Oxidation and extraction of Am(VI) using a monoamidic extractant in 3D printed centrifugal contactors

A series of tests were performed using centrifugal contactors to evaluate the separation of Am(VI) from cerium, as well as to determine the efficiency of the contactors. All experiments were performed using 2-cm, acrylic 3D-printed centrifugal contactors. Solvent extraction tests were performed using 1 M N,N-di(2-ethylhexyl)butyramide (DEHBA)/dodecane and a nitric acid feed solution spiked with ²⁴³Am and ¹³⁹Ce and oxidized with 60 mg mL^?1 sodium bismuthate. Approximately 72% of the Am was extracted with a single contactor stage. Co-stripping of Am and Ce was demonstrated but attempts at selective stripping were not successful. Successful recycle of the used organic phase was demonstrated. Contactor efficiencies of 95–100% were obtained.     

Uranium and Plutonium Extraction by N,N-dialkylamides Using Multistage Mixer-settler Extractors

N,N-Dialkylamides (monoamides) are known as extractants for U and Pu, and many studies have been carried out mainly by single-stage batch method. We have focused on two monoamides: N,N-di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA) and N,N-di(2-ethylhexyl)butanamide (DEHBA), and proposed a multistage extraction process for recovering U and Pu by these monoamides. A continuous counter-current experiment was carried out to demonstrate the validity of this process. This process consisted of two cycles, and the 1st cycle and the 2nd cycle employed DEHDMPA and DEHBA as extractants, respectively. The feed solution for the 1st cycle was 5.1 mol/dm³ (M) nitric acid containing 0.92 M U, 1.6 mM Pu, and 0.6 mM Np. The raffinate collected in the 1st cycle was used as the feed for the 2nd cycle. The ratios of U recovered in the U fraction and U-Pu fraction were 99.1% and 0.8%, respectively, and the ratios of U in the used solvents were <0.04%. The ratio of Pu recovered in the U-Pu fraction was 99.7%, and the ratio of Pu in the used solvents was in the order of 10^–3–10^–4%. The concentration ratio of U with respect to Pu in the U-Pu fraction was 9, and this indicated that Pu was not isolated. The decontamination factor of U with respect to Pu in the U fraction was obtained as 4.5×10⁵. These results supported the validity of the proposed process.     

Di(2-ethyl hexyl) butyramide and di(2-ethyl hexyl)isobutyramide as extractants for uranium(VI) and plutonium(IV)

The extraction of uranium(VI) and plutonium(IV) from nitric acid into n-dodecane was studied using two isomeric branched alkyl amides, di(2-ethyl hexyl) butyramide (DEHBA) and di(2-ethyl hexyl) isobutyramide (DEHIBA). The extraction ratios of Pu(IV) at relatively high acidities were higher than the corresponding values for U(VI) in the case of DEHBA. However, with DEHIBA the values for Pu(IV) were negligibly small. Pu(IV) was found to be extracted as trisolvate by DEHBA and as disolvate by DEHIBA. U(VI) was extracted by both the amides. From the study of the extraction reactions at different temperatures, it was shown that all the reactions in the present investigation were enthalpy favoured and entropy disfavoured. Separation of Pu(IV) from bulk of U(VI) was feasible. However, the purity of the separated plutonium was not satisfactory in batch extraction studies.     

Study of the isotope effect in the isotope exchange reaction between PuIV and PuIII by extraction redox-chromatography

The equilibrium isotope effect in the isotope exchange reaction between Pu^IV extracted with tributyl phosphate and Pu^III in an aqueous nitric acid solution has been studied by extraction chromatography. For the 238/242Pu isotope pair the isotope separation coefficient () at 25 °C has been found to be 1.0022±0.0005.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1557–1558, September, 1994.The authors are grateful to Prof. N. N. Krot for discussion of the results and valuable remarks and to V. P. Perminov for help in designing the computer programs.This work was financially supported by the International Science Foundation (Grant MDB 000).     

