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.     

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).     

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.     

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.     

Redox Kinetics of U,Pu, and Np in TBP Solutions: VI. Reactions of Neptunium and Plutonium with Organic Reducing Agents: Determination of the Final Oxidation States and Reaction Rates

Reactions of Pu(IV) and Np(VI) with organic reducing agents of various types (substituted hydroxylamines, oximes, aldehydes, etc.) in tributyl phosphate solutions containing nitric acid were studied spectrophotometrically. The molar extinction coefficients of neptunium and plutonium in various oxidation states [Np(IV,V,VI), Pu(III,IV,VI)] in TBP solutions were determined as influenced by HNO₃ and H₂O concentrations and temperature. It was found that organic reducing agents at low HNO₃ concentration convert plutonium and neptunium to Pu(III) and Np(V), respectively. With increasing HNO₃ concentration Pu(III) and Np(V) are partly oxidized back to Pu(IV) and Np(VI), respectively, by reaction with nitrous acid. The rate constants of Pu(VI) and Np(VI) reduction and Np(V) oxidation as influenced by concentration of organic reducing agents and HNO₃ were evaluted from the kinetic data.     

Reduction of Np(VI) and Pu(VI) with anions of some substituted carboxylic acids

The reaction of Np(VI) with organic acid anions in solutions containing lithium salts of tartaric, malic, α-aminoglutaric, and trihydroxyglutaric acids was studied. Changes in the solution spectra show that Np(VI) forms complexes with organic acid anions, which is followed by the reduction of Np(VI) to Np(V). Similar processes occur in solutions containing Pu(VI) and sodium phenylglycolate or ammonium salicylate. In weakly acidic solutions, the loss of the Np(VI) and Pu(VI) concentrations is a linear function of time. The possible mechanism of the redox reactions was suggested.     

Solubility of mixed-valence U(IV–VI) and Np(IV–V) hydroxides in simulated groundwater and 0.1 M NaClO4 solutions

The kinetics of U(VI) accumulation in the phase of U(IV) hydroxide and of Np(V) in the phase of neptunium(IV) hydroxide, and also the solubility of the formed mixed-valence U(IV)-U(IV) and Np(IV)-Np(V) hydroxides in simulated groundwater (SGW, pH 8.5) and 0.1 M NaClO₄ (pH 6.9) solutions was studied. It was found that the structure of the mixed U(IV–VI) hydroxide obtained by both oxidation of U(IV) hydroxide with atmospheric oxygen and alkaline precipitation from aqueous solution containing simultaneously U(IV) and U(VI) did not affect its solubility at the U(VI) content in the system exceeding 16%. The solubility of mixed-valence U(IV–VI) hydroxides in SGW and 0.1 M NaClO₄ is (3.6±1.9) × 10^?4 and (4.3 ± 1.7) × 10^?4 M, respectively. The mixed Np(IV–V) hydroxide containing from 8 to 90% Np(V) has a peculiar structure controlling its properties. The solubility of the mixed-valence Np(IV–V) hydroxide in SGW [(6.5 ± 1.5) × 10^?6 M] and 0.1 M NaClO₄ [(6.1±2.4) × 10^?6 M] is virtually equal. Its solubility is about three orders of magnitude as high as that of pure Np(OH)₄ (10^?9–10^?8 M), but considerably smaller than that of NpO₂(OH) (～7 × 10^?4 M). The solubility is independent of the preparation procedure [oxidation of Np(OH)₄ with atmospheric oxygen or precipitation from Np(IV) + Np(V) solutions]. The solubility of the mixed-valence Np hydroxide does not increase and even somewhat decreases [to (1.4±0.7) × 10^?6 M] in the course of prolonged storage (for more than a year).     

Coprecipitation of neptunium(IV) and plutonium(IV) with hydrolyzed iron(III) in carbonate solutions

In regeneration of Np(IV)-and Pu(IV)-containing recycled solvent by treatment with aqueous sodium carbonate contaminated with iron, some portion of Np(IV) and Pu(IV) coprecipitates with hydrolyzed iron. The degree of coprecipitation of Np and Pu depends on both the iron and sodium carbonate concentrations. The presence of n-dibutyl hydrogen phosphate in the recycled solvent before its regeneration does not noticeably affect the coprecipitation of Np and Pu. The possible mechanisms of coprecipitation of actinides with hydrolyzed iron in carbonate solutions are discussed.     

