Actinide metals plutonium, thorium, uranium

The chemical similarity between lanthanide and actinide metals suggests that C2H I2 might also react with actinide metals. Preliminary experiments found no reaction between thorium or uranium metals and a THF solution of Plutonium and neptunium... 

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. 

If an actinide metal is available in sufficient quantity to form a rod or an electrode, very efficient methods of purification are applicable electrorefining, zone melting, and electrotransport. Thorium, uranium, neptunium, and plutonium metals have been refined by electrolysis in molten salts (84). An electrode of impure metal is dissolved anodically in a molten salt bath (e.g., in LiCl/KCl eutectic) the metal is deposited electrochemically on the cathode as a solid or a liquid (19, 24). To date, the purest Np and Pu metals have been produced by this technique. 

The most widely used neutral extractants, however, are the organophosphoms compounds, of which the ester, TBP, is the most important. TBP forms complexes with the actinide elements thorium, uranium, neptunium, and plutonium by bonding to the central metal atom via the phosphoryl oxygen in the structure... 

The chemistry of the early actinide metals has been most extensively studied for many reasons. Chief among these is the availability of materials for study. Thorium and uranium obtained from ores as described above have been available for chemical investigations for well over 100 years. In fact, all early actinide elements may be found in nature, although only thorium, protactinium, and uranium are present in sufficient quantities to justify extraction. The remaining early actinide elements, neptunium and plutonium, are produced in large quantities in nuclear reactors. 

Salt Transport Processing (8, 9, 10, 11) The selective transfer of spent fuel constitutents between liquid metals and/or molten salts is being studied for both thorium-uranium and uranium-plutonium oxide and metal fuels. The chemical basis for the separation is the selective partitioning of actinide and fission-product elements between molten salt and liquid alloy phases as determined by the values of the standard free energy of formation of the chlorides of actinide elements and the fission products. Elements to be partitioned are dissolved in one alloy (the donor... 

The last chapter (134) in this volume is an extensive review by Colinet and Pasturel of the thermodynamic properties of landianide and actinide metallic systems. In addition to compiling useful theiTnodynamic data, such as enthalpies, entropies, and free eneigies of formation and of mixing, the authors have made an extensive comparative analysis of the thermodynamic behavior of the rare earths and actinides when alloyed with metallic elements. They note that when alloyed with non-transition metals, the enthalpies of formation of uranium alloys are less negative than those of the rare earths while those of thorium and plutonium are about the same as the latter. For transition metal alloys the formation enthalpies of thorium and uranium are more negative than diose of the rare earths and plutonium (the latter two are about the same). The anomalous behaviors of cerium, europium and ytterbium in various compounds and alloys are also discussed along with the effect of valence state changes found in uranium and plutonium alloys. 

The vast majority of the studies reported have concerned the metals thorium and uranium, particularly the latter, due to accessibility of raw materials, ease of handling, and the long lifetimes of the relatively weakly a-emitting elements Th and U. In many cases, compounds of neptunium and plutonium with similar formulae to U and Th analogues have been made and found to be isomorphous and thus presumably isostructural. This chapter will therefore commence with, and concentrate largely on, the chemistry of complexes of these elements, followed by sections on the other actinides. 

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