The analysis of plutonium uranium carbide-iron cermets by electrochemical method

Summary Electrochemical methods have been developed for the direct determination of the main metallic constituents of 15 w/o (Pu, U) C — 10 w/o Fe cermets. Samples are dissolved in nitric acid, followed by wet oxidation with a mixture of sulphuric and nitric acids to destroy organic matter. Plutonium is determined by a potentiometric titration procedure based upon the reduction of Pu^VI to Pu^IV with ferrous iron added in slight excess, followed by the titration of this excess with ceric sulphate. The precision of this determination on 4 mg amounts of plutonium is 0.1%. Both uranium and iron are determined by controlled-potential coulometry, but the method for iron includes a contribution from plutonium and allowance has to be made for this. The precision of the uranium determination on 10 mg amounts is 0.25%, and the value for iron on 1 mg amounts is also 0.25%. Results for the complete analysis of typical cermet samples are given.

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Zusammenfassung Elektrochemische Verfahren wurden ausgearbeitet zur direkten Bestimmung der metallischen Hauptbestandteile in Metall-keramischen Materialien (Cermets) der Zusammensetzung 15% (Pu,U)C-10% Fe. Hierbei wird die Probe in Salpetersäure aufgelöst und anschließend zur Zerstörung organischer Substanz einer nassen Oxydation mit einem Gemisch von Schwefel- und Salpetersäure unterworfen. Plutonium wird mit Hilfe eines potentiometrischen Verfahrens bestimmt, das auf der Reduktion von Pu^VI zu Pu^IV mit Fe^II in geringem Überschluß und nachfolgender Titration des Überschusses mit Cer^IV-sulfatlösung beruht. Die Genauigkeit beträgt hierbei 0,1% bei Mengen von 4 mg Pu. Uran und Eisen werden durch Coulometrie mit Potentialkontrolle bestimmt; jedoch wird bei der Eisenbestimmung Plutonium miterfaßt und muß bei der Berechnung berücksichtigt werden. Die Genauigkeit der Uranbestimmung beträgt 0,25% bei 10 mg U, die der Eisenbestimmung 0,25% bei 1 mg Fe. Ergebnisse von vollständigen Analysen typischer Cermetproben werden angeführt.

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Dedicated to Prof. Dr. M. von Stackelberg on his 70th birthday.     

Coordination Chemistry of Homoleptic Actinide(IV)–Thiocyanate Complexes

The synthesis, X‐ray crystal structure, vibrational and optical spectroscopy for the eight‐coordinate thiocyanate compounds, [Et₄N]₄[Pu^IV(NCS)₈], [Et₄N]₄[Th^IV(NCS)₈], and [Et₄N]₄[Ce^III(NCS)₇(H₂O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu^III in acidic solutions (pH<1) in the presence of NCS^?. The optical spectrum of [Et₄N][SCN] containing Pu^III solution was indistinguishable from that of aquated Pu^III suggesting that inner‐sphere complexation with [Et₄N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et₄N]₄[Pu^IV(NCS)₈] was crystallized when a large excess of [Et₄N][NCS] was present. This compound, along with its U^IV analogue, maintains inner‐sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand‐to‐metal charge‐transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An^IV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.     

How 5 f Electron Polarisability Drives Covalency and Selectivity in Actinide N-Donor Complexes

We report a series of isostructural tetravalent actinide (Th, U−Pu) complexes with the N-donor ligand N,N’-ethylene-bis((pyrrole-2-yl)methanimine) (H₂ L , H₂pyren). Structural data from SC-XRD analysis reveal [An(pyren)₂] complexes with different An−N_imine versus An−N_pyrrolide bond lengths. Quantum chemical calculations elucidated the bonding situation, including differences in the covalent character of the coordinative bonds. A comparison to the intensely studied analogous N,N′-ethylene-bis(salicylideneimine) (H₂salen)-based complexes [An(salen)₂] displays, on average, almost equal electron sharing of pyren or salen with the An^IV, pointing to a potential ligand-cage-driven complex stabilisation. This is shown in the fixed ligand arrangement of pyren and salen in the respective An^IV complexes. The overall bond strength of the pure N-donor ligand pyren to An^IV (An=Th, U, Np, Pu) is slightly weaker than to salen, with the exception of the Pa^IV complex, which exhibits extraordinarily high electron sharing of pyren with Pa^IV. Such an altered ligand preference within the early An^IV series points to a specificity of the 5f¹ configuration, which can be explained by polarisation effects of the 5 f electrons, allowing the strongest f electron backbonding from Pa^IV (5f¹) to the N donors of pyren.     

