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

TL;DR

This study uses advanced quantum chemical calculations to analyze how gaseous ruthenium oxides form through reactions with air radiolysis products during nuclear accidents, improving understanding of radiocontaminant release.

Contribution

It provides detailed reaction pathways and kinetic data for gaseous Ru oxide formation, addressing uncertainties in environmental release predictions.

Findings

Oxidation of Ru by nitrogen oxides is the least kinetically limiting pathway.

Reaction pathways and transition states for Ru oxidation are fully characterized.

Rate constants for reactions are calculated over 250-2500 K.

Abstract

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 RuO$_3$ and RuO$_4$. 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 RuO$_2$ 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.