Insights into the Mechanism of Neptunium Oxidation to the Heptavalent State

Kravchuk, Dmytro V.; Augustine, Logan J.; Rajapaksha, Harindu; Benthin, Grant C.; Batista, Enrique R.; Yang, Ping; Forbes, Tori Z.

doi:10.1002/chem.202304049

Title: Insights into the Mechanism of Neptunium Oxidation to the Heptavalent State

Journal Article · 12 March 2024 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202304049 · OSTI ID:2323373

Kravchuk, Dmytro V. ^[1]; Augustine, Logan J. ^[2]; Rajapaksha, Harindu ^[1]; Benthin, Grant C. ^[1]; Batista, Enrique R. ^[3]; Yang, Ping ^[3];

^[1]

Department of Chemistry University of Iowa Iowa City Iowa 52242 United States
Department of Chemistry University of Iowa Iowa City Iowa 52242 United States, Theoretical Division Los Alamos National Laboratory Los Alamos New Mexico 87545 United States
Theoretical Division Los Alamos National Laboratory Los Alamos New Mexico 87545 United States

Abstract Neptunium can exist in multiple oxidation states, including the rare and poorly understood heptavalent form. In this work, we monitored the formation of heptavalent neptunium [Np(VII)O ₄ (OH) ₂ ] ³⁻ during ozonolysis of aqueous M OH ( M =Li, Na, K) solutions using a combined experimental and theoretical approach. All experimental reactions were closely monitored via absorption and vibrational spectroscopy to follow both the oxidation state and the speciation of neptunium guided by the calculated vibrational frequencies for various neptunium species. The mechanism of the reaction partly involves oxidative dissolution of transient Np(VI) oxide/hydroxide solid phases, the identity of which are dependent on the co‐precipitating counter‐cation Li ⁺ /Na ⁺ /K ⁺ . Additional calculations suggest that the most favorable energetic pathway occurs through the reaction of a [Np(V)O ₂ (OH) ₄ ] ³⁻ with the hydroxide radical to form [Np(VI)O ₂ (OH) ₄ ] ²⁻ , followed by an additional oxidation with HO⋅ to create [Np(VII)O ₄ (OH) ₂ ] ³⁻ .

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States); University of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

Grant/Contract Number:: 89233218CNA000001; AC52-06NA25396; SC0014664; SC0021420

OSTI ID:: 2323373

Report Number(s):: LA-UR--23-32946; e202304049

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 23 Vol. 30; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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