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1.
A. R. Felmy 《Journal of Radioanalytical and Nuclear Chemistry》2001,250(1):27-37
The effect of iron powder (Fe0) on the reduction of Pu(VI),Np(V), and U(VI) was investigated in dilute NaCl and synthetic brines. Thetotal concentrations and oxidation states of the actinides in these solutionswere monitored as functions of pC H +, Eh, and time using techniques includingVis/Near IR absorption spectrophotometry, solvent extraction, activity counting,and inductively coupled plasma spectroscopy-mass spectrometry (ICP-MS). Whenconcentrations were too low and the oxidation states could not be directlydetermined by spectrophotometry or solvent extraction, comparing the measuredconcentrations with the solubility of reference systems helped to define thefinal oxidation states. In general, the reduction was more rapid, and couldproceed further, in the dilute NaCl solution than in the brine solutions.The experimental observations can be summarized as follows: (1) in the diluteNaCl solutions (pC H + 7 to 12), all three actinides, Pu(VI), Np(V) and U(VI),were reduced to lower oxidation states (most likely the tetravalent state)within a few days to a few months in the presence of Fe0; (2) insynthetic brines containing Fe0 (pC H + 8 to 13), the reductionof Pu(VI) was much slower than in the dilute NaCl solution. The dominant oxidationstate of Pu in the brine solution was Pu(V), the concentration of which wascontrolled by the electrochemical potential and could probably be representedby a heterogeneous redox reaction PuO2 . xH2O(s) PuO2 + +e —; (3) in synthetic brines containing Fe0 (pC H + 8 to 13), Np(V) was probably reduced to Np(IV) and precipitatedfrom the solution; (4) in synthetic brines containing Fe0 (pC H+ 8 to 13), no significant reduction of U(VI) was observed within 55 days. 相似文献
2.
S. A. Perevalov G. I. Malofeeva E. V. Kuzovkina B. Ya. Spivakov 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(1):1-6
Solid-phase extraction of plutonium in different individual and mixed oxidation states from simulated groundwater (pH 8.5) was studied. The extraction of plutonium species was carried out in a dynamic mode using DIAPAK C16 cartridges modified by N-benzoylphenylhydroxylamine (BPHA). It was shown that the extent of recovery depends on the oxidation state of plutonium. The extraction of Pu(IV) was at the level of 98–99% regardless of the volume and flow-rate of the sample solution. Pu(V) was extracted by 90–95% and 75–80% from 10- and 100-mL aliquots of the samples, respectively, whereas the extraction of Pu(VI) did not exceed 45–50%. An equimolar mixture of Pu(IV), Pu(V), and Pu(VI) was extracted by 74%. The distribution coefficients (K d) and kinetic exchange capacities (S) of plutonium in various oxidation states were measured. It was found that during the sorption process, Pu(V) was reduced to Pu(IV) by 80–90% after an hour-long contact with the solid phase. Pu(VI) is reduced to Pu(V) by 34% and to Pu(IV) by 55%. In the case of mixed-valent solution of plutonium, only Pu(V) and Pu(IV) were found in the effluents. 相似文献
3.
