Temperature and pentavalent plutonium

Two reasons for understanding the increasing fraction of pentavalent plutonium with rising temperature in dilute acid are presented. The reasons make the results of calculations easier to understand.     

Determination of uranium and plutonium in plutonium based fuels by sequential amperometric titration

A method is described for the sequential determination of uranium and plutonium in plutonium bearing fuel materials. Uranium and plutonium are reduced to U(IV) and Pu(III) with titanous chloride and then titrated with dichromate to two end points which are detected amperometrically using two polarized platinum electrodes. Uranium-plutonium solutions of known concentrations containing plutonium in the proportions of 4, 30, 50, and 70% were analyzed with precisions better than 0.3%, maintaining the amounts of plutonium per aliquot in the range of 2–10 mg. No significant bias could be detected. Several samples of (U, Pu)O₂ and (U, Pu)C were analyzed by this procedure. The effects of iron, fluoride, oxalic acid and mellitic acid on the method were also studied.     

Triple points and plutonium equilibrium

Summary Equilibrium prevails at all points in plutonium predominance region diagrams. Triple points combine equilibrium with equal fractions of three Pu oxidation states. A rearrangement equation can be used to describe plutonium at a triple point. Two-reaction-product disproportionation equations are not satisfactory for that purpose.     

Dosage du plutonium dans les alliages plutonium aluminium par fluorescence-x

An X-ray fluorescence method is described for the determination of plutonium in Pu-Al alloys. In order to obtain satisfactory reproducibility, the alloy is first dissolved in a nitric acid-mercury (II) nitrate mixture. The Lα emission of plutonium is measured, to eliminate matrix effects, an internal standard with a wavelength near that of the Pu emission is used. Equipment and sample preparation are described. Extension of the method to other determinations is discussed.     

Chemical separation of plutonium

Plutonium in nanogram quantities was isolated from uranium targets irradiated with charged particles. High decontamination was achieved using a method that combines anion exchange with extraction chromatography in tributyl phosphate/hydrochlorid acid solution system.     

Redox speciation of plutonium

Knowledge of the oxidation state distribution of plutonium in natural waters is necessary in modeling its behavior in environmental systems. The redox speciation of plutonium is complicated by such effects as hydrolysis, complexation, disproportionation, solubility, and redox interchange reactions. The insolubility of Pu(OH)₄ is often the limiting factor of the net solubility of plutonium in oxic natural waters where Pu(V)O ₂ ⁺ is the most stable oxidation state. Perturbations to the oxidation state speciation due to the complexation chemistry of the different oxidation states of plutonium and to the insolubility of plutonium(IV) in neutral aquatic systems are discussed. The merits and limitations of some chemical separation techniques used to study redox speciation of plutonium are presented, and recommendations made for obtaining reliable oxidation state distribution data.     

Potentiometric titration of plutonium

In the potentiometric titration of plutonium(III), it has been customary to take the equivalence point as the inflection point on a plot of potential vs. volume of titrant.¹ That the stoichiometric end point corresponds to the inflection point does not seem to have been theoretically demonstrated, however. The purpose of this letter is to suggest that these points may not correspond in the potentiometric titration of plutonium(III). Mound Laboratory is operated by Monsanto Research Corporation for USERDA under contract No. EY-76-C-04-0053.     

Problems of plutonium and uranium determination

The experience with the determination of plutonium and uranium in the samples of nuclear fuel obtained during a 10-years period of the activity of the Central Control Laboratory of the Nuclear Research Institute at e is evaluated. The paper describes the principles of the methods used and the reproducibilities and accuracies of the results obtained with the aid of the titrimetric methods used for the determination of plutonium and uranium.     

Airborne plutonium monitoring

Methods of monitoring low plutonium concentration in the inner and outer atmosphere are analyzed and compared. It is shown that monitors based on the gross alpha counting of air filters are not sensitive enough to measure reliably plutonium activities below 1 MPC. A spectrometric discontinuously operating monitor using a gridded ionization chamber and a membrane filter having 70 cm² active area is described. Plutonium activities of the order of 0.01 MPC /1 mBq.m^–3/ can be measured by the spectrometer at 1 h sampling and 1 h counting time.     

Application of plutonium radiochronometry to the analysis of plutonium age dating reference materials

Journal of Radioanalytical and Nuclear Chemistry - Radiochronometry is an important tool for nuclear forensic analysis. Plutonium has a wide array of parent/progeny pairs that can be measured to...     

