The dehydrogenation kinetics of pure and nickel (Ni)-doped (2w/w%) magnesium hydride (MgH2) have been investigated by in situ time-resolved powder X-ray diffraction (PXD). Deactivated samples, i.e. air exposed, are investigated in order to focus on the effect of magnesium oxide (MgO) surface layers, which might be unavoidable for magnesium (Mg)-based storage media for mobile applications. A curved position-sensitive detector covering 120 degrees in 20 and a rotating anode X-ray source provide a time resolution of 45 s and up to 90 powder pattems collected during an experiment under isothermal conditions. A quartz capillary cell allowed the in situ study of gas/solid reactions. Three phases were identified: Mg, MgH2 and MgO and their phase fractions were extracted by Rietveld refinement or integration of selected reflections from each phase. Dehydrogenation curves were constructed and analysed by the Johnson-Mehi-Avrami formalism in order to derive rate constants at different temperatures. The apparent activation energies for dehydrogenation of pure and Ni-doped magnesium hydride were E-A approximate to 300 and 250 kJ/mol, respectively. Differential scanning calorimetry gave, E-A = 270 kJ/mol for dehydrogenation of the Ni-doped sample. The relatively high activation energies are due to MgO surface layers, retarding the diffusion of hydrogen (H-2) out of MgH2/Mg. The observed difference in E-A of ca. 50 kJ/moI is likely due to the catalytic effect of Ni on the recombination of H atoms to H-2 molecules verified by theoretical considerations. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.