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.     

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.     

Kinetics of Plutonium(IV) Reduction with 3,3'-Bis(diaziridinyl) in HNO3 Solution

3,3'-Bis(diaziridinyl), H₂N₂C₂H₂N₂H₂, is oxidized with Pu(IV) ions in excess of reductant to bis(diazirinyl), N₂C₂H₂N₂, and in excess of oxidant, to nitrogen and acetic acid. The reaction rate in the HNO₃ solution at a constant ionic strength is described by the equation -d[Pu(IV)]/dt = k[Pu(IV)]²× [H₂N₂C₂H₂N₂H₂]^{1 . 7}[H⁺]^{- 3}, where k = 28400±1400 mol^{0 . 3} l^{- 0 . 3} min^{- 1} at 35°C. The activation energy of the reaction amounts to 126±11 kJ mol^{- 1}.     

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 Redox Reactions of U, Pu, and Np in TBP Solutions: VIII. Kinetics of Reduction of Pu(VI) and Np(VI) with N,N-Dibutylhydroxylamine in Undiluted TBP

The kinetics of Pu(VI) and Np(VI) reduction in TBP containing HNO₃ was studied spectrophotometrically. The rate of the reduction of Pu(VI) with N,N-dibutylhydroxylamine in undiluted TBP is independent of the Pu(VI) concentration and is described by the equation -d[Pu(VI)]/dt = k[(C₄H₉)₂NOH][H₂O]⁵, with k = (2.17±0.13) × 10^-5 l⁵ mol^-5 min^-1 at 12°C. The activation energy of the reaction, E = 85.2± 4.6 kJ mol^-1, was determined from the temperature dependence of k in the range 12.0-33.5°C. Reduction of Np(VI) in undiluted TBP is approximately described by the kinetic equation -d[Np(VI)]/dt = k[Np(VI)] × [(C₄H₉)₂NOH]/[HNO₃], with k 40 min^-1 at 25°C, and in a 30% solutio of TBP in n-dodecane, by the equation -d[Np(VI)]/dt = k[Np(VI)][(C₄H₉)₂NOH]/[HNO₃]0.7 with the rate constant k = 18.4±1.8 l0.3 mol-0.3 min^-1 at 25°C.     

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.     

Oxidation of U(IV) in HNO<Subscript>3</Subscript> Solutions Containing Urea and Tc(VII)

The kinetics of U(IV) oxidation with nitric acid in aqueous solutions containing urea, catalyzed with technetium ions, were studied by sampling with subsequent colorimetric determination of the U(IV) concentration. At the constant ionic strength of the solution μ = 2 in the range of the initial concentrations of U(IV) from 2 × 10⁻³ to 1.28 × 10⁻², Tc(VII) from 5 × 10⁻⁵ to 1 × 10⁻³, urea from 0.01 to 0.1, and hydrogen ions from 0.4 to 1.96 M, the reaction rate is described by the equation -d[U(IV)]/dt = k ₁[U(IV)][Tc]^0.5[CO(NH₂)₂] × {[H⁺]² + β₁[H⁺] + β₂}⁻¹ - k ₂[U(IV)]₂[H⁺]^0.4[CO(NH₂)₂]^1.6{ [H⁺]² + β₁[H⁺]+ β₂}⁻², where k ₁ = 172 ± 10 mol^0.5 l^−0.5 min⁻¹ and k ₂ = (9.4±1.2)×10² mol l⁻¹ min⁻¹ at 25°C, β₁ and β₂ are the hydrolysis constants of U⁴⁺ ions. The activation energy is 63±2 kJ mol⁻¹. A reaction mechanism is proposed, in which in the slow stages the complex ion U(OH) ₂ ²⁺ ·CO(NH₂)₂ reacts with TcO²⁺ and TcO²⁺ · CO(NH₂)₂ ions.__________Translated from Radiokhimiya, Vol. 47, No. 1, 2005, pp. 61–66.Original Russian Text Copyright © 2005 by Dvoeglazov, Marchenko, Koltunov.     

