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.     

Stereochemistry of Neptunium in Oxygen-Containing Compounds

Coordination of Np(III–VII) atoms in the crystal structures of all the oxygen-containing compounds characterized with the R-factor lower than 0.1 was analyzed with the aid of Voronoi–Dirichlet polyhedra (VDPs). Nine types of NpO _n coordination polyhedra (6 ≤ n ≤ 12) are realized. The most characteristic of them are trigonal dodecahedra [Np(IV)], penta- and hexagonal bipyramids [Np(V) and Np(VI)], and octahedra [Np(VII)] based on square NpO₄^– cores. For Np atoms of a fixed oxidation state, the volume of their VDPs in the NpO _n complexes is virtually independent of the coordination number n. The VDP parameters can be used for determining the valence state of the Np atoms, finding compounds with the maximal nonlinearity of the NpO₂⁺ and NpO₂²⁺ dioxocations, and revealing errors in the crystal structure data. Anion–anion interactions involving NpO₄^– and OH^– ions are an important structure-forming factor in Np(VII) compounds. In sublattices consisting of Np atoms only (Np sublattices), the rule of 14 neighbors is fulfilled. Compounds in which binding Np···Np 5f interactions in crystal structures are possible were revealed by analysis of the VDPs of the atoms in the Np sublattices. In such compounds, the metal atoms form bent Np=O–Np bridging fragments and the Np^VO₇ bipyramids are combined in dimers sharing a common axial edge, with the Np atoms of the dimers being also bound via two carboxylate bridges.     

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 Structure of the Np(VII) Complex with Guanidinium,Li[C(NH<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>[NpO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]·6H<Subscript>2</Subscript>O

The previously unknown Np(VII) compound Li[C(NH₂)₃]₂[NpO₄(OH)₂]·6H₂O (I), containing organic cations, was synthesized and studied by single crystal X-ray diffraction. In contrast to the relatively numerous structurally characterized salts of [NpO₄(OH)₂]^3– anions with Na⁺, K⁺, Rb⁺, and Cs⁺ cations, which were prepared only from strongly alkaline media, crystals of I were isolated from solutions with a very low concentration of OH^– ions (about 0.1 M). The compound is relatively stable in storage in the dry form, but is strongly hygroscopic. In the structure of I, there are two independent Np(VII) atoms with the oxygen surrounding in the form of tetragonal bipyramids. In contrast to the other salts of the [NpO₄(OH)₂]^3– anions with singlecharged alkali metal cations, the C(NH₂) ₃ ⁺ ions and hydrated Li⁺ ions in I interact with the oxygen surrounding of Np(VII) only via hydrogen bonds of types O_w–H···O and N–H···O with the formation of a three-dimensional H-bond network.     

Kinetics of Np(VI) Reduction with Butanal Oxime

Reduction of Np(VI) to Np(V) with butanal oxime in the presence of excess reductant is presumably described by the equation 4NpO₂ ²⁺ + 2C₃H₇CHNOH + H₂O = 4NpO₂ ⁺ + 2C₃H₇CHO + N₂O + 4H⁺, and the reaction rate, by the equation -d[Np(VI)]/dt = k[Np(VI)][C₃H₇CHNOH]/[H⁺], with k = 230±15 min^-1 at 25°C and the ionic strength of the solution = 2. This equation holds for solutions with different values of the ionic strength and HNO₃ concentration. The activation energy is 69.4±12.4 kJ mol^-1.     

Oxidation of Np(V) with Xenon Trioxide in an HClO<Subscript>4</Subscript> Solution

Oxidation of Np(V) to Np(VI) with xenon trioxide in a 0.5–1.4 M HClO₄ solution was studied by spectrophotometry. The reaction rate is described by the equation–d[Np(V)]/dt = k[Np(V)][XeO₃], where k = 4.6 × 10^–3 L mol^–1 s^–1 in 1 M HClO₄ at 92°С. The activation energy is close to 92 kJ mol^–1. The activated complex is formed in contact of NpO ₂ ⁺ and ХеО₃ without participation of Н⁺ ions. The activated complex transforms into NpO ₂ ²⁺ and the products: ОН, Хе, and О₂. The ОН radical oxidizes Np(V). Admixtures of Со²⁺ and especially Fe³⁺ accelerate the Np(V) oxidation.     

