Mechanisms of neptunium redox reactions in nitric acid solutions

Chatterjee, Sayandev; Bryan, Samuel A.; Casella, Amanda J.; Peterson, James M.; Levitskaia, Tatiana G.

doi:10.1039/c6qi00550k

Mechanisms of neptunium redox reactions in nitric acid solutions

Journal Article · Sun Jan 01 04:00:00 EST 2017 · Inorganic Chemistry Frontiers (Online)

DOI:https://doi.org/10.1039/c6qi00550k· OSTI ID:1378005

; Bryan, Samuel A.; Casella, Amanda J.; Peterson, James M.; Levitskaia, Tatiana G.

First transuranium element neptunium (Np) exhibits complicated behavior in acidic solutions because it can adopt wide range of oxidation states typically from +3 to +6 and coordinate large variety of ligands. In particular, accurate determination of Np redox potentials in nitric acid solutions is challenging due to overlapping chemical and electrochemical reactions leading to significant experimental uncertainties. Furthermore, over past decades spectrophotometry has been extensively applied to identify and characterize Np solution species in different oxidation states. However, relevant spectral database of Np in nitric acid solutions that can serve for the reference purposes has yet to be established due to the experimental difficulty to isolate and stabilize Np species in pure oxidation states without compromising solution optical properties. This work demonstrates that combination of voltammetry and controlled-potential in situ thin-layer spectropotentiometry overcomes these challenges so that Np species in pure +3, +4, +5, or +6 oxidation states were electrochemically generated in the systematically varied 0.1 – 5 M nitric acid solutions, and corresponding vis-NIR spectral signatures were obtained. In situ optical monitoring of the interconversion between adjacent Np oxidation states resulted in elucidation of the mechanisms of the involved redox reactions, in-depth understanding of the relative stability of the Np oxidation states, and allowed benchmarking of the redox potentials of the NpO22+/NpO2+, NpO2+/Np4+ and Np4+/Np3+ couples. Notably, the NpO2+/Np4+ couple was distinguished from the proximal Np4+/Np3+ process overcoming previous concerns and challenges encountered in accurate determination of the respective potentials.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1378005

Report Number(s):: PNNL-SA-122161

Journal Information:: Inorganic Chemistry Frontiers (Online), Journal Name: Inorganic Chemistry Frontiers (Online) Journal Issue: 4 Vol. 4; ISSN 2052-1553; ISSN ICFNAW

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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