Uranyl ion

Uranyl ions (UO ) are strong photo-oxidants, [171,343,1109], and photo-oxidize alcohols to produce aldehydes or ketones [343]. With primary and secondary alcohols, the reaction normally occurs via abstraction of an a-hydrogen atom by the excited uranyl ion to produce a-hydroxyalkyl radicals (159, 343, 838)  

Photodegradation of poly(vinyl alcohol) in the presence of uranyl ions has been studied, though not in detail [342, 892, 1424]. 

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The effect is more than just a matter of pH. As shown in Fig. XV-14, phospholipid monolayers can be expanded at low pH values by the presence of phosphotungstate ions [123], which disrupt the stmctival order in the lipid film [124]. Uranyl ions, by contrast, contract the low-pH expanded phase presumably because of a type of counterion condensation [123]. These effects caution against using these ions as stains in electron microscopy. Clearly the nature of the counterion is very important. It is dramatically so with fatty acids that form an insoluble salt with the ion here quite low concentrations (10 M) of divalent ions lead to the formation of the metal salt unless the pH is quite low. Such films are much more condensed than the fatty-acid monolayers themselves [125-127]. 

LIF is also used witii liquid and solid samples. For example, LIF is used to detect lJO ions in minerals the uranyl ion is responsible for the bright green fluorescence given off by minerals such as autunite and opal upon exposure to UV light [23],... 

The solvent, a solution of either sulfuric acid or sodium carbonate, forms the stable complex uranyl ions U02(S04) "2) U02(SO ) )... 

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). 

Crystals of uranyl perchlorate, U02(C10[13093-00-0] have been obtained with six and seven hydration water molecules. The uranyl ion is coordinated with five water molecules (4) in the equatorial plane with a U—O(aquo) distance of 245 nm (2.45 E). The perchlorate anion does not complex the uranyl center. The unit cells contain two [0104] and one or two molecules of hydration water held together by hydrogen bonding (164). 

The known uranium(VI) carbonate soHds have empirical formulas, 1102(003), M2U02(C03)2, and M4U02(C03)3. The soHd of composition 1102(003) is a well-known mineral, mtherfordine, and its stmcture has been determined from crystals of both the natural mineral and synthetic samples. Rutherfordine is a layered soHd in which the local coordination environment of the uranyl ion consists of a hexagonal bipyramidal arrangement of oxygen atoms with the uranyl units perpendicular to the orthorhombic plane. Each uranium atom forms six equatorial bonds with the oxygen atoms of four carbonate ligands, two in a bidentate manner and two in a monodentate manner. 

Before leaving consideration of this group of compounds, mention should be made of one unusual species of this general class. Tabushi, Kobuke and Nishiya have reported a polymer-bound hexaketone, illustrated below as compound 29, which is apparently of use in binding uranyl (UO2++) ions. The polymer has, in fact, been utilized in extraction of the uranyl ion directly from seawater . 

The 0s 02 " group has a formal similarity to the more familiar uranyl ion [U02] " and is present in a variety of octahedral complexes... 

Chemical analyses reveal that measurable amounts of uranyl ion are actually present in Pu(IV) polymers grown in mixtures of Pu(IV) and uranyl nitrate suggesting that uranyl ion is being taken up in the polymer network and consequently hampers the growth through a chain termination process as suggested in Fig. 3. The uranyl serves to terminate active sites because it does not typically form extensive polymeric aggregates as does Pu(IV) instead it tends only to dimerize and, at most, tri-merize (4). 

Conceptual Flowsheet for the Extraction of Actinides from HLLW. Figure 5 shows a conceptual flowsheet for the extraction of all the actinides (U, Np, Pu, Am, and Cm) from HLLW using 0.4 M 0< >D[IB]CMP0 in DEB. The CMPO compound was selected for this process because of the high D m values attainable with a small concentration of extractant and because of the absence of macro-concentrations of uranyl ion. Distribution ratios relevant to the flowsheet are shown in previous tables, IV, V, VI, and VII and figures 1 and 2. One of the key features of the flowsheet is that plutonium is extracted from the feed solution and stripped from the organic phase without the addition of any nitric acid or use of ferrous sulfamate. However, oxalic acid is added to complex Zr and Mo (see Table IV). The presence of oxalic acid reduces any Np(VI) to Np(IV) (15). The presence of ferrous ion, which is... 

