Reaction of ozone with Np(V) and Np(IV) in carbonate solutions

A spectrophotometric study showed that ozone in concentrated carbonate solutions forms complexes with CO ₃ ^2? ions, which inhibits the ozone decomposition. Free ozone oxidizes Np(V) at high rate. The bound ozone reacts with Np(V) at moderate rate. Np(IV) reacts with O₃ slowly, with Np(VI) formed in NaHCO₃ solution and only Np(V) formed in Na₂CO₃ solution.     

Reaction of ozone with uranium(IV) oxalate in water

Decomposition of aqueous suspensions of uranium(IV) oxalate under the action of an ozone–oxygen mixture was studied. The process occurs in two steps. In the first step, the U(IV) oxidation with the formation of oxalic acid uranyl solutions prevails. The second step involves decomposition of oxalate ions and hydrolysis of uranyl ions. An increase in temperature accelerates the transformation of uranium(IV) oxalate into uranium(VI) hydroxide compounds. In solutions containing KBr or UO₂Br₂, the following reaction occurs: O₃ + Br^– → O₂ + BrO^–. The arising hypobromite ions and hypobromous acid oxidize uranium(IV) oxalate extremely efficiently. The possible mechanism of ozonation of aqueous uranium(IV) oxalate suspensions is discussed.     

Reduction of Pu(IV) and Np(VI) with carbohydrazide in nitric acid solution

The reduction of Pu(IV) and Np(VI) with carbohydrazide (NH₂NH)₂CO in 1–6 M HNO₃ solutions was studied. The Pu(IV) reduction is described by a first-order rate equation with respect to Pu(IV). At [HNO₃] ≥ 3 M, the reaction becomes reversible. The rate constants of the forward and reverse reactions were determined, and their activation energies were estimated. Neptunium(VI) is reduced to Np(V) at a high rate, whereas the subsequent reduction of Np(V) to Np(IV) is considerably slower and is catalyzed by Fe and Tc ions. The possibility of using carbohydrazide for stabilizing desired combinations of Pu and Np valence states was examined.     

Behavior of Cs, Np(V), Pu(IV), and U(VI) in pore water of bentonite

Sorption of Cs, Pu(IV), Np(V), and U(VI) with bentonite from solutions was studied. Physicochemical species of radionuclides in the liquid phase were determined, the sorption mechanisms were established, and the influence of bentonite colloids on the behavior of radionuclides was studied. It was shown that Cs is sorbed by the ion-exchange mechanism, whereas the sorption of actinides at pH > 5 is governed by the reaction with surface hydroxy groups of betonite, and at pH < 5 the competing processes are ion exchange and complex formation. Reduction of Np(V) and U(VI) to Np(IV) and U(IV) in the solution with Fe(II) compounds present in the system was proved by the extraction method. Various methods of separating the solid phase were used in studying the dependence of the distribution coefficients of Np and Pu on the ratio of pore water and bentonite; it was shown that Np and Pu are sorbed on bentonite colloids.     

Kinetics of Reactions of Np and Pu Ions with Hydrazine Derivatives: XVII. Reaction of Pu(VI) with Hydroxyethylhydrazine

Reduction of Pu(VI) to Pu(III) with hydroxyethylhydrazine (HOC₂H₄N₂H₃) in HNO₃ solutions involves the following consecutive steps²: Pu(VI) + HOC₂H₄N₂H₄ Pu(V) + ...; Pu(V) + HOC₂H₄N₂H₄ ⁺ Pu(IV) + ...; Pu(V) + Pu(III) 2Pu(IV); and Pu(IV) + HOC_2H4N₂H₄ ⁺ Pu(III) + .... The overall kinetic equations of these steps were suggested, and their rate constants and activation energies were determined. The mechanisms of the four reaction steps, consistent with the experimental kinetic data, are discussed.     

