Actinide radii

For each of the various transition series, ions of the same charge show an overall trend towards decreasing radii with increasing Z. However, in the d block, these trends are not smooth, for reasons given in accounts of ligand field theory. The behavior of the lanthanide and actinide radii is discussed in Chapters 19 and 20, respectively. 

The metal radii, calculated for the same coordination number, demonstrate the special position of the actinides the radii of the lighter actinides (like those of the d transition metals) pass through a minimum. However, when the middle of the series is approached, the actinide radii decrease again with increasing atomic number, as is the case for the lanthanide series because of the 4f electron contraction (Figure 1). 

A full discussion of thorium electrochemistry is available (3). Thorium is generally more acidic than the lanthanides but less acidic than other light actinides, such as U, Np, and Pu, as expected from the larger Th" " ionic radius (108 pm). 

By contrast, the ionic radius in a given oxidation state falls steadily and, though the available data are less extensive, it is clear that an actinide contraction exists, especially for the -f3 state, which is closely similar to the lanthanide contraction (see p. 1232). 

The uncertainty of the proper coordination number of any particular plutonium species in solution leads to a corresponding uncertainty in the correct cationic radius. Shannon has evaluated much of the available data and obtained sets of "effective ionic radii" for metal ions in different oxidation states and coordination numbers (6). Unfortunately, the data for plutonium is quite sparse. By using Shannon s radii for other actinides (e.g., Th(iv), U(Vl)) and for Ln(III) ions, the values listed in Table I have been obtained for plutonium. These radii are estimated to have an uncertainty of 0.02 X ... 

Most of the known borides are compounds of the rare-earth metals. In these metals magnetic criteria are used to decide how many electrons from each rare-earth atom contribute to the bonding (usually three), and this metallic valence is also reflected in the value of the metallic radius, r, (metallic radii for 12 coordination). Similar behavior appears in the borides of the rare-earth metals and r, becomes a useful indicator for the properties and the relative stabilities of these compounds (Fig. 1). The use of r, as a correlation parameter in discussing the higher borides of other metals is consistent with the observed distribution of these compounds among the five structural types pointed out above the borides of the actinides metals, U, Pu and Am lead to complications that require special comment. 

The distribution of the observed higher borides among the five structural types (MB2, MB4, MBg, MB]2 and Mg ) presented in Table 1, which shows correlations with the metallic radius r. values of which are in order of decreasing magnitude (r, corresponds to coordination number 12). In order to discuss the existence of the actinide borides, the table also shows the unit cell volume V of the borides MB4, MBg and MB,2. 

Among the tetraborides, UB4 has the smallest volume and hence the smallest effective radius. Thus an actinide element having a metallic radius of 1.59 A (Pu) or smaller forms a diboride, while those having larger radii do not. As in the rare-earth series, the actinides able to form MB4, MBg and MB,2 borides form also MB2 diborides (Table 1). 

The overall distribution of lanthanides in bone may be influenced by the reactions between trivalent cations and bone surfaces. Bone surfaces accumulate many poorly utilized or excreted cations present in the circulation. The mechanisms of accumulation in bone may include reactions with bone mineral such as adsorption, ion exchange, and ionic bond formation (Neuman and Neuman, 1958) as well as the formation of complexes with proteins or other organic bone constituents (Taylor, 1972). The uptake of lanthanides and actinides by bone mineral appears to be independent of the ionic radius. Taylor et al. (1971) have shown that the in vitro uptakes on powdered bone ash of 241Am(III) (ionic radius 0.98 A) and of 239Pu(IV) (ionic radius 0.90 A) were 0.97 0.016 and 0.98 0.007, respectively. In vitro experiments by Foreman (1962) suggested that Pu(IV) accumulated on powdered bone or bone ash by adsorption, a relatively nonspecific reaction. On the other hand, reactions with organic bone constituents appear to depend on ionic radius. The complexes of the smaller Pu(IV) ion and any of the organic bone constituents tested thus far were more stable (as determined by gel filtration) than the complexes with Am(III) or Cm(III) (Taylor, 1972). 

The ionic radii of the commonest oxidation states are presented in Table 2. There is evidence of an actinide contraction of ionic radii as the 5/ orbitals are filled and this echoes the well established lanthanide contraction of ionic radii as the 4/orbitals are filled. Actinides and lanthanides in the same oxidation state have similar ionic radii and these similarities in radii are obviously paralleled by similarities in chemical behaviour in those cases where the ionic radius is relevant, such as the thermodynamic properties observed for halide hydrolysis. 

Symbol Pa atomic number 91 atomic weight 231.04 an actinide series radioactive element an inner-transition metal electron configuration [Rn]5/26di7s2 valence states +4 and +5 atomic radius 1.63A (for coordination number 12) twenty-two isotopes are known in the mass range 215-218,... 

Symbol Th atomic number 90 atomic weight 232.04 an actinide series radioactive element electron configuration XRn]6d27s2 valence state +4 atomic radius 1.80 A ionic radius, Th4+ 1.05 A for coordination number 8 standard electrode potential, E° for Th4+ -1- 4e Th is -1.899V all isotopes are radioactive the only naturally-occurring isotope, Th-232, ti/2 1.4xl0i° year twenty-six isotopes are known in the mass range 212-237. 

