Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states

We present an efficient scheme for combining ab initio calculated solid states with experimental aqueous states through a framework of consistent reference energies. Our work enables accurate prediction of phase stability and dissolution in equilibrium with water, which has many important application areas. We formally outline the thermodynamic principles of the scheme and show examples of successful applications of the proposed framework on (1) the evaluation of the water-splitting photocatalyst material Ta3N5 for aqueous stability, (2) the stability of small nanoparticle Pt in acid water, and (3) the prediction of particle morphology and facet stabilization of olivine LiFePO[subscript 4] as a function of aqueous conditions.United States. Dept. of Energy. (Contract number DEAC02- 05CH11231)United States. Dept. of Energy. (Grant No. DE-FG02-96ER45571

A thermodynamic study of liquid Fe-Si-B alloys : an influence of ternary associates on a liquid → glass transition

Knudsen-cell mass spectrometry and the integral variant of effusion method have been applied to investigate the thermodynamic properties of liquid Fe-Si-B alloys at temperatures from 1423 to 1894 K over concentration intervals of 9-88.8 at. pct Fe. 2.6-81.4 at. pct Si, and 7.5-50 at. pct B. The activity values of the components and the Gibbs energy of the Fe-Si-B melt formation have been determined over a wide temperature-concentration range. The concentration and temperature dependences of the thermodynamic functions of liquid Fe-Si-B alloy have been described adequately within the ideal associated-solution model under the assumption that binary and ternary associates exist in the melt. The relevance of the model was tested in the undercooled region. The glass-forming ability of the melt as shown could be interpreted in terms of the thermodynamic parameters of the association reactions. A specific role of ternary interaction was clarified