Properties of Protactinium

Figuie 9.1 Oxidation-reduction diagrams. Formal and standard potentials in volts. Calculated or imcertain couples are listed in parentheses. Continued) 

amu Half-life Radioactive decay Reaction with 2200 m/s neutrons  

Because of epithermal resonance absorption of neutrons in Pa, its effective cross section in a thermal-neutron spectrum is much greater than the 2200 m/s cross section listed in Table 

During thorium irradiation Pa may exist in sufficient concentration that its destruction by chain-branching neutron absorption can reduce the rate of formation of For this reason, thorium-uranium breeder reactors tend to optimize at lower neutron fluxes, and at lower specific power, than do uranium-plutonium breeders. 

2Mmpa The isotope Pa is formed by the beta decay of Th, and by (n, 7) reactions in Pa. A small fraction (0.13 percent) of the decays of Pa are isomeric transitions to Pa, and the rest are beta transitions to 

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The isolation and identification of 4 radioactive elements in minute amounts took place at the turn of the century, and in each case the insight provided by the periodic classification into the predicted chemical properties of these elements proved invaluable. Marie Curie identified polonium in 1898 and, later in the same year working with Pierre Curie, isolated radium. Actinium followed in 1899 (A. Debierne) and the heaviest noble gas, radon, in 1900 (F. E. Dorn). Details will be found in later chapters which also recount the discoveries made in the present century of protactinium (O. Hahn and Lise Meitner, 1917), hafnium (D. Coster and G. von Hevesey, 1923), rhenium (W. Noddack, Ida Tacke and O. Berg, 1925), technetium (C. Perrier and E. Segre, 1937), francium (Marguerite Percy, 1939) and promethium (J. A. Marinsky, L. E. Glendenin and C. D. Coryell, 1945). 

The first actinide metals to be prepared were those of the three members of the actinide series present in nature in macro amounts, namely, thorium (Th), protactinium (Pa), and uranium (U). Until the discovery of neptunium (Np) and plutonium (Pu) and the subsequent manufacture of milligram amounts of these metals during the hectic World War II years (i.e., the early 1940s), no other actinide element was known. The demand for Pu metal for military purposes resulted in rapid development of preparative methods and considerable study of the chemical and physical properties of the other actinide metals in order to obtain basic knowledge of these unusual metallic elements. 

The probable existence of protactinium was predicted as early as 1871 by Mendeleev to fill up the space on his peiiodic table between thorium (at, no. 90) and uranium (at. no, 92). He termed the unconfirmed element ekatantalum. In 1926, O. Hahn predicted the properties of the element in considerable detail, including descriptions of its compounds. In 1930, Aristid v. Grosse isolated 2 milligrams of what then was termed ekatantalum pentoxide and showed that element 91 differed m all reactions with comparable amounts of tantalum compounds with exception of precipitation by NH3. However, credit for the discovery of protactinium generally is attributed to Lise Meitner and Otto Hahn in 1917,... 

The predominant oxidation stale of the element is (V). There is some evidence that the (IV) state is obtained under certain reduction conditions. When the pentapositive form is not in the form of a complex ion it may exist in solution as PaC>2+. The compounds are very readily hydrolyzed in aqueous solution yielding aggregates of colloidal dimensions, thus showing marked similarity to niobium and tantalum in this respect. These properties play a dominant role in the chemical properties of aqueous solution, because the element is so easily removed from solution by hydrolysis and adsorption Protactinium coprecipilates with a wide variety of substances, and it seems likely that the explanation for this lies in the hydrolytic and adsorptive behavior. 

Progress in the preparative and structural fields of protactinium chemistry has been rapid during the past 6 years and there is now sufficient information available, particularly in the halide and oxide fields, to permit a more balanced comparison than has previously been possible with the properties of the actinide elements, on the one-hand, and those of niobium and tantalum, on the other. In this connection one must, of course, bear in mind the fact that the ionic radii of protactinium in its various valence states [Pa(V), 0.90 A and Pa(IV), 0.96 A] are appreciably larger than those of niobium or tantalum and this itself will have a considerable influence on the chemical and crystallographic properties of the elements. 

The preparation of the metal was first reported by von Grosse (80) who obtained it by bombarding protactinium pentoxide with 35 keV electrons in a high vacuum and by decomposing the pentachloride on a hot wire. No properties were reported for these products and more recently the pure metal has been obtained by reduction of protactinium tetrafluoride with lithium (73) or barium (65,125) vapor at 1300°-1400°C using the double crucible technique and on a larger scale by reduction with barium (106) or 10% magnesium in zinc alloy (107). 

Protactinium tetrafluoride, like the other actinide tetrafluorides, possesses the 8-coordinate UF4-type of structure (Table III) but no bond distances are available. It is easily the most stable tetravalent halide of protactinium and can be handled in the atmosphere, at least for a limited period, without hydrolysis or oxidation occurring. As mentioned earlier it is the usual starting material for the preparation of protactinium metal. Tetrafluoride hydrates have not been fully characterized, but a mixed fluorosulfate, PaF2S04 2H20 can be precipitated from aqueous solution (131). Protactinium tetrafluoride is soluble in aqueous ammonium fluoride solutions, for which some spectral properties have been recorded (4, 83). 

Crystallographic Properties of the Tetravalent Protactinium Fluoro Complexes"... 

Actinide halides and oxyhalides are known to form numerous complexes with oxygen and nitrogen donor ligands and the preparation and properties of such compounds have recently been reviewed (12, 13). Relatively few protactinium halide complexes are known, but this situation reflects the lack of research rather than a tendency not to form complexes. However, there is sufficient information available for certain ligands to permit a comparison with the behavior of other actinide halides, and to illustrate the similarities and differences observed with the tetrahalides of thorium to plutonium inclusive and, to a lesser extent, with the protactinium and uranium pentahalides. 

The results of solid state reactions of protactinium dioxide and pentoxide with other metal oxides (89, 93-96) support the view that the oxide systems of protactinium resemble those of other actinide elements rather than those of niobium and tantalum. However, when assessing results of this type one must always bear in mind the relative ionic radii of the respective M " and M + ions since they obviously play a large part in determining the structures of the complex phases. This comment applies equally well, of course, to the structural properties of other types of compound and in particular to the high coordination numbers exhibited by protactinium(V) in its chloro and nitrato complexes. 

Tn reviewing the chemistry of the actinides as a group, the simplest approach is to consider each valence state separately. In the tervalent state, and such examples of the divalent state as are known, the actinides show similar chemical behavior to the lanthanides. Experimental diflB-culties with the terpositive actinides up to plutonium are considerable because of the ready oxidation of this state. Some correlation exists with the actinides in studies of the lanthanide tetrafluorides and fluoro complexes. For other compounds of the 4-valent actinides, protactinium shows almost as many similarities as dijSerences between thorium and the uranium-americium set thus investigating the complex forming properties of their halides has attracted attention. In the 5- and 6-valent states, the elements from uranium to americium show a considerable degree of chemical similarity. Protactinium (V) behaves in much the same way as these elements in the 5-valent state except for water, where its hydrolytic behavior is more reminiscent of niobium and tantalum. 

Protactinium is one of the rarest elements on Earth. It is formed when uranium and other radioactive elements break down. For many years, the only supply of protactinium of any size was kept in Great Britain. The British government had spent 500,000 to extract about 4 ounces (125 grams) of the element from about 65 short tons (60 metric tons) of radioactive waste. Relatively little is known about the properties of the element, and it has no commercial uses. 

Table 9.9 lists the isotopes of protactinium important in nuclear technology and some of the important nuclear properties. 

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