SEARCH · Engineering Papers

Results for “URANYL NITRATES”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

45 records · Page 3

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision‐Induced Dissociation

The infrared multiphoton dissociation spectrum of the gas-phase uranyl perchlorate anion ([UO 2 (ClO 4 ) 3 ] − ) was measured. Here, the asymmetric uranyl stretch lies somewhere between 930 and 1030 cm −1 , though it could not be deconvoluted from a closely located perchlorate stretching mode. The experimentally measured spectrum was in good agreement with spectra calculated using density functional theory with the B3LYP and TPSSh functionals and Grimme's D3 dispersion corrections with Becke–Johnson damping. The calculations suggest that the asymmetric uranyl stretch lies in the range of 970–980 cm −1 , about 20–30 cm −1 higher than for the analogous uranyl trinitrato complex and consistent with perchlorate as a weaker ligand than nitrate. Like the uranyl trinitrato anion, fragmentation of [UO 2 (ClO 4 ) 3 ] − by collision-induced dissociation resulted in loss of a ClO 3 • radical to form [UO 3 (ClO 4 ) 2 ] − . Infrared multiphoton dissociation measurements of [UO 3 (ClO 4 ) 2 ] − indicate that the structure of the product ion has an O − ligand bound to the uranyl in a T-arrangement and two perchlorate ligands, matching the findings from uranyl nitrato complexes. The uranyl stretch in this complex was slightly separated from the perchlorate modes and was measured at 906 cm −1 , slightly higher than for the analogous nitrate complex, again consistent with perchlorate as a weaker ligand than nitrate in the gas phase.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

DOE OSTI2021

Characterization of Uranyl Coordinated by Equatorial Oxygen: Oxo in UO 3 versus Oxyl in UO 3 +

Uranium trioxide, UO 3 , has a T-shaped structure with bent uranyl, UO 2 2+ , coordinated by an equatorial oxo, O 2– . The structure of cation UO 3 + is similar but with an equatorial oxyl, O •– . Neutral and cationic uranium trioxide coordinated by nitrates were characterized by collision induced dissociation (CID), infrared multiple-photon dissociation (IRMPD) spectroscopy, and density functional theory. CID of uranyl nitrate, [UO 2 (NO 3 ) 3 ] – (complex A1), eliminates NO 2 to produce nitrate-coordinated UO 3 + , [UO 2 (O • )(NO 3 ) 2 ]– (B1), which ejects NO 3 to yield UO 3 in [UO 2 (O)(NO 3 )] – (C1). Finally, C1 associates with H 2 O to afford uranyl hydroxide in [UO 2 (OH) 2 (NO 3 )] – (D1). IRMPD of B1, C1, and D1 confirms uranyl equatorially coordinated by nitrate(s) along with the following ligands: (B1) radical oxyl O •– ; (C1) oxo O 2– ; and (D1) two hydroxyls, OH – . As the nitrates are bidentate, the equatorial coordination is six in A1, five in B1, four in D1, and three in C1. Ligand congestion in low-coordinate C1 suggests orbital-directed bonding. Hydrolysis of the equatorial oxo in C1 epitomizes the inverse trans influence in UO 3 , which is uranyl with inert axial oxos and a reactive equatorial oxo. The uranyl ν 3 IR frequencies indicate the following donor ordering: O 2– [best donor] >> O •– > OH – > NO 3 – .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Optical vibrational spectroscopic signatures of ammonium diuranate process parameters

Ammonium diuranate (ADU) is commonly encountered in the nuclear fuel cycle; however, previous investigations have shown that ADU is a complex mixture of distinct compounds. Moreover, production parameters are known to heavily influence the composition of the resulting ADU. Here, we examine four samples of ADU prepared at Oak Ridge National Laboratory (ORNL), and one sample of ADU made at Pacific Northwest National Laboratory (PNNL), with the goal of further characterizing and elucidating the effect of processing parameters such as stir rate, strike direction, and temperature on material composition. Process parameters during ADU precipitation at ORNL and PNNL were well documented, and we relate process variables to optical vibrational spectroscopic signatures observed using Raman and infrared (IR) spectroscopy. In addition, powder X-ray diffraction (PXRD) reveals differences in the solid-phase composition of ADU precipitates, but we find that the primary phase is similar to the uranyl oxyhydroxyhydrate mineral metaschoepite. Despite the significant phase contributions of a metaschoepite-like phase, spectroscopic evidence of both nitrate and ammonium are observed for all samples. To gain a more holistic understanding of spectroscopic features of process parameters in ADU, principal component analysis (PCA) is employed and results in observable signatures that relate to the stir rate used during synthesis. These results provide further information about the process-dependence of ADU precipitate composition.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Part II: Predicting performance of $\mathrm{DOWEX 21K}$ resin for remediation of comingled contaminants in groundwater

