Radiation Chemical Kinetics of Actinide Redox Speciation
Concluding Russell L. Heath Distinguished Postdoctoral Fellowship presentation to DOE leadership.
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Covalency in Actinide Compounds
Covalency in actinides has emerged as a resounding research topic on account of the technological importance in separating minor actinides from lanthanides for spent nuclear fuel processing, and utilization of their distinct bonding properties has been realized as a route towards overcoming this challenge. Because of the limited radial extent of the 4f orbitals, there is almost no 4f electron participation in bonding in lanthanides; this is not the case for the actinides, which have extended 5f orbitals that are capable of overlapping with ligand orbitals, although not to the degree of overlap as in the d orbitals of transition metals. In this concept paper, we provide a general description of covalency in actinide compounds. After introducing two main approaches to enhance covalency, either by exploiting increased orbital overlap or decreasing energy differences between the orbitals causing orbital energy degeneracy, we show the current state of the field using several examples from the recent literature. Here, we will conclude by proposing the use of actinide chalcogenides as a convenient auxiliary tool to study covalency in actinide compounds.
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Recovery of Oxidized Actinides, Np(VI), Pu(VI), and Am(VI), from Cocrystallized Uranyl Nitrate Hexahydrate: A Single Technology Approach to Used Nuclear Fuel Recycling
In this work, the utility of recovering cocrystallized Np, Pu, and Am from a uranyl nitrate hexahydrate crystalline phase has been examined. Progressive dissolution studies were carried out on samples of either Np(VI), Pu(VI), or Am(VI) cocrystallized with uranyl nitrate hexahydrate, resulting in a linear relationship between the amount of actinides dissolved as a function of volume of HNO 3 added, which indicates homogeneous distribution of the transuranic species throughout the crystalline solid. The ratio of the concentration of U to the heavier actinides was maintained over the entire dissolution and mimicked that of the starting cocrystallization solution. A series of five crystallization–dissolution–recrystallization cycles of uranyl nitrate hexahydrate from nitric acid have been achieved in the presence of Am(VI), where the behavior of Am(VI) followed that of U(VI) for each step of all five cycles. Negligible reduction of Am(VI) to Am(III) was observed between each recrystallization cycle. These results indicate the utility of a group hexavalent actinide cocrystallization approach toward used nuclear fuel recycling.
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Chemistry and Metallurgy Research Building Historical Perchlorate Data and Discussion
The Chemistry and Metallurgy Research Building (CMR), located at TA-03-0029, was built in 1952 and was occupied by Los Alamos National Laboratory (LANL) employees in 1953. The facility was built to perform actinide analytical chemistry and material characterization in support of LANL and Department of Energy (DOE) mission of stockpile stewardship and research.
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Quantifying neptunium oxidation states in nitric acid through spectroelectrochemistry and chemometrics
Controlled-potential in situ thin-layer spectropotentiometry was leveraged to generate visible/near-infrared (VIS/NIR) absorption spectral data sets for the development of chemometric models to quantify Np(III/IV/V/VI) oxidation states in HNO 3 . This technology would be valuable in laboratory studies and when monitoring process solutions to guide feed adjustments for radiochemical separations—the performance of which depends on oxidation state. This approach successfully isolated and stabilized Np species in pure (~99%) oxidation states without compromising solution optical properties. Multivariate curve resolution–alternating least squares models were evaluated to resolve spectral and component concentrations from a scan that sequentially produced Np(VI), Np(V), Np(IV), and Np(III) spectra with mixtures of two valences at a time. Although it provided a useful approximation, the method was not able to quantitively resolve each component likely because of rotational ambiguity. Additionally, partial least squares regression models were built from artificial and electrochemically generated VIS/NIR spectral training sets to study the effect of interionic interactions on spectral characteristics. Models built with true Bi-chemical mixtures of coexisting Np oxidation states and spectra generated from additive combinations of pure end points had similar prediction performance. This methodology can be used to directly quantify Np concentration and the ratio of Np oxidation states and other actinides in remote settings such as hot cells.
