Synthesis and Structure of Complexes of Np(V) Benzoate,o-Fluorobenzoate,and p-Fluorobenzoate with 1,10-Phenanthroline

Radiochemistry - The structures of three new Np(V) complexes [(NpO2)2(phen)2(C7H5O2)2] (I), [(NpO2)2(phen)2. (o-C7H4FO2)2] (II), and [(NpO2)2(phen)2(p-C7H4FO2)2] (III), where phen =...     

Molybdate Complexes of Np(V) with Outer-Sphere Cs+ Cations

Radiochemistry - Structure of two new molybdate complexes of Np(V) with composition of Cs2[(NpO2)2(MoO4)2(H2O)]·H2O (I) and Cs3[(NpO2)(MoO4)2] (II) has been studied. In structure I, two...     

Synthesis and study of Np(V) sesquioxalates

Neptunium(V) at its relatively high concentrations in oxalate solutions forms, along with the mono-and bioxalate complexes, the intermediate binuclear anion (NpO₂)₂(C₂O₄) ₃ ^4? . This anion gradually crystallizes from cold aqueous-ethanol solutions in the form of the compound Na₄(NpO₂)₂(C₂O₄)₃ · 6H₂O, and from hot aqueous-ethanol solutions, in the form of a lower hydrate, Na₄(NpO₂)₂(C₂O₄)₃ · 2H₂O. Both compounds were characterized by powder X-ray diffraction and by electronic absorption and IR spectra. The thermal behavior of the hexahydrate in air was studied. Attempts to prepare the related crystalline compounds M₄(NpO₂)₂(C₂O₄)₃ · nH₂O with M = Li or NH₄ failed.     

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.     

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.     

Synthesis and study of new complex Pu(V) and Np(V) acetates

Double Pu(V) and Np(V) acetates of the compositions BaPuO₂Ac₃·2H₂O and SrAnO₂Ac₃·3H₂O with An = Pu and Np were synthesized in a well-crystallized form. In the dry state the compounds are stable in prolonged storage and are not hygroscopic. The plutonyl(V) and neptunyl(V) salts of the similar composition are isostructural. The IR spectra of the compounds were measured, and their behavior in heating was studied.     

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.     

Complexation of Np(V) with Silicate Ions

It was shown that Np(V) forms complexes with anions of orthosilicic acid and other silicate ions at pH higher than 8–8.5. At pH < 9.5, the reaction is mainly described by the equation NpO ₂ ⁺ + OSi(OH) ₃ ⁻ ⇄ NpO₂OSi(OH)₃; the stability constant of the NpO₂OSi(OH)₃ complex is equal to log β₁ = 2.1 ± 0.3. Thus, interaction is weak and hardly significant under real conditions. Carbonate ions in equilibrium with air at pH > 8.5 are the substantially stronger ligands for NpO ₂ ⁺ , and in their presence it is impossible to reveal Np(V) complexation with silicate ions.__________Translated from Radiokhimiya, Vol. 47, No. 1, 2005, pp. 39–43.Original Russian Text Copyright © 2005 by Yusov, Fedoseev, Isakova, Delegard.     

Synthesis and study of complexes of Pu(V) and Np(V) formates and acetates with α,α′-bipyridine

Crystalline NpO₂OOCH·C₁₀H₈N₂·nH₂O and NpO₂OOCCH₃·C₁₀H₈N₂·H₂O were synthesized by the addition of a small excess of α,α′-bipyridine to neutral Np(V) formate and acetate solutions. In the wet state and after drying in air, these compounds have essentially different powder X-ray patterns. In the dry state, these compounds are monohydrates. In formate solutions with addition of α,α′-bipyridine, Pu(V) behaves similarly, whereas attempts to prepare the related Pu(V) acetate complexes failed. The Np(V) and Pu(V) compounds AnO₂OOCCH₃·C₁₀H₈N₂·nH₂O are isostructural. According to the results of spectrophotometric studies, the coordination polyhedron of the central atom in all the compounds studied is a pentagonal bipyramid. The IR spectra were recorded and the thermal behavior of the compounds was studied.     

Mechanism of transformation of Np(V) into Np(IV) in sodium 1,2-cyclohexanediaminetetraacetate solutions

The kinetics of the transformation of Np(V) into Np(IV) in 0.1 M potassium biphthalate solutions containing 5–74 mM sodium 1,2-cyclohexanediaminetetraacetate (Na₂CHDTA) or in a 96–97 mM Na₂CHDTA solution at 25–45°С was studied. The reaction rate at Na₂CHDTA concentrations in the range 5–60 mM and pH 3.5–5.9 is described by the equation V = k[Np(V)]^1.4[CHDTA], and at Na₂CHDTA concentrations in the range 70–100 mM and pH 4.1–5.2, by the equation V = k _A[Np(V)]^1.4. Neptunium(V) forms with the CHDTA ion an activated complex in which Np(V) is reduced to Np(IV). The dimer {Np(V)}₂ forming another activated complex with the CHDTA ion is formed concurrently. The latter complex decomposes along the disproportionation pathway to give Np(IV) and Np(VI). Np(VI) is reduced with the CHDTA ion to Np(V).     