Stability of Pu(VI) and Pu(V) in aqueous formate solutions

The behavior of Pu(VI), Pu(V), and Pu(IV) in K(Li,Na)HCO₂ and HCOOH + Li(Na)HCO₂ solutions was studied by spectrophotometry. Changes in the spectra of a Pu(VI) solution, observed on adding alkali metal formates, suggest formation of Pu(VI) formate complexes. Changes in the absorption spectra of Pu(V), observed with an increase in the concentration of LiHCO₂ or NaHCO₂, suggest the appearance of Pu(V) formate complexes. The absorption spectra of Pu(IV) indicate that, in a wide range of formate concentrations, the composition of the Pu(IV) formate complexes under the examined conditions is constant. The Pu(VI) content in formate solutions decreases at a rate exceeding the rate of the Pu(VI) disappearance in 0.5–2 M HClO₄ under the action of the ²³⁹Pu α-radiation. The tendency of Pu(V) to reduction and disproportionation in formate solutions depends in a complex fashion on the formate ion concentration and kind of the alkali metal. The kinetics of the Pu(V) consumption in HCOOH + Li(Na)HCO₂ solutions was studied. The reaction starts with the formation of a Pu(V) formate complex, which interacts with Pu(V) aqua ions and Pu(V) formate complex to form dimers, with their subsequent protonation and transformation into Pu(VI) and Pu(IV).     

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.     

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).     

Behavior of plutonium(IV) and neptunium(IV) at acidification of spent carbonate solutions prior to extraction

The precipitation of poorly soluble Pu(IV) and Np(IV) dibutyl phosphates on acidifying Pu(IV)-and Np(IV)-containing carbonate solutions contaminated with dibutyl hydrogen phosphate was studied. The degree of precipitation of Pu and Np is dependent on the final acidity and the storage time of the resulting suspension. The presence of iron in carbonate solutions (<0.5 g/l) does not noticeably affect the distribution of the actinides in the neutralized solutions.     

Disproportionation of Pu(V) in aqueous HCOOH solutions

The behavior of Pu(VI), Pu(V), and Pu(IV) in the HCOOH-H₂O system was studied by spectrophotometry. The Pu(VI) absorption spectrum in solutions containing less than 1 mM HClO₄ changes on adding HCOOH to a concentration of 0.53 M. Along with a decrease in the intensity of the absorption maximum at 830.6 nm, corresponding to an f-f transition in the Pu₂²⁺ aqua ion, a new band arises with the maximum shifted to 834.5 nm. These transformations are due to formation of a Pu(VI) formate complex (1: 1). The Pu(IV) absorption spectra in HCOOH solutions vary insignificantly in going from 3.0 to 9.0 M HCOOH and are similar to the spectrum of Pu(IV) in a 0.88 M HCOOH + 0.41 M NaHCOO + 0.88 M NaClO₄ solution, which indicates that the composition of the Pu(IV) formate complexes is constant. Pu(V) is unstable in HCOOH solutions and disproportionates to form Pu(VI) and Pu(IV). The reaction rate is approximately proportional to [Pu(V)]² and grows with an increase in [HCOOH]. The reaction products affect the reaction rate: Pu(IV) accelerates the process, and Pu(VI) decelerates the consumption of Pu(V) by binding Pu(V) in a cationcation complex. The disproportionation occurs via formation of a Pu(V)-Pu(V) cation-cation complex whose thermal excitation yields an activated complex with its subsequent decomposition to Pu(VI) and Pu(IV).     

Interaction of U(VI), Np(VI), Pu(VI), and Np(V) with benzenetricarboxylic acids: Complexation in aqueous solutions, synthesis, and crystal structure of uranyl complexes [UO2(H2O)2{C6H3(COO)2(COOH)}]2·2H2O and [(UO2)3(H2O)4{C6H3(COO)3}2]

The complexation of U(VI), Np(VI), and Pu(VI) and of Np(V) with 1,2,3- and 1,2,4-benzenetricarboxylic acids (BTC) in aqueous solutions was studied in wide ranges of pH and actinyl ion concentrations. The compositions of the forming hexavalent actinide complexes were determined. Their apparent stability constants β₁′ depend on pH of the solution: in the pH range 2–4, logβ₁′ from 2 to 4 for the complexes of U(VI), Np(VI), and Pu(VI) with 1,2,3-BTC and from 1.5 to 3.5 for the complexes with 1,2,4-BTC. For Np(V), the β₁′ values are close with both acids, and at equal pH values the Np(V) complexes are less stable than the An(VI) complexes (An = U, Np, Pu). With an increase in pH from ～3 to 6.2–6.9, logβ₁′ of the Np(V) complexes increases approximately from 0.5 to 3. Solid U(VI) complexes with 1,2,3- and 1,2,4-benzenetricarboxylic acids were synthesized by the hydrothermal method, their crystal structure was determined, and the IR spectra were examined.     

