Actinoid metals elements

In the heavier transition-metal elements, especially the lanthanoids and actinoids, there are numerous exceptions to the regular order of orbital occupation predicted by the building-up principle. Suggest why more exceptions would be noted for these elements. 

A = Alkali metal AE = Alkaline-earth metal a-P = Amorphous phosphorus CN = Mean coordination number (i(M-P) = Distance between M and P atom Distances between P atoms E = Element = Band gap M = Metal PBO = Pauling bond order (P) = Formal charge of a P atom (M) = Formal charge of a M atom R = Zr, Ftf, rare earth metal or actinoid metal RE = Rare earth element / cov = Covalent radius ... 

G.T. Seaborg, J.J. Katz and L.R. Moss (1986) The Chemistry of the Actinide Elements, 2nd edn, Kluwer, Dordrecht - An excellent account of the actinoid metals. 

The actinoid series encompasses the fourteen chemical elements with atomic numbers from 90 to 103, thorium (Th) to lawrencium (Lr). The actinoid series derives its name from the group-IIla element actinium (Ac) which can be included in the series for the purpose of comparison. Only Th and uranium (U) occur in usable quantities in nature. The other actinoids are man-made elements. Pure Th is a silvery-white metal which is air-stable and retains its luster for several months. U exhibits three crystallographic modifications as follows a (688°C) —> P (776°C) —> U is a heavy, silvery-white metal. The luster of freshly prepared americium (Am) is white and more silvery than neptunium (Np) or plutonium (Pu) prepared in the same manner. All actinoid elements are radioactive. Table 2.113 sutnmarizes some physical properties of actinoid metals (Th, U and Am). 

The carbides of the lanthanoids and actinoids can be prepared by heating M2O3 with C in an electric furnace or by arc-melting compressed pellets of the elements in an inert atmosphere. They contain the C2 unit and have a stoichiometry MC2 or M4(C2)3. MC2 have the CaC2 structure or a related one of lower symmetry in which the C2 units lie at right-angles to the c-axis of an orthogonal NaCl-type cell. They are more reactive than the alkaline-earth metal... 

The lanthanoids also form metal-rich carbides of stoichiometry M3C in which individual C atoms occupy at random one-third of the octahedral Cl sites in a NaCl-like structure. Several of the actinoids (e.g. Th, U, Pu) form monocarbides, MC, in which all the octahedral Cl sites in the NaCl structure are occupied and this stoichiometry is also observed for several other carbides of the early transition elements, e.g. M = Ti, Zr, Hf V, Nb, Ta Mo, W. These... 

Compounds with Sc, Y, lanthanoids and actinoids are of three types. Those with composition ME have the (6-coordinated) NaCl structure, whereas M3E4 (and sometimes M4E3) adopt the body-centred thorium phosphide structure (Th3P4) with 8-coordinated M, and ME2 are like ThAsi in which each Th has 9 As neighbours. Most of these compounds are metallic and those of uranium are magnetically ordered. Full details of the structures and properties of the several hundred other transition metal-Group 15 element compounds fall outside the scope of this treatment, but three particularly important structure types should be mentioned because of their widespread occurrence and relation to other structure types, namely C0AS3,... 

The rules above gave maximum and minimum oxidation numbers, but those might not be the only oxidation numbers or even the most important oxidation numbers for an element. Elements of the last six groups of the periodic table for example may have several oxidation numbers in their compounds, most of which vary from each other in steps of 2. For example, the major oxidation states of chlorine in its compounds are -1, +1, +3, +5, and +7. The transition metals have oxidation numbers that may vary from each other in steps of 1. The inner transition elements mostly form oxidation states of + 3, but the first part of the actinoid series acts more like transition elements and the elements have... 

Since 1975, porphyrin complexes of all metals of the periodic table of elements are known, with the exception of some actinoids (20-22). The most fascinating property of all metalloporphyrins is their intense color porphyrlike in the solid state, brick-red, pinkish red, olive-green, or brown in dilute solutions. The absorption spectra vary with the metal, the porphyrin, and the axial ligand many attempts to rationalize the different types of spectra have been undertaken (20-22, 24, 42-48). As the. .periodic table of metalloporphyrins (24) is now nearly complete, a new approach... 