Crystal Structure of a Double Oxalate of Np(V) and Co(NH3)

The crystal structure of a dioxalate complex Co(NH₃)₆NpO₂(C₂O₄)₂·1.5H₂O was studied. The structure consists of centrosymmetrical dimeric anions [NpO₂(C₂O₄)₂] ₂ ⁶⁻ , [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. The NpO ₂ ⁺ dioxocations have close Np-O bond lengths (average 1.824 Å) and are noticeably bent (ONpO angle 175.6°). Each dioxocation in the [NpO₂(C₂O₄)₂] ₂ ⁶⁻ anion is surrounded by five oxygen atoms of three C₂O ₄ ²⁻ anions; the Np coordination polyhedra are pentagonal bipyramids sharing a common edge. __________ Translated from Radiokhimiya, Vol. 47, No. 6, 2005, pp. 495–499. Original Russian Text Copyright ? 2005 by Charushnikova, Krot, Polyakova.     

Synthesis and Structure of U(VI), Np(VI), and Pu(VI) Phenylacetates

Radiochemistry - Phenylacetates [AnO2(C6H5CH2COO)2], where An = U (I), Np (II), or Pu (III), were synthesized and studied by single crystal X-ray diffraction. Compounds I–III are...     

Interaction of tetravalent actinides and Np(V) with some hydroxy carboxylic acids

Interaction of actinides(IV) with hydroxyisobutyric acid (HHIB) in aqueous solutions and in the course of crystallization of solid compounds was studied. The complexes ML _n ^(4-n)+ (M = U, Np, Pu; L^? is hydroxyisobutyrate anion; n = 1, 2, 3) exist in solution. Their apparent stepwise stability constants K?? _i were measured, and the overall concentration stability constants ??₃ of the complexes ML ₃ ⁺ were calculated. For U(IV) and Np(IV), log??₃ is close to 13.3?C13.4, and for Pu(IV), log??₃ = 14.5 ± 0.9 (ionic strength I = 0.1?C0.3). In the course of crystallization in air, complexes of U(IV) with hydroxyisobutyric acid, as well as those with citric acid, undergo oxidative degradation, which can be accompanied by complete oxidation of U(IV). The crystalline compounds formed in the process are oxalates of U(IV) or U(VI). The complexation of Np(V) with HHIB was studied. NpO ₂ ⁺ forms with HHIB the complexes NpO₂L and NpO₂L ₂ ^? . Their concentration stability constants are logK ₁ = 2.04 ± 0.15 and logK ₂ = 0.71 ± 0.10 (I = 0.4), i.e., log??₂ = 2.75 ± 0.25.     

Behavior of Np(V) Malonates under Hydrothermal Conditions

Two new Np(V) malonates, LiNpO₂L·2H₂O and KNpO₂L, where L = CH₂(COO)₂, were synthesized, and their characteristics were studied. Similar to their chemical analogs with Na⁺, NH₄ ⁺, and Cs⁺ ions in the outer sphere, these compounds transform into well crystallized neptunyl(V) compounds of the MNpO₂CO₃·nH₂O type on heating in sealed ampules beneath the layer of the corresponding alkali metal or ammonium malonate solution at a temperature higher than 140°C. Under hydrothermal conditions (NpO₂)₂L·4H₂O is not converted to lower hydrates, and above 135°C it decomposes to form a dark gray amorphous product.     

Synthesis and Structure of U(VI), Np(VI), and Pu(VI) 2-Fluorobenzoates

The compounds NH₄[AnO₂(C₆H₄FCOO₃], where An = U (I), Np (II), or Pu (III), CgH₄COO^? is the 2-fluorobenzoate anion, were synthesized and studied by single crystal X-ray diffraction. Compounds I–III are isostructural and crystallize in the cubic system, space group P2₁3, Z = 4. The main structural units of I–III are mononuclear complexes [AnO₂(C₆H₄COO)₃]^? belonging to crystal-chemical group AB₃¹ (A = AnO₂²⁺, B⁰¹ = C₆H₄FCOO^?). The actinide contraction in the structures of I–III is manifested in a regular decrease in the lengths of the An=0 bonds in the AnO₂²⁺ cations and in the volumes of the Voronoi-Dirichlet polyhedra (VDPs) of the An atoms in the series U-Np-Pu. The intermolecular interactions in crystal structures of I–III were analyzed by the method of molecular VDPs.

     

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.     

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.     

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.     

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.     

Sorption Recovery of Np(V) from Aqueous Solutions with POLIORGS Complexing Sorbents

Sorption of neptunium with fibrous complexing sorbents containing amidoxime and hydrazidine groups was studied. The influence of solution pH and the nature and concentration of salts on sorption of neptunium was examined; the sorption kinetics and the exchange capacity of the sorbents were evaluated. The sorbents are suitable for recovery and concentration of neptunium from aqueous solutions to solve production and environmental problems at the Mayak Production Association.