Uptake of Pu(IV) on Bio-Rex 63 from nitric acid medium: A kinetic study

Back-extraction of tri- and tetravalent actinides from diisodecylphosphoric acid (DIDPA) is studied using hydrazine carbonate as back-extractant. In experiments using 0.5M DIDPA–0.1M TBP n-dodecane solution, Am(III), Eu(III), Pu(IV) and Np(IV) are back-extracted, and the distribution ratios are decreased with an increase of hydrazine carbonate concentration. The back-extraction equilibria are confirmed by slope analysis in consideration of neutralization between DIDPA and hydrazine carbonate, which occurs quantitatively during back-extraction. In particular, oxidation of Np(IV) to Np(V) during back-extraction is observed by measuring absorption spectra. The hydrazinium ion acts as an oxidation reagent in the back-extraction of Np(IV). Separation factors of those metals are compared with the results of HDEHP. Hydrazine carbonate back-extracts Np(IV) more selectively from DIDPA than from HDEHP.     

Back-Extraction of Uranium(VI) from Organophosphoric Acid with Hydrazine Carbonate

The back-extraction of uranium(VI) from di(2-ethylhexyl)phosphoric acid (HDEHP) and diisodecylphosphoric acid (DIDPA) was studied by using hydrazine carbonate as back-extractant. U(VI) was back-extracted from n-dodecane solutions of 0.5M HDEHP - 0.2M TBP and 0.5M DIDPA - 0.1M TBP by hydrazine carbonate. The distribution ratios were decreased with an increase of hydrazine carbonate concentration. The back-extraction equilibria were expressed by slope analysis in consideration of neutralization between the extractant (DIDPA, HDEHP) and hydrazine carbonate, which occurred quantitatively during the back-extraction.     

Abtrennung des Uran(IV) aus in der Kerntechnik anfallenden Lösungen mittels Extraktionschromatographie

Zusammenfassung Die extraktionschromatographische Abtrennung von Uran(IV) aus salpetersauren Lösungen wird beschrieben. Kolonnen mit Di-(2-äthylhexyl)-phosphorsäure (HDEHP) in Xylol als stationärer Phase wurden verwendet. Bei alleiniger Anwesenheit von Uran(IV) und Uran(VI) genügte es, mit Salpetersäure/0,1-m Hydrazin zu eluieren. Aus Lösungen komplexerer Zusammensetzung, die neben Uran(IV) und Uran(VI) auch noch längerlebige Spaltprodukte (¹⁴⁴Ce,¹⁰⁶Ru,⁹⁵Nb und¹³⁷Cs), Plutonium (III) und Korrosionsprodukte von Stahl [Fe(III), Co(II), Ni(II) und Cr(III)] enthielten, wurde das Uran(IV) auf zwei Arten abgetrennt. Bei der ersten Variante wurde es durch 5%iges HDEHP in Xylol an der Kolonne festgehalten und alle Begleitionen mit 2-n Salpetersäure/0,1-m Hydrazin entfernt. Bei der zweiten Variante konnte neben dem Uran (IV) auch das Uran(VI) in einer gesonderten Fraktion aufgefangen werden. Als stationäre Phase wurde 30%iges HDEHP, als Elutionsmittel 11,7-n Salpetersäure/0,1-m Hydrazin verwendet. Bei beiden Varianten konnte das Uran(IV) mit einem Gemisch aus 15% Schwefelsäure/5% Phosphorsäure von der Kolonne eluiert werden. Bei der ersten Variante konnte das Uran(IV) auch mit 11,7-n Salpetersäure/0,1-m Hydrazin eluiert werden, wenn es nach der Trennung in salpetersaurer Lösung vorliegen sollte. Die Stabilität der Kolonnen und des Uran(IV), der Einfluß der HDEHP-Konzentration in Xylol und der Salpetersäurekonzentration sowie das Verhalten einiger Ionen bei den Trennbedingungen werden besprochen.