There remains the possibility of g-values which depart substantially from 2.00 but are isotropic because of cubic symmetry. In practice such conditions are rare for transition metal complexes, as the Jahn-Teller theorem ensures departure from cubic symmetry in the electronic structure. However, for the lanthanoid and actinoid elements, where the spin—orbit coupling constant is very much larger than kT, the Jahn—Teller theorem may not be relevant and effective cubic symmetry certain. For the lanthanoids, g-values often depart considerably from 2.00, although some anisotropy arising from ligand field splittings is common. For the actinoids, direct observation of ESR is less common but there is evidence of a similar situation. 

Exhaustive compilations of magnetic properties of transition metal complexes are available.166-192-194 The following sections describe very briefly the magnetic behaviour of a selection of complexes or groups of complexes, from the various electronic configurations which arise for the transition metals. They are intended to be illustrative of the points made in the earlier sections no attempt at completeness of coverage is made. More detailed and intensive accounts of magnetic properties of transition metal complexes are available.99 166 169-174-175 186-195-197 No mention is made of results for lanthanoid and actinoid elements, nor of ESR g-values. 

The analytical chemistry of the transition elements see Transition Metals), that is, those with partly filled shells of d (see (f Configuration) or f electrons see f-Block Metals), should include that of the first transition period (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) and that of the second transition series (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, and Ag). The third transition series embraces Hf, Ta, W, Re, Os, Ir, Pt, and An, and although it formally begins with lanthanum, for historical reasons this element is usually included with the lanthanoids (rare-earth elements) see Scandium, Yttrium the Lanthanides Inorganic Coordination Chemistry Rare Earth Elements). The actinoid elements see Actinides Inorganic Coordination Chemistry) are all radioactive see Radioactive Decay) and those with atomic number see Atomic Number) greater than uranium (Z = 92) are artificial the analytical chemistry of these elements is too specialized to consider here. 

Merinis and Boussieres [2,3] pioneered the method of thermochromatography (TC) in application to radiochemistry. With the equipment schematically pictured in Fig. 1.1, they investigated thermochromatographic behavior of some 20 elements, mostly in the form of chlorides. The elements were some alkaline, alkaline earth, rare earth, transition, noble, and actinoid (Th and Pa) metals. The authors experimental technique was based on slow batch chemical volatilization. They obtained data on the shift in position of TC peaks as a function of the experiment duration. 

An example of exploiting chemisorption in radiochemistry of heavy elements was given by the adsorption studies of the atoms of heaviest actinoids on refractory metals to judge the metallic valence of trace elements see Sect. 1.5.2. Another case of interest was the high adsorption energy of some molecular halides on the surface of alkali halides. It takes place owing to the formation of complexes like K2ZrCl6, which are well known as bulk phases see Sect. 5.1.2 below. 

For the remaining elements in Table 1.3 beginning at francium (Fr), hlling of the orbitals follows a similar sequence as that from Cs but the sequence is incomplete and some of the heaviest elements are too unstable for detailed investigations to be possible. The metals from Th to Lr are the actinoid elements, and in discussing their chemistry, Ac is generally considered with the actinoids (see Chapter 24). 

In this chapter we look at /-block metals and their compounds. There are two series of metals the lanthanoids (the 14 elements that follow lanthanum in the periodic table) and the actinoids (the 14 elements following actinium). The lanthanoids and actinoids (Table 24.1) are collectively known as the inner transition metals, while scandium, yttrium, lanthanum and the lanthanoids are together called the rare earth metals. Although La and Ac are strictly group 3 metals, the chemical similarity of La to the elements... 

The lanthanoids resemble each other much more closely than do the members of a row of t/-block metals. The chemistry of the actinoids is more complicated, and in addition, only Th and U have naturally occurring isotopes. Studies of the transuranium elements (those with Z > 92) require specialized techniques. The occurrence of artihcial isotopes among the /-block elements can be seen from Appendix 5 all the actinoids are unstable with respect to radioactive decay (see Section 24.9), although the half-lives of the most abundant isotopes of thorium and uranium ( Th and t = 1.4 x lO and 4.5 x 10 yr respectively) are... 

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