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The redox chemistry of neptunium in γ-irradiated aqueous nitric acid

  • Bruce J. Mincher , Martin Precek , Stephen P. Mezyk , Gracy Elias , Leigh R. Martin and Alena Paulenova
Published/Copyright: March 25, 2013

Abstract

The redox chemistry of neptunium in irradiated 4 M nitric acid was investigated using γ-ray irradiation and UV/Vis spectroscopic measurements. Irradiation caused changes in the abundances of Np(V) and Np(VI) regardless of the initial fractional components of these oxidation states. At low absorbed doses Np(V) was oxidized to Np(VI) in irradiated solution, due to its reaction with oxidizing, radiolytically-produced, free radicals. However, when sufficient radiolytically-produced nitrous acid accumulated, the reduction of Np(VI) to Np(V) occurred, even at this high nitric acid concentration. Neptunium(IV) was not produced. A kinetic model which incorporates the standard water radiolysis reactions, estimated radical yields for 4 M HNO3, and rate constants for neptunium reactions available from the literature was used to successfully reproduce the experimental results.


* Correspondence address: Idaho National Engineering and Environmental Laboratory, P.O. Box 1625, Idaho Falls ID 83415-6180, U.S.A.,

Published Online: 2013-03-25
Published in Print: 2013-04

© by Oldenbourg Wissenschaftsverlag, München, Germany

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