Mechanochemically driven nonequilibrium processes in MNH_2-CaH_2 systems (M = Li or Na)

摘要

Mechanochemical transformations of lithium and sodium amides with calcium hydride have been investigated using gas volumetric analysis, X-ray powder diffraction, and residual gas analysis. The overall mechanochemical transformations are equimolar, and they proceed as the following solid state reaction: MNH_2 + CaH_2 → CaNH + MH + H_2, where M = Li or Na. The transformation kinetics of the lithium containing system is markedly faster compared to the system with sodium. The difference in the rates of solid state transformations, and therefore, in hydrogen release kinetics can be explained by difference in mobility of lithium and sodium atoms. Total energies and enthalpies of formation for different reaction products during the dehydrogenation of CaH2-MNH2 mixtures were calculated using density functional theory. Compared to thermochemical transformations, which proceed in accordance with thermodynamic equilibrium, reactions induced by mechanical energy drive the MNH_2-CaH_2 systems to nonequilibrium configurations with different final products.