Actinide elements metals

The concept of valence developed in the preceding section is the basis of the first correlations aiming at a global theory of the actinide metallic bond. These correlations were established between the atomic volumes of actinide elemental metals, and the electronic configuration of the actinide atoms Their aim was to provide a general theory of actinides (i.e. to give an answer to the questions i. and ii. of Sect. A.I.l.) within the framework of a simple model of the metallic bond. 

In this part, the photoelectron spectra of actinide elemental metals are reviewed. The organization of this part is the following ... 

Figure 3. The lattice parameter for the family of rock-salt structure actinide-antimonide compounds is shown where the line is for the corresponding lanthanide compounds. The metallic radii for the light actinide elements are plotted. The smooth line simply connects Ac to the heavy actinides. In both cases the smooth line represents the ideal tri-valent behavior.

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). 

Compounds containing group-lIB-transition-metal bonds arc characterized for almost every transition metal. Although there are more derivatives containing Hg than Zn or Cd, there is no difficulty in producing analogous compounds of each of these metals. No compound is known in which Zn, Cd or Hg is bonded to either lanthanide or actinide elements. 

As the computational effort in the LDF approach grows, in the limit, only with the third power in the number of orbitals, it can be expected that fairly large systems with a hundred atoms, including transition metals, rare earth, and actinide elements, will become tractable. 

In this chapter, the results that have been obtained to date by the various techniques are reviewed. Sections 2 to 7 deal with metal elements in the same order as their periodic group classification, with the exception of the transition, rare earth and actinide elements which are dealt with in sections 8, 9 and 10, respectively. 

In terms of gross features of mechanism, a redox reaction between transition metal complexes, having adjacent stable oxidation states, generally takes place in a simple one-equivalent change. For the post-transition and actinide elements, where there is usually a difference of two between the stable oxidation states, both single two-equivalent and consecutive one-equivalent changes are possible. 

Americium (pronounced,, am-8- ris(h)-e-8m) is a man-made, radioactive, actinide element with an atomic number of 95. It was discovered in 1945. Actinides are the 15 elements, all of whose isotopes are radioactive starting with actinium (atomic number 89), and extending to lawrencium (atomic number 103). When not combined with other elements, americium is a silvery metal. Americium has no naturally occurring or stable isotopes. There are two important isotopes of... 

Krebs, Robert E. The history and use of our earth s chemical elements a reference guide. Westport (CT) Greenwood P, 1998. ix, 346p. ISBN 0-313-30123-9 A short history of chemistry — Atomic structure The periodic table of the chemical elements — Alkali metals and alkali earth metals - Transition elements metals to nonmetals — Metallics and metalloids - Metalloids and nonmetals — Halogens and noble gases - Lanthanide series (rare-earth elements) — Actinide, transuranic, and transactinide series... 

Herein we have reported the synthesis, characterization, and reactivity of both transition metal and actinide elements supported by tripodal ligand scaffolds. The carbon-anchored ligands TIME normally form polynuclear species while the nitrogen-anchored ligands TIMEN can coordinate to transition metals in a 1 1, fashion, rendering the coordinated metal centers in well-protected pockets. 

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. 

This article presents a general discussion of actinide metallurgy, including advanced methods such as levitation melting and chemical vapor-phase reactions. A section on purification of actinide metals by a variety of techniques is included. Finally, an element-by-element discussion is given of the most satisfactory metallurgical preparation for each individual element actinium (included for completeness even though not an actinide element), thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, and einsteinium. 

Americium may be separated from other elements, particularly from the lanthanides or other actinide elements, by techniques involving oxidation, ion exchange and solvent extraction. One oxidation method involves precipitation of the metal in its trivalent state as oxalate (controlled precipitation). Alternatively, it may be separated by precipitating out lanthanide elements as fluorosilicates leaving americium in the solution. Americium may also he oxidized from trivalent to pentavalent state by hypochlorite in potassium carbonate solution. The product potassium americium (V) carbonate precipitates out. Curium and rare earth metals remain in the solution. An alternative approach is to oxidize Am3+ to Am022+ in dilute acid using peroxydisulfate. Am02 is soluble in fluoride solution, while trivalent curium and lanthanides are insoluble. 

Previous results of the preparation chemistry of actinide elements have been reviewed in detail by F. WeigeF In the following chapter, the actual state of the possibihties for the preparation and refining of actinide metals will be described the principles and trends in synthesis and crystal growth of (simple) actinide compounds will be shown. 

As many physical properties of the actinide metals depend significantly on the sample purity, refining of the metals is mandatory. The choice of the refining methods is determined by the chemical reactivity of the actinide metal in the presence of the constituents of air, by high temperature reactions with crucible materials, by the specific radioactivity and the availability of the actinide elements. 

In actinide binary compounds an equation of state can also be developed on the same lines. The difference in electronegativity of the actinide and the non-actinide element plays an important role, determining the degree of mixing between the actinide orbitals (5 f and 6 d) and the orbitals of the ligand. A mixture of metallic, ionic and covalent bond is then encountered. In the chapter, two classes of actinide compounds are reviewed NaCl-structure pnictides or chalcogenides, and oxides. 

It is possible to pass the same curve through the experimental AHf values of two truly trivalent actinide elements. Am and Cm, and interpolate from the curve AH° (trivalent) for all other actinide metals. 

In the chapter, we have illustrated some results of photoelectron spectroscopy on two classes of actinide materials, elemental metals and oxides, which we thought particularly relevant as they represent metallic and almost completely ionic bonding. Our interest having been focused on the localization vs. itineracy problem of the 5 f states, as well as on their hybridization with other electron states, we have particularly concentrated on those results which could throw light on these two aspects. 

Electrodeposition of Pa metal has been performed from both aqueous and nonaqueous solutions. An isopropanol solution of 10-20 p,gmL Pa from 8M HCl/0.01 M HE/Pa stock was employed for quantitative electrodeposition [41]. The cell consisted of a gold-plated A1 cathode and a Pt wire anode. During deposition the current was maintained at 1 mA, which produced a potential of 400-600 V during the 90-min electrolysis. The progress of the electrolysis was externally monitored by alpha-counting of the electrolysis solution before and during the electrodeposition. Deposition studies of metal from aqueous solutions are more common. Pa was electrodeposited on platinum in 95% yield at tracer concentrations from an electrolyte of [NH4]C1/HC1 [42]. Electrochemical and chemical conditions of the plating process were described for Pu solutions, which served as a model for the other actinide elements studied. Another tracer... 

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