The selectivity of ion exchange (IX) resins for aqueous contaminant removal can be impacted by changing concentrations of competing natural groundwater ions. In a two-part investigation, the Hanford Site 200 West Area pump-and-treat (P&T) facility in Washington State, USA is used as a case study to evaluate the performance of two IX resins for groundwater treatment: Purolite® A532E for pertechnetate (TcO 4 - ) removal, explored in Part I, and DOWEX 21K (DOWEX) for uranium (U) removal. In Part II, DOWEX selectivity for U, as uranyl carbonate species, and uptake kinetics is quantified in a series of laboratory-scale aqueous batch experiments containing Hanford-relevant concentrations of competing anions nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ), as well as co-mingled contaminant TcO 4 - . Here the results demonstrate that DOWEX trimethylammonium functional groups are highly selective for U carbonate species (85–100 % uptake) under all conditions investigated. Only NO 3 - concentrations of 100 mM were shown to decrease U removal, with the extent (85–99 %) depending on competing anion concentrations present in solution. However, at the highest NO 3 - concentrations reported for groundwaters treated at the P&T facility (25 mM), the effect on U uptake is minimal. The batch sorption results are modeled to obtain chloride normalized equilibrium exchange coefficients (K) for predicting DOWEX performance: K SO4--/Cl- = 2.0, K NO3-/Cl- = 5.0, K HCO3-/Cl- = 1.5, K TcO4-/Cl- = 2,000, and K U/Cl- = 50,000. These K values predict little effect of current and future influent chemistries on U removal by DOWEX, where both uranyl carbonate species and TcO 4 - are removed such that effluent concentrations meet groundwater treatment requirements.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Preparation of Neptunyl and Plutonyl Acetates To Access Nonaqueous Transuranium Coordination Chemistry

Uranyl diacetate dihydrate is a useful reagent for the preparation of uranyl (UO 2 2+ ) coordination complexes, as it is a well-defined stoichiometric compound featuring moderately basic acetates that can facilitate protonolysis reactivity, unlike other anions commonly used in synthetic actinide chemistry such as halides or nitrate. Despite these attractive features, analogous neptunium (Np) and plutonium (Pu) compounds are unknown to date. Here, in this study, a modular synthetic route is reported for accessing stoichiometric neptunyl(VI) and plutonyl(VI) diacetate compounds that can serve as starting materials for transuranic coordination chemistry. The new NpO 2 2+ and PuO 2 2+ complexes, as well as a corresponding molecular UO 2 2+ complex, are isomorphous in the solid state, and in solution show similar solubility properties that facilitate their use in synthesis. In both solid and solution state, the +VI oxidation state (O.S.) is maintained, as demonstrated by vibrational and optical spectroscopy, confirming that acetate anions stabilize the oxidizing, high-valent +VI states of Np and Pu as they do for the more stable U(VI). All three acetate salts readily react with a model diprotic ligand, affording incorporation of U(VI), Np(VI), and Pu(VI) cores into molecular coordination compounds that occurs concomitantly with elimination of acetic acid; the new complexes are high-valent, yet overall charge neutral, facilitating entry into nonaqueous chemistry by rational synthesis. Computational studies reveal that the dianionic ligand framework assists in stabilizing the +VI O.S. via donation to the 5f shells of the actinides, highlighting the potential usefulness of protonolysis reactivity toward preparation of stabilized high-valent transuranic species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties

In this work, a series of actinyl(VI) nitrate salts of the form MAnO 2 (NO 3 ) 3 , where M = NH 4 + K + , Rb + , Cs + , and Me 4 N + and AnO 2 2+ = U, Np, Pu, and AnO 2 (NO 3 ) 2 (H 2 O) 2 ·H 2 O, and the uranyl tetranitrates M 2 UO 2 (NO 3 ) 4 have been synthesized from aqueous solution and their structures determined using single-crystal X-ray diffraction. Together, these complexes represent an isostructural series of actinide complexes among the salts crystallized with the same charge-compensating cation and have been studied using vibrational spectroscopy including Raman and Fourier-transform infrared. Periodic trends in both the structural properties of these complexes and their vibrational spectra are presented and discussed, in particular the invariant nature of the O≡An≡O asymmetric stretching frequencies observed across the actinyl series. Electronic structure calculations were performed at a variety of levels of theory to aid in the interpretation of the vibrational data and to correlate trends in the data with the underlying electronic properties of these molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Coupling geophysical, geological, geochemical and mineralogical assessments to examine preferential contaminant transport pathways in interbedded fractured bedrock

