Energetics of cobalt phosphate frameworks: α, β, and red NaCoPO 4

Abstract

Thermal behavior, relative stability, and enthalpy of formation of α (pink phase), β (blue phase), and red NaCoPO 4 are studied by differential scanning calorimetry, X-ray diffraction, and high-temperature oxide melt drop solution calorimetry. Red NaCoPO 4 with cobalt in trigonal bipyramidal coordination is metastable, irreversibly changing to α NaCoPO 4 at 827 K with an enthalpy of phase transition of −17.4±6.9 kJ mol −1. α NaCoPO 4 with cobalt in octahedral coordination is the most stable phase at room temperature. It undergoes a reversible phase transition to the β phase (cobalt in tetrahedra) at 1006 K with an enthalpy of phase transition of 17.6±1.3 kJ mol −1. Enthalpy of formation from oxides of α, β, and red NaCoPO 4 are −349.7±2.3, −332.1±2.5, and −332.3±7.2 kJ mol −1; standard enthalpy of formation of α, β, and red NaCoPO 4 are −1547.5±2.7, −1529.9±2.8, and −1530.0±7.3 kJ mol −1, respectively. The more exothermic enthalpy of formation from oxides of β NaCoPO 4 compared to a structurally related aluminosilicate, NaAlSiO 4 nepheline, results from the stronger acid–base interaction of oxides in β NaCoPO 4 (Na 2O, CoO, P 2O 5) than in NaAlSiO 4 nepheline (Na 2O, Al 2O 3, SiO 2).