High‐Pressure‐High‐Temperature Polymorphism of the Oxides of Lead

Abstract

The common oxides of lead, PbO, PbO 2 , and Pb 3 O 4 , were examined at pressures of 0 to 60,000 atmospheres and temperatures of 100° to 600° C. The pressure‐temperature curve for the litharge‐massicot transition was measured, giving a ΔH of transition of 57 cal. per mole. Unusual meta‐stability and inversion characteristics of the massicot phase were examined in detail. PbO 2 (rutile) transformed at pressures in excess of 13,000 atmospheres at 300°C. to an ortho‐rhombic form. The univariant equilibrium curve for the transition gave a Δ H of 11 cal. per mole. Pb 3 O 4 underwent a disproportionation reaction yielding PbO and “Pb 2 O 3 .” The equilibrium curve for this reaction was measured, and Δ H was determined to be 4500 cal. per mole.