is reduced to the dioxide, UO2, with hydrogen. A fluidized bed of uranium dioxide is treated with hydrogen fluoride to produce uranium tetrafluoride, UF4, which then is treated with fluorine to form hexafluoride. The preparation should be done in copper apparatus. 

The synthesis of bis(rj8-cyclooctatetraene)uranium(IV) (uranocene)J from uranium tetrachloride and (cyclooctatetraene)dipotassium was first published in 1968.1 The method reported here is a modification of that procedure and is suitable for a large variety of cyclooctatefraene complexes.2-4 BisO 8-cyclo-octatetraene)uranium(IV) has also been prepared by the reaction of uranium tetrafluoride with (cyclooctatetraene)magnesium in the absence of solvent.5 Direct reaction of finely divided uranium metal with cyclooctatetraene vapors at 150° also gives some uranocene.5 However, both methods give low yields. 

Uranium tetrafluoride serves as a starting material for the preparation of the other fluorides, It is best prepared by hydrofluonnation of uranium dioxide ... 

Uranium tetrafluoride precipitated from aqueous solutions exists as UF4 5H20, and it is difficult to remove the waters of hydration so that the dry reaction above is preferred.) UF4 is frequently used to make accelerator targets of uranium by vacuum volatilization. 

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