Effects of stereochemistry and β-substituents on the rates of vinylic SN2 reaction of hypervalent vinyl(phenyl)-λ-iodanes with tetrabutylammonium halides

Both stereoisomers of β-(2-phenylethoxy)vinyl-λ³-iodane and (Z)-β-aroyloxyvinyl-λ³-iodane were prepared stereoselectively. These substituted vinyl-λ³-iodanes undergo nucleophilic vinylic substitutions with n-Bu₄NX (X=Cl, Br, I) under mild conditions, yielding vinyl halides. The observed inversion of configuration at the ipso vinylic carbon atom is compatible with a concerted vinylic S_N2 mechanism. Kinetic measurements indicated that the rates for vinylic S_N2 reaction of (Z)-vinyl-λ³-iodane are greater than those of the E-isomer, probably because of the higher ground state energy of the Z-isomer. Electronic effects of β-substituents of vinyl-λ³-iodanes in the vinylic S_N2 reaction are also discussed.     

STRUCTURE,STEREOCHEMISTRY, AND MECHANISM OF FORMATION OF N-ACYLSULFILIMINES

Abstract

The methods for the preparation of sulfilimines are summarized, and the stereochemistry and electronic structure of N-acylsulfilmines are discussed. Sulfilimines have a non-planar structure, but the S^IV[sbnd]N bond character cannot be determined from their resolvability. N-Sulfonylsulfilimines (RR'SNSO₂Q) contain a delocalized S^IVNS^VI d bond system, the S^IVN and S^VIn bonds are of intermediate bond order. S^IV[sbnd]CH₃ hyperconjugation causes strong bond shortening. An asymmetric conformation of a sulfilimine containing two identical S^IV substituents was found in the crystalline state which could be accounted for theoretically. The rotation of the SN bond is not restricted in solution. The structure of N-carboacylsulfilimines (RR'SNCOQ) is strongly polar due to the strong NCO conjugation, and the instability of these compounds can be ascribed to the polar structure. The reaction between thioethers and chloramine-T is a nucleophilic substitution; the rate of the reaction is influenced by the nucleophilic character of the thioether sulfur atom. Thioether carboxylic acids are usually oxidized by chloramine-T and only give a sulfilimine if the carboxyl group is fixed sufficiently distant from the sulfur atom. The formation of sulfilimines from an optically active sulfoxide by the action of a sulfonamide (or N-sulfinylsulfonamide) proceeds via a trigonal bipyramidal intermediate with complete inversion. The intermediate of the sulfilimine synthesis starting from arylsulfonyl azides is a sulfonyl imene.     

Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt‐free complexing and reducing reagent, glutarimidedioxime (H₂A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1 m HNO₃ with H₂A. The complexation‐reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu^IV complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu^IV, through the complexation‐reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.     

Template synthesis in the M(II)–thiocarbohydrazide–diacetyl triple system

Novel complexing processes in the Cu^II-thiocarbohydrazide-diacetyl triple system proceeding to a copper(II)hexacyanoferrate gelatin-immobilized matrix system in contact with aqueous-alkaline (pH 12) solutions containing thiocarbohydrazide and diacetyl, have been studied. It has been shown that mild template synthesis of copper(II) coordination compounds with (N,S,N,S)- and (N,N,N,N)- tetradentate ligands - 4,5-dimethyl-2,3,6,7-tetraazaoctadien-3,5-dithiohydrazide-1,8 and 3,10-dithio--6,7,13,14-tetramethyl-1,2,4,5,8,9,11,12-octaazacyclotetradecatetraene-1,5,7,12 take place, respectively. At the same time, the complexing process in the system under examination, when it occurs in aqueous-ethanol solution between CuCl₂ and the organic compounds indicated, leads to copper(II) coordination compounds with another (N,S,N,S)-tetradentate ligand - 3,9,10,16-tetramethyl-6,13--dimercapto-2,17-dioxo-4,5,7,8,11,12,14,15-tetraazaoctadecahexaene - 3,6,8,10,12,15. In both cases, thiocarbohydrazide and diacetyl are ligand synthons in these complexing processes.     

