Plutonium ions reduction

The chemistry of plutonium ions in solution has been thoroughly studied and reviewed (30,94—97). Thermodynamic properties of aqueous ions of Pu are given in Table 8 and in the Uterature (64—66). The formal reduction potentials in aqueous solutions of 1 Af HCIO or KOH at 25°C maybe summarized as follows (66,86,98—100) ... 

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

Ammonium ions, tetradecyldimethylbenzyl-liquid—Liquid extraction, 1, 548 Ammonium molybdate, 3,1257 Ammonium nitrate, hydroxyl-as plutonium(IV) reductant Purex process, 6, 949 Amphotericin B metal complexes, 2, 973 a-Amylase zinc, 6, 607 Anabaena spp. 

The control of the actinide metal ion valence state plays a pivotal role in the separation and purification of uranium and plutonium during the processing of spent nuclear fuel. Most commercial plants use the plutonium-uranium reduction extraction process (PUREX) [58], wherein spent fuel rods are initially dissolved in nitric acid. The dissolved U and Pu are subsequently extracted from the nitric solution into a non-aqueous phase of tributyl phosphate (TBP) dissolved in an inert hydrocarbon diluent such as dodecane or odourless kerosene (OK). The organic phase is then subjected to solvent extraction techniques to partition the U from the Pu, the extractability of the ions into the TBP/OK phase being strongly dependent upon the valence state of the actinide in question. 

Another complication in plutonium solution is the gradual, spontaneous reduction of Pu(VI) to Pu(IV), and Pu(IV) to Pu(III), caused by ionization products of alpha particles emitted in radioactive decay [SI]. The rate of alpha reduction is slow, however. For example, the observed rate of reduction of Pu(VI) in 0.5 M HCl at 25°C is 0.0035 g-equiv/day per mole of plutonium, which corresponds to a half-life of 199 days for reduction of Pu(VI) to Pu(TV). From these rates and the known alpha-decay rate and decay energies of plutoniiun, it is estimated that approximately 80 eV of dissipated alpha energy in this solution brings about the addition of one electron in reducing plutonium ions. After several hundred days the plutonium reaches an average oxidation state intermediate between Pu(III) and Pu(IV). 

TABLE rV-6. Oxidation-Reduction Reactions of Plutonium Ions... 

Table 6 presents a summary of the oxidation—reduction characteristics of actinide ions (12—14,17,20). The disproportionation reactions of UO2, Pu , PUO2, and AmO are very compHcated and have been studied extensively. In the case of plutonium, the situation is especially complex four oxidation states of plutonium [(111), (IV), (V), and (VI) ] can exist together ia aqueous solution ia equiUbrium with each other at appreciable concentrations. 

Historically, ferrous sulfamate, Fe(NH2S02)2, was added to the HNO scmbbing solution in sufficient excess to ensure the destmction of nitrite ions and the resulting reduction of the Pu to the less extractable Pu . However, the sulfate ion is undesirable because sulfate complexes with the plutonium to compHcate the subsequent plutonium purification step, adds to corrosion problems, and as SO2 is an off-gas pollutant during any subsequent high temperature waste solidification operations. The associated ferric ion contributes significantly to the solidified waste volume. 

Plutonium(III) in aqueous solution, Pu " ( 4)> is pale blue. Aqueous plutonium(IV) is tan or brown the nitrate complex is green. Pu(V) is pale red-violet or pink in aqueous solution and is beUeved to be the ion PuO Pu(VI) is tan or orange in acid solution, and exists as the ion PuO. In neutral or basic solution Pu(VI) is yellow cationic and anionic hydrolysis complexes form. Pu(VII) has been described as blue-black. Its stmcture is unknown but may be the same as the six-coordinate NpO (OH) (91). Aqueous solutions of each oxidation state can be prepared by chemical oxidants or reductants... 

Nitrite ion is often used in plutonium solvent extraction systems to oxidize Pu(III) to Pu(IV) and to reduce Pu(VI) to Pu(IV). But HONO, produced in HN03 media, is extractable into TBP-diluent systems and can interfere with subsequent reductive stripping of plutonium. There is thus a need to find a reagent comparable to nitrite ion in its reactions with Pu(III) and Pu(VI), but which does not extract into TBP solutions. 

An overview is presented of plutonium process chemistry at Rocky Flats and of research in progress to improve plutonium processing operations or to develop new processes. Both pyrochemical and aqueous methods are used to process plutonium metal scrap, oxide, and other residues. The pyrochemical processes currently in production include electrorefining, fluorination, hydriding, molten salt extraction, calcination, and reduction operations. Aqueous processing and waste treatment methods involve nitric acid dissolution, ion exchange, solvent extraction, and precipitation techniques. 

Dissolution. Plutonium is solubilized in nitric acid solutions at Rocky Flats. The feed material consists of oxide, metal and glass, dissolution heels, incinerator ash and sand, slag, and crucible from reduction operations. The residues are contacted with 12M HNO3 containing CaF2 or HF to hasten dissolution. Following dissolution, aluminum nitrate is added to these solutions to complex the excess fluoride ion. 

A primary goal of chemical separation processes in the nuclear industry is to recover actinide isotopes contained in mixtures of fission products. To separate the actinide cations, advantage can be taken of their general chemical properties [18]. The different oxidation states of the actinide ions lead to ions of charges from +1 (e.g., NpOj) to +4 (e.g., Pu" " ) (see Fig. 12.1), which allows the design of processes based on oxidation reduction reactions. In the Purex process, for example, uranium is separated from plutonium by reducing extractable Pu(IV) to nonextractable Pu(III). Under these conditions, U(VI) (as U02 ) and also U(IV) (as if present, remain in the... 

F. P.L. Boxall, C. Oxidation-reduction reactions of simple hydroxamic acids and plutonium(IV) ions in nitric acid, Radiochim. Acta 96 (2008) 333-343. 

Since the uranyl ion is so obviously its own category, it is very interesting to compare with the analogous species formed by transuranium elements. M = Np, Pu and Am form all three MO 72 and MO which are, by no means, the most stable oxidation states of their elements, and which tend toward reduction by the radiochemical products concomitant with the high specific radioactivity of the isotopes normally studied of plutonium and americium (whereas e.g. 244Pu with the half-life 82 million years would not present this problem). Contrary to some reports in literature, it does not seem that curium (and the subsequent elements) form such dioxo complexes. 

The oxidation-reduction behavior of plutonium is described by the redox potentials shown in Table I. (For the purposes of this paper, the unstable and environmentally unimportant heptavalent oxidation state will be ignored.) These values are of a high degree of accuracy, but are valid only for the media in which they are measured. In more strongly complexing media, the potentials will change. In weakly complexing media such as 1 M HClOq, all of the couples have potentials very nearly the same as a result, ionic plutonium in such solutions tends to disproportionate. Plutonium is unique in its ability to exist in all four oxidation states simultaneously in the same solution. Its behavior is in contrast to that of uranium, which is commonly present in aqueous media as the uranyl(VI) ion, and the transplutonium actinide elements, which normally occur in solution as trlvalent... 

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