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Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands
Here, we report the synthesis and characterization of substituted aryldimethylsilyldiisopropylanilide ligands and their respective bisamido complexes of U(III), (3,5-R 2 -PhMe 2 SiNDipp) 2 UI(dioxane) x (1, R = H, x= 0; 2, R = Me, x = 0; 3, R = t Bu, x = 1). We found that the steric bulk of the 3,5-R 2 -Ph ring affects the hapticity of the U–arene interaction. In the solid-state, 1 is a U–(η 6 -arene) complex, while 2 is a bis(U–(η 1 -arene)) complex. Theoretically calculated bond orders at PBE0 and PBE0-D3 levels of theory support these hapticity assignments. The 3,5- t Bu 2 -Ph rings of 3 are too bulky to interact with U and solid-state metrical parameters initially suggested a U–(η 1 -arene) interaction with one of the Dipp rings. However, bond order calculations show that this interaction is even weaker than in the previously reported ((PhMe 2 Si) 2 N) 3 U complex, leading to the conclusion that 3 is best described as a U–(η o -arene) complex. Molecular orbital analyses in conjunction with electron localization methods reveal that the U–(η 6 -arene) bonding in 1 is primarily electrostatic in nature. Some charge transfer takes place from the arene π orbitals to the U 6d/5f hybrid orbitals in addition to subtle δ-back-bonding. In 2 and 3, both π and δ interactions are substantially weaker, in agreement with the differences in the U–arene coordination modes. Surprisingly, attempts to generate less sterically bulky (3,5-R 2 -PhMe 2 SiNPh) 2 UI complexes results in disproportionation to homoleptic tetraamido (3,5-R 2 -PhMe 2 SiNPh) 4 U(IV) (4, R = H; 5, R = Me) complexes.
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Chemical Understanding of Actinide Separations
This work provides a broad overview of the separation processes used to isolate actinides and the experimentally and computationally determined chemical characteristics that define those separations. The redox chemistry of the actinides plays a pivotal role in both aqueous and pyrochemical processing separations. The near-overlapping energies of the 6d and 5f orbitals in the light actinides allow for facile adjustment of actinide oxidation states, which is used in many established separation methods. In contrast, the stable, generally 3+ oxidation states of the mid- and heavy actinides can make it difficult to separate them from the similarly lanthanides(III). In aqueous separations, the tendency of the actinides to form anionic and neutral aqueous complexes with a variety of complexants (especially soft donors) is used to achieve high separation factors between chemically similar elements in both solid–liquid separations and liquid–liquid extraction. This selectivity can be further tuned through the use of specialized organic or solid-phase ligands. Pyroprocessing separations utilize the unique redox behavior of the actinides to adjust their distribution between a molten salt electrolyte and either a solid electrode or molten metal phase. Atomic-level insights into the mechanisms underlying actinide separation processes, with the ultimate goal of predicting separation behavior, can be provided by electronic structure and statistical mechanical-based calculation methods.
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Facile Oxide to Chalcogenide Conversion for Actinides Using the Boron–Chalcogen Mixture Method
Actinide chalcogenides are of interest for fundamental studies of the behavior of 5f electrons in actinides located in a soft ligand coordination environment. As actinides exhibit an extremely high affinity for oxygen, the synthesis of phase pure actinide chalcogenide materials free of oxide impurities is a great challenge and, moreover, requires the availability and use of oxygen free starting materials. Herein, we report a new method, the Boron-Chalcogen Mixture (BCM) method, for the synthesis of phase pure uranium chalcogenides based on the use of a boron/chalcogen mixture, where boron functions as an “oxygen sponge” to remove oxygen from an oxide precursor and where the elemental chalcogen effects transformation of the oxide precursor into an oxygen free chalcogenide reagent. Here, the boron oxide can be separated from the reaction mixture that is left to react to form the desired chalcogenide product. Several syntheses are presented that demonstrate the broad functionali-ty of the technique and thermodynamic calculations that show the underlying driving force are discussed. Specifically, three classes of chalcogenides that include both new (rare earth uranium sulfides and alkali-thorium thiophosphates) and previously reported compounds were prepared to validate the approach: binary uranium and thorium sulfides, oxide to sulfide transfor-mation in solid state reactions, and in situ generation of actinide chalcogenides in flux crystal growth reactions.
