Lead orthophosphates—III. Stabilities of fluoropyromorphite and bromopyromorphite at 25°C

The reactions of secondary lead orthophosphate with approximately 10^?1 M sodium fluoride and sodium bromide solutions have been investigated at 25°C. Interpretation of the solubility data resulted in solubility product constants for fluoropyromorphite and bromopyromorphite of 10^?71.6 and 10^?78.1, respectively. According to these constants, the stability sequence for lead pyromorphites is Pb₅(PO₄)₃Cl > Pb₅(PO₄)₃Br > Pb₅(PO₄)₃OH > Pb₅(PO₄)₃F. The derived free energy data have been used to evaluate the respective stabilities of fluoro-pyromorphite and bromopyromorphite within the systems PbF₂-PbO-P₂O₅-H₂O and PbBr₂-PbO-P₂O₅-H₂O and to predict the equilibrium behavior of the Pb₅(PO₄)₃F-Pb₅(PO₄)₃OH solid solution under aqueous conditions.