Uranium Solution Chemistry

In aqueous solution, uranium may occur as trivalent U , the tetravalent uianous ion l/, pentavalent U 02, or the hexavalent uranyl ion However, is unstable, reducing 

only the uranous and uranyl ions are of practical importance. 

Solutions of tetravalent uranium salts are usually prepared by reduction of the corresponding uranyl compounds. Reduction may be effected by metallic zinc or at the cathode of an electrolytic cell  

Pure uranous compounds may be prepared by precipitating U(OH)4 from aqueous solution with ammonium hydroxide and dissolving the precipitate in the appropriate acid. Uranous sulfate, the most common salt, is soluble in water, as are the chloride, bromide, and iodide. Uranous nitrate is unstable, gradually undergoing oxidation to uranyl nitrate with liberation of oxides of nitrogen. 

Tetravalent uranium can be precipitated from aqueous solution as the insoluble oxalate, fluoride, or phosphate. UF4 precipitated from aqueous solution contains water of crystallization. When this compound is heated to drive off the water, it is partially hydrolyzed to an oxyfluoride. The phosphate U3(P04)4 is soluble in hot, concentrated phosphoric acid and appears in this form when uranium in phosphate rock, Ca3(P04)2, is dissolved in sulfuric acid. 

The solution chemistry of uranium is that of the +4 and +6 oxidation states, that is, U4+ and U02+. The formal reduction potential of uranium in aqueous solution (i.e., 1 M HC104) is 

The U(IV) chemistry is similar to that of Th4+, except for the difference in the charge/radius ratio of the ions. U4+ solutions are green in color, stable, and slowly oxidized by air to U02+. Solutions of U4+ are generally prepared by reduction of solutions of the uranyl (U02+) ion. U(IV) forms complexes with many anions (C204-,C2H302, C03-, Cl-, and NO3 ). The chlorides and bromides of U(IV) are soluble while the fluorides and hydroxides are insoluble. In aqueous solution, U(IV) hydrolyzes via the reaction, 

The U(VI) can be prepared by dissolving UO3 in acid or U metal in HNO3. Solutions of the uranyl ion show a characteristic yellow-green color and are very 

Uranyl ions form complexes in solutions with most anions. Uranyl sulfate and carbonate complexes are especially strong and are used in extracting uranium from its ores. Of great practical importance are the complexes of the uranyl ions with nitrate that are soluble in organic liquids such as alcohols, ethers, ketones, and esters. One of the most important of these reactions is that involving the extraction of uranyl nitrate into TBP (the Purex process)  

Neglecting activity coefficients, the coefficient for the distribution of uranium between the organic and aqueous phases is written as 

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Syn-sedimentary chemical deposits form by chemical and biochemical precipitation of valuable metal components carried in solution, concomitant with the formation of the enclosing sedimentary rock. The manner of such deposition depends on the concentration of the metal in the solvent, the solubility of the precipitating product, the solution chemistry, and the deposition environment. Iron, manganese, phosphorus, lead, zinc, sulfur and uranium are some of the elements that have formed economically valuable deposits by chemical precipitation during sedimentation. 

Chisholm-Brause, C. J., Berg, J. M., Matzner, R. A. Morris, D. E. 2001. Uranium(VI) sorption on montmorillonite as a function of solution chemistry. Journal of Colloid and Interface Science, 233, 38-49. 

Figure 9.51 Transient signal of238U+ using nanovolume flow injection of a lOngT1 uranium solution (sample loop =54nm). (D. Schaumloffel, P. Ciusti, M. Zoriy, C. Pickhardt, j. Szpunar, R. Lobinski and j. S. Becker, J. Anal. At. Spectrom., 20, 17(2005). Reproduced by permission of the Royal Society of chemistry.)...

If the environmental condition of the ore zone changes as a result of either natural or manmade causes, the uranium can become very mobile. This is evidenced by the in situ mining process in which relatively minor modifications are made to the ground-water chemistry to produce a solution that can rapidly dissolve uranium and maintain uranium solution concentrations of hundreds of parts per million. We have shown in our laboratory experiments that when this uranium-rich solution contacts aquifer sediments containing minerals capable of reducing uranium from (VI) to (IV), large portions of the uranium are rapidly removed from solution and immobilized. 

The hexavalent state of uranium ion is the usually encountered ion in the solution chemistry of uranium and its exceptional stability, relative to its other oxidation states as well as to other hexavalent actinide ions, makes studies with this ion much simple. Though chelating acids, in general, extract U(VI) by the equilibrium,... 

As with uranium, the solution chemistry is complicated, owing to hydrolysis and polynuclear ion formation, complex formation with anions other than perchlorate, and disproportionation reactions of some oxidation states. The tendency of ions to displace a proton from water increases with increasing charge and decreasing ion radius, so that the tendency to hydrolysis increases in the same order for each oxidation state, th at is, Am > Pu > Np > U and M4+ > M02+ > M3+ > M02 simple ions such as Np02OH+ or PuOH3+ are known in addition to polymeric species that in the case of plutonium can have molecular weights up to 1010. 

The chemical properties span a range similar to the representative elements in the first few rows of the periodic table. Francium and radium are certainly characteristic of alkah and alkaline earth elements. Both Fr and Ra have only one oxidation state in chemical comhina-tions and have little tendency to form complexes. Thallium in the 1+ oxidation state has alkah-like properties, but it does form complexes and has extensive chemistry in its 3+ state. Similarly, lead can have alkaline earth characteristics, hut differs from Ra in forming complexes and having a second, 4+, oxidation state. Bismuth and actinium form 3+ ions in solution and are similar to the lanthanides and heavy (Z > 94) actinides. Thorium also has a relatively simple chemistry, with similarities to zirconium and hafiuum. Protactinium is famous for difficult solution chemistry it tends to hydrolyze and deposit on surfaces unless stabilized (e.g., by > 6 M sulfuric acid). The chemistry of uranium as the uranyl ion is fairly simple, hut... 

The separation of the lanthanides from thorium, uranium, plutonium, and neptunium can fairly readily be achieved by exploiting the greater extractability of the higher oxidation states of the light-actinide elements. However, the transplutonium actinides do not have stable higher oxidation states. In this case, separation of the lanthanide fission products from the transplutonium actinides must exploit the small differences in the solution chemistry of the lanthanides and actinides in the trivalent oxidation state. It is the separation of the lanthanides from the trivalent actinide cations that is the focus of this chapter. 

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. 

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). 

Because of the technical importance of solvent extraction, ion-exchange and precipitation processes for the actinides, a major part of their coordination chemistry has been concerned with aqueous solutions, particularly that involving uranium. It is, however, evident that the actinides as a whole have a much stronger tendency to form complexes than the lanthanides and, as a result of the wider range of available oxidation states, their coordination chemistry is more varied. 

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