Crystal structure of mixed-valent Np(IV)/Np(V) chloride, [Np(NpO2)6(H2O)8(OH)Cl9]·H2O

A new mixed-valent Np(IV)/Np(V) chloride, [Np(NpO₂)₆(H₂O)₈(OH)Cl₉]·H₂O, was synthesized, and its crystal structure was determined. The crystals consist of NpO ₂ ⁺ and Np⁴⁺ cations, of Cl^? and OH^? anions, of coordination-bonded water molecules, and of water molecules of crystallization. The Np(V) atom, Np(1), has pentagonal bipyramidal coordination surrounding with O atoms in the apical position and with the equatorial plane formed by three Cl^? anions, O atom of the adjacent NpO ₂ ⁺ cation, and O atom of water molecule. The mutual coordination of the neptunyl(V) ions, cation-cation (CC) interaction, links the Np(1) coordination polyhedra via common vertices into rings around sixfold axes, with the Np(V)?Np(V) distance in these fragments of 4.276 Å. The ring fragments are linked with each other via common equatorial edges of the bipyramids into layers perpendicular to c-axis. The Np(IV) atom, Np(2), has coordination surrounding in the form of tricapped trigonal prism (CN 9) with the tetragonal lateral faces formed by the O atoms of the NpO ₂ ⁺ cations and the capping positions occupied by the O atoms of two water molecules and one hydroxy group. The Np(2) atoms act in CC interactions as coordination center for six NpO ₂ ⁺ ions, with the Np(IV)?Np(V) distance of 4.183 Å. The Np(2) polyhedra are arranged in the crystal between layers of the Np(1) coordination polyhedra, linking them with each other.     

Effect of O2, H2O2, and HNO2 on the stability of Np(III–VII) in aqueous solutions

Published data on reactions of Np ions with O₂, H₂O₂, HNO₂, and HNO₃ in solutions of various compositions in a wide pH range are considered. O₂ oxidizes Np(III) in acid solution and Np(IV) and Np(V) in alkaline solutions. H₂O₂ exhibits dual behavior. In weakly acidic solutions, it converts Np(III) and (IV) to Np(V), in 0.75?C1 M NaHCO₃ it oxidizes Np(V) to Np(VI), whereas in dilute HClO₄ and HNO₃ and in carbonate and alkali solutions it reduces Np(VI), and in alkali solutions it reduces Np(VII). The first step of reduction in most cases is the formation of the Np(VI) peroxide complex, and the next step is the intramolecular charge transfer. In concentrated HNO₃ solutions, H₂O₂ converts Np(V) to Np(IV) and Np(VI) and then reduces Np(VI). Some radiation-, photo-, and sonochemical reactions occur via formation of excimers, i.e., of dimers arising from excited and unexcited Np ions. The excimer decomposes into two ions with higher and lower oxidation states. In reduction reactions, the excimer eliminates H₂O₂ (in addition to the H₂O₂ arising as primary product of water radiolysis). In HNO₃ solutions, oxidation of Np ions occurs only in the presence of HNO₂ arising as reaction product or upon radiolysis, photolysis, or sonolysis. The active species are NO ₂ ^? , NO₂, and NO⁺ present in equilibrium with HNO₂.     

Crystal structure of a double Np(V) and Co(NH3)63+ maleate, Co(NH3)6[NpO2(HL)2(H2O)3](HL)2?H2O [L = OOC(HC)2COO]

Crystal structure of a double Np(V) and Co(NH₃) ₆ ³⁺ maleate Co(NH₃)₆[NpO₂(HL)₂(H₂O)₃](HL)₂H₂O [L = OOC(HC)₂COO] was studied. The crystal structure consists of complex anions [NpO₂(HL)₂(H₂O)₃]^–, HL^– anions, [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. Hydrogen bonds in which proton donors are water molecules and hexaamminecobalt cations link structural fragments to form a 3D network. The coordination polyhedra of the Np(V) atoms are pentagonal bipyramids whose equatorial planes are formed by oxygen atoms of two HL^– anions and three water molecules. Four crystallographically independent maleate anions were identified in the structure. Two of these anions enter into the Np(V) surrounding, and their coordination capacity is 1.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 521–523.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

A Spectrophotometric Study of the Interaction of Np(VI) with Orthosilicic Acid and Polymeric Silicic Acids in Aqueous Solutions

