Free energies of (Co, Fe, Ni, Zn)Fe2O4 spinels and oxides in water at high temperatures and pressure from density functional theory: results for stoichiometric NiO and NiFe2O4 surfaces.

A set of effective chemical potentials (ECPs) are derived that connect energies of (Co, Fe, Ni, Zn)Fe2O4 spinels and oxides calculated at 0 K from density functional theory (DFT) to free energies in high temperature and pressure water. The ECPs are derived and validated by solving a system of linear equations that combine DFT and experimental free energies for NiO, ZnO, Fe2O3, Fe3O4, FeO(OH), CoFe2O4, ZnFe2O4, NiFe2O4 and H2O. To connect to solution phase chemistry, a set of ECPs are also derived for solvated Ni(2+), Zn(2+), Fe(2+) and Fe(3+) ions using an analogous set of linear equations and the solid ECPs. The ECPs are used to calculate free energies of low index stoichiometric surfaces of nickel oxide (NiO) and nickel ferrite (NiFe2O4) in water as a function of temperature from 300 to 600 K at a pressure of 155 bar. Surface denuding at high temperatures is predicted, the implications of which for the formation of oxide corrosion products on heat transfer surfaces in light-water nuclear reactors are discussed.