Electrochemical characterization of plutonium in n-tributyl phosphate.

This work investigates the electrochemical behavior of Pu(iv) and Pu(vi) complexes in n-tributylphosphate (TBP) as an entry to the electrochemical characterization of these complexes in organic extractants related to nuclear fuel reprocessing. Glassy carbon electrodes were used to show that Pu(iv) and Pu(vi) complexes display a reversible electrochemical reduction wave in TBP previously equilibrated with aqueous nitric acid solution. We investigated the reduction of Pu(iv) and Pu(vi) nitrato complexes extracted into TBP, with the aim to get thermodynamic (formal potential) and kinetic (diffusion coefficient) information about Pu(iv)/Pu(iii) and Pu(vi)/Pu(v) redox couples in the TBP medium. The formal potentials of the two redox couples were respectively 0.510 ± 0.005 and 0.478 ± 0.005 V per SCE in TBP equilibrated with 3 mol L-1 nitric acid at room temperature. The diffusion coefficient values of Pu(iv) and Pu(vi) species were estimated to be 0.72 × 10-6 and 0.77 × 10-6 cm2 s-1 respectively. Also, the Pu(iv) reduction showed a Nernstian dependence on the logarithm of nitric acid concentration in the organic phase, featuring the exchange of nitrates upon reduction of Pu(iv).

On the use of speciation techniques and ab initio modelling to understand tetravalent actinide behavior in a biological medium: An(IV)DTPA case.

In the case of an accidental nuclear event, contamination of human bodies by actinide elements may occur. Such elements have the particularity to exhibit both radiological and chemical toxicities that may induce severe damages at several levels, depending on the biokinetics of the element. In order to eliminate the actinide elements before they are stored in target organs (liver, kidneys, or bone, depending on the element), sequestering agents must be quickly injected. However, to date, there is still no ideal sequestering agent, despite the recent interest in this topic due to contamination concerns. DTPA (diethylene triamine pentaacetic acid) is currently generating interest for the development of oral or alternative self-administrable forms. Although biokinetics data are mostly available, molecular scale characterization of actinide-DTPA complexes is still scarce. Nevertheless, strong interest is growing in the characterization of An(IV)DTPA(-) complexes at the molecular level because this opens the way for predicting the stability constants of unknown systems or even for developing new analytical strategies aimed at better and more selective decorporation. For this purpose, Extended X-ray Absorption Fine Structure (EXAFS) and Ab Initio Molecular Dynamics (AIMD) investigations were undertaken and compared with capillary electrophoresis (CE) used in a very unusual way. Indeed, it is commonly believed that CE is incapable of extracting structural information. In capillary electrophoresis, the electrophoretic mobility of an ion is a function of its charge and size. Despite very similar ratios, partial separations between An(IV)DTPA(-) species (An(IV) = Th, U, Np, Pu) were obtained. A linear relationship between the electrophoretic mobility and the actinide--oxygen distance calculated by AIMD was evidenced. As an example, the interpolated U-O distances in U(IV)DTPA(-) from CE-ICPMS experiments, EXAFS, AIMD, and the relationship between the stability constants and the ratio z/dAn-O, are all in agreement. This results in the capability to evaluate the stability constants for the formation of Pa(IV)DTPA(-), Am(IV)DTPA(-) or Bk(IV)DTPA(-).

Speciation in aqueous solutions of nitric acid.

In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

Potential applications of sonochemistry in spent nuclear fuel reprocessing: a short review.

The industrial treatment of spent nuclear fuel is based upon a hydrometallurgical process in nitric acid medium. In order to minimize the volume of radioactive waste it seems interesting to generate the reactive species in situ in such solutions using ultrasonic irradiation without addition of salt-forming reagents. This review summarizes for the first time the versatile sonochemical processes with uranium, neptunium and plutonium in homogeneous nitric acid solutions and heterogeneous systems. The dissolution of refractory solids, ultrasonically driven liquid-liquid extraction and the sonochemical degradation of the volatile products of organic solvent radiolysis issued from PUREX process are considered. Also the guidelines for required further work to ensure successful application of the studied processes at industrial scale are discussed.

Anion effect on radiochemical stability of room-temperature ionic liquids under gamma irradiation.

