Plutonium halides

Thermodynamics of Plutonium Halides and Halogeno Complexes in the Solid State and in Aqueous Media... 

Pressure of Plutonium Halides. J. chem. Phys. 18, 713 (1950) Paper 6.1 a in Seaborg, G. T., J. J. Katz and W. M. Manning, The Transuranium Elements. National Nuclear Energy Series Div. IV, Vol. 14B. NewYork McGraw Hill 1949. 

Binary plutonium halides, 79 689 Binary plutonium oxide, 79 688 Binary polymer blends, 20 330-334, 343. See also Binary heterogeneous polymer blends... 

Plutonium compounds, 19 687-691 protection against, 19 702 Plutonium dioxide, 19 688—689 Plutonium fuel fabrication facilities, 17 547 Plutonium-gallium alloys, 19 683-684 Plutonium halides, 19 689-690 Plutonium hexafluoride, 19 689 Plutonium hydrides, 19 690 Plutonium ions... 

Rand, M. H., Fuger, J., The thermodynamic properties of the transuranium halides Part 1, Neptunium and plutonium halides, ITU, European Commission Joint Research Centre report. Report 17332 EN, (2000). Cited on pages 500, 513, 522, 528, 546, 547. 

Plutonium halides. Table 9.18 lists plutonium halides together with some of their more significant properties. 

The most widely employed method for plutonium reprocessing used today in almost all of the world s reprocessing plants is the Purex (plutonium-uranium reduction extraction) process. Tributylphosphate (TBP) is used as the extraction agent for the separation of plutonium from uranium and fission products. In effecting a separation, advantage is taken of differences in the extractability of the various oxidation states and in the thermodynamics and kinetics of oxidation reduction of uranium, plutonium, and impurities. Various methods are in use for the conversion of plutonium nitrate solution, the final product from fuel reprocessing plants, to the metal. The reduction of plutonium halides with calcium proved to be the best method... 

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. 

Evidence foi the anionic complex PuCP is the precipitation of complex halides such as Cs2PuClg from concentrated HCl (aq). The ability of Pu(IV) to form stable nitrate complexes provides the basis for the Purex and ion-exchange (qv) process used in the chemical processing of Pu (107). Pu(VI) is similar to Pu(IV) in its abihty to form complex ions. Detailed reviews of complex ion formation by aqueous plutonium are available (23,94,105). 

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]... 

Complex chlorides of plutonium (34, 41) do not present such a wide range of formulae as the complex fTuorides but we have at hand thermodynamic information on two important species which have also been characterized with other actinides. In table II we have disregarded the complex halides for which no thermodynamic data are available. The enthalpy of formation of Cs2NaPuClg(c) (55) and Cs2PuClg(c) (56) have been obtained from enthalpy of solution measurements."The selected (8) values are AHf(Cs2NaPuCl6,c) =... 

Plutonium reacts with hydrogen at high temperatures forming hydrides. With nitrogen, it forms nitrides, and with halogens, various plutonium hahdes form. Halide products also are obtained with halogen acids. Reactions with carbon monoxide yields plutonium carbides, whde with carbon dioxide, the products are both carbides and oxides. Such reactions occur only at high temperatures. 

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 halides. 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 tribromide [1575246-2], PuBr3, and plutonium triiodide [134554)1 -1/, Pul3, both bright green solids, have no practical applications. Comprehensive reviews of the binary and ternary halides are available (147,154,155). 

All of die halides except tile hexafluoride and the triiodide may be prepared by the hydrohalogenation of rhe dioxide or of the oxalate of plutonium(lll) at a temperature of about 700°C. With hydrogen fluoride the reaction product is PUF4, unless hydrogen is added to the gas stream, in which case the trifluoride is produced. With hydrogen iodide the reaction product is PuOi, and the other oxyhalides may be formed by the addition of appropriate quantities of water vapor to the hydrogen halide gas. Plutonium triiodide is produced by the reaction of the metal with hydrogen iodide at about 400°C. The hexafluoride is produced by direct combination of the... 

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