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Separation of uranium(VI) by extraction chromatography from the solutions resulting from nuclear technology

Summary The extraction-chromatographic separation of uranium(VI) from nitric acid solutions is described. Columns were employed containing di-(2-ethylhexyl)-phosphoric acid (HDEHP) in xylene as stationary phase. If only uranium(IV) and uranium(VI) are present, it is sufficient to elute with nitric acid/0.1M hydrazine. From solutions of more complex composition, which in addition to uranium(IV) and uranium(VI) also contain longer-lived fission products (¹⁴⁴Ce,¹⁰⁶Ru,⁹⁵Nb and¹³⁷Cs), plutonium(III) and corrosion products of steel [Fe(III), Co(II), Ni(II) and Cr(III)], the uranium(IV) was separated by two varieties. In the first variant it was retained on the column by 5% HDEHP in xylene and all accompanying ions were removed with 2N nitric acid/0.1M hydrazine. In the second variant, in addition to the uranium(IV), the uranium(VI) also was captured in a separate fraction. 30% HDEHP was employed as stationary phase, while the elution agent was 11.7N nitric acid/0.1M hydrazine. In both variants, the uranium(IV) could be eluted from the column by a mixture of 15% sulfuric acid/5% phosphoric acid. In the first variant, the uranium(IV) could also be eluted by means of 11.7N nitric acid/0.1M hydrazine in case it was planned to have it present after the separation in nitric acid solution. The stability of the columns and of the uranium(IV) and the influence of the HDEHP concentration in xylene and the nitric acid concentration as well as the behavior of several ions under the separation conditions are discussed.

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Herrn o. Univ.-Prof. Dr.Hans Nowotny zum 60. Geburtstag gewidmet.     

Bicyclic and acyclic diamides: comparison of their aqueous phase binding constants with Nd(III), Am(III), Pu(IV), Np(V), Pu(VI), and U(VI)

This report describes affinity measurements for two, water-soluble, methyl-alkylated diamides incorporating the malonamide functionality, N,N,N',N' tetramethylmalonamide (TMMA) and a bicyclic diamide (1a), toward actinide metal cations (An) in acidic nitrate solutions. Ligand complexation to actinides possessing oxidation states ranging from +3 to +6 was monitored through optical absorbance spectroscopy, and formation constants were obtained from the refinement of the spectrophotometric titration data sets. Species analysis gives evidence for the formation of 1, 4, 1, and 2 spectrophotometrically observable complexes by TMMA to An(III, IV, V, and VI), respectively, while for 1a, the respective numbers are 3, 4, 2, and 2. Consistent with the preorganization of 1a toward actinide binding, a significant difference is found in the magnitudes of their respective formation constants at each complexation step. It has been found that the binding affinity for TMMA follows the well-established order An(V) < An(III) < An(VI) < An(IV). However, with 1a, Np(V) forms stronger complexes than Am(III). The complexation of 1a with Np(V) and Pu(VI) at an acidity of 1.0 M is followed by reduction to Np(IV) and Pu(IV), whereas TMMA does not perturb the initial oxidation state for these dioxocations. These measurements of diamide binding affinity mark the first time single-component optical absorbance spectra have been reported for a span of actinide-diamide complexes covering all common oxidation states in aqueous solution.     

Dosage spectrophotometrique du neptunium

(Spectrophotometric determination of neptunium.) Use of the absorption peak of the NpO⁺₂ ion at 981 nm is discussed. Quantitative conversion to Np(V) requires oxidation of Np(IV) by Ce(IV), reduction of Np(VI) and excess of Ce(IV) with hydrazinium nitrate, and destruction of excess of hydrazine by nitrite. The measurable concentration range in the cuvette is 2–1000 mg l^-1 and the precision is± 1% in the higher range. Uranium and plutonium at ratios Me/Np ? 10^-3 do not interfere.     

Electrochemical and complexation behavior of neptunium in aqueous perchlorate and nitrate solutions

Electrochemical and complexation properties of neptunium (Np) are investigated in aqueous perchlorate and nitrate solutions by means of cyclic voltammetry, bulk electrolysis, UV-visible absorption, and Np L(III)-edge X-ray absorption spectroscopies. The redox reactions of Np(III)/Np(IV) and Np(V)/Np(VI) couples are reversible or quasi-reversible, while the electrochemical reaction between Np(III/IV) and Np(V/VI) is irreversible because they undergo structural rearrangement from spherical coordinating ions (Np(3+) and Np(4+)) to transdioxoneptunyl ions (NpO2(n+), n = 1 for Np(V) and 2 for Np(VI)). The redox reaction of the Np(V)/Np(VI) couple involves no structural rearrangement on their equatorial planes in acidic perchlorate and nitrate solutions. A detailed analysis on extended X-ray absorption fine structure (EXAFS) spectra suggests that Np(IV) forms a decaaquo complex of [Np(H2O)10](4+) in 1.0 M HClO4, while Np(V) and Np(VI) exist dominantly as pentaaquoneptunyl complexes, [NpO2(H2O)5](n+) (n = 1 for Np(V) and 2 for Np(VI)). A systematic change is observed on the Fourier transforms of the EXAFS spectra for all of the Np oxidation states as the nitrate concentration is increased in the sample, revealing that the hydrate water molecules are replaced by bidentate-coordinating nitrate ions on the primary coordination sphere of Np.     