J. T. Coates R. A. Fjeld A. Paulenova T. DeVol 《Journal of Radioanalytical and Nuclear Chemistry》2001,248(2):501-506
A system using an ion chromatograph coupled to a flow-cell scintillation detector for rapidly measuring the oxidation states of actinides at low concentrations (<10–6M) in aqueous solutions was evaluated. The key components of the system are a cation–anion separation column (Dionex, CS5) and a flow cell detector with scintillating cerium activated glass beads. The typical procedure was to introduce a 0.5 ml aliquot of sample spiked with actinides in the +III to +VI oxidation states into a 5 ml sample loop followed by 4 ml of synthetic groundwater simulant. Separation was achieved at a flow rate of 1 ml/min using an isocratic elution with oxalic, diglycolic, and nitric acids followed by distilled water. Tests were first conducted to determine elution times and recoveries for an acidic solution (pH 2) and a ground water simulant (pH 8) containing Am(III), Pu(IV), Th(IV), Pu(V), and U(VI). Then, an analysis was performed using a mixture of Pu(IV), Pu(V), and Pu(VI) in the ground water simulant and compared to results using the DBM extraction technique. Approximate elution times were the same for both the acidic solution and the ground water simulant. These were as follows: Pu(V) at 10 min, Am(III) at 15 min, Pu(IV) at 25 min, Th (IV) at 28 min and U(VI) at 36 min. Recoveries for the acidic solution were quantitative for U(VI) and Th(IV) and exceeded 80% for Am(III). Recoveries for the ground water simulant were quantitative for U(VI), but they were generally not quantitative for Th(IV), Pu(IV), and Am(III). For Th(IV) and Pu(IV), less than quantitative recoveries were attributed to the formation of neutral hydroxides and colloids; for Am(III) they were attributed to insoluble carbonates and/or hydroxycarbonates. When applied to the measurement of plutonium in the ground water simulant, the technique provided showed good agreement with the dibenzoylmethane (DBM) extraction technique, but it could not distinguish between Pu(V) and Pu(VI). This was likely due to the reduction of Pu(VI) to Pu(V) in the sample by the oxalic acid eluent. However, in spite of this limitation, the technique can be used to distinguish between Pu(IV) and Pu(V) in aqueous environmental samples within a pH range of 4 to 8 and an E
H range of -0.2 to 0.6 V, the predominance region for Pu(III), (IV), and (V). In addition, this technique can be used to corroborate oxidation state analysis from the dibenzoylmethane (DBM) extraction method for environmental samples. 相似文献
4.
Determination of plutonium oxidation states at trace levels pertinent to nuclear waste disposal 总被引:2,自引:0,他引:2
H. Nitsche S. C. Lee R. C. Gatti 《Journal of Radioanalytical and Nuclear Chemistry》1988,124(1):171-185
A scheme was developed for the determination of oxidation states of plutonium in environmental samples. The method involves a combination of solvent extractions and coprecipitation. It was tested on solutions with both high-level and trace-level concentrations. The scheme was used to determine Pu oxidation states in solutions from solubility experiments in groundwater from a potential nuclear waste disposal site. At steady-state conditions, Pu was found to be soluble predominantly as Pu(V) and Pu(VI). 相似文献
5.
M. H. Lee Y. J. Park W. H. Kim 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(2):375-382
Absorption spectroscopic properties for various Pu oxidation states in nitric and hydrochloric acid solutions were investigated
with UV-Visible spectrophotometry. As a result, it was confirmed that the intensities of the major absorption peaks had a
tendency to decrease for Pu(III), Pu(IV) and Pu(VI) in HCl and HNO3 media, and the major peak positions were shifted to longer or shorter wavelengths depending on the complexforming abilities
of Pu(III), Pu(IV) and Pu(VI) with the chloride or nitrate ion with increasing acid concentrations. The values of the wavelength
and the molar absorptivity for the principal peaks of Pu(III), Pu(IV) and Pu(VI) in NHO3 and HCl solutions were similar to those reported in other works. The values of the molar absorptivity for the principal peaks
of Pu(III), Pu(IV) and Pu(VI) in the HNO3 solution were a little higher than those in the HCl solution. 相似文献
6.