The interaction of NpO ₂ ²⁺ ions with orthosilicic acid Si(OH)₄ and polymeric silicic acids (PSAs) in aqueous solutions was studied spectrophotometrically. The interaction at pH ≤ 4.5 is described by the equation NpO ₂ ²⁺ + Si(OH)₄ = NpO₂OSi(OH) ₃ ⁺ + H⁺ with the equilibrium constant log K = − 2.88±0.12 at the ionic strength I = 0.1–0.2 (log K ⁰ = −2.61±0.12 recalculated to I = 0); the stability constant of the complex NpO₂OSi(OH) ₃ ⁺ (I = 0) is log β⁰ = 7.20± 0.12. At pH > 5, a second complex of NpO ₂ ²⁺ with PSAs of the presumed composition NpO₂(≡ SiO)₂(≡SiOH) _{m − 2}, where (≡SiOH)_m denotes a PSA molecule with surface Si-OH groups, is formed. The absorption spectra of the complexes NpO₂OSi(OH) ₃ ⁺ and NpO₂(≡ SiO)₂(≡SiOH) _{m − 2} were obtained. In contrast to the hydroxo complexes, they have pronounced maxima at 560 – 600 nm with the molar extinction coefficients of about 25–30 l mol⁻¹ cm⁻¹, which is several times higher compared to the Np(VI) aqua ion.__________Translated from Radiokhimiya, Vol. 47, No. 4, 2005, pp. 322–327.Original Russian Text Copyright © 2005 by Yusov, Shilov, Fedoseev, Astafurova, Delegard.     

Reduction of Am(IV) with Water in KHCO3 + K2CO3 Solutions

Reduction of Am(IV) with water in KHCO₃, K₂CO₃ solutions (pH 8.5-10.5) was studiedspectrophotometrically at 54-70°C. The Am(IV) concentration decreases, following the first-order rate law.The reduction rate increases with pH (logk/pH = 0.4), but decreases with increase in (HCO₃ ^- + CO₃ ^{2 -}) concentration. It was assumed that the thermally excited Am(IV) ion forms a dimer with unexcited Am(IV). The dimer dissociates into two Am(III) ions and H₂O₂. Hydrogen peroxide reduces two more Am(IV) ions. In this process, the excited Am(III) ion appears, which transfers the excitation to Am(IV) at collision. Thus, a chain process is initiated. This scheme can also explain the kinetics of Am(VI) and Np(VII) reduction in carbonate solutions.     

Potential of the NP(VI)/Np(V) couple in solutions of various alkalis

The formal potentials of the Np(VI)/Np(V) couple E ^f in alkaline solutions were measured potentiometrically. In 1 M LiOH, NaOH, KOH, CsOH, and (CH₃)₄NOH, the potentials are equal to 0.163⊥0.004, 0.125⊥0.005, 0.112⊥0.005, 0.107⊥0.005, and 0.109⊥0.005 V, respectively. In solutions of MOH+MCl [M=Li, Na, K, Cs, and (CH₃)₄N] at the ionic strength of 1, the dependence of E ^f on log[OH^?] is a straight line with a slope of 0.118⊥0.010, i.e., two OH^? ions participate in the electrochemical reaction between Np(VI) and Np(V). Taking into account the well-known structure of Np(VI), it can be stated that Np(V) in solutions with [OH^?]=1 M and less exists in the form of the NpO₂(OH) ₂ ^? anion. In 2–4 M LiOH and 2–11 M NaOH or KOH, the potential decreases with increasing alkali concentration. In these media, the anion NpO₂(OH) ₃ ^2? is formed.     

Cation-cation interaction in mixed-valent An(IV)/Np(V) tribromoacetates [An(NpO2)(H2O)3(CBr3COO)5]·CBr3COOH·nH2O,An = Th(IV), Np(IV)

