RESUMO

The reaction of HF molecules with brucite, Mg(OH)(2), leading to the formation of Mg(OH)(2-x)F(x), was theoretically studied by ab initio density functional theory (DFT) with periodic boundary conditions. We proposed as mechanism for this reaction four elementary steps: adsorption of the HF molecule, OH(-) liberation from brucite as a water molecule, desorption of the newly formed H(2)O, and rearrangement of the F(-) anion into a hydroxyl position. For the Mg(OH)(2-x)F(x) formation, with x = 1/9, the final product, outcome from an initially adsorbed HF molecule, we computed the Helmholtz free energy variation DeltaF = -23 kcal/mol. The calculated frequency for the most intense infrared band, a Mg-F stretching mode, was 342 cm(-1). Two transition states, corresponding to the hydroxyl reacting with a proton forming a water molecule and migration of a fluoride anion into a hydroxyl vacancy, were computed. The calculated reaction barriers indicate that the reaction between Mg(OH)(2) layers and HF molecules is slow and irreversible.