Heat capacity of vanadium-oxygen alloy

Heat capacities of vanadium-oxygen alloys with various compositions, VO_0.0834, VO_0.1127, VO_0.1245, and VO_0.1296, were measured from 320 to 920K by adiabatic scanning calorimetry. A heat capacity anomaly due to order-disorder rearrangement of oxygen atoms was observed for all the compositions. The transition temperatures from α′ to β phase were found to be 780, 791, 786, and 768K for VO_0.0839, VO_0.1127, VO_0.1245, and VO_0.1296, respectively. The transition temperatures from β′ to β were also observed to be 665 and 660K for VO_0.1245 and VO_0.1296, respectively, but they shifted to lower temperatures in repeated measurements. The excess heat capacity due to order-disorder transition was obtained by assuming that the heat capacity can be expressed as the sum of a harmonic term of lattice vibration, a dilational term, an electronic term, and an anharmonic term of lattice vibration. The entropy changes due to the transition for VO_0.0834, VO_0.1127, VO_0.1245, VO_0.1296 were determined from the excess heat capacities to be 1.90, 2.88, 2.82, and 2.88 J K^?1 mole^?1, respectively, values which were explained by calculating the entropy changes due to the order-disorder rearrangement of oxygen atoms in the superstructures of VO_x alloys. From the O/V dependence of the transition temperature and entropy change, the most stable composition of the α′ phase was thought to be V₄₈O₅.