Enthalpy-entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.

The structural, optical and dc electrical properties of Mg _xAl_1-x (0.2 ≤ x ≤ 0.9) gradient thin films covered with Pd/Mg are investigated before and after exposure to hydrogen. We use hydrogenography, a novel high-throughput optical technique, to map simultaneously all the hydride forming compositions and the kinetics thereof in the gradient thin film. Metallic Mg in the Mg_xAl_1-x layer undergoes a metal-to-semiconductor transition and MgH₂ is formed for all Mg fractions x investigated. The presence of an amorphous Mg-Al phase in the thin film phase diagram enhances strongly the kinetics of hydrogenation. In the Al-rich part of the film, a complex H-induced segregation of MgH₂ and Al occurs. This uncommon large-scale segregation is evidenced by metal and hydrogen profiling using Rutherford backscattering spectrometry and resonant nuclear analysis based on the reaction ¹H(¹⁵N, αγ)¹²C. Besides MgH₂, an additional semiconducting phase is found by electrical conductivity measurements around an atomic [Al]/[Mg] ratio of 2 (x = 0.33). This suggests that the film is partially transformed into Mg(AlH₄)₂ at around this composition.