Neptunium(III) application in extraction chromatography

This paper describes a novel strategy for actinide separation by extraction chromatography with Np(III) valence adjustment. Neptunium(IV) was reduced to Np(III) using Cr(II) and then selectively separated from uranium (IV) on a TEVA resin. After elution, Np(III) was retained on a DGA resin in order to remove any detrimental chromium impurities. Neptunium(III) formation was demonstrated by the complete and selective elution of Np from TEVA resin (99 ± 7%) in less than 12 mL of 9 M HCl from U(IV) (0.7 ± 0.7%). It was determined by UV–visible and kinetic studies that Cr(II) was the only species responsible for the elution of Np(IV) as Np(III) and that the Cr(II) solution could be prepared from 2 to 30 min before its use without the need of complex degassing systems to prevent the oxidation of Np(III) by oxygen. The methodology proposed here with TEVA/DGA resins provides removal of Cr(III) impurities produced at high decontamination factors (2.8 × 10³ and 7.3 × 10⁴ respectively).     

Kinetics and mechanism of stripping of Np(IV) by acetohydroxamic acid using a Lewis cell

Kinetic studies of stripping of Np(IV) from 30% Tri-Butyl-Phosphate/Odourless Kerosene (TBP/OK) into a nitric acid solution containing acetohydroxamic acid (CH₃CONHOH) have been investigated using a Lewis cell. The different parameters affecting the back-extraction rate of Np(IV) such as Np, TBP, nitric acid, nitrate, acetohydroxamic acid(AHA) concentration in addition to temperature, stirring speed and special interfacial area were separately studied and a rate equation was deduced. Results have been compared among themselves and other published works on similar systems. Mechanisms of stripping processes have been proposed.     

Extraction of Am(III) from different acid media by di-2-ethyl hexyl phosphoric acid containing phosphorous pentoxide

The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P₂O₅) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P₂O₅ in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P₂O₅ mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P₂O₅ in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H₂SO₄, HNO₃, HClO₄ and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions.     

Kinetics of the radiation chemical reactions of tervalent and quadrivalent actinides and lanthanides in carbonate solutions

The reactions of the ions of tervalent and quadrivalent actinides and lanthanides with hydrated electrons e_aq ^– and CO₃ ^– radicals in concentrated carbonate solutions have been studied by microsecond pulse radiolysis, using spectrophotometric recording of short-lived particles. It is shown that the rate of the reactions of e_aq ^– with carbonato complexes of Ce(IV), Pu(IV), and Np(IV) is controlled by diffusion. The carbonato complex of Eu(III) reacts with e_aq ^–appreciably more slowly. A linear relationship is obtained between the logarithm of the rate constant for the reactions of CO₃ ^– with the carbonato complexes of Am(III), Ce(III), and Pu(III) and the redox potential of the complexes. The rate of the reaction of CO₃ ^– with Np(III) in carbonate solutions is controlled by diffusion.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 28–32, January, 1990.     

Reduction of Np(VI) in Irradiated Solutions of Nitric Acid

The reliable separation of neptunium from dissolved nuclear fuel assumes the ability to maintain a preferred oxidation state. However, regardless of its initial redox speciation, a series of reactions occurs in nitric acid to create a mixture of oxidation states including Np(V), Np(VI) and sometimes Np(IV). To further complicate the situation, irradiated solutions such as fuel dissolution contain both transient and long-lived radiolysis products which may be strongly oxidizing or reducing. Thus, irradiation may be expected to impact the equilibrium distributions of the various neptunium valences.We have irradiated nitric acid solutions of neptunium with ⁶⁰Co gamma-rays, and measured radiolytically-induced changes in neptunium valences, as well as the nitrous acid concentration, by UV/Vis spectroscopy. It was found that in 4 M HNO3 at low absorbed doses, the oxidizing radicals oxidized Np(V) to Np(VI). However, as the irradiation proceeded the concentration of nitrous acid became sufficient to reduce Np(VI) to Np(V), and then continued irradiation favored this reduction until an equilibrium was achieved in balance with the oxidation of Np(V) by nitric acid itself. The starting abundances of the two neptunium valences did not affect the final equilibrium concentrations of Np(V) and Np(VI), and no Np(IV) was detected.     