Sinkov SI Rapko BM Lumetta GJ Hay BP Hutchison JE Parks BW 《Inorganic chemistry》2004,43(26):8404-8413
This report describes affinity measurements for two, water-soluble, methyl-alkylated diamides incorporating the malonamide functionality, N,N,N',N' tetramethylmalonamide (TMMA) and a bicyclic diamide (1a), toward actinide metal cations (An) in acidic nitrate solutions. Ligand complexation to actinides possessing oxidation states ranging from +3 to +6 was monitored through optical absorbance spectroscopy, and formation constants were obtained from the refinement of the spectrophotometric titration data sets. Species analysis gives evidence for the formation of 1, 4, 1, and 2 spectrophotometrically observable complexes by TMMA to An(III, IV, V, and VI), respectively, while for 1a, the respective numbers are 3, 4, 2, and 2. Consistent with the preorganization of 1a toward actinide binding, a significant difference is found in the magnitudes of their respective formation constants at each complexation step. It has been found that the binding affinity for TMMA follows the well-established order An(V) < An(III) < An(VI) < An(IV). However, with 1a, Np(V) forms stronger complexes than Am(III). The complexation of 1a with Np(V) and Pu(VI) at an acidity of 1.0 M is followed by reduction to Np(IV) and Pu(IV), whereas TMMA does not perturb the initial oxidation state for these dioxocations. These measurements of diamide binding affinity mark the first time single-component optical absorbance spectra have been reported for a span of actinide-diamide complexes covering all common oxidation states in aqueous solution. 相似文献
7.
In a solvent intended for use within group actinide extraction CyMe4-BTBP and TBP are combined together in cyclohexanone. After irradiating the solvent in acid contact a latency period before extraction reduced the extraction capability of plutonium. This reduction was larger when the solvent was kept in contact with the acid after irradiation. The decrease in plutonium extraction could be an effect of both a reduced extraction performance of CyMe4-BTBP caused by hydrolysis as well as a shift in oxidation state of the plutonium as it was shown that oxidizing Pu(IV) to Pu(VI) decreased the extraction by the solvent. 相似文献
8.
A two-step flow-coulometry method has been developed for rapid determination of elements (plutonium, iron, etc) which exist in various oxidation states in solution, and applied to the determination of plutonium in 0.5M sulphuric acid medium. The first-step column electrode potential is fixed at between +0.10 and +0.35 V vs. Ag-AgCl, and all plutonium ions are reduced to Pu(III). The second-step column electrode potential is fixed at +0.75 V vs. Ag-AgCl, and Pu(III) which flows from the first column electrode is oxidized to Pu(IV). The quantity of plutonium is determined from the number of coulombs used in the oxidation. It is possible to eliminate interference by diverse ions by electroanalysis at the first column electrode. About a 10-mul sample is necessary and the electrolysis for determination is finished in 1 min. 相似文献
9.
By means of differential pulse polarography, Pu ions of different oxidation states have been investigated in 1M Na2CO3 solution. Redox reactions of Pu/III/, Pu/IV/, Pu/V/ and Pu/VI/, which are mostly of irreversible nature, have been observed within the potential range of the dropping mercury electrode /DME/, from 0 to –1.5 V, against a Ag/AgCl/NaCl (3M) reference electrode. Based on the peak potential observed for each reaction, the stability of a given oxidation state in the solution could be ascertained. The redox potential of the Pu/IV/–Pu/III/ pair, which was found to be –1.0 V, indicated that the Pu/IV/ carbonate complex was of high stability. The detection sensitivity of the Pu/IV/ ion was found to be 1×10–6M. 相似文献
10.
M. Alyapyshev V. Babain L. Tkachenko E. Kenf I. Voronaev D. Dar’in P. Matveev V. Petrov S. Kalmykov Y Ustynyuk 《Journal of Radioanalytical and Nuclear Chemistry》2018,316(2):419-428
Extraction of actinides from aqueous nitric acid by three different heterocyclic dicarboxamides (2,6-pyridinedicarboxamide, 2,2′-bipyridine-6,6′-dicarboxamide and 1,10-phenanthroline-2,9-dicarboxamides) was studied. It was shown that all studied ligands extract actinides at different oxidation states (U(VI), Np(V), Pu(IV), Am(III), Cm(III)) from acidic solutions. All studied diamides extract Am(III) better than Cm(III). Et(pHexPh)ClPhen contains electron-withdrawing chlorine atoms at the positions 4 and 7 of the phenanthroline moiety (SFAm/Cm = 4–6) and possesses the highest separation factor Am(III)/Cm(III). The studied ligands possess high extraction ability to all actinides present in HLW and therefore they could be used for simultaneous extraction of actinides in the GANEX-type process. 相似文献
11.
