Title :

Reactivity of Ru oxides with air radiolysis products investigated by theoretical calculations

Author(s) :

Miradji, Faoulat [Auteur correspondant]
Laboratoire d'étude de transfert des radioéléments [IRSN/PSN-RES/SAM/LETR]
Physico-Chimie Moléculaire Théorique [PCMT]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Sidi, Souvi [Auteur]
Laboratoire d'étude de transfert des radioéléments [IRSN/PSN-RES/SAM/LETR]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Cantrel, Laurent [Auteur]
Laboratoire d'étude de transfert des radioéléments [IRSN/PSN-RES/SAM/LETR]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Louis, Florent [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Vallet, Valérie [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]

Journal title :

Journal of Nuclear Materials
558

Pages :

153395

Publisher :

Elsevier

Publication date :

2022-01-15

ISSN :

0022-3115

HAL domain(s) :

Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

Quantitative predictions of the release of volatile radiocontaminants of ruthenium (Ru) in the environment from either nuclear power plants (NPP) or fuel recycling accidents present significant uncertainties while estimated ...
Show more >Quantitative predictions of the release of volatile radiocontaminants of ruthenium (Ru) in the environment from either nuclear power plants (NPP) or fuel recycling accidents present significant uncertainties while estimated by severe accidents nuclear analysis codes. Observations of Ru from either experimental or modeling works suggest that the main limitations relate to the poor evaluation of the kinetics of gaseous Ru in the form of RuO₃ and RuO₄. This work presents relativistic correlated quantum chemical calculations performed to determine the possible reactions pathways leading to the formation of gaseous Ru oxides under NPP severe accident conditions, as a result of reactions of RuO₂ gaseous with air radiolysis products, namely nitrous and nitrogen oxides. The geometries of the relevant species were optimized with the TPSSh-5%HF functional of the density, while the total electronic energies were computed at the CCSD(T) level with extrapolations to the complete basis set CBS limit. The reaction pathways were fully characterized by localizing the transition states and all intermediate structures using the internal coordinate reaction algorithm (IRC). The rate constants were determined over the temperature range 250-2500 K. It is revealed that the less kinetically limiting pathway to form Ru gaseous fraction is the oxidation of Ru by nitrogen oxide, corroborating experimental observations.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

Physiques et Chimie de l'Environnement Atmosphérique

Comment :

9 pages, 7 tables, 5 figures

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL