The energetics of the TiO2 polymorphs (rutile, anatase, and brookite) were studied by high temperature oxide melt drop solution calorimetry. Relative to bulk rutile, bulk brookite is 0.71 ؎ 0.38 kJ͞mol (6) and bulk anatase is 2.61 ؎ 0.41 kJ͞mol higher in enthalpy. The surface enthalpies of rutile, brookite, and anatase are 2.2 ؎ 0.2 J͞m 2 , 1.0 ؎ 0.2 J͞m 2 , and 0.4 ؎ 0.1 J͞m 2 , respectively. The closely balanced energetics directly confirm the crossover in stability of nanophase polymorphs inferred by Zhang and Banfield (7). An amorphous sample with surface area of 34,600 m 2 ͞mol is 24.25 ؎ 0.88 kJ͞mol higher in enthalpy than bulk rutile.

A major discrepancy in the literature concerning the enthalpy of formation of GaN has been resolved using oxidative oxide melt solution calorimetry. Four samples of differing nitrogen contents were measured by dropping them into molten 3Na 2 O‚4MoO 3 in a calorimeter at 975 K with oxygen gas bubbling through the solvent. The samples were characterized by X-ray diffraction, chemical analysis, transmission electron microscopy, particle size analysis, and BET measurements. The enthalpy of drop solution (kJ/g) varied approximately linearly with nitrogen content. Extrapolated to stoichiometric GaN, the data yield a value of -156.8 ( 16.0 kJ/mol for the standard enthalpy of formation from the elements at 298 K. The relatively large error reflects the deviation of individual points from the straight line rather than uncertainties in each set of data for a given sample. This new directly measured enthalpy of formation is in excellent agreement with that obtained from the temperature dependence of the equilibrium pressure of nitrogen over GaN, -157.7 kJ/mol, measured by Madar et al.