Fig. 3. Wigner-Seitz radii of d-transition metals and actinides vs atomic number Z. To the plot, elements displaying empty and full d- and f-shell have been added. In abscissae, the groups of the Periodic Chart of Elements have been indicated (see, e.g. Handbook of Chemistry and Physics). The figure shows the sudden jump in radius between Pu and Am discussed in this chapter, and, more deeply, in Chap. C...

This treatment aiming to evaluate thermodynamically the orbital character of the bond in actinide metals, follows closely the general features illustrated above and has a particular value inasmuch as it is accompanied by a fairly comprehensive survey of the chemical and physical properties of actinide metals known at that time. In it, the metallic radius and the crystal structures are taken as valence indicators AH nd Tm as the bonding indicators . The metallic valence, however, is not taken as constant throughout the actinide series, but rather allowed to vary. The particular choices are justified by physical and chemical arguments, which are taken in support of the hypothesis chosen. 

The obvious first step in checking for the consistency of the data is comparing equilibrium constants of cations with the same charge and similar ionic radius. Comparison of the formation constants of complexes and solids of tet-ravalent actinides (Th, U4+, Np4+, Pu4+), Zr4+, and Sn4+ reveals that the selected data are very similar, which is to be expected from a chemical point of view, and none of the formation constants appears to be improbable (for details see Hummel et al. 2002). Similar pictures of chemical consistency emerge from the triva-lent Np3+, Pu3+, Am, and Eu3+ complexes and solids, and from the hexavalent UOz"1", NpOl4, and PuO complexes and solids (Hummel et al. 2002). 

Most commonly, metal ions M2+ and M3+ (M = a first transition series metal), Li+, Na+, Mg2+, Al3+, Ga3+, In3+, Tl3+, and Sn2+ form octahedral six-coordinate complexes. Linear two coordination is associated with univalent ions of the coinage metal (Cu, Ag, Au), as in Ag(NH3)2+ or AuCL Three and five coordination are not frequently encountered, since close-packing considerations tell us that tetrahedral or octahedral complex formation will normally be favored over five coordination, while three coordination requires an extraordinarily small radius ratio (Section 4.5). Coordination numbers higher than six are found among the larger transition metal ions [i.e., those at the left of the second and third transition series, as exemplified by TaFy2- and Mo(CN)g4 ] and in the lanthanides and actinides [e.g., Nd(H20)93+ as well as UC Fs3- which contains the linear uranyl unit 0=U=02+ and five fluoride ligands coordinated around the uranium(VI) in an equatorial plane]. For most of the metal complexes discussed in this book a coordination number of six may be assumed. 

When Z is a simple aquacation, two types of complex are formed depending upon the ionic radius of Z. For alkali, alkaline earth and most transition metal cations the product contains Z"+ in quasi-octahedral coordination. Equilibrium constants for reaction (6) have been determined for Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Fe2+, Co2+, Ni, Cu2+ and Zn2+.93 For the transition metals, log K lies between 3 and 9, and is sensitive both to Z and to the lacunary polyanion involved. Larger cations, Sr24, Ba2+, and tri- and tetra-valent lanthanides and actinides are also able to bind two lacunary ligands in a manner similar to that illustrated in Figure 18. Although the stepwise formation of 1 1 and 2 1 complexes of the... 

A new field of coordination chemistry is that of polymetallic cage and cluster complexes [Mm(p-X)xLJz with molecular (i.e. discrete) structure. They contain at least three metal atoms, frequently with bridging ligands X and terminal ligands L. These compounds link the classical complexes (m = 1) and the non-molecular (m - oo) binary and ternary compounds of the metals.1 Molecular polymetallic clusters (with finite radius) also provide a link with the surfaces (infinite radius) of metals and their binary compounds.2"5 Polymetallic complexes are known for almost all metals except the actinides. 

ACTINIDE CONTRACTION. An effect analogous to the Lanthanide contraction, which lias been found in certain elements of the Actinide series. Those elements from thorium (atomic number 90) to curium (atomic number 96) exhibit a decreasing molecular volume in certain compounds, such as those which the actinide tetrafluoiides form with alkali metal fluorides, plotted in Eig. 1. The effect here is due to the decreasing crystal radius of the tetrapositive actinide ions as the atomic number increases. Note that in the Actinides the tetravalent ions are compared instead of the trivalent ones as in the case of the Lanthanides, in which the trivalent state is by far the most common. 

The redox chemistry of the actinide elements, especially plutonium, is complex (Katz et al., 1980). Disproportionation reactions are especially important for the +4 and +5 oxidation states. Some of the equilibria are kinetically slow and irreversible. All transuranium elements undergo extensive hydrolysis with the +4 cations reacting most readily due to their large charge/radius ratio. Pu (IV) hydrolyzes extensively in acid solution and forms polymers. The polymers are of colloidal dimensions and are a serious problem in nuclear fuel reprocessing. 

For the trivalent lanthanides99-100 and actinides,99 as well as for yttrium and scandium,75 the equilibrium constant for the extraction reaction has been shown to vary inversely with the ionic radius of the metal ion. It has therefore been concluded that the extracted complexes are all of the M(HA2)3 type, involving predominantly ionic metal—ligand bonds.75 The similarity of the IR spectra of the scandium(III) and thorium(IV) complexes of D2EHPA to those of the alkali metals is also indicative of the importance of ionic bonding.102... 

---