Formation enthalpy of ThSiO4 and enthalpy of the thorite → huttonite phase transition

The standard enthalpy of formation of thorite and huttonite and the enthalpy of the phase transition between these polymorphs were determined using high-temperature oxide melt solution calorimetry and transposed temperature drop calorimetry. Standard enthalpies of formation of thorite and huttonite are reported for the first time and are −2117.6 ± 4.2 kJ/mol and −2110.9 ± 4.7 kJ/mol, respectively. Based on our measurements, thorite and huttonite are metastable relative to SiO2 (quartz) and ThO2 (thorianite) at standard conditions, but are presumably stabilized at high temperature by the entropy contribution. Based on the measured enthalpy of the thorite-huttonite phase transition of 6.7 ± 2.5 kJ/mol, a dP/dT slope for the transformation was calculated as −1.21 ± 0.45 MPa/K.