Redox Reactions of Platinum Elements: XV. Kinetics of Rhodium(III) Oxidation with Xenon Difluoride in Nitric Acid Solutions

The rate of the reaction 2Rh(H₂O)₆ ^{3 +} + XeF₂ = 2Rh(OH)₃ ⁺ + Xe + 2HF + 4H⁺ + 6H₂O is described by the second-order equation -d[Rh(III)]/dt = k ₁[Rh(III)][XeF₂], where k ₁ = 15.4±0.8 l mol^-1 min^-1 at 17.8°C and the solution ionic strength = 2. The activation energy of the reaction is E ₁ = 60.6±1.0 kJ mol^-1. This reaction is complicated by the parallel hydrolysis reaction 2XeF₂ + 2H₂O = 2Xe + O₂ + 4HF. The reaction mechanism includes a slow stage of H atom transfer from Rh(H₂O)₆ ³⁺ to XeF₂ molecule with formation of XeF^. radical as an intermediate. The subsequent stages of Rh(H₂O)₅(OH)³⁺ hydrolysis and reduction of XeF^· radical to Xe proceed rapidly.     

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.     

Kinetics and Mechanism of Np(IV) Oxidation with Nitric Acid

Neptunium (IV) is oxidized to Np(V) with nitric acid in the presence of U(VI) under conditions of low acidity (<∼0.1 M). The reaction rate is described by the equation d[Np(V)]/dt = k ₁[Np(IV)]/[H⁺]² + k ₂[Np(IV)]²[U(VI)]/[H⁺]³, in which k ₁ = (2.0±0.3) × 10⁻⁵ mol² l⁻² min⁻¹ and k ₂ = (5.50±0.47) × 10⁻² mol l⁻¹ min⁻¹ at 50°C and solution ionic strength μ = 0.5. The activation energies of the two pathways are 148±31 and 122±12 kJ mol⁻¹. The reaction along the main pathway (with the rate constant k ₂) is limited by disproportionation of Np(IV) involving NpOH³⁺ and Np(OH)₂UO ₂ ⁴⁺ complex ions.__________Translated from Radiokhimiya, Vol. 47, No. 3, 2005, pp. 228–233.Original Russian Text Copyright © 2005 by Koltunov, Taylor, Marchenko, Savilova, Dvoeglazov, Zhuravleva.     

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.     

Formation of Unusual U,Pu, and Cf Oxide Species under Conditions of Gas Thermochromatography

Experiments were performed on the preparation of volatile oxidation products from trace amounts of plutonium and on thermochromatographic (TC) separation of these species, taking into account the previously obtained data on different behaviour of some micro- and macrocomponents in the gas phase. The volatility of products formed by thermal oxidation of traces of U and ²⁴⁹Cf with an He-O₂ (1 : 1 vol.) mixture was studied with the aim to simulate the behavior of Pu(IV) and Pu(VI) oxides. Hollow quartz columns were used. Under the experimental conditions, volatile UO₂, UO₃, and 249CfO₂ were formed; the dioxides were deposited at 450±25°C, and UO₃, at 250±25°C. The enthalpies of adsorption -H _a ⁰ of these compounds on quartz were calculated. Experimental evidence of existence in the gas phase of volatile uranic acid was obtained. The TC behavior of 238,239Pu traces was studied under conditions of thermal oxidation in an He-O₂ flow at the oxygen concentration cO ₂ varied from 50 to 10^{- 7}%. In the cO ₂ range of 50-5 × 10^{- 2}%, deposition of volatile Pu species at 460±25 and 250±25°C was observed. The identical deposition temperatures and close values of -H _a ⁰ of the products of U and Pu oxidation suggest the transfer of Pu in the form of PuO₂ and PuO₃. In the cO ₂ range from 50 to 1%, an abnormally volatile Pu species was detected, which was deposited at -105±25°C. Its -H _a ⁰, 41±6 kJ mol^{- 1}, was close to that of OsO₄. The deposition zones of ¹⁸⁵OsO₄ and of the highly volatile Pu species were superimposed. As cO ₂ decreased, the yield of the highly volatile Pu species decreased; a similar trend is also characteristic of OsO₄. This volatile Pu species was tentatively identified as Pu(VIII) oxide, PuO₄.     

Separation of transuranium and transplutonium elements on S-957 sorbent

Sorption of Pu⁴⁺, UO₂²⁺, NpO₂⁺, Am³⁺, and Eu³⁺ ions on S-957 cation exchanger from 2–7 M HNO₃ solutions was studied. The following selectivity series was obtained: Pu⁴⁺ > UO₂²⁺ > NpO₂⁺ > Am³⁺ ≈ Eu³⁺. The static and dynamic capacities of the sorbent for Pu were determined, and the eluent composition for the efficient desorption was chosen. The possibility of separating Pu(IV)-Am(III) and Pu(IV)-Np(V) pairs on the sorbent in the column chromatography mode was demonstrated.     

