We report a combined experimental/theoretical approach to studying heterogeneous gas/solid catalytic processes using low-pressure pulse response experiments achieving a controlled approach to equilibrium that combined with quantum mechanics (QM)-based computational analysis provides information needed to reconstruct the role of the different surface reaction steps. We demonstrate this approach using model catalysts for ammonia synthesis/decomposition. Polycrystalline iron and cobalt are studied via low-pressure TAP (temporal analysis of products) pulse response, with the results interpreted through reaction free energies calculated using QM on Fe-BCC(110), Fe-BCC(111), and Co-FCC(111) facets. In TAP experiments, simultaneous pulsing of ammonia and deuterium creates a condition where the participation of reactants and products can be distinguished in both forward and reverse reaction steps. This establishes a balance between competitive reactions for D* surface species that is used to observe the influence of steps leading to nitrogen formation as the nitrogen product remains far from equilibrium. The approach to equilibrium is further controlled by introducing delay timing between NH3 and D2 which allows time for surface reactions to evolve before being driven in the reverse direction from the gas phase. The resulting isotopic product distributions for NH2D, NHD2, and HD at different temperatures and delay times and NH3/D2 pulsing order reveal the role of the N2 formation barrier in controlling the surface concentration of NHx* species, as well as providing information on the surface lifetimes of key reaction intermediates. Conclusions derived for monometallic materials are used to interpret experimental results on a more complex and active CoFe bimetallic catalyst.