Leciejewicz J, Alcock NW, Kemp TJ (1995) Carboxylato Complexes of The Uranyl Ion Effects of Ligand Size and Coordinat. Geometry Upon Molecular and Crystal Structure. 82 43-84... 

Figure 5. Two- and three-dimensional representations of relative luminescence flux of uranyl ion-doped glass beads, measured in a 100 X 100 raster with 10,000 data points. Depicted are a homogeneously doped bead (a) and a nonhomogeneously doped bead (b).

Identical kinetics are found for the uranyl ion-catalysed aerobic oxidation of ascorbic acid and a similar mechanism has been put forward These results and others afford a sequence of catalytic activity for the aerobic oxidation of ascorbic acid ... 

Uranium is readily mobilized in the meteoric environment, principally as the highly soluble uranyl ion (U02 ) and its complexes, the most important of which are the stable carbonate complexes that form in typical groundwaters (pH > 5, pC02 = 10 bar) (Gascoyne 1992b Grenthe et al. 1992 see also Langmuir (1997) for review). Uranium is... 

Czerwinski KR, Buckau G, Scherbaum F, Kim JI (1994) Complexation of the uranyl ion with aquatic humic acid. Radiochim Acta 65 111-119... 

Morse JW, Shanbhag PM, Saito A, Choppin GR (1984) Interaction of uranyl ions in carbonate media. Chem Geol 42 85-99... 

It is interesting to note that some metal ions may exist in solution partly as cationic and partly as anionic species. The uranyl ion is a good example. From sulfate solution it is possible to extract species such as U02(S04)2 with amines. The uranyl cation, on the other hand, can be extracted with acidic extractants such as D2EHPA. 

The ion exchange process involves the ability of hexavalent uranium as the uranyl ion, UO+, to form anionic complexes with sulfate ions, SO2-, and carbonate ions, CO2-. In a general way, it may be mentioned that the uranyl ion exits in dynamic equilibrium with its sulfate complexes,... 

Partial regeneration of the product of the electrode reaction by a disproportionation reaction is characteristic for the reduction of the uranyl ion in acid medium, which, according to D. H. M. Kern and E. F. Orleman and J. Koutecky and J. Koryta, occurs according to the scheme... 

NMR measurements also provide information on the coordination of the ligands in the uranyl polymers. Solid-state I c-NMR confirms the coordination modes of the carboxylate ligands to the uranyl ion that is, both monodentate and bidentate carboxylate coordination modes are evident. The uranyl dicarboxyl ate polymers which possess two moles of coordinated DMSO exhibit two carbon-13 carbonyl resonances, one at about 175 ppm downfield from tetramethylsilane (TMS) and one at about 185 ppm. The polymers which possess only one mole of coordinated DMSO exhibit only the carbonyl peak near 185 ppm. Based on other known coordination compounds, the 175 ppm peak can be assigned to monodentate carboxylate and the 185 ppm peak to bidentate carboxylate. Thus, 7-coordination predominates in the polymers with either one or two moles of solvent coordinated to the uranyl ion, which is consistent with the infrared results reported elsewhere (5). 

The uranyl ion (UOj +) absorbs light in both the visible and ultraviolet spectral regions. In the presence of oxalic acid in excess of the uranyl ion concentration, the excited ion transfers its energy to the oxalic acid, which decomposes to form water, carbon dioxide, and carbon monoxide ... 

The amount of oxalic acid thus decomposed under conditions where all the light is absorbed by the uranyl ion is determined by titrating a sample of the solution with potassium permanganate before and after irradiation. Since... 

Several cations that consist of more than one atom are important in general chemistry. There are few enough of these important ions to learn them individually. They are presented in Table 6-3. There are several ions like uranyl ion, also of limited importance in general chemistry. More will be said about these ions in the sections on oxidation states (Chap. 13). 

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