Kinetics of Reactions of Np and Pu Ions with Hydrazine Derivatives: XVIII. Reaction between Np(V) and Hydroxyethylhydrazine

The Np(V) reduction with hydroxyethylhydrazine is described by the equation −d[Np(V)]/dt = k ₁[Np(V)][HOC₂H₄N₂H ₄ ⁺ ] + k ₂[Np(V)][Np(IV][H⁺]^1.8, reflecting its main and autocatalytic pathways. The rate constants are k ₁ = 0.31±0.04 l mol⁻¹ min⁻¹ and k ₂ = 4.04±0.11 l^2.8 mol^−2.8 min⁻¹ at 80°C and ionic strength μ = 4. The activation energies are E ₁ = 90±6 and E ₂ = 116±4 kJ mol⁻¹, respectively. The autocatalytic pathway is limited by the reaction between hydroxyethyldiazenium ions, HOC₂H₄N₂H ₂ ⁺ and protonated Np(V) ions. __________ Translated from Radiokhimiya, Vol. 47, No. 2, 2005, pp. 150–153. Original Russian Text Copyright ? 2005 by V. Koltunov, Baranov, G. Koltunov.     

Kinetics of Redox Reactions of Np and Pu Ions with Hydrazine Derivatives: XVI. Reaction of Np(V) with Phenylhydrazine

The rate of Np(V) reduction with phenylhydrazine in a perchloric acid solution is described by the equation d[Np(IV)/dt = k ₁[Np(V)][C₆H₅N₂H₄ ⁺] + k ₃[Np(V)][C₆H₅N₂H₄ ⁺][H⁺]² + k ₂[Np(V)][Np(IV)], where k ₁ = 1.27 × 10^{- 3}, 2.81 × 10^{- 3}, and 5.86 × 10^{- 3} l mol^{- 1}min^{- 1}; k ₃ = 2.32 × 10^{- 3}, 1.21 × 10^{- 2}, and 5.75 × 10^{- 2} l³ mol^{- 3} min^{- 1}; and k ₂ = 1.1, 8.3, and 50 l mol^{- 1} min^{- 1} at the ionic strength = 4 and 40, 60, and 80°C, respectively. The activation energies of three reaction pathways are E ₁ = 35±7, E ₃ = 74±17, and E ₂ = 88±1 kJ mol^{- 1}. The reaction is self-accelerated owing to formation of the reactive intermediate, hydroquinone. Its concentration in the reaction mixture is proportional to the concentration of the final product, Np(IV) ion. Probable slow stages of two main and autocatalytic pathways of the reaction are discussed.     

Features of Pu(IV) and Np(IV) Extraction from Nitric Acid Solutions of Uranyl Nitrate with 30% TBP

The extraction of Pu(IV) and Np(IV) from nitric acid solutions containing high concentrations of uranyl nitrate with 30% TBP in hydrocarbon diluent was studied. It was found that, as the Pu(IV) and Np(IV) concentration grows from tens milligrams to several grams at fixed uranyl nitrate (100 g l^-1 and higher) and nitric acid concentrations in the aqueous phase, the distribution coefficients of actinides(IV) increase (for Np to a greater extent than for Pu). This trend becomes more pronounced at higher temperatures. Correlation equations describing this effect are suggested.     

Reduction of Pu(IV) and Np(VI) with hydroxylamine in solutions of low acidity with high uranium content

Decomposition of hydroxylamine in HNO₃ solutions containing 350 to 920 g l^?1 U(VI) was studied. In the absence of fission and corrosion products (Zr, Pd, Tc, Mo, Fe, etc.), hydroxylamine is stable for no less than 6 h at [HNO₃] < 1 M and 60°C. In the presence of these products, the stability of hydroxylamine appreciably decreases. The reduction of Pu(IV) and Np(VI) with hydroxylamine in aqueous 0.33 and 0.5 M HNO₃ solutions containing 850 g l^?1 U(VI) and fission and corrosion products at 60°C was studied. Np(VI) is rapidly reduced to Np(V), after which Np(V) is partially reduced to Np(IV). The rate of the latter reaction in such solutions is considerably higher than the rate of the Np(V) reduction with hydroxylamine in HNO₃ solutions without U(VI). At [HNO₃] = 0.33 M, the use of hydroxylamine results in the conversion of Pu to Pu(III) and of Np to a Np(IV,V) mixture, whereas at [HNO₃] = 0.5 M the final products are Pu(IV) and Np(V).     