Crystal Structure of U(VI) Peroxo Complex with Triphenylphosphine Oxide {(UO2)2O2[OP(C6H5)3]6}(ClO4)2

The peroxo complex {(UO₂)₂O₂[OP(C₆H₅)₃]₆}(ClO₄)₂ was synthesized, and its crystal structure was determined [triclinic unit cell: a = 10.523(2), b = 16.242(3), c = 16.978(3) Å, = 65.79(3)°, = 85.06(3)°, = 77.14(3)°, space group P-1, Z = 1, V = 2580.1(9) ų, d _{c a l c} = 2.789 g cm^{- 3}; CAD4, MoK , graphite monochromator, direct method, R ₁ = 0.0368 for 3115 observed reflections, wR ₂ = 0.1107 for 4403 unique reflections, 622 refined parameters]. {(UO₂)₂O₂[OP(C₆H₅)₃]₆}(ClO₄)₂ has monomeric structure and consists of the complex cations {(UO₂)₂O₂[OP(C₆H₅)₃]₆}^{2 +} and ClO₄ ^- anions. The uranium atom has a pentagonal-bipyramidal oxygen surrounding (CN 7). Uranyl groups UO₂ ^{2 +} are linear and symmetrical, the U = O bond lengths are 1.780(8) and 1.787(8) Å, the O(1) = U = O(2) bond angles are 178.7(4) Å. The equatorial planes of bipyramids are formed by oxygen atoms of three TPPO molecules [U-O_{T P P O} 2.352(8)-2.368(7) Å, average 2.362 Å] and peroxo group O₂ ^{2 -} [U-O_{p e r} 2.285(8) and 2.323(8) Å, average 2.305 Å]. Two pentagonal bipyramids sharing the common edge O(3)-O(3)^(a) form the centrosymmetrical peroxo-bridged diuranyl complex {(UO₂)₂O₂[OP(C₆H₅)₃]₆}^{2 +} with the [UO₂O₂UO₂]^{2 +} core. The length of the O(3)-O(3)^{( 9a )} edge is 1.426(15) Å.     

Solubility of Pu(IV) in Weakly Alkaline Solutions (pH 9-14) Containing Silicate Anions

Behavior of hydrated ^238-242Pu(IV) oxide in 0.09-0.9 M NaOH containing 1 ×10^{- 3} M Na2SiO3 and in 0.1-0.2 M NaClO₄ containing 1×10^{- 3}-0.09 M Na2SiO3 (pH 11 and 9) was studied radiometrically with the aid of a scintillation counter. In alkaline solutions with pH 13.8-11 and high Na₂SiO₃ content, the Pu(IV) solubility increases owing to the reaction Pu(IV) + nSiO₃ ^{2 -} = Pu^{I V}(SiO₃ ^{2 -}) _n . At pH 9, Na₂SiO₃ has virtually no effect on the Pu(IV) solubility.     

Tc(VII)-catalyzed oxidation of U(IV) with nitric acid in solution of TBP in <Emphasis Type="Italic">n</Emphasis>-dodecane

Oxidation of U(IV) with nitric acid in 30% solution of TBP in n-dodecane is catalyzed by Tc ions; the rate-determining steps are 3U(IV) + 2Tc(VII) → 3U(VI) + 2Tc(IV) and Tc(IV) + Tc(VII) → Tc(V) + Tc(VI). Oxidation of U(IV) is inhibited by the reaction product, HNO₂, which partially binds Tc(IV) ions (TcO²⁺) in an inert complex. The overall rate equation of U(IV) oxidation is-d[U(IV)]/dt = k ₁[U(IV)][Tc][HNO₃]^?3 ? k ₄[U(IV)]²[HNO₂]²[HNO₃]^?1, where k ₁ = 4.8 ± 1.0 mol²1^?2 min^?1 and k ₄ = (2.4 ± 1.0) × 10⁵ 1² mol^?2 min^?1 at 25°C, [H₂O] = 0.4 M ([Tc] is the total Tc concentration in the reaction mixture). Water and U(VI) have no effect on the reaction rate.     