Studies on chiral thiophosphoric acids and their derivatives: 4. The stereospecific synthesis of optically active O-ethyl O-phenyl O-(1-methyl-2-ethoxycarbonyl) vinyl phosphorothionate

The stereoisomers (3 and 4) of O-ethyl O-phenyl O-(1-methyl-2-ethoxycarbonyl) vinyl phosphorothionate have been synthesized by the reaction of optically active O-ethyl O-phenyl phosphorothiochloride 2 with ethyl acetoacetate under different conditions. 3 (100% Z-isomer, determined by ¹H NMR) was synthesized by the reaction of 2 with ethyl sodio-acetoacetate in the mixed solvent of 1:3 toluene-dioxane at 50°C. 4 (>95% E-isomer) was obtained by the reaction of 2 with ethyl acetoacetate in presence of t-BuOK in DMSO at 15°C. 100% E-isomer 4 was separated from crude 4(>95% E-isomer) by column chromatography on silica gel (petroleum ether-ether 6:1). By this reaction either Z- or E-isomers were formed with inversion of the configuration at phosphorus atom. Thus, six stereoisomers of 3 and 4 which were prepared from 2 (RS, S, R) by the above method namely (RS)-Z, (R)-Z, (S)-Z and (RS)-E, (R)-E, (S)-E.     

A one‐dimensional platinum mixed‐valence complex with bridging thiocyanate S atoms: [[PtII(en)2](μ‐SCN)[PtIV(en)2](μ‐SCN)](ClO4)4 (en is ethane‐1,2‐diamine)

A new one‐dimensional platinum mixed‐valence complex with nonhalogen bridging ligands, namely catena‐poly[[[bis(ethane‐1,2‐diamine‐κ²N,N′)platinum(II)]‐μ‐thiocyanato‐κ²S:S‐[bis(ethane‐1,2‐diamine‐κ²N,N′)platinum(IV)]‐μ‐thiocyanato‐κ²S:S] tetrakis(perchlorate)], {[Pt₂(SCN)₂(C₂H₈N₂)₄](ClO₄)₄}_n, has been isolated. The Pt^II and Pt^IV atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thiocyanate ligands, forming an infinite one‐dimensional chain. The Pt^IV—S and Pt^II...S distances are 2.3933 (10) and 3.4705 (10) Å, respectively, and the Pt^IV—S...Pt^II angle is 171.97 (4)°. The introduction of nonhalogen atoms as bridging ligands in this complex extends the chemical modifications possible for controlling the amplitude of the charge‐density wave (CDW) state in one‐dimensional mixed‐valence complexes. The structure of a discrete Pt^IV thiocyanate compound, bis(ethane‐1,2‐diamine‐κ²N,N′)bis(thiocyanato‐κS)platinum(IV) bis(perchlorate) 1.5‐hydrate, [Pt(SCN)₂(C₄H₈N₂)₂](ClO₄)₂·1.5H₂O, has monoclinic (C2) symmetry. Two S‐bound thiocyanate ligands are located in trans positions, with an S—Pt—S angle of 177.56 (3)°.     

Recovery of plutonium from oxalate supernatant using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

Summary Extraction of Pu(IV) from oxalate supernatant was carried out employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) in xylene as extractant. The conditions for quantitative extraction were determined by the variation of ligand, oxalic acid and nitric acid concentration. Quantitative stripping was achieved using a mixture of 0.4M oxalic acid and 0.4M ammonium oxalate. Extraction of Pu(IV) from synthetic oxalate supernatant solution containing 3M nitric acid and 0.2M oxalic acid was investigated under various loading conditions employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone in xylene as extractant. Under uranium loading conditions the Pu extraction decreased significantly while with increased Pu loading whereas the D_Pu value was influenced marginally. The effect of a redox reagent on Pu extraction was also investigated.     

Experimental and Quantum Mechanical Characterization of an Oxygen-Bridged Plutonium(IV) Dimer

We report the synthesis and characterization of K₄{[PuCl₂(NO₃)₃]₂(μ₂-O)}⋅H₂O, which contains the first known μ₂-oxo bridge between two Pu^IV metal centers. Adding to its uniqueness is the Pu−(μ₂-O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu−(μ₂-O)−Pu bridge is characterized by the mixing of s-, d-, and p-orbitals from Pu with the p-orbitals of O; the 5f-orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σ_Pu-O-Pu and two 3c-2e π_Pu-O-Pu bonding orbitals and that the electron density is highly polarized on the μ₂-O. Bond topology properties analysis indicates that the Pu−(μ₂-O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.     