Reaction of Np(V) with U(IV) in solutions with pH > 2

Oxidation of U(IV) with Np(V) in bicarbonate-carbonic acid solutions and the nature and reactivity of actinide(IV) compounds formed in these media were studied spectrophotometrically.     

Kinetics of Redox Reactions of U, Pu, and Np in TBP Solutions: VII. Kinetics of Reduction of Pu(IV) and Np(VI) with Butanal Oxime in Undiluted TBP

The kinetics of reduction of Pu(IV) and Np(VI) with butanal oxime in undiluted TBP containing HNO₃ was studied spectrophotometrically. In the range [HNO₃] = 0.08-0.75 M the rate of Pu(IV) reduction is described by the equation -d[Pu(IV)]/dt = k[Pu(IV)]²[C₃H₇CHNOH]/{[Pu(III)][HNO₃]²} with the rate constant k = 0.068±0.017 mol l^-1 min^-1 at 20°C. The kinetic equation of the reduction of Np(VI) to Np(V) in the range [HNO₃] = 0.01-0.27 M is -d[Np(VI)]/dt = k[Np(VI)][C₃H₇CHNOH][H₂O]²/[HNO₃]0.5, where k = 0.058±0.007 l2.5 mol-2.5 min^-1 at 25°C, and the activation energy is 79±9 kJ mol^-1.     

Hydrolysis of Np(IV)

Hydrolysis of Np(IV) at p[H⁺] from 0 to 2.7 and ionic strength I = 0.1-1.0 was studied spectrophotometrically. In the p[H⁺] range from 0 to 2.2 and Np(IV) concentrations of 4.5 ×10^{- 5}-1.75 ×10^{- 4} M, polymerization and formation of colloids are negligible and do not noticeably affect the hydrolysis constant measurements. The hydrolysis is completely reversible. With increasing p[H⁺] to 2, only the NpOH^{3 +} complex is formed; the spectrum of this hydroxy complex was calculated. The typical narrow band of Np(IV) aqua ion occurs at 732.2 nm; in hydroxy complex, it is shifted to 729.5 nm and its intensity decreases by a factor of about 2.7. The average constant of Np(IV) hydrolysis equilibrium [Np^{4 +} + H₂O NpOH^{3 +} + H⁺] recalculated to the ionic strength I = 0 was determined as logK ₁ ⁰ = -1.23±0.06, which corresponds to the stability constant of the complex NpOH^{3 +} log₁ ⁰ = 12.77±0.06. The stability constant of the complex Np(OH)₂ ^{2 +} was calculated to be log₂ ⁰ = 24.3.     

Reaction of Np(IV) with Orthosilicic Acid,Si(OH)4, in Acid Solutions

Reaction of Np(IV) with Si(OH)₄ within the range of pH 0-2.2 was studied spectrophotometrically. Under these conditions, a complex NpOSi(OH)₃ ^{3 +} is formed. This composition was derived from the dependences of the complex concentration on [H⁺] and [Si(OH)₄]. From the experimental electronic absorption spectra, the spectrum of NpOSi(OH)₃ ^{3 +} was reconstructed. In this spectrum, the narrow band of the aqua ion at 723.2 nm shifts to 729.2 nm and becomes weaker by approximately half. The equilibrium constant K ₁ of the complex formation reaction and the stability constant of the complex ₁ at the ionic strengths I = 0.1 and 1.0 were determined: logK ₁ = 0.71±0.05 and 0.41±0.02, ₁ = 10.52±0.05 and 10.22±0.02, respectively. The Np(IV) speciation in the acid solution in the presence of Si(OH)₄ was calculated.     

