Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

Lines, Amanda M.; Adami, Susan R.; Casella, Amanda J.; Sinkov, Sergey I.; Lumetta, Gregg J.; Bryan, Samuel A.

doi:10.1002/elan.201700465

Title: Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

Journal Article · Wed Sep 20 00:00:00 EDT 2017 · Electroanalysis

DOI:https://doi.org/10.1002/elan.201700465· OSTI ID:1414529

Lines, Amanda M. ^[1]; Adami, Susan R. ^[1]; Casella, Amanda J. ^[1]; Sinkov, Sergey I. ^[1]; Lumetta, Gregg J. ^[1]; Bryan, Samuel A. ^[1]

Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352

The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1414529

Report Number(s):: PNNL-SA-127756; AF5805010

Journal Information:: Electroanalysis, Vol. 29, Issue 12; ISSN 1040-0397

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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