Surprising coordination for plutonium in the first plutonium(III) borate

The first plutonium(III) borate, Pu(2)[B(12)O(18)(OH)(4)Br(2)(H(2)O)(3)]·0.5H(2)O, has been prepared by reacting plutonium(III) with molten boric acid under strictly anaerobic conditions. This compound contains a three-dimensional polyborate network with triangular holes that house the plutonium(III) sites. The plutonium sites in this compound are 9- and 10-coordinate and display atypical geometries.     

Rearrangement equations for plutonium

The percents of all oxidation states produced by Pu disproportionation, including unreacted starting material, can be obtained by new equations that are easy to apply. The equations are useful for quantifying the extent and the stoichiometry of disproportionation, the consequences of complexation, and the effects of temperature changes on the composition of the oxidation-state mixture.     

Adsorption of plutonium oxide nanoparticles

Adsorption of monodisperse cubic plutonium oxide nanoparticles ("Pu-NP", [Pu(38)O(56)Cl(x)(H(2)O)(y)]((40-x)+), with a fluorite-related lattice, approximately 1 nm in edge size) to the muscovite (001) basal plane from aqueous solutions was observed in situ (in 100 mM NaCl background electrolyte at pH 2.6). Uptake capacity of the surface quantified by α-spectrometry was 0.92 μg Pu/cm(2), corresponding to 10.8 Pu per unit cell area (A(UC)). This amount is significantly larger than that of Pu(4+) needed for satisfying the negative surface charge (0.25 Pu(4+) for 1 e(-)/A(UC)). The adsorbed Pu-NPs cover 17% of the surface area, determined by X-ray reflectivity (XR). This correlates to one Pu-NP for every 14 unit cells of muscovite, suggesting that each particle compensates the charge of the unit cells onto which it adsorbs as well as those in its direct proximity. Structural investigation by resonant anomalous X-ray reflectivity distinguished two different sorption states of Pu-NPs on the surface at two different regimes of distance from the surface. A fraction of Pu is distributed within 11 ? from the surface. The distribution width matches the Pu-NP size, indicating that this species represents Pu-NPs adsorbed directly on the surface. Beyond the first layer, an additional fraction of sorbed Pu was observed to extend more broadly up to more than 100 ? from the surface. This distribution is interpreted as resulting from "stacking" or aggregation of the nanoparticles driven by sorption and accumulation of Pu-NPs at the interface although these Pu-NPs do not aggregate in the solution. These results are the first in situ observation of the interaction of nanoparticles with a charged mineral-water interface yielding information important to understanding the environmental transport of Pu and other nanophase inorganic species.     

Preparation and characterization of plutonium/IV/ phenyl acetate and plutonium/IV/ α-naphthyl acetate

Plutonium/IV/ compounds obtained in the reactions with phenylacetic acid and -naphthyl acetic acid in the pH range of 3.5–5.0 have been isolated and studied. Carbon, hydrogen and plutonium analyses have shown that plutonium/IV/ phenyl acetate and plutonium/IV/ -naphthyl acetate have the composition Pu/OH/₃/C₁₀H₇CH₂COO/, respectively. Infra-red and ultra-violet absorption spectral studies and thermogravimetric analysis have corroborated these chemical formulas.     

Work integrals for plutonium

Free energy changes in Pu disproportionation reactions can be measured by integrating the reaction isotherm with respect to one of the reaction products. Separate integrations can be made for the isotherms of the component reactions contributing to the equilibrium.Mound is operated for the U.S. Department of Energy by EG&G Mound Applied Technologies Incorporated under contract No. DE-AC04-88DP43495.     

Determination of plutonium in soil

A procedure for the determination of plutonium isotopes in soil is described. The method involves conversion of plutonium to acid-soluble form, dissolution, purification, electrodeposition and alpha-spectrometric determination. Final recovery is in the range from 27 to 51%. In this work increased attention was paid to the problem of equilibration of the chemical yield monitor with plutonium present in the soil sample.     

Zone refining of plutonium metal

An experiment demonstrated the possibility of developing a zone refining process that would produce the first plutonium metal of extremely high purity. Plutonium rods containing known amounts of impurities were melted inside tantalum boats and passed horizontally through a three-turn, high-frequency coil so as to cause a narrow molten zone to pass through each rod 10 times. The impurity elements cobalt, chromium, iron, nickel, neptunium, and uranium moved in the same direction as the molten zone, as predicted; the elements aluminum, americium, and gallium moved in the opposite direction of the molten zone, as predicted. As the impure alloy was zone refined, δ-phase plutonium metal crystals formed.