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Actinides: What we should do and what we do—and how to connect the two [Slides]
Abstract not provided.
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Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?
A comprehensive ab initio study of periodic actinide–ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete active-space (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3– , [An(CN) 6 ] 3– , [An(NCS) 6 ] 3– , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3– , and [An(HOPO)] – series of actinide (An = U–Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin–orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted “breaks” in chemical trends. As a result, bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.
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Exploring the Structural Behavior of Hydrophilic Diglycolamide Complexes with the Lanthanides and Actinides
In the ongoing effort to meet the anticipated rise in energy demand while maintaining the full-scale abandonment of natural gas and coal, a substantial shift in our considerations of green energy is required through the wider adoption of nuclear power. However, the advantages of nuclear power are hindered by the challenges of safely managing nuclear waste. Hydrophilic diglycolamides (DGA) ligands have been explored for use as stripping agents in various lanthanide and actinide partitioning processes. Additionally, the separation of lanthanide fission products and transplutonic actinides can serve multifaceted advantages in that the separation neutron poisoning rare earth element (REE) fission products from minor actinides from used nuclear fuel (UNF) can be mutually beneficial to the fundamental research behind REE separations and UNF separations. With this in mind, understanding the bonding differences between the Ln3+ and An3+ ions as a function of DGA structure, such as varying the alkyl groups on each of the amide functional groups, has an influence on the molecule’s selectivity and solubility and whose changes in molecular architecture also impact the radiolytic behavior of these molecules. As such, crystal structures of (Y3+, La-Lu3+, excl. Pm, Pu3+/4+, Am3+, Bk3+, and Cf3+) with hydrophilic diglycolamides show the systematic progression, and changes in coordination habits, as a function of a f-element ions. These coordination complexes see a consistent decrease in bond lengths and changes in the coordination environment while traversing across the f-elements, owing to the effects of the lanthanide contraction as well as local geometry around the metal centers. Direct comparisons of lanthanide with actinide DGA structures display both striking similarities in coordination with earlier actinides of Pu and Am, while later actinides of Bk and Cf display a complete breakdown of these observed trends. This work has also presented the rare opportunity to study homoleptic DGA compounds across multiple oxidation states have provided insight into their nuanced differences in structural chemistry.
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Synthesis and structure of Americium(III) diglycolate oxalate Trihydrate, Am(ODA)(C 2 O 4 )(H 2 O) 3
Improving f-element separations is important for actinide(III) (An 3+ ) and lanthanide(III) (Ln 3+ ) based technologies. Unfortunately, An 3+ and Ln 3+ ions are difficult to separate from one another because they have similar chemical characteristics. One successful separation method utilizes anion exchange chromatography. This approach exploits differences in An 3+ and Ln 3+ Lewis acidities and their varying abilities to attract anionic complexing agents, like oxalates (C 2 O 4 2– ) and diglycolates (ODA 2– ). The resulting negatively charged complexes are then separated using an anion exchange resin. To better understand how this anion exchange separation works, we reacted Am 3+ (aq) (aq designates Am 3+ dissolved in water) with the anion exchange complexing agents (H 2 C 2 O 4 and H 2 ODA). Here, the resulting Am(ODA)(C 2 O 4 )(H 2 O) 3 product was characterized using single crystal X-ray diffraction and UV-Vis-NIR spectroscopy. The Am(ODA)(C 2 O 4 )(H 2 O) 3 structure was similar to that established previously for Ln 3+ analogues, namely Ln(ODA)(C 2 O 4 )(H 2 O) x . These compounds were all isomorphous, had bridging C 2 O 4 2– and ODA 2– ligands, and crystallized as 2-dimensional extended solids. In addition, the Am 3 +–O bond distances could be predicted based on relative differences in Am 3+ and Ln 3+ 9-coordinate metal ionic radii. Overall, isolation of Am(ODA)(C 2 O 4 )(H 2 O) 3 showcased similarities in complexation and crystallization chemistry for Am 3+ and Ln 3+ .