Lin Li Haijun Dang Qichu Xu Wengang Jiang Mei Li Jihong Zhang 《Journal of Radioanalytical and Nuclear Chemistry》2014,301(3):789-795
The extraction behavior of Pu(III), Pu(IV), Np(IV) and Np(V) with di(chlorophenyl)-dithiophosphinic acid (DCPDTPA) in toluene from nitric acid solutions was studied systematically. In aqueous solution with high nitric acid concentration, the extraction capability (represented by distribution ratio D) for Pu and Np in different valences with DCPDTPA comes as D Np(IV) > D Pu(IV) > D Np(V) > D Pu(III). A new radiochemical procedure for Np/Pu separation based on DCPDTPA extraction was proposed and tested with simulated samples. The recoveries of Np and Pu are as high as 80 % after the whole separation procedure, with the decontamination factor of trivalent lanthanide fission product element (e.g. Eu) greater than 1.5 × 104. The decontamination factor of Pu–Np is 2.0 × 103, while the decontamination factor of Np–Pu is greater than 4.8 × 103 after additional purification. 相似文献
12.
R. T. Chitnis S. G. Talnikar V. A. Thakur A. H. Paranjape 《Journal of Radioanalytical and Nuclear Chemistry》1979,49(1):63-70
The method for plutonium determination based on secondary controlled-potential coulometry, as described by SHULTS, is applied
for analysis in the range of 0.1–5 mg plutonium. The method involves the oxidation of plutonium to Pu(VI) with perchloric
acid followed by its reduction by an internally generated ferrous mediator. This is a two step procedure, involving the reduction
of Pu(VI) and Fe(III) to a mixture of Pu(III) and Fe(II), followed by the oxidation of Pu(III) and Fe(II) to Pu(IV) and Fe(III),
respectively. The net results is the reduction of Pu(VI) to Pu(IV), measured as the difference between the currents consumed
during the reduction and oxidation steps. The original method of SHULTS involves 10–25 mg plutonium for each determination.
Since the present method is intended for the analysis of smaller amounts of plutonium, the oxidation procedure described in
the original version had to be modified. The method is found to work satisfactorily with a precision better than 0.1% at 5
mg level and 1.2% for 0.1 mg plutonium. 相似文献
13.
Shekhar Kumar U. Kamachi Mudali 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(3):1951-1955
Hexavalent plutonium (Pu(VI)) is an important solute in the PUREX (plutonium uranium extraction) process. In 30 % TBP based PUREX solvent extraction system, distribution coefficient of Pu(VI) is much lower than that of Pu(IV). This lower distribution coefficient of Pu(VI) may cause unexpected Pu loss during primary HA extraction in low acid flowsheets. An empirical model for Pu(VI) distribution coefficients in 30 % TBP and its temperature dependency has been reported in this paper. Comparison with literature data revealed a reasonably good agreement between the reported experimental and model predicted values. 相似文献
14.
The complexation and solvent extraction of Eu(III) and actinides in different oxidation states (Am(III), Pu(IV), Np(V)) by bitopic molecules with a dipyridyl-phenanthroline cycle as nitrogen unit and one or two amido functions are described. The complexation has been studied in methanol-water solution with hydrophilic molecules to enhance knowledge about this new family of ligands and to identify the most interesting structural effect. Some extraction tests have been performed with lipophilic molecules of the family to check the possible utility of the new class of ligands under representative fuel reprocessing conditions. These first studies have demonstrated that the presence of a preorganized N-donors unit like dipyridyl-phenanthroline improves the ligand's affinity for actinides and its An/Ln selectivity. 相似文献
15.
