Neptunium oxidation state

Figure 13.4 Stability fields (redox potential vs hydrogen ion concentration) of the more important neptunium oxidation-state species in perchlorate solution.

An alternative procedure for the study of neptunium oxidation states at trace concentrations has been described by Inoue and Tochiyama (1977). They showed that, in the pH range 6-7, Nplv may be quantitatively absorbed on silica gel whilst Npv remains in solution. In acid solution, however, a precipitate of barium sulfate selectively absorbs Nplv leaving the higher oxidation states in solution. The authors gave no environmental data for neptunium in their publication but Nelson and Orlandini (1979) subsequendy adapted the procedure to demonstrate that the dominant oxidised plutonium species in natural waters is Puv and not Puvl. 

Fig. 18.4 The spectra of four neptunium oxidation states showing quadrupole...

T. W. Newton, D. E. Hobart, and P. D. Palmer, The Preparation and Stability of Pure Oxidation States of Neptunium, Plutonium, andMmericium, LAUR-86-967, Los Alamos National Laboratory, Calif., 1986. 

The chemistry of plutonium is unique in the periodic table. This theme is exemplified throughout much of the research work that is described in this volume. Many of the properties of plutonium cannot be estimated accurately based on experiments with lighter elements, such as uranium and neptunium. Because massive amounts of plutonium have been and are being produced throughout the world, the need to define precisely its chemical and physical properties and to predict its chemical behavior under widely varying conditions will persist. In addition to these needs, there is an intrinsic fundamental interest in an element with so many unusual properties and with so many different oxidation states, each with its own chemistry. 

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. 

Neptunium is similar to uranium in that the potentials of the four oxidation states are widely separated. There have been only a few studies on the hydrolytic reactions of neptunium. Np02 unlike U02 is comparatively stable and represents a transition... 

Some examples of halogen compounds of neptunium that are formed by its ions with oxidation states of +3, +4, +5, and +6 follow ... 

Although americiums main valence (oxidation state) is +3, it is tetravalent. It can form compounds with its ions of +4, +5, and +6, particularly when oxidized. Its most stable isotope is americium-243, with a half-life of 7,379 years, which, over time through alpha decay, transmutates into neptunium-239. 

As mentioned in the Introduction, the actinyl ions are not stable under all chemical conditions. Plutonium can coexist in solution in several oxidation states, the stability of which often depends strongly on acidity (26). As a result, great care must be taken to obtain pure solutions of PuOl(27). On the other hand, the neptunyl ion NpO is the most stable form of neptunium in aqueous solution. It is noteworthy that the exchange between the oxygen atoms of PuO and H20 is very slow (ti/2 > 10 h) (25), whereas it is quite fast (h/2 2.2 s) in the case of NpO. ... 

Neptunium forms a number of halides in various oxidation states. These include tri-, tetra- and hexafluorides of compositions NpFs, NpF4, and NpFe, respectively trichloride, NpCF and tetrachloride, NpCh tribromide, NpBrs and the triiodide NpN. Neptunium fluorides are formed by heating neptunium dioxide at elevated temperatures with fluorine in the presence of hydrogen fluoride. The tetrachloride, NpCh is obtained similarly by heating the dioxide with carbon tetrachloride vapor at temperatures above 500°C. Neptunium tribromide and triiodide are prepared by heating the dioxide in a sealed vessel at 400°C with aluminum bromide and aluminum iodide, respectively. 

Neptunium has been characterized from the +3 to +7 oxidation states in aqueous solution. The standard potentials for various Np ions have been determined from measured formal potentials of the various redox couples. These data have been thoroughly reviewed by Martinet [94] and Fahey [95]. Recently the standard potentials for the redox couples Np02 /Np02, Np +/Np +, and Np02 /Np" in acidic aqueous solution have been reevaluated with more detailed consideration of activity coefficients [49,50]. The standard potential accepted here for the Np02 /Np02 couple is 1.161 0.011 V as determined from... 

McMillan had been sure that another element was present in his neptunium fractions. In December, 1940, Seaborg, A. C. Wahl, and J. W. Kennedy separated from neptunium a fraction which had alpha activity and which showed at least two oxidation states. It required stronger oxidizing agents to oxidize this substance than were needed for neptunium. The new element was identified as 94. The notes reporting this discovery were submitted to the journals early in 1941, but were not published until 1946 (67, 68). 

All the early work on plutonium was done with unweighable amounts on a tracer scale. When it became apparent that large amounts would be needed for the atomic bomb, it was necessary to have a more detailed knowledge of the chemical properties of this element. Intensive bombardment of hundreds of pounds of uranium was therefore begun in the cyclotrons at Berkeley and at Washington University in St. Louis. Sepa-ration of plutonium from neptunium was based on the fact that neptunium is oxidized by bromate while plutonium is not, and that reduced fluorides of the two metals are carried down by precipitation of rare earth fluorides, while the fluorides of the oxidized states of the two elements are not. Therefore a separation results by repeated bromate oxidations and precipitations with rare earth fluorides. 

The lower oxidation states are more stable than those of neptunium (59). Much that is known has not been disclosed, but the information is slowly emerging. Thus, only in 1954 was it revealed that the metallurgists at Los Alamos in 1945 knew that plutonium metal had the unique property of possessing at least five allotropic modifications at atmospheric pressure (74). 

Because of the ease of oxidation of protactinium(IV) and uranium(IV), peroxides and peroxo complexes are limited to their higher oxidation states. The compounds M04"JcH20 precipitated from dilute acid solutions of neptunium(IV) and plutonium(IV) by hydrogen peroxide appear to be actinide(IV) compounds. Soluble intermediates of the type [Pu( U-02)2Pu]4+ are formed at low hydrogen peroxide concentrations. 

Neptunium has the oxidation states (VI), (V), (IV), and (III) with a general shift in stability toward the lower oxidation states as compared to uranium. The compounds which are formed are very similar to the corresponding compounds of uranium. 

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... 

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