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Effect and measurement of residual water in CaCl 2 intended for use as electrolyte in molten salt electrochemical processing
We report CaCl 2 has applications for electrochemical processing of nuclear materials. Thermal dehydration leads to formation of oxide ions, which are shown to react and cause precipitation of dissolved CeCl 3 that was selected as a surrogate for actinide chlorides. Thus, measurement of residual water in CaCl 2 is an essential capability. Thermogravimetric analysis (TGA) was shown to underestimate starting water concentration. Subsequent analysis of solid samples via acid–base titration and cyclic voltammetry (CV) of the molten salt yielded consistent values within 5% for residual water. Hydroxides were shown to be unstable, thus oxygen is retained as oxide ions. Thus, total water in a sample of CaCl 2 can be quantified by combining TGA with with either CV of molten salt or titration of salt samples. The importance of quantifying residual water in the salt was demonstrated by showing that cerium chloride (surrogate for actinide chlorides) will react with oxide ions in CaCl 2 to form insoluble oxides and oxychlorides.
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Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study
The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th IV O 2 , Pa IV O 2 , U IV O 2 , Pa V O 2 (OH), U V O 2 (OH), U VI O 3 , Np VI O 3 , Np VII O 3 (OH), and Pu VII O 3 (OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H 2 O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H 2 O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An VI are a turning point in terms of favoring hydration over hydrolysis. For An VII O 3 (OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH) 7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. Here, the ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.
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Determination of distribution coefficients of 41 elements in nitric and hydrochloric acids for actinide resin
The distribution coefficients of 41 elements were determined on Eichrom’s Actinide resin in HCl and HNO 3 solutions of molarities between 0.01 M and 9 M. Herein a separation scheme for these 41 elements was designed utilizing these distribution coefficients that combines the Actinide resin with Eichrom’s TRU resin. Overall, these values improve the ability to create separations targeting specific analytes utilizing Actinide resin.
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Advancing Rare-Earth (4 f ) and Actinide (5 f ) Separation through Machine Learning and Automated High-Throughput Experiments
Not Available
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Incorporation of actinides into iron (oxyhydr)oxides: A long-term environmental barrier to radionuclide migration
Not Available
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Multiplicity of Th(IV) and U(VI) HEH[EHP] Chelates at Low Temperatures from Concentrated Nitric Acid Extractions
Organophosphorus extractants have been widely investigated for lanthanide recovery from ore and for application in the reprocessing of spent nuclear fuel, such as in Advanced TALSPEAK schemes. Determining the speciation of the extracted metal complex in the organic phase remains a significant challenge. A better understanding of the variability of HEH[EHP]–actinide complexes and the speciation of chelates for tetra- and hexavalent actinides can improve the predictability of actinide phase transfer in such biphasic systems. Here, the extraction of Th(IV) and U(VI) from nitric acid media using HEH[EHP] in heptane is examined. The distribution ratio as a function of nitric acid concentration was quantified using UV–vis spectroscopy, and then the speciation of HEH[EHP]–metal complexes in the organic phase was investigated using Fourier transform infrared (FTIR) spectroscopy and low-temperature 31 P nuclear magnetic resonance (NMR) spectroscopy. In addition to perturbation of the vibrational modes proximal to the phosphonic moiety in HEH[EHP] in the FTIR spectra, the appearance of a nitrate signal was found in the organic phase following extraction from the highest acidity conditions for U(VI). The 31 P NMR spectra of the organic phase at a low temperature (-70 °C) exhibited a surprising number (n) of resonances (n ≥ 7 for Th(IV) and n ≥ 11 for U(VI)), with the distribution between these resonances changing with the initial concentration of nitric acid in the aqueous phase. These results indicate that the compositions of the inner and outer spheres of the extracted actinides in the organic phase are more diverse than initially thought.
31P NMR↗