Use of organophosphorus extractants impregnated on silica gel for the extraction chromatographic separation of minor actinides from high level waste solutions

Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO₃ and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO₃ solutions was studied batchwise. Several parameters, like time of equilibration, HNO₃ and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO₃ followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO₃ concentration, D _Pu increased up to 3.0M of HNO₃ for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO₃, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO₃, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO₃ solutions were evaluated. With increasing NaNO₃ concentration up to 3.0M, D _Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.     

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

PuO₂(am) solubility was investigated as a function of time, for pH from 0.5 to 11, and in the presence of 0.001 M FeCl₂ or 0.00052 M hydroquinone to determine the effect of environmentally important reducing agents on PuO₂(am) solubilization under geological conditions. Equilibrium was reached in <4 days. The observed PuO₂(am) solubilities were many orders of magnitude higher than the Pu(IV) concentrations predicted from thermodynamic data. Spectroscopic, solvent extraction, and thermodynamic analyses of data showed that Pu(III) was the dominant aqueous oxidation state. The experimental pH, pe, and Pu(III) concentrations from both the Fe(II) and hydroquinone systems provided a log K ⁰ value of 15.5 ± 0.7 for [PuO₂(am) + 4H⁺ + e ^– Pu³⁺ + 2H₂O]. The data show that reduction reactions involving Fe(II) and hydroquinone are relatively rapid and that reductive dissolution of PuO₂(am), hitherto ignored, may play an important role in controlling Pu behavior under reducing environmental conditions.     

Elasticity theory. IV. The stress–strain relation

The stress–strain relation is analyzed in terms of the gyration tensor where the sum is over all N atomic groups comprising the elastomeric material. All groups are taken for convenience to have the same mass. This tensor is linear in the strain, and furthermore it may be evaluated from a configuration integral. The definition of the strain by use of S^αβ gives new insight into the connection between statistical and continuum mechanics, and further clarifies the significance of “affine deformation.” Stress components are obtained as derivatives of the (Helmholtz) free energy A with respect to the invariants of S^αβ. The first invariant is just the radius of gyration S² of the network, and the dependence of A on S² alone provides a basis for analysis of stress–strain isotherms.     

Structural Characterization of a Series of N5-Ligated MnIV-Oxo Species

Analysis of extended X-ray absorption fine structure (EXAFS) data for the Mn^IV-oxo complexes [Mn^IV(O)(^DMMN4py)]²⁺, [Mn^IV(O)(2pyN2B)]²⁺, and [Mn^IV(O)(2pyN2Q)]²⁺ (^DMMN4py=N,N-bis(4-methoxy-3,5-dimethyl-2-pyridylmethyl)-N-bis(2-pyridyl)methylamine; 2pyN2B=(N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine, and 2pyN2Q=N,N-bis(2-pyridyl)-N,N-bis(2-quinolylmethyl)methanamine) afforded Mn=O and Mn−N bond lengths. The Mn=O distances for [Mn^IV(O)(^DMMN4py)]²⁺ and [Mn^IV(O)(2pyN2B)]²⁺ are 1.72 and 1.70 Å, respectively. In contrast, the Mn=O distance for [Mn^IV(O)(2pyN2Q)]²⁺ was significantly longer (1.76 Å). We attribute this long distance to sample heterogeneity, which is reasonable given the reduced stability of [Mn^IV(O)(2pyN2Q)]²⁺. The Mn=O distances for [Mn^IV(O)(^DMMN4py)]²⁺ and [Mn^IV(O)(2pyN2B)]²⁺ could only be well-reproduced using DFT-derived models that included strong hydrogen-bonds between second-sphere solvent 2,2,2-trifluoroethanol molecules and the oxo ligand. These results suggest an important role for the 2,2,2-trifluoroethanol solvent in stabilizing Mn^IV-oxo adducts. The DFT methods were extended to investigate the structure of the putative [Mn^IV(O)(N4py)]²⁺⋅(HOTf)₂ adduct. These computations suggest that a Mn^IV-hydroxo species is most consistent with the available experimental data.