Radiochemical stability of imidazolium-based ionic liquids constituted of the BuMeIm(+) cation and associated with four commonly used anions (X(-): Tf(2)N(-), TfO(-), PF(6)(-) and BF(4)(-)) has been investigated under gamma irradiation for high irradiation doses (up to 2.0 MGy). The anion effect has been examined by quantifying the radiolytic yields of disappearance for cation and anions and by identifying corresponding radiolysis products with several analytical techniques. On the one hand, a large number of radiolysis products are formed throughout the irradiation in ionic liquid solutions, resulting from reactions of primary generated species of cation and anion by indirect radiolysis. Primary generated species can react together throughout the irradiation by indirect radiolysis to form numerous radiolysis products in small quantities, indicating that several complex degradation pathways are involved for these radiation doses. This degradation pattern has been confirmed by identification of numerous gaseous radiolytic products. On the other hand, quantitative studies show that radiochemical stabilities of ionic liquids are in the same range of values as systems envisioned in nuclear fuel reprocessing with relatively low hydrogen yields. Indeed, this present work emphasizes the suitability of ionic liquids for applications in the nuclear fuel cycle.

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes.

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.

Local structure of actinide dioxide solid solutions Th(1-x)U(x)O2 and Th(1-x)Pu(x)O2.

Extended X-ray absorption fine structure (EXAFS) has been utilized to investigate the local atomic structure around Th, U, and Pu atoms in polycrystalline mixed dioxides Th(1-x)M(x)O2 (with M = U, Pu) for x ranging from 0 to 1. The composition dependence of the two first-coordination-shell distances was measured throughout the entire composition range for both solid solutions. The first-shell distances vary slightly across the solid-solution composition with values close to those of the pure dioxide parents, indicating a bimodal cation-oxygen distribution. In contrast, the second-shell distance varies strongly with composition, with values close to the weighted amount average distances. Nevertheless, in both systems, the lattice cell parameters, deduced from the first- and second-shell bond determined by EXAFS, are very close to those measured from X-ray diffraction (XRD). They vary linearly with composition, accurately following Vegard's law.

Spectroscopic and electrochemical studies of U(IV)-hexachloro complexes in hydrophobic room-temperature ionic liquids [BuMeIm][Tf2N] and [MeBu3N][Tf2N].

The behavior of U(IV) octahedral complexes [cation]2[UCl6], where the [cation]+ is [BuMeIm]+ and [MeBu3N]+, is studied using UV/visible spectroscopy, cyclic staircase voltammetry, and rotating disk electrode voltammetry in hydrophobic room-temperature ionic liquids (RTILs) [BuMeIm][Tf2N] and [MeBu3N][Tf2N], where BuMeIm+ and MeBu3N+ are 1-butyl-3-methylimidazolium and tri-n-butylmethylammonium cations, respectively, and Tf2N- is the bis(trifluoromethylsulfonyl)imide anion. The absorption spectra of [cation]2[UCl6] complexes in the RTIL solutions are similar to the diffuse solid-state reflectance spectra of the corresponding solid species, indicating that the octahedral complex UCl6(2-) is the predominant chemical form of U(IV) in Tf2N--based hydrophobic ionic liquids. Hexachloro complexes of U(IV) are stable to hydrolysis in the studied RTILs. Voltammograms of UCl(6)2- at the glassy carbon electrode in both RTILs and at the potential range of -2.5 to +1.0 V versus Ag/Ag(I) reveal the following electrochemical couples: UCl6-/UCl6(2-) (quasi-reversible system), UCl(6)2-/UCl6(3-) (quasi-reversible system), and UCl(6)2-/UCl6(Tf2N)x-3+x (irreversible reduction). The voltammetric half-wave potential, Ep/2, of the U(V)/U(IV) couple in [BuMeIm][Tf2N] is positively shifted by 80 mV compared with that in [MeBu3N][Tf2N]. The positive shift in the Ep/2 value for the quasi-reversible U(IV)/U(III) couple is much greater (250 mV) in [BuMeIm][Tf2N]. Presumably, the potential shift is due to the specific interaction of BuMeIm+ with the uranium-hexachloro complex in ionic liquid. Scanning the negative potential to -3.5 V in [MeBu3N][Tf2N] solutions of UCl6(2-) reveals the presence of an irreversible cathodic process at the peak potential equal to -3.12 V (at 100 mV/s and 60 degrees C), which could be attributed to the reduction of U(III) to U(0).

Kinetics of hydrazinium nitrate decomposition in nitric acid solutions under the effect of power ultrasound.

The effect of ultrasound (f = 20 kHz) on the decomposition of hydrazinium nitrate was investigated in a nitric acid medium. The kinetics of N2H5+ decomposition and initial HN3 formation increase in a linear manner with the HNO3 concentration (from 1 to 6 M) and with the ultrasonic intensity (from 0.5 to 3.1 W cm-2). Both rates were equal to that of HNO2 formation in the absence of N2H5+, indicating that the N2H5+ decomposition mechanism is the same as observed without ultrasound between HNO2 and N2H5+. The variation of the steady-state HN3 concentration with the HNO3 concentration and the ultrasonic intensity suggests the existence of a nonexplosive HN3 thermal decomposition mechanism in the cavitation bubble under the effect of ultrasound. It was also observed at ultrasonic intensities exceeding 3.5 W cm-2 that the decomposition of HN3 led to the accumulation of NH4+ in solution.

