Systematic thermodynamics of Magneli-phase and other transition metal oxides.
Both the molar enthalpies of formation and the absolute entropies of eight transition metal oxides are found to correlate very strongly with their formula unit volumes at room temperature. The metals are Ti, V, Cr, Nb, Mo, Ce, Pr, and Tb. In particular, the thermodynamic values of additive entities (such as TiO(2) in Ti(n)O(2n-1)) in Magneli phases (that is, recombination phases based on rebuilding after shear) are very close to those of the entity as a pure compound. Thus, reliable values of these thermodynamic properties can readily be predicted for unmeasured or even unsynthesized examples, and literature values can be checked. These assertions are checked against published results for which incomplete data is available. The contributions of the disordered regions which form between the added entities is tentatively estimated.
Glasser
Leslie
L
Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia. l.glasser@curtin.edu.au