Oxidation State and Extraction of Neptunium with TBP

The change of Np oxidation state in nitric acid and the effect of nitrous acid on the oxidation state were analyzed by spectrophotometry, solvent extraction, and electrochemical methods. The Np extraction with 30 vol.% TBP was enhanced by the adjustment of the Np oxidation state using a glassy carbon fiber column electrode system. The knowledge of electrolytic behavior of nitric acid was important because the nitrous acid affecting the Np redox reaction was generated during the adjustment of the Np oxidation state. The Np solution used in this work consisted of Np(V) and Np(VI) but no Np(IV). The ratio of Np(V) in the range of 0.5M5.5 M nitric acid was 32%19%. The electrolytic oxidation of Np(V) to Np(VI) in the solution enhanced the Np extraction efficiency about five times higher than without electrolytic oxidation. It was confirmed that the nitrous acid in a concentration of less than about 10^–5 M acted as a catalyst to accelerate the chemical oxidation reaction of Np(V) to Np(VI).     

Das Ionenaustauschverhalten von Neptunium in salpetersauren Lösungen

Zusammenfassung Das Verteilungsverhalten von²³⁷Np–²³⁹Np zwischen salpetersauren Lösungen verschiedener Konzentration und einem Anionenaustauscher (Dowex 1X8) wurde untersucht. Durch Reduktion mit Fe²⁺+Hydrazin konnte quantitativ das Np(IV) hergestellt und dessen Verteilungskoeffizient (D) in 1n-10n-HNO₃ bestimmt werden. Mit Hydrazin allein und bei Lösungen ohne Reduktionsmittel wurden stark schwankendeD-Werte gefunden, die auf unterschiedliche Prozentsätze an Np(IV), Np(V) und Np(VI) zurückzuführen waren. Durch die Bestimmung der Anteile der einzelnen Oxidationsstufen konnten jedoch die jeweiligenD-Werte [D(IV),D(V),D(VI)] berechnet werden. Die mit dieser Methode erhaltenen Werte stimmten gut mit den Daten überein, die an Systemen gewonnen wurden, in denen jeweils nur eine Neptuniumoxidations-stufe vorlag.

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The ion exchange behaviour of neptunium in nitric acid solutions

The distribution of²³⁷Np–²³⁹Np between nitric acid solutions of different concentration and an anion exchanger (Dowex 1X8) was investigated. By reduction with Fe²⁺+hydrazine, the Np(IV) was obtained quantitatively and its distribution coefficients (D) in 1n to 10n-HNO₃ were determined. With hydrazine alone and without any reduction media, strongly varyingD-values were found. This was due to different amounts of Np(IV), Np(V), and Np(VI) in the solutions. By determining the fractions of the individual oxidation states the correspondingD-values [D(IV),D(V), andD(VI)] could be calculated. The data obtained by this method agreed well with theD-values resulting from determinations of systems, in which the individual Np-oxidation state was the only component of the corresponding solution.

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Mit 4 Abbildungen

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Herrn Prof. Dr.Hans Nowotny gewidmet.     

Methyl isobutyl ketone extraction of iodide complexes from sulphuric acid-potassium iodide media and back-extraction into an aqueous phase

The methyl isobutyl ketone extraction of 15 elements (Cu, Ag, Zn, Cd, In, Tl, Ge, Sn, As, Sb, Bi, Se, Te, Mo and Pd) as iodide complexes from 0.1-5 M sulphuric acid/0.01-0.5M potassium iodide media has been studied. At the optimum potassium iodide concentrations, and a 1:2 v v ratio of organic to aqueous phase, Cu(II), Ag, Cd, In(III), Tl(III), Sb(III), Bi, Te(IV) and palladium(II) are completely extracted in a single step from 1-5M sulphuric acid. All these elements except palladium are also quantitatively extracted from 0.05-0.5M iodide/2M sulphuric acid. Zn, Sn(IV) and As(III) are completely extracted at high acid and iodide concentrations, and at the highest concentrations of acid and iodide investigated, Ge is partly extracted and Mo(VI) is slightly extracted. The extraction of Se(IV) is incomplete because of its reduction to the elemental state by iodide. The back-extraction of the elements has also been investigated and the forms in which they are extracted and potential analytical separations and interferences are discussed.     

