Neptunium reduction

With the exception of thorium, the actinides form trihalides. For uranium and neptunium, reduction of the MX4 compounds with hydrogen is necessary, but for the elements from plutonium onwards the action of the carbon tetrahalide or aluminium halide on the dioxide is usually employed. The trifluorides are insoluble but the rest dissolve to give solutions containing ions. 

Its importance depends on the nuclear property of being readily fissionable with neutrons and its availability in quantity. The world s nuclear-power reactors are now producing about 20,000 kg of plutonium/yr. By 1982 it was estimated that about 300,000 kg had accumulated. The various nuclear applications of plutonium are well known. 238Pu has been used in the Apollo lunar missions to power seismic and other equipment on the lunar surface. As with neptunium and uranium, plutonium metal can be prepared by reduction of the trifluoride with alkaline-earth metals. 

T. W. Newton, The Kinetics of the Oxidation Reduction Reactions of Uranium, Neptunium, Plutonium, andMmericium inMqueous Solution, TlD-26506, U.S. Energy, Research, and Development Administration (ERDA) Technical Information Center, Washington, D.C., 1975. 

Reduction Reactions of Uranium, Neptunium, Plutonium and Americium in Aqueous Solutions" National Technical Information Service, U. S. Department of Commerce Springfield, Virginia, 1975. (b) Buxton, G. V. and... 

The Table shows a great spread in Kd-values even at the same location. This is due to the fact that the environmental conditions influence the partition of plutonium species between different valency states and complexes. For the different actinides, it is found that the Kd-values under otherwise identical conditions (e.g. for the uptake of plutonium on geologic materials or in organisms) decrease in the order Pu>Am>U>Np (15). Because neptunium is usually pentavalent, uranium hexavalent and americium trivalent, while plutonium in natural systems is mainly tetravalent, it is clear from the actinide homologue properties that the oxidation state of plutonium will affect the observed Kd-value. The oxidation state of plutonium depends on the redox potential (Eh-value) of the ground water and its content of oxidants or reductants. It is also found that natural ligands like C032- and fulvic acids, which complex plutonium (see next section), also influence the Kd-value. 

Table 3. Formal reduction potentials (in volts) of uranium, neptunium, plutonium and americium for 1 M perchloric add solutions at 25 °C. (F. A. Cotton and G. Wilkinson Advanced Inorganic Chemistry. Interscience Publishers 1972)...

Neptunium may be prepared in the metallic state by the reduction of its trifluoride with barium vapor at 1,200°C followed by rapid cooling. Its tetraflu-oride may be reduced with excess calcium metal at about 750°C under argon atmosphere. 

C. Licour, L. Lopes, Contribution to the Knowledge of the Electrochemical Properties of Actinides in Non-Aqueous Media III. The Reduction of Tetravalent Thorium and Tetravalent Neptunium in Various Organic Solvents, Pages 6-12, 1995, with permission from Elsevier). 

In research at the Institute of Radiochemistry, Karlsruhe, West Germany, during the early 1970s, investigators prepared alloys of neptunium with indium, palladium, platinum, and rhodium. These alloys were prepared by hydrogen reduction of the neptunium oxide in (he presence of finely divided noble metals. The reaction is called a coupled reaction because the reduction of the metal oxide can be done only m the presence of noble metals. The hydrogen must be extremely pure, with an oxygen content of less than 10 25 torr. 

A single oxo bridge may subtend an angle between 140° and 180°, this angle being determined by steric or electronic factors (Table 3).95 103 Almost all these examples refer to the solid state, but there are also several homo- and hetero-nuclear M—O—M and M—O—M—O—M species known in solution. Often these are intermediates in, or products of, electron transfer reactions with oxide-bridging inner-sphere mechanisms. Examples include V—O—V in V(aq)2+ reduction of VO(aq)2+, and Act—O—Cr in Cr(aq)2+ reduction of UOj+ or PuOj+ a useful and extensive list of such species has been compiled. Tlie most recent examples are another V—O—V unit, this time from VO(aq)2+ and VOJ,105 and an all-actinide species containing neptunium(VI) and uranium-(VI).106 An example of a trinuclear anion of this type, with the metal in two oxidation states, is provided by (31).107... 

The oxidation-reduction behaviors of neptunium, plutonium and americium in basic solution have been determined via polarographic and coulometric studies (6-9). These studies, which showed that the more soluble (V), (VI), and (VII) oxidation states of these actinides are stable in alkaline solution under certain redox conditions, helped identify possible actinide species and oxidation states in our experiments. Actual identification of radioelement oxidation states was not done in the present experiments. 

Especially interesting in a discussion of radionuclide speciation is the behaviour of the transuranium elements neptunium, plutonium, americium and curium. These form part of the actinide series of elements which resemble the lanthanides in that electrons are progressively added to the 5f instead of the 4f orbital electron shell. The effective shielding of these 5f electrons is less than for the 4f electrons of the lanthanides and the differences in energy between adjacent shells is also smaller, with the result that the actinide elements tend to display more complex chemical properties than the lanthanides, especially in relation to their oxidation-reduction behaviour (Bagnall, 1972). The effect is especially noticeable in the case of uranium, neptunium and plutonium, the last of which has the unique feature that four oxidation states Pum, Pu, Puv and Pu are... 

Magnusson, L. B., J. C. Hindman, and T. J. LaChapelle Chemistry of Neptunium. Kinetics and Mechanism of Aqueous Oxidation-Reduction Reactions of Neptunium. In G. T. Seaborg, J. J. Katz, and W. M. Manning (Eds.) The Transuranium Elements, National Nuclear Energy Scries, Div. IV-14B, p. 1134. New York McGraw-Hill Co. 1949. 

Newton, T. W and F. B. Baker Aqueous Oxidation-Reduction Reactions of Uranium, Neptunium, Plutonium, and Americium. In if. F. Gould (Ed.), Lanthanide/Actinide Chemistry, Advances in Chemistry Series, Vol. 71, p. 268. Washington American Chemical Society 1967. 

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