In order to clarify the roles that secondary minerals may have in determining the extent of dispersion of Sb in the supergene environment, syntheses and stability studies of the Sb(V) oxides byströmite, MgSb2O6, ordoñezite, ZnSb2O6 and rosiaite, PbSb2O6, have been undertaken. Solubilities in aqueous HNO3 were determined at 298.2 K and the data obtained used to calculate values of Δ at the same temperature. The derived Δ(s, 298.2 K) values for MgSb2O6 (–1554.1 ±3.6 kJ mol–1), ZnSb2O6 (–1257.0 ±2.6 kJ mol–1) and PbSb2O6 (–1154.2 ±2.6 kJ mol–1) have been used in subsequent calculations to determine their relative stabilities and relationships with other secondary Sb minerals.