Formation of Excited Uranyl in Oxidation of U(IV) with Oxygen in HClO4 Aqueous Solutions: I. Effect of pH on Kinetic and Chemiluminescence Parameters of the Reaction

Chemiluminescence accompanying U(IV) oxidation with atmospheric oxygen in 0.1-0.0004 M HClO₄ was studied. It was found that the electronically excited uranyl ion, (UO₂ ^{2 +})*, is the luminescence emitter. The maximum on the kinetic curve is due to accumulation in the solution of UO₂ ⁺ and H₂O₂, which are intermediates of U(IV) oxidation. The kinetic scheme of U^{4 +} reaction with O₂ suggests that uranyl excitation proceeds in the elementary stage of electron transfer from UO₂ ⁺ to the oxidant, which is OH radical. With increasing pH from 1 to 3.4, the rate constant of the chemiluminescent stage (k) of the reaction increases almost 50 times and the luminescence efficiency (_cl), 3 times. The effect of pH on the oxidation rate is due to the high reactivity of U^{4 +} hydrolysis products UOH³⁺ and U(OH)₂₂₊ with respect to O₂. The rate constant k of the reaction between U⁴⁺ and O₂ and the chemiluminescence efficiency are the least among the other U(IV) chemiluminescence reactions: at 298 K and 0.1 M HClO₄, k (l mol^{- 1} s^-1) is equal to 3, 36, 40, and 108 and _{c l}, to 7.4 × 10^{- 8}, 8.1 × 10^{- 5}, 1.6 × 10^{- 6}, and 3 × 10^{- 7} for O₂, XeO₃, H2O2, and HSO₅ ^- as oxidants, respec- tively. The activation energy of the chemiluminescent stage of U(IV) oxidation with oxygen in 0.001 M HClO₄ E _a is 90.5 kJ mol^-1 within the 285-310 K range.     

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 Technetium Reactions: XV. Tc(IV) Oxidation with Persulfate Ions in HClO<Subscript>4</Subscript> Solution

Tc(IV) is oxidized with persulfate ions in HClO₄ solution by reactions with both S₂O ₈ ²⁻ ion and product of its thermal decomposition, Caro acid, H₂SO⁵. The reaction rate at 35°C and solution ionic strength μ = 1 is described by the equation d[Tc(IV)]/dt = k ₁[Tc(IV)][S₂O ₈ ²⁻ ] + k ₃[Tc(IV)][HSO ₅ ⁻ ]/[H⁺], where k ₁ = 0.88±0.04 l mol⁻¹ min⁻¹ and k ₃ = 110±5 min⁻¹. With increasing ionic strength to μ = 2, both rate constants decrease (k ₁ = 0.58±0.08 l mol⁻¹ min⁻¹ and k ₃ = 52±2 min⁻¹ at 35°C). The activation energy of the overall reaction is 77.7±8.1 kJ mol⁻¹. The mechanisms of both reactions are discussed. __________ Translated from Radiokhimiya, Vol. 47, No. 2, 2005, pp. 145–149. Original Russian Text Copyright ? 2005 by V. Koltunov, Gomonova, G. Koltunov.     

Kinetics of Redox Reactions of U,Np, and Pu in TBP Solutions: IX. Reduction of Np(VI) with Dibenzylhydrazine

The kinetics of reduction of Np(VI) with dibenzylhydrazine in TBP nitric acid solutions was studied. At the reductant excess Np(V), nitrogen, and benzyl alcohol were the reaction products. At low HNO₃ concentration (<0.03 M), the reaction went to completion, while at a higher acid content in TBP the equilibrium was attained, shifting to Np(VI) with increasing acidity. Taking into account direct and reverse reactions, the rate of Np(VI) to Np(V) transformation was described by the equation -d[Np(VI)]/dt = k[Np(VI)]× [(C₆H₅CH₂)₂N₂H₂][H₂O]^0.4 - k ₃[Np(V)]²[HNO₃]^1.2, where k = 64±6 l^1.4 mol^{- 1.4} min^-1 and k ₃ = 4480± 450 l^2.2 mol^{- 2.2} min^-1 at 40°C. The activation energy of the direct reaction was E = 42.7±2.2 kJ mol^{- 1}. The dilution of TBP with n-dodecane did not affect the reaction rate. The reaction mechanism was discussed.