Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks

Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO4, RbCoPO4, NH4CoPO4, and NH4ZnPO4 polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry. α-KCoPO4 and γ-KCoPO4 are very similar in enthalpy. γ-KCoPO4 slowly transforms to α-KCoPO4 near 673 K. The high-temperature phase, β-KCoPO4, is 5–7 kJ mol−1 higher in enthalpy than α-KCoPO4 and γ-KCoPO4. HEX phases of NH4CoPO4 and NH4ZnPO4 are about 3 kJ mol−1 lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid–base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid–base interactions. Enthalpies of formation from ammonia and oxides of NH4CoPO4 and NH4ZnPO4 are similar, reflecting the similar basicity of CoO and ZnO.