Fluoride speciation in stainless steel pickling liquor

Mixtures of hydrofluoric and nitric acids are used in the pickling of stainless steels, in order to remove oxide scale, generating pickling waste liquors with high HF concentration. Species appearing in this mixed acid solution are fluoride-metal complexes with high stabilization constants. This work discusses about the modelling of equilibrium reactions that could take place, like complexation of iron and chromium. As observed in the literature, 31 species could be present in pickling liquor with 25 equilibrium reactions. Activity coefficients are calculated using Bromley's methodology that depends on cation-anion interaction parameter B. New parameters at 25°C have been calculated, using Neider and Mead Simplex Algorithm. The new model shows that FeF₃, CrF²⁺ and Ni²⁺ are the main metallic forms in the solution and undissociated hydrofluoric acid has a high relative concentration, while free fluoride practically does not exist in solution. In neutralization processes, free fluoride is released from undisocciated hydrofluoric acid. Therefore, high fluoride complexes are formed, which could precipitate instead of metal hydroxides.