Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work, two-dimensional simulations with detailed chemistry are used to study the reaction pathways of the transient flow and ignition of a stoichiometric hydrogen/air mixture by moving hot spheres. For temperatures above the ignition threshold, ignition takes place after a short time between the front stagnation point and separation location depending upon the spheres surface temperature. Closer to the threshold, the volume of gas adjacent to the separation region ignites homogeneously after a longer time. These results demonstrate the importance of boundary layer development and flow separation in the ignition process. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.