Kinetics of Np(V) Reduction with Carbohydrazide Catalyzed by Tc(VII) in the Presence of U(VI)

Radiochemistry - The kinetics of Np(V) reduction with carbohydrazide in nitric acid medium in the presence of Tc(VII) and U(VI) ions was studied by spectrophotometry. The reduced form of Np(IV) is...     

Kinetics of Pu(V) disproportionation in CH<Subscript>3</Subscript>COOH-CH<Subscript>3</Subscript>COOLi aqueous solutions

The behavior of Pu(IV–VI) in CH₃COOH-CH₃COOLi solutions was studied by spectrophotometry. The Pu(VI) absorption spectrum changes essentially with an increase in the CH₃COOLi concentration. Owing to formation of Pu(VI) acetate complexes, the maximum of the main absorption band is shifted from 830.6 (in HClO₄ solution) to 845 nm, with the band intensity decreasing by a factor of approximately 8. The Pu(V) and Pu(IV) absorption spectra at low concentrations of acetate ions vary insignificantly relative to the spectra in noncomplexing media. With an increase in the acetate concentration in the system to 1–3 mM, the effect of Pu(V) complexation on its absorption spectrum becomes noticeable (the absorption intensity considerably decreases), whereas the Pu(IV) absorption spectra remain essentially unchanged. Solutions containing 1–2 mM Pu(V) and 0.2–0.5 M CH₃COOLi remain unchanged at 18–25°C for 2 days. In solutions with [CH₃COOLi] = 1–3 M, Pu(V) disproportionates with the formation of soluble Pu(VI) complexes and a suspension of Pu(IV) hydroxide. Introduction of CH₃COOH to a concentration of 0.1–1.0 M prevents the formation of a suspension of Pu(IV) hydroxide, but only up to a temperature of 45°C. The Pu(V) loss follows a second-order rate law, with the reaction products, Pu(IV) and Pu(VI), accelerating the Pu(V) consumption. The reaction rate at a constant concentration of acetate ions is proportional to [H⁺]. The reaction order with respect to Ac⁻ ions is close to 1.6. The activation energy of the Pu(V) disproportionation in the range 19–45°C is estimated at 74.5 kJ mol⁻¹. It is assumed that the disproportionation mechanism involves the formation of dimers from Pu(V) acetate complexes and aqua ions, their protonation, and decomposition with the transformation into Pu(IV) and Pu(VI).     

Disproportionation of polymeric Pu(IV) in weakly acidic solutions

Polymeric Pu(IV) in aqueous solutions in the pH range 0.5–3 disproportionates with time to form Pu(III) and Pu(VI). The arising Pu(III) is bound by hydroxyl groups of polymeric Pu(IV) and does not exhibit intrinsic absorption bands in the spectrum of a solution of polymeric Pu(IV). However, after ultrafiltration of the solution through a filter with a pore size of ∼3 nm Pu(III) is clearly identified in the filtrate by its absorption maxima. Pu(VI) occurs in the solution in the ionic state and is not bound by hydroxy groups of polymeric Pu (IV). Therefore, Pu(VI) is identified in the solution absorption spectrum both before ultrafiltration and after it. Thus, storage of solutions of polymeric Pu(IV) with pH 0.5–3 is accompanied by formation of Pu(III) and Pu(VI) ions.     

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.     

Role of U(VI) complexes in the chemiluminescent reaction U(IV) + O3 in H2SO4 solution

Data on the effect of U(VI) on the reaction U(IV) + O₃ in H₂SO₄ solution are analyzed. The chemiluminescence enhancement is caused by the formation of a complex of an excited U(VI) ion with an unexcited U(VI) ion, so-called excimer. The decomposition of the excimer to two U(V) ions and H₂O₂ is followed by the reaction of U(V) with ozone, giving rise to the excited U(VI) ion. Thus, a chain reaction develops.