Protactinium oxide

Protactinium oxides can be stabilized in the tetravalent and pentavalent state. The most stable oxide phase obtained by the burning of metal or protactinium compoimds is the white pentoxide, Pa20s. The structme of the pentoxide is related to fluorite and has cubic symmetry. Pa02 is a black solid that crystallizes in the cubic fluorite structure. 

Protactinium is a bright shiny metal. When exposed to air, it combines easily with oxygen to form a whitish coating of protactinium oxide. Its melting point is 2,840°F (1,560°C) and its density about 15.37 grams per cubic centimeter, more than 15 times the density of water. 

Protactinium oxides. Protactinium forms the fee dioxide PaOj, which, like UOj, adds additional oxygen to form the hyperstoichlometric Pa02+ j. TTie most stable oxide is the pentavalent PajOs, which exists in five different crystalline forms. The pentoxide results from heating any... 

The thermodynamic behavior of protactinium oxides is not as well established as for the Th02 system. The free energy of formation of Pa02(s) has been derived from carbothermic reductions. The entropy of formation of the dioxide is comparable to the other actinide dioxides (see table 27 data from Ackermann and Chandrasekharaiah (1974)]. A partial study of the reduction of Pa205 has also provided data for the protactinium oxide system (Kleinschmidt and Ward 1986). 

The actinide elements exhibit uniformity in ionic types. In acidic aqueous solution, there are four types of cations, and these and their colors are hsted in Table 5 (12—14,17). The open spaces indicate that the corresponding oxidation states do not exist in aqueous solution. The wide variety of colors exhibited by actinide ions is characteristic of transition series of elements. In general, protactinium(V) polymerizes and precipitates readily in aqueous solution and it seems unlikely that ionic forms ate present in such solutions. 

The extensive hydrolysis of protactinium in its V oxidation state makes the chemical investigation of protactinium extremely difficult. Ions of protactinium(V) must be held in solution as complexes, eg, with fluoride ion, to prevent hydrolysis. 

The known halides of vanadium, niobium and tantalum, are listed in Table 22.6. These are illustrative of the trends within this group which have already been alluded to. Vanadium(V) is only represented at present by the fluoride, and even vanadium(IV) does not form the iodide, though all the halides of vanadium(III) and vanadium(II) are known. Niobium and tantalum, on the other hand, form all the halides in the high oxidation state, and are in fact unique (apart only from protactinium) in forming pentaiodides. However in the -t-4 state, tantalum fails to form a fluoride and neither metal produces a trifluoride. In still lower oxidation states, niobium and tantalum give a number of (frequently nonstoichiometric) cluster compounds which can be considered to involve fragments of the metal lattice. 

An additional material based on the extractant octyl-phenyl-N,N-diisobutyl-carbamoylmethylphosphine oxide, or CMPO, (marketed under the name TRU-Spec) has also been widely utilized for separations of transuranic actinides (Horwitz et al. 1993a) but is also useful for uranium-series separations (e.g., Burnett and Yeh 1995 Luo et al. 1997 Bourdon et al. 1999 Layne and Sims 2000). This material has even greater distribution coefficients for the uranium-series elements U (>1000), Th (>10000), and Pa. As shown in Figure 1, use of this material allows for sequential separations of Ra, Th, U, and Pa from a single aliquot on a single column. Separations of protactinium using this material (Bourdon et al. 1999) provide an alternative to liquid-liquid extractions documented in Pickett et al. (1994). 

Protactinium is a relatively heavy, silvery-white metal that, when freshly cut, slowly oxidizes in air. AH the isotopes of protactinium and its compounds are extremely radioactive and poisonous. Proctatinium-231, the isotope with the longest half-life, is one of the scarcest and most expensive elements known. It is found in very small quantities as a decay product of uranium mixed with pitchblende, the ore of uranium. Protactiniums odd atomic number (gjPa) supports the observation that elements having odd atomic numbers are scarcer than those with even atomic numbers. 

Examples of compounds of protactinium s oxidation states of +4 and +5 follow ... 

Protactinium (continued) pentachloride, 12 10, II complexes with phosphine oxides, 12 30, 31... 

The most stable oxidation states for protactinium are Pa(V) and Pa(IV). The chemical behavior of Pa(V) closely mimics that of Nb(V) and Ta(V), and experimental data are consistent with a 5f(l) rather than a 6d(l) electron configuration for the Pa(IV) species [37]. The electrochemical literature for Pa is mainly focused on the characteristics of the Pa(V)/Pa(IV) couple and the electrodeposition of Pa metal films from aqueous and nonaqueous electrolyte solutions. In aqueous solutions, only Pa(V) and Pa(IV) ions are known to exist, and the standard potential for the Pa(V)/Pa(IV) redox couple is in the range of —0.1 to -0.32 V [38]. 

In the fall of 1934, Dr. Grosse reduced this pure oxide by two methods and obtained from it the metal protactinium, which is even rarer than radium, but much more permanent in air. In die first method, he bombarded the oxide on a copper target, in a high vacuum, with a stream of electrons. After a few hours, he obtained a shiny, partly sintered, metallic mass, stable in air. In his second method, he converted the oxide to the iodide (or chloride or bromide) and cracked it in a high vacuum on an electrically heated tungsten filament, according to the reaction ... 

Thorium(III) and protactinium(III) complexes are unknown, and relatively few uranium(III), neptunium(III) and plutonium(III) compounds have been described. This is mainly because of the ease of oxidation to the +4 state in all three cases, accentuated for plutonium(III) by the oxidizing nature of the a-radiolysis products formed in solutions. 

Because of the ease of oxidation of protactinium(IV) and uranium(IV), peroxides and peroxo complexes are limited to their higher oxidation states. The compounds M04"JcH20 precipitated from dilute acid solutions of neptunium(IV) and plutonium(IV) by hydrogen peroxide appear to be actinide(IV) compounds. Soluble intermediates of the type [Pu( U-02)2Pu]4+ are formed at low hydrogen peroxide concentrations. 

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