The kinetics of the reduction reaction of plutonium(IV) with N,N-dimethylhydroxylamine

Chen, Yanxin; Tang, Honbing; Liu, Jinping; He, Hanwei

doi:10.1007/s10967-011-1030-1

Cited by 9 publications

(7 citation statements)

References 21 publications

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“…In contrast to the reactions of Pu(IV) with 1,1-dimethylhydrazine and tert-butylhydrazine, which are accelerated with UO 2 2+ ions, in reduction of Np(VI) with diethylhydroxylamine [55] and of Pu(IV) with diethyl- [54] and dimethylhydroxylamine [50] no effect of U(VI), present in a concentration of up to 0.5 M, on the reaction rate was noted.…”

Section: Substituted Hydrazinesmentioning

confidence: 95%

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Organic reductants of Pu and Np ions in wet technology for spent nuclear fuel reprocessing

Marchenko

Alekseenko²,

Dvoeglazov

2015

Radiochemistry

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Scientific, technical, and patent information on the use of organic compounds as reductants of Pu and Np ions in wet technology for spent nuclear fuel reprocessing is summarized and correlated. Organic derivatives of hydrazine and hydroxylamine, and also oximes and urea derivatives at relatively low acidities and temperatures reduce Np(VI) to Np(V) and Pu(IV) to Pu(III). As the acidity and temperature are increased, Np(V) is slowly reduced to Np(IV). Alcohols, aldehydes, hydrocarbons, and acetic acid were identified among products of oxidation of the organic compounds in nitric acid medium. The above-named organic reductants can be used in different steps of the PUREX process: separation of Pu and Np from U in the first extraction cycle, purification of U to remove Np in the second cycle of uranium purification, and Pu stripping in the step of its final purification. Laboratory experiments performed on countercurrent extraction installations of mixersettlers and of centrifugal contactors demonstrated the possibility of reaching high separation factors of U from Pu and/or Np and high degrees of plutonium concentration to obtain Pu strips containing up to 150 g L -1 Pu.

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Section: Substituted Hydrazinesmentioning

confidence: 95%

“…Zhang et al [54] emphasize that the content of these ions in the solution solution acidity. Also, the reactions with methyl-, dimethyl-, and diethylhydroxylamines are inhibited by the reduction product, Pu(III) [46,49,50]. In the general form, the rate equation is presented as follows:…”

Section: Substituted Hydrazinesmentioning

confidence: 99%

Organic reductants of Pu and Np ions in wet technology for spent nuclear fuel reprocessing

Marchenko

Alekseenko²,

Dvoeglazov

2015

Radiochemistry

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“…For Advanced PUREX (Plutonium Uranium Reduction EXtraction) − and SUPERPUREX, the Np separation can be achieved in the PUREX process according to the extraction difference of tributyl phosphate (TBP) for three oxidation states (Np(VI) > Np(IV) ≫ Np(V)). Some highly efficient and green free-salt reductants have been studied to reduce Np(VI) in the experiment such as aldehydes, − hydroxylamine, − oximes, , hydrazine, − and their derivatives. Reduction of Np(VI) by butyraldehyde isomers had been studied in nitric acid solution and demonstrated that iso -butyraldehyde has a higher reduction rate than n -butyraldehyde, reflecting that the structures of the isomers affect the reduction ability of Np(VI) .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insights into the Reduction Mechanism of Np(VI) with Phenylhydrazine

Wang

et al. 2021

J. Phys. Chem. A

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Effectively adjusting and controlling the valence state of neptunium from the spent fuel reprocessing process is essential to separating neptunium. Hydrazine and its derivatives as free-salt reductants have been experimentally demonstrated to effectively reduce Np(VI) to Np(V). We have theoretically investigated the reduction mechanisms of Np(VI) with hydrazine and three derivatives (HOC2H4N2H3, CH3N2H3, and CHON2H3) in previous works. Herein, we further explored the reduction reaction of Np(VI) with phenylhydrazine (C6H5N2H3) including the free radical ion mechanism and the free radical mechanism. Potential energy profiles (PEPs) indicate that the rate-determining step of both mechanisms is the first stage. Moreover, for the free radical ion mechanism, phenylhydrazine possesses better reduction ability to Np(VI) compared to HOC2H4N2H3, CH3N2H3, and CHON2H3, which falls completely in line with the experimental results. Additionally, the analyses of the quantum theory of atoms in molecules (QTAIM), natural bond orbitals (NBOs), electron localization function (ELF), and localized molecular orbitals (LMOs) have been put forward to elucidate the bonding evolution for the structures of the reaction pathways. This work offers insights into the reduction mechanism of Np(VI) with phenylhydrazine from the theory point of view and contributes to design more high-efficiency reductants for the separation of U/Np and Np/Pu in spent fuel reprocessing.

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“…One important trend in the developing future reprocessing extraction processes is the use of high efficient salt-free reductants in U/Pu separation and purification process, such as butyraldehyde and isobutyraldehyde [8][9][10], hydrazine [11] and hydroxylamine [12][13][14][15][16] as well as their derivatives [17][18][19][20][21][22][23][24]. , -dimethylhydroxylamine (DMHAN) is one derivative of hydroxylamine in which two H atoms are both substituted by methyl group.…”

Section: Introductionmentioning

confidence: 99%

An advanced purex process based on salt-free reductants

Guoan

Tang

et al. 2014

Radiochimica Acta

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An advanced plutonium and uranium recovery process has been established based on two organic reductants, , -dimethylhydroxylamine (DMHAN) and methylhydrazine (MH), as U/Pu separation reagents. This Advanced Purex process based on Organic Reductants (APOR) is composed of three cycles, including U/Pu codecontamination/separation cycle, uranium purification cycle and plutonium purification cycle. Using DMHAN and MH as plutonium stripping reagents in the U/Pu codecontamination/separation cycle and plutonium purification cycle, the APOR process exhibits high performance with following highlights: 1) the process is much simpler because of the elimination of Tc scrubbing operation and the supplement extraction operation, 2) high efficiency of U/Pu separation can be achieved in the first cycle, 3) plutonium product solution of high concentration can be obtained in the Pu purification cycle with a simple extraction operation instead of circumfluent extraction or evaporation of the plutonium solution.

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The kinetics of the reduction reaction of plutonium(IV) with N,N-dimethylhydroxylamine

Cited by 9 publications

References 21 publications

Organic reductants of Pu and Np ions in wet technology for spent nuclear fuel reprocessing

Organic reductants of Pu and Np ions in wet technology for spent nuclear fuel reprocessing

Theoretical Insights into the Reduction Mechanism of Np(VI) with Phenylhydrazine

An advanced purex process based on salt-free reductants

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