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Radiolysis of aqueous solution of plutonium; Radiolyse des solutions aqueuses de plutonium

Abstract

This study is concerned first with the effects of gamma rays on plutonium aqueous solutions at various valency states, in presence of sulfuric, perchloric, nitric and hydrochloric acids. The main feature is the reduction of Pu VI into Pu V, followed by dismutation from V to IV and VI. For sulfuric and perchloric acid solutions (0,2 N) the following process is given: radiolysis of water produces OH, H{sub 2}O{sub 2}, H and H{sub 2}. H and H{sub 2}O{sub 2} reduce Pu VI while Pu V is oxidised by OH radicals. However the reaction of hydrogen peroxide is slow and leads to an after effect. A parallel study of the action of H{sub 2}O{sub 2} has given a confirmation. Spectrophotometric measurements were carried out on disappearance of Pu VI and formation of Pu IV and it was possible to make determination of G{sub H{sub 2}}{sub O{sub 2}} = 0,8 and G{sub H} - G{sub OH} = 0,8. G{sub H{sub 2}} = 0,41 was measured by gas analysis. The calculation of G{sub {sup -}}{sub H{sub 2}}{sub O} gave 4,35. The re-oxidation of Pu V is dependant on the concentration of sulfate ions. In perchloric acid solution reduction goes on to Pu Ill.  More>>
Authors:
Pages nee Flon, M [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Jul 01, 1960
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-1420
Resource Relation:
Other Information: TH: These ES sciences physiques; 48 refs
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; ALPHA BEAMS; ALPHA SOURCES; AQUEOUS SOLUTIONS; GAMMA RADIATION; GAMMA SOURCES; HOT ATOM CHEMISTRY; IRRADIATION DEVICES; PERCHLORIC ACID; PEROXIDES; PLUTONIUM; PLUTONIUM COMPOUNDS; PLUTONIUM IONS; RADIATION CHEMISTRY; RADIOLYSIS; REDOX REACTIONS; SULFURIC ACID; VALENCE; WATER CHEMISTRY
OSTI ID:
20943000
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France); Faculte des Sciences de l'Universite de Paris, 75 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR07R1420096453
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
80 pages
Announcement Date:
Dec 13, 2007