Behavior of Pu(VI) and Np(VI) in malonate solutions

Complexation of PuO ₂ ²⁺ in solutions containing malonate anions C₃H₂O ₄ ^2? (L^2?) is studied by spectrophotometry. Mono-and bimalonate complexes are formed. The monomalonate complex was isolated as PuO₂L · 3H₂O. It is isostructural to UO₂L · 3H₂O and forms rhombic crystals with the unit cell parameters a = 9.078(2), b = 7.526(2), and c = 6.2005(15) Å, space group Pmn2₁. The electronic absorption spectrum of the monomalonate complex is characterized by a strong band at 843 nm. In malonate solutions, Pu(VI) is slowly reduced to the pentavalent state even in the cold. The reduction of Np(VI) is considerably faster and more sensitive to increasing temperature. Some kinetic features of the reduction are discussed.     

Mechanism of Np(VI) oxidation with ozone in alkaline solutions

Bubbling of an ozone-oxygen mixture containing 0.1?C0.5 vol % O₃ at a rate of 15?C20 l h^?1 through 13 ml of a 2 × 10^?5?1 × 10^?4 M solution of Np(VI) in 0.1 and 1 M LiOH leads to the formation of Np(VII). The initial rate increases approximately in proportion to [Np(VI)] and [O ₃ ^gas ]^0.5. Up to 80% of Np(VI) is oxidized at maximum. At the O₃ concentration in the gas phase increased to 1?C4 vol %, Np(VI) is oxidized completely. Under the same conditions, Np(VI) in a concentration of (1?C5) × 10^?3 M is oxidized to almost 100%. Analysis of published data and additional experiments on the reaction of O₃ with Np(VI) ions in LiOH solutions allow a conclusion that the ozonation involves the reactions O₃ + OH^? = HO ₂ ^? + O₂, O₃ + HO ₂ ^? + OH^? = O ₃ ^? + O ₂ ^? + H₂O, and O₃ + O ₂ ^? = O ₃ ^? + O₂, followed by O ₃ ^? + NpO₂(OH) ₄ ^2? = O₂ + NpO₄(OH) ₂ ^3? + H₂O. In addition, HO ₂ ^? reduces Np(VII) and Np(VI) and reacts with O ₃ ^? . Certain contribution is made by the reaction Np(VI) + O₃ = Np(VII) + O ₃ ^? . The dependence of the Np(VII) accumulation rate on [O ₃ ^gas ]^0.5 was interpreted in terms of the concept of a heterogeneous-catalytic process.     

Synthesis and properties of Np(VI) and Pu(VI) monophthalates

Neptunium(VI) and plutonium(VI) monophthalates were prepared and characterized. The complexes AnO₂ (COO)₂C₆H₄ 2H₂O were isolated from cold solutions, and AnO₂ (COO)₂C₆H₄ 1.33H₂O, from hot solutions. NpO₂ (COO)₂C₆H₄ b. 2H₂O and PuO₂ (COO)₂C₆H₄ 2H₂O crystalize in the triclinic and monoclinic systems, respectively. The complexes AnO₂(COO)₂C₆H₄ 1.33H₂O are isostructural and crystallize in the rhombohedral system. The thermal behavior of these complexes was studied. Their IR and electronic absorption spectra were recorded. The properties of these complexes were compared to those of known U(VI) monophthalates.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 389–395.Original Russian Text Copyright © 2004 by Krot, Bessonov, Grigorev, Charushnikova, Makarenkov.     

Synthesis and study of Np(V) and Pu(V) benzoate complexes with bipyridine

Heteroligand compounds AnO₂(bipy)OOCC₆H₅ (An = Np, Pu; bipy = α,α-bipyridine, C¹⁰H⁸N²) were synthesized and studied. It follows from powder X-ray patterns that these compounds are isostructural. Their unit cell parameters, determined by indexing of the powder X-ray patterns, are as follows: a = 9.2162 (7), b = 10.2339(8), c = 17.4083(17) Å, and β = 96.48(1)° for Np and a = 9.1983(18), b = 10.2052(18), c = 17.370(3) Å and β = 96.51(1)° for Pu. The compounds crystallize in the monoclinic system space group P2₁/n, Z = 4. The electronic absorption spectra of crystalline compounds suggest pentagonal-bipyramidal surrounding of the central atom and the prescence of cation-cation bonds with AnO ₂ ⁺ ions acting as monodentate ligands with respect to each other. The IR spectra of the compounds were recorded, and their thermal behavior in air was studied.     