The reliable separation of neptunium from dissolved nuclear fuel assumes the ability to maintain a preferred oxidation state. However, regardless of its initial redox speciation, a series of reactions occurs in nitric acid to create a mixture of oxidation states including Np(V), Np(VI) and sometimes Np(IV). To further complicate the situation, irradiated solutions such as fuel dissolution contain both transient and long-lived radiolysis products which may be strongly oxidizing or reducing. Thus, irradiation may be expected to impact the equilibrium distributions of the various neptunium valences.We have irradiated nitric acid solutions of neptunium with 60Co gamma-rays, and measured radiolytically-induced changes in neptunium valences, as well as the nitrous acid concentration, by UV/Vis spectroscopy. It was found that in 4 M HNO3 at low absorbed doses, the oxidizing radicals oxidized Np(V) to Np(VI). However, as the irradiation proceeded the concentration of nitrous acid became sufficient to reduce Np(VI) to Np(V), and then continued irradiation favored this reduction until an equilibrium was achieved in balance with the oxidation of Np(V) by nitric acid itself. The starting abundances of the two neptunium valences did not affect the final equilibrium concentrations of Np(V) and Np(VI), and no Np(IV) was detected. 相似文献
16.
S. A. Perevalov N. P. Molochnikova 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(3):603-608
The sorption of Pu(IV), polymeric Pu(IV), Pu(V) and Pu(VI) from the 0.1 M NaClO4 solution onto multiwalled carbon nanotubes was investigated. The kinetic study of the sorption process have shown that the
polymeric Pu(IV) has the highest sorption rate, while decrease of sorption rate for plutonium aqua-ions in the order Pu(VI) > Pu(IV) > Pu(V)
was found. Strong dependence of sorption kinetics of ionic plutonium species on pH was shown, in contrast to polymeric species,
that were shown to quantitatively sorb (99%) in the wide pH range (pH 2–10). Two different sorption mechanisms for ionic and
polymeric plutonium species were proposed: on the bases of sorption isotherms chemisorptions of plutonium aqua-ions onto carbon
nanotubes and through intermolecular interaction for the polymeric plutonium species was defined. Distribution coefficients
of plutonium in various oxidation states were found to increase with pH, showing the highest values for polymeric plutonium
sorption (K
d
= 2.4 × 105 mL g−1 at pH = 6). 相似文献
17.
Rios D Michelini MC Lucena AF Marçalo J Bray TH Gibson JK 《Inorganic chemistry》2012,51(12):6603-6614
The following monopositive actinyl ions were produced by electrospray ionization of aqueous solutions of An(VI)O(2)(ClO(4))(2) (An = U, Np, Pu): U(V)O(2)(+), Np(V)O(2)(+), Pu(V)O(2)(+), U(VI)O(2)(OH)(+), and Pu(VI)O(2)(OH)(+); abundances of the actinyl ions reflect the relative stabilities of the An(VI) and An(V) oxidation states. Gas-phase reactions with water in an ion trap revealed that water addition terminates at AnO(2)(+)·(H(2)O)(4) (An = U, Np, Pu) and AnO(2)(OH)(+)·(H(2)O)(3) (An = U, Pu), each with four equatorial ligands. These terminal hydrates evidently correspond to the maximum inner-sphere water coordination in the gas phase, as substantiated by density functional theory (DFT) computations of the hydrate structures and energetics. Measured hydration rates for the AnO(2)(OH)(+) were substantially faster than for the AnO(2)(+), reflecting additional vibrational degrees of freedom in the hydroxide ions for stabilization of hot adducts. Dioxygen addition resulted in UO(2)(+)(O(2))(H(2)O)(n) (n = 2, 3), whereas O(2) addition was not observed for NpO(2)(+) or PuO(2)(+) hydrates. DFT suggests that two-electron three-centered bonds form between UO(2)(+) and O(2), but not between NpO(2)(+) and O(2). As formation of the UO(2)(+)-O(2) bonds formally corresponds to the oxidation of U(V) to U(VI), the absence of this bonding with NpO(2)(+) can be considered a manifestation of the lower relative stability of Np(VI). 相似文献
18.
