Effect of metal complexation on diglycolamide radiolysis: a comparison between <i>ex situ</i> gamma and <i>in situ</i> alpha irradiation

Kimberlin, Ashleigh; Saint-Louis, Georges; Guillaumont, Dominique; Camès, B.; Guilbaud, Philippe; Berthon, Laurence

doi:10.1039/d1cp05731f

Cited by 16 publications

(34 citation statements)

References 102 publications

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“…Less than 0.5% of the Cf(SCN) 2+ complex would be present based on the reported binding constant (β) = 1.57 value at 30 °C . By monitoring the decrease in the (SCN) 2 •– radical absorption intensity at 470 nm with added Cf(III), the standard competition kinetics equation can be applied where Abs(0) is the peak intensity in the absence of any Cf(III), and Abs is the reduced intensity when Cf(III) is present (Figure ). In the absence of a measured Abs(0) value, we can rearrange this equation to give with a plot of 1/Abs versus [Cf(III)]/[SCN – ] giving a linear fit slope/intercept ratio of k 13 / k 12 .…”

Section: Resultsmentioning

confidence: 99%

“…The observed NO 3 • radical transient decays were fit to a mixed-order decay function where Abs is the initial NO 3 • radical absorption, and B allows for any limiting product absorption (baseline shift). The k 18 rate coefficient corresponded to the dimerization reaction , …”

Section: Resultsmentioning

confidence: 99%

“…•− radical absorption intensity at 470 nm with added Cf(III), the standard competition kinetics equation can be applied 33 k k…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…• radical absorption, and B allows for any limiting product absorption (baseline shift). The k 18 rate coefficient corresponded to the dimerization reaction 33,53 k NO NO N O 7.9 10 M s…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The majority of actinide radiation chemistry knowledge is concentrated toward the beginning of the series, − for which radiation-induced reactions have been demonstrated to significantly impact the accessibility and lifetime of actinide oxidation states at both ultrafast (pico- to microseconds) − and steady-state timescales. − Furthermore, there is precedence for these radiation-induced actinide redox reactions altering the radiolytic integrity of their corresponding complexes, relative to the free ligand, through facilitation of inner- versus outer-sphere reaction pathways. − Concerning the late actinidesamericium (Am) onwardminimal information is available, and yet it remains an area of significant fundamental interest owing to paradigm shifts in the oxidation state metastability from trivalency to divalency in californium (Cf), − and an accessible tetravalent state for berkelium (Bk) . Both of these redox states are at odds to their predominantly trivalent neighbors, Am and curium (Cm) .…”

Section: Introductionmentioning

confidence: 99%

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Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

et al. 2022

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Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New and first-of-a-kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (eaq –) and hydrogen atom (H•), demonstrating a significant reactivity (up to 1011 M–1 s–1) indicative of a preference of these metals to adopt divalent states. Additionally, we report the first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by a reaction with hydroxyl (•OH) and nitrate (NO3 •) radicals, which also exhibited fast reactivity (ca. 108 M–1 s–1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…•− radical absorption intensity at 470 nm with added Cf(III), the standard competition kinetics equation can be applied 33 k k…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…• radical absorption, and B allows for any limiting product absorption (baseline shift). The k 18 rate coefficient corresponded to the dimerization reaction 33,53 k NO NO N O 7.9 10 M s…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

et al. 2022

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Effect of Europium Complexation on N,N,N′,N′-Tetraoctyldiglycolamide Degradation Against Gamma Radiation

Sánchez-García,

Galán

2023

Arab J Sci Eng

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Diglycolamide extractants (DGAs) are playing an important role for many of aqueous separation processes under development for the advanced nuclear fuel cycle. This family of ligands exhibits excellent extracting and resistant properties, with TODGA (N,N,N′,N′-tetraoctyldiglycolamide) being a particularly successful extractant studied intensively in recent decades. Nowadays, the main issues for TODGA-based solvents are related to the understanding and simulation of the radiolytic degradation under realistic conditions, which is limiting aspect for the development of an advanced aqueous nuclear separation process. In that sense, in this work, TODGA ligand stability, solvent composition and performance were evaluated considering the effect of metal complexation under gamma radiation. For that, the irradiation of a TODGA solvent in the presence of Eu metal was carried out, varying the ligand/metal ratio. The goal was to not only study TODGA degradation using HPLC–MS technique but also to identify and quantify its degradation compound under these experimental conditions. The results revealed a protection of TODGA molecules due to metal ion complexation, with no observed changes in the degradation pathway, as confirmed by the quantification of formed degradation compounds.

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Dioctyl ether radiolysis under used nuclear fuel reprocessing conditions: Foundational knowledge for the development of sacrificial ligand grafts

Horne,

Morco,

Cook

et al. 2023

Radiation Physics and Chemistry

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Effect of metal complexation on diglycolamide radiolysis: a comparison between ex situ gamma and in situ alpha irradiation

Abstract: Radiolytic degradation is an important aspect to consider when developping a ligand or a complexant for radionucleides. Diglycolamide extractants (DGAs) have been playing an important role in many partition processes...

Cited by 16 publications

References 102 publications

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Effect of Europium Complexation on N,N,N′,N′-Tetraoctyldiglycolamide Degradation Against Gamma Radiation

Dioctyl ether radiolysis under used nuclear fuel reprocessing conditions: Foundational knowledge for the development of sacrificial ligand grafts

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