Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO2 has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl2+) and hydrolyzed species (MoOH2+, Mo(OH)2+, and Mo(OH)30) in addition to the Mo3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.