Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Thermodynamic assessment of the Na-O and Na-U-O systems: Margin to the safe operation of SFRs

Smith, A. L., Gueneau, C., Fleche, J.-L., Chatain, S., Benes, O., Konings, R. J. M.
J. Chem. Thermodyn. 2017, 114, 93-115
ABSTRACT
A thermodynamic model for the Na-O system was developed for the first time using the CALPHAD method after review of the structural, thermodynamic, and phase diagram data available on this system. Differential Scanning Calorimetry measurements were moreover performed to assess the phase equilibria and liquidus temperature in the Na2O-Na2O2 composition range. A CALPHAD model for the Na-U-O system was furthermore developed on the basis of both reviewed experimental data, and thermodynamic functions of the sodium uranates derived by combining ab initio calculations and a quasi-harmonic statistical model. The phase equilibria in this ternary system are particularly relevant for the safety assessment of the nuclear fuel-sodium coolant interaction in Sodium-cooled Fast reactors (SFRs). The model predicts the stability of the ternary phase field UO2-Na3UO4-Na4UO5, which is consistent with the most recent literature data. Further optimization was moreover performed to fit the sodium partial pressures measured experimentally in the NaUO3-Na2U2O7-UO2 and NaUO3-Na2UO4-Na2U2O7 phase fields, yielding an overall consistent description. Finally, the oxygen content required to form pentavalent Na3UO4 and hexavalent Na4UO5 in liquid sodium at 900 K were calculated to be 0.7 and 1.5 wppm, respectively, which are levels typically encountered in SFRs.
Compounds
# Formula Name
1 Na2O2 sodium peroxide
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Normal melting temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1