The Peroxy Complexes of Plutonium (IV)

Connick, Robert E.; McVey, W.H.

doi:10.1021/ja01173a003

Cited by 20 publications

(23 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The sonochemical reduction of Pu(IV) follows a first-order reaction law in agreement with Fig. [8][9][10][11] † Under these conditions, the measured apparent rate constant is ∼5.7 × 10 −3 min −1 .…”

Section: Papersupporting

confidence: 79%

“…Pu(IV) reduction results from the formation of peroxy complexes that decompose in acidic media. 2,[8][9][10][11] Using these conditions, plutonium may therefore be considered as a decomposition catalyst for H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

“…However, Pu(IV) accumulation is generated through Pu(V) dismutation because of its strong proton dependency and the higher kinetics required to break oxo bonds. 2,[8][9][10][11] Using these conditions, plutonium may therefore be considered as a decomposition catalyst for H 2 O 2 . 1,3,8,9 The shifting of this ratio is highly dependent upon the experimental conditions such as the temperature, acidity, counter-ion, or reactant concentrations.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Sonochemical redox reactions of Pu(iii) and Pu(iv) in aqueous nitric solutions

et al. 2015

View full text Add to dashboard Cite

The behavior of Pu(iv) and Pu(iii) was investigated in aqueous nitric solutions under ultrasound irradiation (Ar, 20 kHz). In the absence of anti-nitrous reagents, ultrasound has no effect on Pu(iv), while Pu(iii) can be rapidly oxidized to Pu(iv) due to the autocatalytic formation of HNO(2) induced by HNO(3) sonolysis. In the presence of anti-nitrous reagents (sulfamic acid or hydrazinium nitrate), Pu(iv) can be sonochemically reduced to Pu(iii). The reduction follows a first order reaction law and leads to a steady state where Pu(iv) and Pu(iii) coexist in solution. The reduction process is attributed to the sonochemical generation of H(2)O(2) in solution. The kinetics attributed to the reduction of Pu(iv) are however higher than those related to the formation of H(2)O(2) which, after several hypotheses, is explained by the sonochemical erosion of the titanium-based sonotrode. Titanium particles thereby generated can be solubilized under ultrasound and generate Ti(iii) as an intermediate species, a strong reducing agent able to react with Pu(iv).

show abstract

Section: Papersupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Sonochemical redox reactions of Pu(iii) and Pu(iv) in aqueous nitric solutions

et al. 2015

View full text Add to dashboard Cite

show abstract

“…The present results fit into the picture drawn by various authors over the last 50 years: Connick and coworkers reported [17] that in solutions with approximately 5% polymeric plutonium, disproportionation was violated. Costanzo [18] observed excess reduction of Pu(V) in rather concentrated solutions which were oversaturated with respect to formation of Pu(IV) hydrous oxide and most likely contained Pu(IV) polymers or colloids.…”

Section: Discussionsupporting

confidence: 92%

The redox potential of Pu containing acidic solutions and the fate of "Pu(IV)-colloids": Direct measurement versus optical absorption spectroscopy

Icker¹,

Walther²,

Neck³

et al. 2010

IOP Conf. Ser.: Mater. Sci. Eng.

View full text Add to dashboard Cite

“…The chemistry of plutonium and H 2 O 2 is very complicated. Pu (IV) peroxides have been characterized in the literature under acidic conditions[25]. The structure of neptunium(V,VI) cations and their solution chemistry can be analogous to that of UO 2 2+…”

mentioning

confidence: 99%

Corrosion of commercial spent nuclear fuel. 2. Radiochemical analyses of metastudtite and leachates

McNamara¹,

Hanson²,

Buck³

et al. 2005

Radiochimica Acta

View full text Add to dashboard Cite

Immersing commercial spent nuclear fuel (CSNF) in deionized water produced two corrosion products after a 2-year contact period. Suspensions of aggregates were observed to form at the air-water interface for each of five samples. These suspended aggregates were characterized by X-ray diffraction (XRD) to be metastudtite (UO 4 ·2H 2 O), while the corrosion present on the surface of the fuel itself was determined to be studtiteThe presence of unreacted UO 2 matrix was below the limits of detection by XRD for the three samples examined. The result prompted a radiochemical analysis of the solids collected from the sample air-water interface. The analysis indicated that high concentrations of 90 Sr, 137 Cs, and 99 Tc, relative to the fuel inventory, had concentrated at the air-water interface along with the aggregates of metastudtite. Concentrations of 241 Am were at least two orders of magnitude lower than expected in these solids, and retention of 237 Np and 239 Pu into the corrosion product was observed. The combined radiochemical analyses of the air-water interface aggregates and leachate samples are a rare example of radionuclide partitioning to an alteration phase and may provide preliminary evidence for mechanisms that give rise to such noticeable departures from fuel-inventory values. The leachate radiochemical data are compared to existing data from hydration of the same CSNF.

show abstract

The Peroxy Complexes of Plutonium (IV)

Cited by 20 publications

References 0 publications

Sonochemical redox reactions of Pu(iii) and Pu(iv) in aqueous nitric solutions

Sonochemical redox reactions of Pu(iii) and Pu(iv) in aqueous nitric solutions

The redox potential of Pu containing acidic solutions and the fate of "Pu(IV)-colloids": Direct measurement versus optical absorption spectroscopy

Corrosion of commercial spent nuclear fuel. 2. Radiochemical analyses of metastudtite and leachates

Contact Info

Product

Resources

About