Theoretical studies on the complexation of Eu(III) and Am(III) with HDEHP: structure,bonding nature and stability

Separation of trivalent lanthanides (Ln(III)) and actinides (An(III)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) process, the organophosphorus ligand HDEHP (di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(III) from An(III) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu³⁺ and Am³⁺ complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory (DFT). It was found that HDEHP can coordinate with M(III) (M=Eu, Am) cations in the form of hydrogen-bonded dimers HL₂^- (L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(III) complexes have higher interaction energies, the HL₂^- dimer shows comparable affinity for Eu(III) and Am(III) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(III) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(III) and Ln(III) with HDEHP at the molecular level.     

Sequential determination of uranium (IV), free acidity and hydrazine in a single aliquot

A simple analytical procedure for the sequential determination of uranium (IV), free acidity and hydrazine in presence of hydrolysable ions is developed and described. In this method, first, uranium (IV) is determined using fiber optic aided spectrophotometry then same solution is used for determination of free acidity and hydrazine. Free acid is titrated with standard sodium carbonate solution after uranium (IV) is masked with EDTA. Once the end point for the free acid is determined at pH 3.0, an aliquot of formaldehyde is added to liberate the acid equivalent to hydrazine which is then titrated with the same standard sodium carbonate solution using an automatic titration system. The described method is simple, accurate and reproducible. The overall recovery of uranium (IV), nitric acid and hydrazine is 98% with 3% relative standard deviation respectively. The major advantage of the method is that it uses sodium carbonate a primary standard as titrant and generation of corrosive analytical wastes containing oxalate or sulphate is avoided. Valuable metals like uranium and plutonium can easily be recovered from analytical waste before final disposal.     

The determination of U,Np and Pu in urine by sequential extraction with ALAMINE-336 from hydrochloric acid medium

A method has been developed for the extraction of uranium, neptunium and plutonium from human urine using the comparatively cheap technical amine ALAMINE-336. These elements are coprecipitated with a calcium phosphate carrier, which is then subjected to a wet-ashing procedure with NHO₃/H₂O₂ and HCl/H₂O₂. The residue is dissolved in 10M hydrochloric acid and U, Np and Pu are extracted with a 10% ALAMINE-336/xylene solution, followed by subsequent back-extraction with 10M HCl/NH₄I (Pu), 4M HCl/HF (Np) and 0.1M HCl (U), respectively. The average recoveries are around 95%.     

Determination of stability constants of U(VI), Np(VI) and Pu(VI) with chloride ions by extraction chromatography

The complex formation of U(VI), Np(VI) and Pu(VI) with chloride ions was studied in HClO₄−HCl solutions at ionic strength of 2.0 and [H⁺]=2.0M by the method of extraction chromatography using dilute HDEHP as the stationary phase.     

Cerium isotope partition in HNO3/TBP or HDEHP extraction systems

The^142/140Ce unit separation factors (q) for cerium(III)-cerium(IV) exchange reaction in an extraction system containing Ce(IV) in tri-n-butyl phosphate (TBP) or di(2-ethylhexyl) phosphoric acid (HDEHP) and Ce(III) in nitric acid were determined. The value of q was found to be 1.00054±0.00012 (2) in 6M HNO₃/TBP and 1.00078±0.00028 in 6M HNO₃/HDEHP extraction systems. The dehydration and complex formation processes and their contribution to reduced partition function ratios (RPFR's) are discussed.     

Synthesis of neptunyl(VI) hydroxides and their237Np Mössbauer spectra

Four types of neptunyl(VI) hydroxides have been synthesized by chemical oxidation of Np(IV) instead of ozone oxidation of Np(V) which caused the partial oxidation to the heptavalent state. NpO₂(OH)₂ (I) and NpO₂(OH)₂·H₂O (orthorhombic type) (II) have been obtained by adding pyridine to the solution at 373K and 343K, respectively. NpO₂(OH)₂·H₂O (hexagonal type) (III) and NpO₂(OH)₂·xH₂O·yNH₃ (x+y=1) (IV) have been prepared by using LiOH and NH₄OH, respectively. The four materials have been characterized by X-ray powder diffraction patterns, thermogravimetric analysis and²³⁷Np Mössbauer spectra. The²³⁷Np Mössbauer spectrum of (I) measured first time as anhydrous neptunyl(VI) hydroxide (δ=?46.2 mm/s,e ² qQ=193 mm/s and η=0.16 at 4.8K) has more distinct five-line Mössbauer pattern than those of (II), (III) and (IV). The Mössbauer spectra for (II), (III) and (IV) are slightly different from each other. The structural information has been obtained from these data.