Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 4, 2017
Previous Article Next Article

Mechanisms of neptunium redox reactions in nitric acid solutions

Author affiliations

Abstract

The first transuranium element neptunium (Np) exhibits complicated behavior in acidic solutions as it adopts a wide range of oxidation states typically from +3 to +6 and coordinates with a large variety of ligands. In particular, the accurate determination of Np redox potentials in nitric acid solutions is challenging due to overlapping chemical and electrochemical reactions leading to significant experimental uncertainties. Over the past several decades, spectrophotometry has been extensively applied to identify and characterize Np solution species in different oxidation states. However, relevant spectral databases of Np in nitric acid solutions that can serve for reference purposes are yet to be established due to the experimental difficulty in isolating and stabilizing Np species in pure oxidation states without compromising their solution optical properties. This work demonstrates that a combination of voltammetry and controlled-potential in situ thin-layer spectropotentiometry overcomes these challenges, and vis–NIR spectra of electrochemically generated Np species in pure +3, +4, +5, or +6 oxidation states in the systematically varied 0.5–4 M nitric acid solutions 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 and an 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 the accurate determination of the respective potentials.

Graphical abstract: Mechanisms of neptunium redox reactions in nitric acid solutions

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 01 Dec 2016, accepted on 01 Feb 2017 and first published on 07 Feb 2017


Article type: Research Article
DOI: 10.1039/C6QI00550K
Citation: Inorg. Chem. Front., 2017,4, 581-594
  •   Request permissions

    Mechanisms of neptunium redox reactions in nitric acid solutions

    S. Chatterjee, S. A. Bryan, A. J. Casella, J. M. Peterson and T. G. Levitskaia, Inorg. Chem. Front., 2017, 4, 581
    DOI: 10.1039/C6QI00550K

Search articles by author