Compounds of the Actinides

Thousands of compounds of the actinide elements have been prepared, and the properties of some of the important binary compounds are summarized in Table 8 (13,17,18,22). The binary compounds with carbon, boron, nitrogen, siUcon, and sulfur are not included these are of interest, however, because of their stabiUty at high temperatures. A large number of ternary compounds, including numerous oxyhaUdes, and more compHcated compounds have been synthesized and characterized. These include many intermediate (nonstoichiometric) oxides, and besides the nitrates, sulfates, peroxides, and carbonates, compounds such as phosphates, arsenates, cyanides, cyanates, thiocyanates, selenocyanates, sulfites, selenates, selenites, teUurates, tellurites, selenides, and teUurides. 

Table 31.4 is a list of typical compounds of the actinides and demonstrates the wider range of oxidation states compared to lanthanide compounds. High coordination numbers are still evident, and distortions from the idealized stereochemistries which are quoted are again general. However, no doubt at least partly because the early actinides have received most attention, the widest range of stereochemistries is... 

Table 31.4 Oxidation states and stereochemistries of compounds of the actinides An is used as a general symbol for the actinide elements...

A77. C. Keller, The Chemistry of the Transuranium Elements. Verlag Chemie, Weinheim, 1971. Chapter 8, Organometallic compounds of the actinides, pp. 187-193 (36). Not as comprehensive as reference 4.39. 

The choice of the starting compound of the actinide (oxide or carbide) and of the reductant is determined by the vapour pressure of the actinide metal. For a given temperature, the vapour pressures of the actinide metals (Fig. 2) span a ratio of more than 10 . As the vapour pressure of La is similar to those of Ac, Cm, Pu, only the more volatile... 

Solid Compounds. Thousands of compounds of the actinide elements have been prepared, and the properties of some of the important binary compounds are summarized in Table 4. 

The ionic radii of the M3+ and M4+ ions of the actinides decrease with increasing positive charge of the nucleus (the actinide contraction) (Fig. 15.15). This contraction is due to the successive addition of electrons in an inner f shell where the incomplete screening of the nuclear charge by the added f electron leads to a contraction of the outer valence orbital. Because the ionic radii of ions of the same oxidation state are generally similar (Fig. 15.15), the ionic compounds of the actinides are isostructural. 

This chapter examines some of the most important binary compounds of the actinides, especially the halides. Despite the problems caused by their radioactivity, some binary compounds of most of these elements have been studied in considerable detail, and form a good vehicle for understanding trends in the actinide series. 

Isomorphism among compounds of the actinides is common and only a few examples need be given. The dioxides, MO2, of thorium, uranium, neptunium, plutonium and americium all have a fluorite lattice. The trihalides of the transuranic elements are isomorphous not only with the corresponding trihalides of actinium and uranium but also with those of the lanthanides. Isomorphism is also exhibited in many complex halides thus thorium, ura-... 

The actinide iodate system is one of considerable interest that has attracted chemists for more than 150 years (vide supra). In fact one of the first forms that was isolated in was as the iodate salt, presumably as 1 0(103)4 [63], The precipitation of iodate compounds of the actinides has been used for decades as a method of separated them from lanthanides and other fission products. The precipitation of thorium iodate is perhaps best known in this regard [64-66], but several patents exist describing selective precipitation of transuranium elements [67-72], Despite the key importance of iodate in actinide chemistry the structures of actinide iodates were not described in detail until approximately 2000. 

The RWMC assigned a high priority to the critical review of relevant chemical thermodynamic data of inorganic species and compounds of the actinides uranium, neptunium, plutonium and americium, as well as the fission product technetium. The first four books in this series on the chemical thermodynamics of uranium, americium, neptunium and plutonium, and technetium originated from this initiative. 

It is now recognized that yet another situation pertains to many compounds of the actinides. This may be termed the intermediate-field case, for which spin-orbit c crystal field electronic repulsion. Obviously this situation is more complex theoretically, in the sense that none of the usual perturbation-type calculations are applicable here. Since the advent of highspeed digital computers, however, this need not be a serious limitation. 

Crystal structure data obtained by X-ray diffraction methods for the actinide element halides are collected in Table IV. Crystal structure determinations have been most important in identifying new compounds of the actinide elements the data are sufficiently extensive now for use in drawing conclusions regarding systematic trends and relations among the actinide elements. The tetrafluorides, for instance, supply one of the best illustrations of an actinide contraction that is entirely similar to the well-known lanthanide contraction (Table V). 

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