Uranium chemistry

Uranium was useless as long as the nuclear fuel energy cycle was not closed via uranium mining, uranium chemistry, uranium enrichment technologies, fuel rod production, nuclear reactors, to final storage or plutonium extraction of spent fuel rods. 

This is a convenient, facile, and high-yield preparative route for quantitative preparation of the complexes above no special equipment is required. UI3(THF)4 crystallizes in a P2x/c space group. It is mononuclear with pentagonal-pyramidal coordination geometry around the central uranium atom. This compound is stable until 75°C, then THF molecules are removed by steps, forming UI3 at 162°C. Lewis base adducts of uranium tri-iodide, such as UI3(THF)4 above, are synthetically useful precursors for trivalent uranium chemistry (see Sec. 5.3.2) [360]. 

The use of neodymium borohydride complexes as precursors for (COT)lanthanide complexes has been reviewed by Ephritikhine et al. A comparison has been made to the corresponding uranium chemistry.801... 

The products were formulated as hexaalkyl dianions, [084]] URi . Although these compounds decompose thermally below room temperature, it proved possible partially to characterize them. Some of the spectroscopic and magnetic properties are rather unusual [2]. In reaction with tetramethylethylenediamine (TMEDA), the Li2UR6-8S complexes yield Li2UR6-7TMEDA derivatives. Sigurdson and Wilkinson [IS] also investigated pentavalent uranium chemistry ... 

Iche-Tarrat, N. and Marsden, C. J. 2008. Examining the performance of DFT methods in uranium chemistry Does core size matter for a pseudopotential J. Phys. Chem. A 112 7632-7642. 

IV. Review of Those Features of Uranium Chemistry of Chief Interest to the Radlochemlst... 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

The preparation and structure determination of ferrocene marked the beginning of metallocene chemistry Metallocenes are organometallic compounds that bear cyclo pentadiemde ligands A large number are known even some m which uranium is the metal Metallocenes are not only stucturally interesting but many of them have useful applications as catalysts for industrial processes Zirconium based metallocenes for example are the most widely used catalysts for Ziegler-Natta polymerization of alkenes We 11 have more to say about them m Section 14 15... 

Another area where controlled-potential coulometry has found application is in nuclear chemistry, in which elements such as uranium and polonium can be determined at trace levels. Eor example, microgram quantities of uranium in a medium of H2SO4 can be determined by reducing U(VI) to U(IV) at a mercury working electrode. 

Fluorine was first produced commercially ca 50 years after its discovery. In the intervening period, fluorine chemistry was restricted to the development of various types of electrolytic cells on a laboratory scale. In World War 11, the demand for uranium hexafluoride [7783-81-5] UF, in the United States and United Kingdom, and chlorine trifluoride [7790-91 -2J, CIF, in Germany, led to the development of commercial fluorine-generating cells. The main use of fluorine in the 1990s is in the production of UF for the nuclear power industry (see Nuclearreactors). However, its use in the preparation of some specialty products and in the surface treatment of polymers is growing. 

A variety of nuclear reactor designs is possible using different combinations of components and process features for different purposes (see Nuclear REACTORS, reactor types). Two versions of the lightwater reactors were favored the pressurized water reactor (PWR) and the boiling water reactor (BWR). Each requites enrichment of uranium in U. To assure safety, careful control of coolant conditions is requited (see Nuclearreactors, water CHEMISTRY OF LIGHTWATER REACTORS NuCLEAR REACTORS, SAFETY IN NUCLEAR FACILITIES). 

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). 

Carbonates. Actinide carbonate complexes are of interest not only because of their fundamental chemistry and environmental behavior (150), but also because of extensive industrial appHcations, primarily in uranium recovery from ores and nuclear fuel reprocessing. 

Heteroleptic complexes of uranium can be stabilized by the presence of the ancillary ligands however, the chemistry is dominated by methyl and benzyl ligands. Examples of these materials include UR4(dmpe) (R = alkyl, benzyl) and U(benzyl)4MgCl2. The former compounds coordinate "soft" chelating phosphine ligands, a rarity for the hard U(IV) atom. 

This book presents a unified treatment of the chemistry of the elements. At present 112 elements are known, though not all occur in nature of the 92 elements from hydrogen to uranium all except technetium and promethium are found on earth and technetium has been detected in some stars. To these elements a further 20 have been added by artificial nuclear syntheses in the laboratory. Why are there only 90 elements in nature Why do they have their observed abundances and why do their individual isotopes occur with the particular relative abundances observed Indeed, we must also ask to what extent these isotopic abundances commonly vary in nature, thus causing variability in atomic weights and possibly jeopardizing the classical means of determining chemical composition and structure by chemical analysis. 

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