Plutonium oxide fluorides

Hydrofluoric acid is best known for its ability to dissolve silica, but even small quantities exert a marked catalytic effect on the nitric acid dissolution of many refractory oxides, including ignited plutonium oxide, due to the high stability of the fluoride complexes. Consequently, use of hydrofluoric acid in leaching procedures generally gives more accurate results. However, erratic... 

Table 13.3 Replicate determinations of plutonium oxidation-state species in filtered seawater using neodymium fluoride (100mgl-1) as co-precipitant...

They are black solids with the PbCH (X = Cl) EuBr2 (X = Br) and Euh (X = I) structures. As with plutonium, only fluorides occur in the higher (>3) oxidation states. The trihalides are important they have the usual pastel colours, pink in the case of the fluoride and chloride, white-pale yellow (bromide), and pale yellow (iodide). 

The plutonium purification may be achieved by additional TBP extraction cycles. U(IV) cannot be used as reductant in this part of the process. The final uranium and plutonium products are nitrate solutions whose conversion to oxides, fluorides, etc., have been described earlier ( 5.5.3). 

Molybdenum(III) oxide M02O3 -42.0 Plutonium(VI) fluoride PuFs -rl73... 

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. 

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). 

The pattern of iridium halides resembles rhodium, with the higher oxidation states only represented by fluorides. The instability of iridium(IV) halides, compared with stable complexes IrCl4L2 and the ions IrX (X = Cl, Br, I), though unexpected, finds parallels with other metals, such as plutonium. Preparations of the halides include [19]... 

On the basis of these facts, it was speculated that plutonium in its highest oxidation state is similar to uranium (VI) and in a lower state is similar to thorium (IV) and uranium (IV). It was reasoned that if plutonium existed normally as a stable plutonium (IV) ion, it would probably form insoluble compounds or stable complex ions analogous to those of similar ions, and that it would be desirable (as soon as sufficient plutonium became available) to determine the solubilities of such compounds as the fluoride, oxalate, phosphate, iodate, and peroxide. Such data were needed to confirm deductions based on the tracer experiments. 

We solved the first problem by bombarding large amounts of uranyl nitrate with neutrons at the cyclotrons at the University of California and Washington University plutonium concentrates were derived from these sources through the efforts of teams of chemists who used ether extractions to separate the bulk of the uranium and an oxidation-reduction cycle with rare earth fluoride carrier to concentrate the product. I managed to convince chemists trained in the techniques of ultramicrochemistry to join us to solve the second problem—Burris B. Cunningham and Louis B. Werner of the University of California and Michael Cefola from New York University. 

The reason for the ultramicrochemical test was to establish whether the bismuth phosphate would carry the plutonium at the concentrations that would exist at the Hanford extraction plant. This test was necessary because it did not seem logical that tripositive bismuth should be so efficient in carrying tetrapositive plutonium. In subsequent months there was much skepticism on this point and the ultramicrochemists were forced to make repeated tests to prove this point. Thompson soon showed that Pu(Vl) was not carried by bismuth phosphate, thus establishing that an oxidation-reduction cycle would be feasible. All the various parts of the bismuth-phosphate oxidation-reduction procedure, bulk reduction via cross-over to a rare earth fluoride oxidation-reduction step and final isolation by precipitation of plutonium (IV) peroxide were tested at the Hanford concentrations of... 

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. 

The use of this direct oxide reduction process is replacing fluoride reduction as it eliminates neutron exposure to operating personnel (alpha particles from plutonium decay have sufficient energy to eject neutrons from fluorine by the a,n reaction) and eliminates reduction residues which require subsequent recovery. 

The production of plutonium metal by both fluoride and oxide reduction is well established at Los Alamos. The subsequent purification of this metal by electrorefining is now being performed in production on a 6-kg batch scale. The objective is the production of high-purity plutonium metal. 

All the early work on plutonium was done with unweighable amounts on a tracer scale. When it became apparent that large amounts would be needed for the atomic bomb, it was necessary to have a more detailed knowledge of the chemical properties of this element. Intensive bombardment of hundreds of pounds of uranium was therefore begun in the cyclotrons at Berkeley and at Washington University in St. Louis. Sepa-ration of plutonium from neptunium was based on the fact that neptunium is oxidized by bromate while plutonium is not, and that reduced fluorides of the two metals are carried down by precipitation of rare earth fluorides, while the fluorides of the oxidized states of the two elements are not. Therefore a separation results by repeated bromate oxidations and precipitations with rare earth fluorides. 

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