Abstract
This article shows up the intrinsic thermodynamic boundaries to reversible mass transfer on basis of the ideal gas law and classic equilibrium thermodynamics in relation to chemical hydrogen storage. In the event, a global picture of reversible chemical hydrogen storage is unveiled, including an explanation of partial reversibility. The findings of this work help to clarify problems of metal hydride chemistry which otherwise are difficult if not impossible to solve in convergent manner, e.g. why the substitution of 4 mol % Na by K in Ti-doped NaAlH4 raises the reversible storage capacity by 42 % or the way the dopants take effect in (Rb/K)-co-doped Mg(NH2)2/2LiH. This work's result is of a wider significance since based on two cornerstones of physical chemistry and particularly for the normative role of hydrogen electrodes to electrochemistry.