Plutonium, 137 reduced

The plutonium reduces and separates from the salt phase. In the third step, distillation is used to separate the more volatile zinc and calcium from the plutonium. 

The chemists job was to purify the uranium-235 and plutonium, reduce them to metals, and process... 

Fig. 13. Pu(IV) extraction by di(2-ethylhexyl)-phosphoric acid effect of nitric acid and sodium nitrate concentration. 0.01 MD2EHPA Q M D2EHPA diluent, Amsoo 125-82. Plutonium reduced with hydroxylamine nitrate, reoxidized and stabilized with 0.1-0.5 M NaNOg-... 

Fig. 24. Extraction by tertiary amines from solutions of Pu(in) in nitric acid with and without aluminum nitrate salting. Plutonium reduced with 0.03 M ferrous sulfamate plus 0.05 M excess sulfamic acid, 187...

Uranium—Plutonium Partitioning". The uranium and plutonium are separated in the partitioning column by reducing the plutonium to a less extractable valence state. The plutonium nitrate transfers back to the aqueous phase and the uranium remains with the organic. 

Plutonium Purification. The aqueous feed for the second plutonium cycle is typically prepared by adding HNO and an excess of sodium nitrite, NaN02, to destroy the excess reductant and oxidize the Pu to the more extractable Pu . An alternative approach which reduces the amount of salt in the Hquid waste involves absorbing nitrogen tetroxide, N2O4, as a substitute for the NaN02 ... 

Radiolysis creates oxidants such as the OH radical and reductants such as e (aq), which oxidize or reduce plutonium ions. Self-radiolysis of Pu... 

Only slightly less accurate ( 0.3—0.5%) and more versatile in scale are other titration techniques. Plutonium maybe oxidized in aqueous solution to PuO " 2 using AgO, and then reduced to Pu" " by a known excess of Fe", which is back-titrated with Ce" ". Pu" " may be titrated complexometricaHy with EDTA and a colorimetric indicator such as Arsenazo(I), even in the presence of a large excess of UO " 2- Solution spectrophotometry (Figs. 4 and 5) can be utilized if the plutonium oxidation state is known or controlled. The spectrophotometric method is very sensitive if a colored complex such as Arsenazo(III) is used. Analytically usehil absorption maxima and molar absorption coefficients ( s) are given in Table 10. Laser photoacoustic spectroscopy has been developed for both elemental analysis and speciation (oxidation state) at concentrations of lO " — 10 M (118). Chemical extraction can also be used to enhance this technique. 

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). 

In this process, uranium metal is electrodeposited at the cathode, while plutonium and other transuranium elements remain in the molten salt as trichlorides. Plutonium is reduced in a second step at a metallic cathode to produce Cd—Pu intermetallics. The refined plutonium and uranium metals can then be refabricated into metallic fuel (137). 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

Plutonium has a much shorter half-life than uranium (24.000 years for Pu-239 6,500 years for Pu-240). Plutonium is most toxic if it is inhaled. The radioactive decay that plutonium undergoes (alpha decay) is of little external consequence, since the alpha particles are blocked by human skin and travel only a few inches. If inhaled, however, the soft tissue of the lungs will suffer an internal dose of radiation. Particles may also enter the blood stream and irradiate other parts of the body. The safest way to handle plutonium is in its plutonium dioxide (PuOj) form because PuOj is virtually insoluble inside the human body, gi eatly reducing the risk of internal contamination. 

Congress has decided that reprocessing will not be practiced in this country so that we will not be in the plutonium production business. This seems like a safe thing to do since this action will minimize terrorism threats. Reprocessing generates chemi cal wastes but greatly reduces the volume of the highly radioactive waste. It also isolates plutonium and unused fuel for possible use as new fuel. 

Burger and coworkers (5) in 1952 reported that some distribution coefficients for Pu022+ in organic-aqueous systems at lighted conditions were different from those observed for dark conditions, and those authors believed that some Pu022+ had been photochemically reduced. That reduction was confirmed by others (6) in 1965, and in 1969 a report suggested that most aqueous plutonium reactions were affected by light (7 ). 

Studies of actinide photochemistry are always dominated by the reactions that photochemically reduce the uranyl, U(VI), species. Almost any UV-visible light will excite the uranyl species such that the long-lived, 10-lt seconds, excited-state species will react with most reductants, and the quantum yield for this reduction of UQ22+ to U02+ is very near unity (8). Because of the continued high level of interest in uranyl photochemistry and the similarities in the actinyl species, one wonders why aqueous plutonium photochemistry was not investigated earlier. 

Plutonium, deposited on soil, moves downwards with a rate which depends on precipitation and soil properties. In dry, sandy areas, the downward rate may be 1 mm/year, while in rainy areas it may be 10 times higher (3). The rate is considerably reduced in clay soil. 

The existence of plutonium with an oxidation state of V (or VI) in neutral solutions or at high pH and in the presence of carbonate was previously observed (51). It has also been suggested that Pu(V) is the dominant oxidation state in sea-water and that Pu(VI) is rapidly reduced to Pu(V) in these waters (52). 

In the presence of mineral phases containing anions that would form sparingly soluble compounds (e.g. POt - and F for the lower oxidation states) an enhanced plutonium uptake due to chemisorption can be expected (57). For plutonium in the higher oxidation states the formation of anionic carbonate complexes would drastically reduce the sorption on e.g oxide and silicate surfaces. 

A safety analysis (9) has shown that these cylinders should resist the reducing groundwater, which percolates through Swedish bedrock, for about 106 years. Still, the Swedish authorities have requested information about the consequences of the groundwater coming into contact with the plutonium. 

Research into the aquatic chemistry of plutonium has produced information showing how this radioelement is mobilized and transported in the environment. Field studies revealed that the sorption of plutonium onto sediments is an equilibrium process which influences the concentration in natural waters. This equilibrium process is modified by the oxidation state of the soluble plutonium and by the presence of dissolved organic carbon (DOC). Higher concentrations of fallout plutonium in natural waters are associated with higher DOC. Laboratory experiments confirm the correlation. In waters low in DOC oxidized plutonium, Pu(V), is the dominant oxidation state while reduced plutonium, Pu(III+IV), is more prevalent where high concentrations of DOC exist. Laboratory and field experiments have provided some information on the possible chemical processes which lead to changes in the oxidation state of plutonium and to its complexation by natural ligands. 

The mechanisms by which Pu(IV) is oxidized in aquatic environments is not entirely clear. At Oak Ridge, laboratory experiments have shown that oxidation occurs when small volumes of unhydrolyzed Pu(IV) species (i.e., Pu(IV) in strong acid solution as a citric acid complex or in 45 percent Na2Coj) are added to large volumes of neutral-to-alkaline solutions(23). In repeated experiments, the ratios of oxidized to reduced species were not reproducible after dilution/hydrolysis, nor did the ratios of the oxidation states come to any equilibrium concentrations after two months of observation. These results indicate that rapid oxidation probably occurs at some step in the hydrolysis of reduced plutonium, but that this oxidation was not experimentally controllable. The subsequent failure of the various experimental solutions to converge to similar high ratios of Pu(V+VI)/Pu(III+IV) demonstrated that the rate of oxidation is extremely slow after Pu(IV) hydrolysis reactions are complete. 

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