G. M. Nair G. R. Mahajan D. R. Prabhu 《Journal of Radioanalytical and Nuclear Chemistry》1995,191(2):323-330
The extraction behavior of U(VI) and Pu(IV) with dioctyloctanamide (DOOA), dioctylethylhexanamide (DOEHA) and diisobutylethylhexanamide (DIBEHA) was investigated from nitric acid medium. With DOOA, U(VI) extraction is higher than that for Pu(IV) upto 5M HNO3 and the trend is reversed at higher acid concentrations. Extraction yield of U(VI) is higher than that for Pu(IV) in the case of DOEHA and DIBEHA. DIBEHA extraction of Pu(IV) is found to be very small. The lower value of the distribution ratio for Pu(IV) with branched amides was attributed to steric reasons. The possibility of using these amides for separation of U(VI) and Pu(IV) without valency adjustment was explored. Both U(VI) and Pu(IV) are extracted as their disolvates by DOOA and DOEHA. 相似文献
19.
Antonio MR Williams CW Sullivan JA Skanthakumar S Hu YJ Soderholm L 《Inorganic chemistry》2012,51(9):5274-5281
A freshly prepared solution of Pu(VI) in 2 M NaOH was oxidized to Pu(VII), via ozonolysis, while simultaneously collecting X-ray absorption spectra. Analyses of the XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) data, acquired throughout the in situ experiments, show a dioxo coordination environment for Pu(VI), PuO(2)(2+), typical for it and the hexavalent actinyl species of U and Np, and its evolution into a tetraoxo-coordination environment for Pu(VII), PuO(4)(-), like that known for Np(VII). The EXAFS data provide average Pu-O distances of 1.79(1) and 1.88(1) ?, respectively. The second coordination shells, also fit as O atoms, provide Pu-O distances of 2.29-2.32 ? that are independent of the Pu oxidation state. The coordination numbers for the distant O atoms in sums with those for the nearest O atoms are consistent with 6-O environments for both Pu(VI) and Pu(VII) ions in accordance with their previously proposed speciation as [Pu(VI)O(2)(OH)(4)](2-) and [Pu(VII)O(4)(OH)(2)](3-), respectively. This solution speciation accounts precisely for the Pu(VI) and Pu(VII) coordination environments reported in various solid state structures. The Pu(VII) tetraoxo-dihydroxo anion was found to have a half-life of 3.7 h. Its instability is attributed to spontaneous reduction to Pu(VI) and not to a measurable extent of disproportionation. We found no direct evidence for Pu(VIII) in the X-ray data and, furthermore, the stoichiometry of the oxidation of Cr(III) by Pu is consistent with that expected for a valence-pure Pu(VII) preparation by ozonation and, in turn, stoichiometrically equivalent to the established Np(VII)/Cr(III) redox reaction. 相似文献
20.
Reduction kinetics of Pu(IV) by N,N-dimethylhydrazine (NNDMH) were studied by spectrophotometry, and the reduction rate equation
in 3M (mol/dm3) nitric acid was obtained. The reduction properties of NNDMH for U(VI), Np(VI), and Pu(IV) was studied in the mixture solution
of trin-butylphosphate diluted to 30 vol.% by n-dodecane (30% TBP) and 3M nitric acid. It was confirmed that NNDMH selectively
reduce Np(VI) to Np(V) without affecting the valences of U(VI) and Pu(IV) in a few minutes. Numerical simulation indicated
that 99.9% of Np was separated from U and Pu applying NNDMH for a mixer-settler. 相似文献