{gamma}-Radiolysis of NaCl Brine in the Presence of UO{sub 2}(s): Effects of Hydrogen and Bromide
- Institute for Radioactive Waste Disposal (FZK-INE), Forschungszentrum Karlsruhe / Research Center Karlsruhe, Helmholtz-Platz, Eggenstein-Leopoldshafen, D-76344 (Germany)
- Leibniz-Institut fuer Oberflaechenmodifizierung, IOM, Permoserstr. 15, Leipzig, D-04318 (Germany)
A concentrated NaCl solution was {gamma}-irradiated in autoclaves under a pressure of 25 MPa. A set of experiments were conducted in 6 mol (kg H{sub 2}O){sup -1} NaCl solution in the presence of UO{sub 2}(s) pellets; in a second set of experiments, {gamma}-radiolysis of the NaCl brine was studied without UO{sub 2}(s). Hydrogen, oxygen and chlorate were formed as long-lived radiolysis products. Due to the high external pressure, all radiolysis products remained dissolved. H{sub 2} and O{sub 2} reached steady state concentrations in the range of 5.10{sup -3} to 6.10{sup -2} mol (kg H{sub 2}O){sup -1} corresponding to a partial gas pressure of {approx}2 to {approx}20 MPa. Radiolytic formation of hydrogen and oxygen increased with the concentration of bromide added to solution. Both, in the presence of bromide, resulting in a relatively high radiolytic yield, and in the absence of bromide surfaces of the UO{sub 2}(s) samples were oxidized, and concentration of dissolved uranium reached the solubility limit of the schoepite / NaUO{sub 2}O(OH)(cr) transition. At the end of the experiments, the pellets were covered by a surface layer of a secondary solid phase having a composition close to Na{sub 2}U{sub 2}O{sub 7}. The experimental results demonstrate that bromide counteracts an H{sub 2} inhibition effect on radiolysis gas production, even at a concentration ratio of [H{sub 2}] / [Br{sup -}] > 100. The present observations are related to the competitive reactions of OH radicals with H{sub 2}, Br{sup -} and Cl{sup -}. A similar competition of hydrogen and bromide, controlling the yield of {gamma}-radiolysis products, is expected for solutions of lower Cl{sup -} concentration. (authors)
- Research Organization:
- Materials Research Society, 506 Keystone Drive, Warrendale, PA, 15086-7573 (United States)
- OSTI ID:
- 21062378
- Resource Relation:
- Conference: Symposium on Scientific Basis for Nuclear Waste Management, Boston - Massachusetts (United States), 27 Nov - 1 Dec 2006; Other Information: Country of input: France; 16 refs; Related Information: In: Proceedings of the symposium on Scientific Basis for Nuclear Waste Management XXX, by Dunn, Darrell [ed. Southwest Research Inst., San Antonio, Texas (United States)]; Poinssot, Christophe [ed. CEA-Saclay, 91191 Gif-sur-Yvette cedex (France)]; Begg, Bruce [ed. Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia)], v. 985, 663 pages.
- Country of Publication:
- United States
- Language:
- English
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