Plutonium solution chemistry

Much was also learned at the Metallurgical Laboratory about the solution chemistry of plutonium during these first few years of investigation. This included elucidation of the ionic species present in aqueous solutions of different acids and determination... 

For plutonium in the tri- and tetravalent state, when hydrolysis would dominate the solution chemistry, most sorption phenomena in geologic systems can be looked upon largely as physical adsorption processes. Ion exchange processes, as defined above, would be... 

An overview is given of plutonium process chemistry used at the U. S. Department of Energy Hanford, Los Alamos National Laboratory, Rocky Flats, and Savannah River sites, with particular emphasis on solution chemistry involved in recovery, purification, and waste treatment operations. By extrapolating from the present system of processes, this paper also attempts to chart the future direction of plutonium process development and operation. Areas where a better understanding of basic plutonium chemistry will contribute to development of improved processing are indicated. 

The sorption behaviors of neptunium and plutonium were similar, thus confirming their suspected similarities in solution chemistry. Both NaOH and NaA102 decreased neptunium and... 

As with uranium, the solution chemistry is complicated, owing to hydrolysis and polynuclear ion formation, complex formation with anions other than perchlorate, and disproportionation reactions of some oxidation states. The tendency of ions to displace a proton from water increases with increasing charge and decreasing ion radius, so that the tendency to hydrolysis increases in the same order for each oxidation state, th at is, Am > Pu > Np > U and M4+ > M02+ > M3+ > M02 simple ions such as Np02OH+ or PuOH3+ are known in addition to polymeric species that in the case of plutonium can have molecular weights up to 1010. 

Properties of Plutonium. As nuclear power utilization with its associated reprocessing and waste disposal operations expands, the fate of any released plutonium assumes greater importance. However, there is another rationale for studying the environmental behavior of plutonium. Because of its solution chemistry, it is an element with rather unique qualities as a probe of environmental properties. 

The separation of the lanthanides from thorium, uranium, plutonium, and neptunium can fairly readily be achieved by exploiting the greater extractability of the higher oxidation states of the light-actinide elements. However, the transplutonium actinides do not have stable higher oxidation states. In this case, separation of the lanthanide fission products from the transplutonium actinides must exploit the small differences in the solution chemistry of the lanthanides and actinides in the trivalent oxidation state. It is the separation of the lanthanides from the trivalent actinide cations that is the focus of this chapter. 

Several other useful reviews of reactions involving metal ions have also been published. Redox reactions of chromium(m)-amine species have been described and a survey has been made of the solution chemistry together with reaction paths involved in the redox reactions of various plutonium species. Oxidation reactions of thallium(m) have also been described. Developments in the redox chemistry of peroxides have been reviewed, the nature of the reactions which involve iron(iii) in various complexed forms providing a fascinating example of the manner in which geometry and co-ordination to the metal centre greatly affect the reactivity of the system. Redox properties of cobalt chelates, with delocalized... 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

Plutonium was the first element to be synthesized in weighable amounts (6,7). Technetium, discovered in 1937, was not isolated until 1946 and not named until 1947 (8). Since the discovery of plutonium in 1940, production has increased from submicrogram to metric ton quantities. Because of its great importance, more is known about plutonium and its chemistry than is known about many of the more common elements. The metallurgy and chemistry are complex. MetaUic plutonium exhibits seven aUotropic modifications. Five different oxidation states are known to exist in compounds and in solution. 

The chemistry of plutonium ions in solution has been thoroughly studied and reviewed (30,94—97). Thermodynamic properties of aqueous ions of Pu are given in Table 8 and in the Uterature (64—66). The formal reduction potentials in aqueous solutions of 1 Af HCIO or KOH at 25°C maybe summarized as follows (66,86,98—100) ... 

Investigations of the chemical properties of plutonium have continued in many laboratories throughout the world as it has become available. This has led to the situation where the chemistry of this relative newcomer is as well understood as is that of most of the well-studied elements. The four oxidation states of plutonium—III, IV, V, and VI—lead to a chemistry which is as complex as that of any other element. It is unique among the elements in that these four oxidation states can all exist simultaneously in aqueous solution at appreciable concentration. As a metal, also, its properties are unique. Metallic plutonium has six allotropic forms, in the temperature range from room temperature to its melting point (640 C), and some of these have properties not found in any other known metal. 

The investigation of plutonium chemistry in aqueous solutions provides unique challenges due in large part to the fact that plutonium exhibits an unusually broad range of oxidation states -from 3 to 7-and in many systems several of these oxidation states can coexist in equilibrium. Following the normal pattern for polyvalent cations, lower oxidation states of plutonium are stabilized by more acidic conditions while higher oxidation states become more stable as the basicity increases. 

Disproportionation reactions, which lead to several oxidation states simultaneously in solution, are also a significant aspect of plutonium chemistry, particularly for the IV and V species. 

Previous studies of the plutonium disproportionation reaction have generally, and understandably, emphasized an academic approach with simple acid solutions to elucidate fundamental plutonium chemistry. These past investigations should provide a firm springboard for the more general and advanced research and... 

Precipitation Processes. Plutonium peroxide precipitation is used at Rocky Flats to convert the purified plutonium nitrate solution to a solid (14) the plutonium peroxide is then calcined to Pu02 and sent to the reduction step. The chemistry of the plutonium peroxide precipitation process is being studied, as well as alternative precipitation processes such as oxalate, carbonate, fluoride, and thermal denitration. The latter method shows the most promise for cost and waste reduction. 

The electrolyte salt must be processed to recover the ionic plutonium orginally added to the cell. This can be done by aqueous chemistry, typically by dissolution in a dilute sodium hydroxide solution with recovery of the contained plutonium as Pu(OH)3, or by pyrochemical techniques. The usual pyrochemical method is to contact the molten electrolyte salt with molten calcium, thereby reducing any PUCI3 to plutonium metal which is immiscible in the salt phase. The extraction crucible is maintained above the melting point of the contained salts to permit any fine droplets of plutonium in the salt to coalesce with the pool of metal formed beneath the salt phase. If the original ER electrolyte salt was eutectic NaCl-KCl a third "black salt" phase will be formed between the stripped electrolyte salt and the solidified metal button. This dark-blue phase can contain 10 wt. % of the plutonium originally present in the electrolyte salt plutonium in this phase can be recovered by an additional calcium extraction stepO ). 

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