Kinetics of Pu(IV) reduction with tert-butylhydrazine

The rate of Pu(IV) reduction with tert-butylhydrazine in an HNO₃ solution is described by the equation-d[Pu(IV)]/dt = k[Pu(IV)]²[(CH₃)₃CN₂H ₄ ⁺ ]/[H⁺], where k = 69.4 ⊥ 3.0 l mol^?1 min^?1 at 50°C. The activation energy is E = 122 ⊥ 4 kJ mol^?1. Probable reaction mechanisms are discussed.     

Synthesis and structural features of Np(VI) and Pu(VI) isophthalates

New An(VI) isophthalate complexes [PuO₂(C₈H₄O₄)] (I), Cs₂[(NpO₂)₂(C₈H₄O₄)₃]·4H₂O (II), [H₃O]₂[(NpO₂)₂(C₈H₄O₄)₃]·nH₂O (III), and [H₃O][NpO₂(C₈H₄O₄)(C₈H₅O₄)]·2H₂O (IV) with the An(VI): Lig ratios of 1: 1 (I), 1: 1.5 (II, III), and 1: 2 (IV) were synthesized and studied by single crystal X-ray diffraction. In complex I, the coordination polyhedron of the Pu(1) atom is a pentagonal bipyramid whose equatorial plane is formed by the oxygen atoms of four [C₈H₄O₄]^2– anions. The coordination capacity of the ligand in complex I is maximal among compounds I–IV and equal to 5, with each [C₈H₄O₄]^2– anion binding four PuO₂²⁺ cations into electrically neutral layers. In the structures of II and III, the coordination polyhedra of the Np(1) atoms are hexagonal bipyramids whose equatorial planes are formed by the oxygen atoms of three [C₈H₄O₄]^2– anions. Two crystallographically independent [C₈H₄O₄]^2– anions exhibit the coordination capacity equal to 4, each binding two NpO₂²⁺ cations in the chelate fashion. As a result, doubled anionic layers are formed in the crystals of II and III. Outer-sphere cations influence the packing of doubled layers in the crystals: Complex II crystallizes in the monoclinic system, and complex III, in the orthorhombic system. In the structure of IV, the coordination polyhedron of the Np(1) atom is a hexagonal bipyramid whose equatorial plane is formed by the oxygen atoms of two [C₈H₄O₄]^2– anions and one [C₈H₅O₄]^– anion. The crystallographically independent bridging anion [C₈H₄O₄]^2– exhibits the coordination capacity equal to 4 and binds in the chelate fashion two NpO₂²⁺ cations to form chains, and the independent hydrogen isophthalate anion [C₈H₅O₄]^– binds one neptunyl(VI) cation in the chain in the chelate fashion, exhibiting the coordination capacity equal to 2.     

Synthesis and properties of complexes of Np(V) and Pu(V) benzoates with phenanthroline

Complexes of 1,10-phenanthroline (phen) with Np(V) and Pu(V) benzoates of the compositions NpO₂(phen)(OOCC₆H₅) and PuO₂(phen)(OOCC₆H₅) were synthesized. A powder X-ray diffraction study showed that these compounds, depending on the preparation conditions, exist in the form of two phases having essentially the same composition but different powder patterns. The phases isolated from hot (70–100°C) solutions are isostructural with the previously described complexes AnO₂(bipy)(OOCC₆H₅) (An = Np and Pu, bipy = 2,2′-bipyridine), i.e., in their structure there are dimeric (AnO₂) ₂ ²⁺ cations formed by mutual coordination of two AnO ₂ ⁺ ions via “yl” oxygen atoms. The compounds AnO₂(phen)(OOCC₆H₅) prepared by slow crystallization in the cold or at weak (up to 45°C) heating are isostructural with each other but appreciably differ in the structure from the high-temperature phases. The electronic absorption spectra of the compounds and their thermal behavior were examined.