Modeling of a steam generator crevice in a nuclear power system needs to take into account both thermalhydraulic and chemical phenomena. As a first step towards developing a reliable model, a chemical equilibrium model was developed to predict chemical speciation in a magnetite-packed crevice by adopting the “tableau” method. The model was benchmarked with the available experimental data and the maximum deviation did not exceed two orders of magnitude. The developed model was applied to predict the chemical speciation in a magnetite-packed crevice. It was predicted that caustic environment was developed by the concentration of NaOH and the dissolution of magnetite. The model indicated that the dominant aqueous species of iron in the caustic crevice was $FeO_2;^-$. The increase of electrochemical corrosion potential observed in the experiment was rationalized by the decrease of dissolved hydrogen concentration due to a boiling process. It was predicted that under the deaerated condition magnetite was oxidized to hematite.