The structure of new mixed-valent An(IV)/Np(V) compounds [An(NpO₂)(H₂O)₃(CBr₃COO)₅]·CBr₃COOH·nH₂O, where An(IV) = Th and Np, was studied. Two independent Np(V) atoms have the coordination surrounding in the form of pentagonal bipyramids with the O atoms of NpO ₂ ⁺ dioxocations in apical positions; the equatorial planes of the bipyramids are constituted by the O atoms of five CBr₃COO^? ions. Two independent An(IV) atoms have the oxygen surrounding in the form of distorted tricapped trigonal prisms (CN = 9) constituted by the O atoms of four CBr₃COO^? ions, two NpO ₂ ⁺ cations, and three water molecules. Eight of ten independent CBr₃COO^? anions link the An⁴⁺ and NpO ₂ ⁺ cations in the bidentate bridging fashion into electrically neutral chains [An(NpO₂)(H₂O)₃(CBr₃COO)₅]n, and two CBr₃COO^? anions interact with two independent NpO ₂ ⁺ dioxocations in the monodentate fashion. CBr₃COOH and water molecules are located between the layers. In the [An(NpO₂)(H₂O)₃(CBr₃COO)₅]n chains, NpO ₂ ⁺ cations alternate with An⁴⁺ cations, and mixed-valent An(IV)/Np(V) cation-cation interaction arises, in which each NpO ₂ ⁺ cation acts as a bidentate ligand and An⁴⁺ acts as coordination center for two dioxocations. [Th(NpO₂)(H₂O)₃(CBr₃COO)₅]·CBr₃COOH·2H₂O is the first example of a Th(IV) compound in which cation-cation bonds with the NpO ₂ ⁺ ions are present.     

Oxidation of Np(V) and Np(IV) with Fe(CN) 6 3− ions in carbonate solutions

The formal potential of the Fe(CN) ₆ ^3? /Fe(CN) ₆ ^4? couple in 1 M NaHCO₃ and 1–2 M Na₂CO₃ solutions was determined. It is equal to 505 and 510 mV, respectively, exceeding the potentials of the Np(VI)/(V) and Np(V)/(IV) couples in carbonate solutions. The equilibrium of the reaction Np(V) + Fe(CN) ₆ ^3? = Np(VI) + Fe(CN) ₆ ^4? was studied. Fe(CN) ₆ ^3? ions oxidize Np(IV) to Np(V) and then to Np(VI). The arising Np(VI) oxidizes Np(IV). The Np(IV) oxidation accelerates in going from NaHCO₃ to Na₂CO₃. An increase in [Na₂CO₃] or in the ionic strength (by adding neutral salts) decelerates the oxidation. Np(IV) introduced in an HCl solution reacts with Fe(CN) ₆ ^3? or with Np(VI) faster than Np(IV) introduced in a Na₂CO₃ solution. The activation energy of the reaction of Np(IV) with Fe(CN) ₆ ^4? in the range 20–45°C is 107 kJ mol^?1. The reaction mechanism involves formation of the activated complex from ions of Np(IV) hydroxocarbonate and oxidant.     

Complexation and Disproportionation of Np(V) in K10P2W17O61 Solutions

Complexation of NpO₂ ⁺ and NpO₂ ^{2 +} with unsaturated K _n P₂W₁₇O₆₁ ^{n - 1 0} (L ^x-) heteropolyanion and disproportionation of Np(V) in the presence of L ^x- were studied spectrophotometrically. The logarithms (logK) of the formation constants of NpO₂ ^VL and NpO₂ ^{V I}L are 3 and 7, respectively. The K⁺ and Na⁺ cations bind the L ^x- anions, thus decreasing the yield of the complexes. Neptunium(V) disproportionation in K₁₀P₂W₁₇O₆₁ solutions containing 1 M (HClO₄ + NaClO₄) (pH from 0 to 4) and free from NaClO₄ (pH 2-6.5) was studied. The disproportionation rate is described by the equation -d[Np(V)]/dt = k[Np(V)][L ^x-]. The pH dependence of the rate constant passes through a maximum at pH 1. The rate constant decreases with increasing [Na⁺]. The reaction is inhibited by its product, Np(IV). The Np(V) complex is not involved in disproportionation; the reactive species is NpO₂ ⁺ aqua ion, which is probably converted into NpO^{3 +}L ^x-. Then NpO^{3 +}L ^x- rapidly reacts with NpO₂ ⁺, which occurs simultaneously with, or is preceded by release of the second oxygen atom.     

