Abstract
This article outlines a potent theoretical formalism illuminating the boundaries to reversible solid hydrogen storage based on the ideal gas law and classic equilibrium thermodynamics. A global picture of chemical reversible hydrogen sorption is unveiled including a thermodynamic explanation of partial reversibility. This is utilized to elucidate a multitude of issues from metal hydride chemistry: Highlights are why the substitution of a mere 4 mol % Na by K in Ti-doped NaAlH4 raises the reversible storage capacity by 42 % and elaboration of the reaction pathway in (Rb/K)H-doped Mg(NH2)2/2LiH. The findings of this work allow for a change of paradigm towards the understanding of reversible chemical energy storage and provide a hitherto missing tool of ample analytic and predictive power, complementary to experiment.