High temperature thermal properties of KH2PO4: Phase transitions and decompositions

Phase transitions and the thermal decomposition of KH2PO4 have been examined from room temperature to above 300°C by means of hot-stage microscopy, isothermal gravimetry and differential scanning calorimetry. Phase transitions at 198 and 242°C are confirmed, with corresponding enthalpy changes 4.2 and 2.3 kJ mole−1, but no evidence has been found of a transition reported near 110°C. The thermodynamic and other evidence suggest a structural change at 198°C while the change at 242°C is less profound, perhaps involving only changes in the form of the hydrogen bonding. Thermal decomposition occurs in four stages, under conditions of free vapour escape, with the loss of one-quarter of a mole of water per formula unit of KH2PO4 in each stage. The products of each stage of decomposition are tentatively identified.