Crystal Structure of Double Np(V) Malonate with Co(NH3)6 3 + in the Outer Sphere, [Co(NH3)6][NpO2L]2HL (L = OOCCH2COO)

The single crystal X-ray analysis of [Co(NH₃)₆][NpO₂L]₂HL (L = OOCCH₂COO) was carried out [monoclinic system, a = 17.925(6), b = 7.736(4), c = 7.879(3) Å, = 103.65(3)°, space group C2/m]. The structure consists of infinite anionic chains [NpO₂L] _n ^n-, [Co(NH₃)]₆ ^{3 +} cations, and HL^- anions. The Np(V) atoms have hexagonal-bipyramidal oxygen surrounding. The coordination capacity of malonate ions is 6; two oxygen atoms (one of each carboxylate group) are bridging atoms between two Np atoms, owing to which the CPs of Np atoms share common equatorial edges to form infinite chains.     

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.     

Synthesis of M(NpO<Subscript>4</Subscript>)<Subscript>2</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Mg,Ca, Sr,Ba) Using Н<Subscript>3</Subscript>ВО<Subscript>3</Subscript> Solutions and Properties of These Salts

Two procedures for preparing the compounds M(NpO₄)₂·nH₂O (M = Mg, Ca, Sr, Ba) using boric acid were suggested. In the first procedure, samples of freshly prepared salts M₃(NpO₅)₂·nH₂O (M = Ca, Sr, Ba) are treated with excess 0.5 M H₃BO₃ with vigorous stirring. In the process, the initially light green salts rapidly transform into black products of the general composition M(NpO₄)₂·nH₂O. In the second procedure, a measured volume of a Np(VII) solution with a known LiOH concentration was added to excess 0.5 M H3BO3 solution containing a calculated amount of Mg, Ca, Sr, or Ba nitrate. The reaction yields black precipitates of the same compounds as in the previous case. After washing with water and drying in an oxygen stream, the final products contain a small impurity of Np(VI). The IR spectra suggest that the compounds obtained are structurally related to the previously studied salts MNpO₄ (M = K–Cs), i.e., in their lattices there are neptunium–oxygen layers built of NpO₂³⁺ cations and bridging O atoms. New data on the properties of the compounds M₃(NpO₅)₂·nH₂O with M = Ca, Sr, and Ba were also obtained.     

An XPS study of interaction of neptunyl(V) in aqueous solution with goethite (α-FeOOH)

Sorption and physicochemical state of Np on the goethite (-FeOOH) surface were studied. The oxidation state of Np on the -FeOOH surface was studied by the liquid extraction. The neptunium complexes formed on the surface were studied by X-ray photoelectron spectroscopy. The ionic and elemental composition of the goethite surface and NpO ₂ ⁺ complexes with -FeOOH were determined from the XPS data. No Np(IV) and Np(VI) compounds were detected. Neptunyl(V) Np(V)O ₂ ⁺ forms complexes with the surface groups of -FeOOH. The equatorial plane of these complexes is occupied by the oxygen atoms of -FeOOH and water and/or carbonate group CO ₃ ^2– .Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 503–506.Original Russian Text Copyright © 2004 by Yu. Teterin, Kalmykov, Novikov, Sapozhnikov, Vukcevic, A. Teterin, Maslakov, Utkin, Khasanova, Shcherbina.     

Interaction of An(VI) (An = U, Np, Pu) and Np(V) with 2,3-pyridinedicarboxylic (quinolinic) acid (H2Quin): Complexation in aqueous solutions, synthesis and structure of the complexes [UO2(HQuin)2], [(NpO2)2(HQuin)2(C6H4NO3)2]·2H2O, and [PuO2Quin(H2O)]

Complexation of An(VI) (An = U, Np, Pu), and Np(V) with 2,3-pyridinedicarboxylic (quinolinic, H₂Quin) acid in aqueous solutions was studied. Np(V) can form 1: 1 and 1: 2 complexes, and An(VI), also 1: 3 complexes (at pH ? 6 and [H₂Quin] ? 0.1 M). Quinolinate ion can coordinate to actinide(VI) and (V) ions in solutions in different modes. The apparent stability constants of the complexes in a wide pH range and the concentration stability constants of the An(VI) complexes were measured. In the series from Pu(VI) to U(VI), the stability of the complexes slightly increases. Crystalline complexes [UO₂(HQuin)₂], [(NpO₂)₂(HQuin)₂(HL)₂]·2H₂O (HL is N-protonated 2-hydroxypyridine-3-carboxylic acid anion), and [PuO₂Quin(H₂O)] were synthesized, and their structures were determined by single crystal X-ray diffraction. Different types of coordination of quinolinate ions to actinide ions are also observed in the crystalline complexes.