Citation Formats

Pages nee Flon, M. Radiolysis of aqueous solution of plutonium; Radiolyse des solutions aqueuses de plutonium. France: N. p., 1960. Web.
Pages nee Flon, M. Radiolysis of aqueous solution of plutonium; Radiolyse des solutions aqueuses de plutonium. France.
Pages nee Flon, M. 1960. "Radiolysis of aqueous solution of plutonium; Radiolyse des solutions aqueuses de plutonium." France.
@misc{etde_20943000,
title = {Radiolysis of aqueous solution of plutonium; Radiolyse des solutions aqueuses de plutonium}
author = {Pages nee Flon, M}
abstractNote = {This study is concerned first with the effects of gamma rays on plutonium aqueous solutions at various valency states, in presence of sulfuric, perchloric, nitric and hydrochloric acids. The main feature is the reduction of Pu VI into Pu V, followed by dismutation from V to IV and VI. For sulfuric and perchloric acid solutions (0,2 N) the following process is given: radiolysis of water produces OH, H{sub 2}O{sub 2}, H and H{sub 2}. H and H{sub 2}O{sub 2} reduce Pu VI while Pu V is oxidised by OH radicals. However the reaction of hydrogen peroxide is slow and leads to an after effect. A parallel study of the action of H{sub 2}O{sub 2} has given a confirmation. Spectrophotometric measurements were carried out on disappearance of Pu VI and formation of Pu IV and it was possible to make determination of G{sub H{sub 2}}{sub O{sub 2}} = 0,8 and G{sub H} - G{sub OH} = 0,8. G{sub H{sub 2}} = 0,41 was measured by gas analysis. The calculation of G{sub {sup -}}{sub H{sub 2}}{sub O} gave 4,35. The re-oxidation of Pu V is dependant on the concentration of sulfate ions. In perchloric acid solution reduction goes on to Pu Ill. Cl{sup -} and NO{sub 3}{sup -} ions inhibit the reduction and even suppress it. The effect of alpha particles both from plutonium and from polonium is very similar to the effect of hydrogen peroxyde. Induction time were observed mainly in presence of HSO{sub 4}{sup -}, depending on the accumulation of H{sub 2}O{sub 2} and (or) of plutonium peroxide. At low acidities, Pu IV peroxide seems to lead to polymer forms. In the more simple cases (H{sub 2}SO{sub 4} and HClO{sub 4} 0,2N), the following yields were found: G (equivalent reduced) = 3.2, G{sub H{sub 2}}{sub O{sub 2}} = 1.35, G{sub H{sub 2}} = 1.6 and G{sub H} - G{sub OH} = 0.1, assuming G{sub HO{sub 2}} = 0.2; and the usual hypothesis on radiolysis of water by alpha particles. Radiation induced oxidation of Pu III into Pu IV was also observed in H{sub 2}SO{sub 4} and HNO{sub 3} aqueous solutions, and reduction of IV into III was measured with HClO{sub 4}. (author) [French] On a etudie l'action des rayons gamma sur les solutions aqueuses de plutonium a divers etats de valence, en milieu sulfurique, perchlorique, nitrique et chlorhydrique. Le phenomene principal est la reduction de Pu VI en Pu V suivie de la dismutation de la valence V en VI et IV. Pour les solutions d'acide sulfurique et perchlorique 0,2N on a donne le mecanisme des reactions: la radiolyse de l'eau conduit aux produits OH, H{sub 2}O{sub 2}, H et H{sub 2}. Pu VI est reduit par H and H{sub 2}O{sub 2} tandis que Pu V est reoxyde par OH. Cependant l'action de l'eau oxygenee est lente et provoque un effet prolonge. Une etude menee parallelement sur l'action de H{sub 2}O{sub 2} a confirme ceci. Les mesures de disparition de Pu VI et d'apparition de Pu IV faites par spectrophotometrie ont conduit a determiner G{sub H{sub 2}}{sub O{sub 2}} = 0,8 et G{sub H} - G{sub OH} = 0,8. Par microanalyse de gaz on a mesure G{sub H{sub 2}} = 0,41. Ces donnees permettent de calculer le rendement de radiolyse de l'eau G{sub {sup -}}{sub H{sub 2}}{sub O} = 4,35. Les ions sulfate ont une influence complexe sur la reoxydation de Pu V comme le montrent les resultats obtenus sur des solutions plus concentrees en H{sub 2}SO{sub 4}. La reduction se poursuit jusqu'a la valence Ill en milieu perchlorique. Les ions Cl{sup -} et surtout NO{sub 3}{sup -} inhibent la reduction et peuvent la supprimer completement. L'action des particules {alpha} du plutonium et du polonium est tres analogue a celle de l'eau oxygenee. La reduction a lieu apres des periodes d'induction plus ou moins longues selon l'anion (surtout HSO{sub 4}{sup -} ). Elles sont liees a l'accumulation de H{sub 2}O{sub 2} et (ou) de peroxyde de plutonium. Aux faibles acidites le peroxyde de Pu IV a tendance a conduire a des formes polymerisees. Dans les cas les plus simples (H{sub 2}SO{sub 4} et HClO{sub 4} 0,2N) les rendements suivants ont ete obtenus ou calcules: G (reduction en equivalents) = 3,2, G{sub H{sub 2}}{sub O{sub 2}} = 1.35, G{sub H{sub 2}} = 1.6 et G{sub H} - G{sub OH} = 0.1, en supposant que G{sub HO{sub 2}} = 0,2. On a pris les hypotheses habituellement admises sur la radiolyse de l'eau par les rayons {alpha}. L'oxydation de Pu III en Pu IV par les rayonnements {alpha} ete egalement observee en presence de H{sub 2}SO{sub 4} et HNO{sub 3} tandis que la reduction de Pu IV en Pu III etait mesuree en milieu perchlorique. (auteur)}
place = {France}
year = {1960}
month = {Jul}
}