Preliminary results on the effect of power ultrasound on nitrogen oxide and dioxide atmosphere in nitric acid solutions.

The effect of ultrasound (20 kHz, 3 W cm-2) on the kinetics of HNO2 and H2O2 formation was investigated in a 1 M HNO3 medium for NO2-Ar and NO-Ar gas mixtures in various volume fractions (f(NO2) < 1.7 vol% and f(NO) < 1.1 vol%, respectively). The H2O2 formation rate measured in 1 M HNO3 in the presence of N2H5NO3 was observed to be much lower than that of HNO2 without N2H5NO3, and was relatively independent of the NO2 or NO gas volume fractions in the argon atmosphere. The HNO2 formation rate increased under ultrasound, and was higher with NO than with NO2. The induction period observed without ultrasound disappeared when ultrasound was applied. The first step in the sonochemical mechanism of HNO2 formation in the presence of NO2 involves thermal decomposition of NO2 into NO within the cavitation bubble. In the second step of HNO2 formation, NO reacts either with HNO3 in the cavitation bubble, or with NO2 in the cavitation bubble or at the bubble/solution interface.

Volatile metal beta-diketonates--new precursors for the sonochemical synthesis of nanosized materials--sonolysis of thorium(IV) beta-diketonates.

Ultrasonic irradiation (22 kHz, Ar atmosphere) of Th(IV) beta-diketonates Th(HFAA)4 and Th(DBM)4, where HFAA and DBM are hexafluoroacetylacetone and dibenzoylmethane respectively, causes them to decompose in hexadecane solutions, forming solid thorium compounds. The first-order rate constants for Th(IV) beta-diketonate degradation were found to be (9.3 +/- 0.8) x 10(-3) for Th(HFAA)4 and (3.8 +/- 0.4) x 10(-3) min-1 for Th(DBM)4, (T = 92 degrees C, I = 3 W cm-2). The rate of the sonochemical reaction increased with the rising beta-diketonate volatility and decreased with the rising hydrocarbon solvent vapor pressure. Solid sonication products consisted of a mixture of thorium carbide ThC2 and Th(IV) beta-diketonate partial degradation products. The average ThC2 particle size was estimated to be about 2 nm. ThC2 formation was attributed to the high-temperature reaction occurring within the cavitating bubble. The thorium beta-diketonate partial degradation products formed in the liquid reaction zones surrounding the cavitating bubbles.

Kinetics of nitrous acid formation in a two-phase tri-n-butylphosphate-diluent/aqueous nitric acid extraction system under the effect of power ultrasound

The kinetics of nitrous acid formation were investigated in two-phase tri-n-butylphosphate (TBP)-diluent/HNO3 (1.5-6.0 mol l-1) systems, where diluent is n-C16H34, n-C12H26, n-C9H20 and i-C8H18, under the effect of power ultrasound at 20 kHz frequency under Ar atmosphere. The rate of HNO2 sonochemical formation decreases with the rise in diluent vapor pressure. The HNO2 formed is distributed between the aqueous and organic phases due to its extraction with TBP. The kinetics of HNO2 sonochemical formation in the two-phase system exhibits induction periods due to NOx (NO + NO2) gas reactions in the HNO3 medium. This induction period decreases with increasing HNO3 concentration and ultrasound intensity. The HNO2 steady-state concentration was obtained under long-time sonication as the result of HNO2 sonochemical decomposition. HNO2 decomposes faster under sonication in the aqueous phase than in the organic phase.

Kinetics of nitrous acid formation in nitric acid solutions under the effect of power ultrasound.

Sonochemical nitrous acid formation was investigated in 0.1-4.0 mol dm(-3) aqueous nitric acid solutions under the effect of power ultrasound with 20 kHz frequency. HNO2 steady-state concentration was obtained under long-time sonication; the excess HNO2 formed is decomposed and evoluted from the solution as NO and NO2 gases. The HNO2 steady-state concentration and the HNO2 initial formation rate depend linearly on the HNO3 concentration and acoustic intensity (1.8-3.5 W cm(-2)) and decrease with rising temperature in the range 21-50 degrees C. The HNO2 formation rate depends on the type of saturating gas as follows: Ar > N2 > He > air. NO and O2 are the major gaseous products of HNO3 sonication. The NO2 accumulation of in the gas phase is observed only when the decomposition of HNO2 formed becomes noticeable. The gaseous products formation rates depend on the HNO3 concentration, acoustic intensity and the type of saturating gas. The mechanism of HNO2 sonochemical formation is assumed to be the thermal decomposition of HNO3 in the gaseous vicinity of collapsing bubbles or in the overheated liquid reaction zone surrounding the cavitational bubbles.