This study shows that a multi-faceted approach, combining borehole geophysical logging and surface seismic P-wave first-arrival tomography with confirmatory coring, well installation, and chemical and mineralogical analysis, is effective for identifying difficult-to-locate preferential contaminant transport pathways in deeper fractured bedrock. Seismic tomography detected porous 10–20 m wide elongated fractured conduits that allow acidic groundwater contaminated with uranium (U) and nitrate (NO 3 - ) to migrate within interbedded shale-limestone bedrock over 1000 m from a former disposal facility (S-3 Ponds site) located at the DOE Y-12 National Security Complex in Tennessee (USA). Conventional drilling techniques would easily miss these conduits because they are oriented parallel with fractured bedding planes. Synchrotron analysis of aquifer solids revealed that > 95 % of the U is hexavalent (U VI ). This uranyl (UO 2 2+ ) species is coordinated with carbonate, iron oxide, silicate and phosphate minerals within cemented white to yellow precipitates, which contain U concentrations as high as ∼21.6 % by weight fraction. Identifying the presence of these mineral phases, enables a further understanding of the potential effectiveness of remediation actions. The combination of methodologies presented here can also be applied to other explorations, such as the detection of water supply.

Fate and transport↗

DOE OSTI2024

Radiation‐Induced Defects in Uranyl Trinitrate Solids

Abstract Actinides are inherently radioactive; thus, ionizing radiation is emitted by these elements can have profound effects on its surrounding chemical environment through the formation of free radical species. While previous work has noted that the presence of free radicals in the system impacts the redox state of the actinides, there is little atomistic understanding of how these metal cations interact with free radicals. Herein, we explore the effects of radiation (UV and γ) on three U(VI) trinitrate complexes, M[UO 2 (NO 3 ) 3 ] (where M=K + , Rb + , Cs + ), and their respective nitrate salts in the solid state via electron paramagnetic resonance (EPR) and Raman spectroscopy paired with Density Functional Theory (DFT) methods. We find that the alkali salts form nitrate radicals under UV and γ irradiation, but also note the presence of additional degradation products. M[UO 2 (NO 3 ) 3 ] solids also form nitrate radicals and additional DFT calculations indicate the species corresponds to a change from the bidentate bound nitrate anion into a monodentate NO 3 • radical. Computational studies also highlight the need to include the second sphere coordination environment around the [UO 2 (NO 3 ) 3 ] 0,1 species to gain agreement between the experimental and predicted EPR signatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Influence of uranyl complexation on the reaction kinetics of the dodecane radical cation with used nuclear fuel extraction ligands (TBP, DEHBA, and DEHiBA)

Specialized extractant ligands – such as tri-butyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-2-ethylhexylisobutryamide (DEHiBA) – have been developed for the recovery of uranium from used nuclear fuel by reprocessing solvent extraction technologies. These ligands must function in the presence of an intense multi-component radiation field, and thus it is critical that their radiolytic behaviour be thoroughly evaluated. This is especially true for their metal complexes, where there is negligible information on the influence of complexation on radiolytic reactivity, despite the prevalence of metal complexes in used nuclear fuel reprocessing solvent systems. Here we present a kinetic investigation into the effect of uranyl (UO 2 2+ ) complexation on the reaction kinetics of the dodecane radical cation (RH˙ + ) with TBP, DEHBA, and DEHiBA. Complexation had negligible effect on the reaction of RH˙ + with TBP, for which a second-order rate coefficient (k) of (1.3 ± 0.1) × 10 10 M -1 s -1 was measured. For DEHBA and DEHiBA, UO 2 2+ complexation afforded an increase in their respective rate coefficients: k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHBA) 2 ]) = (2.5 ± 0.1) × 10 10 M -1 s -1 and k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHiBA) 2 ]) = (1.6 ± 0.1) × 10 10 M -1 s -1 . This enhancement with complexation is indicative of an alternative RH˙ + reaction pathway, which is more readily accessible for [UO 2 (NO 3 ) 2 (DEHBA) 2 ] as it exhibited a much larger kinetic enhancement than [UO 2 (NO 3 ) 2 (DEHiBA) 2 ], 2.6× vs. 1.4×, respectively. Complementary quantum mechanical calculations suggests that the difference in reaction kinetic enhancement between TBP and DEHBA/DEHiBA is attributed to a combination of reaction pathway (electron/hole transfer vs. proton transfer) energetics and electron density distribution, wherein attendant nitrate counter anions effectively ‘shield’ TBP from RH˙ + electron transfer processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