Double pyrovanadates CaMgV2O7: Formation mechanism, phase structure, and thermodynamic properties

A double pyrovanadate CaMgV2O7 sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV2O7 were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates-pyrovanadates-double pyrovanadate CaMgV2O7) was proposed to describe the formation of the CaMgV2O7 considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV2O7 sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 angstrom, b = 14.495 angstrom, c = 11.253 angstrom, beta = 99.12, and V = 108.806 angstrom(3). X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV2O7. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV2O7, respectively. The comprehensive thermodynamic properties of CaMgV2O7 were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K-1) and entropy (198 J mol K-1) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO-MgO-V2O5 system.