Kinetic studies are vital for gathering mechanistic insights into heterogeneously catalyzed hydrogenation of unsaturated organic compounds (olefins), where the Horiuti-Polanyi mechanism is ubiquitous on metal catalysts. While this mechanism envisions nonpairwise H addition due to the rapid scrambling of surface hydride (H*) species, a pairwise H addition is experimentally encountered, rationalized here based on density functional theory (DFT) simulations for the ethene (CH) hydrogenation catalyzed by two-dimensional (2D) MXene MoC(0001) surface and compared to Rh(111) surface. Results show that ethyl (CH*) hydrogenation is the rate-determining step (RDS) on MoC(0001), yet CH* formation is the RDS on Rh(111), which features a higher reaction rate and contribution from pairwise H addition compared to 2D-MoC(0001). This qualitatively agrees with the experimental results for propene hydrogenation with parahydrogen over 2D-MoC MXene and Rh/TiO. However, DFT results imply that pairwise selectivity should be negligible owing to the facile H* diffusion on both surfaces, not affected by H* nor CH* coverages. DFT results also rule out the Eley-Rideal mechanism appreciably contributing to pairwise addition. The measurable contribution of the pairwise hydrogenation pathway operating concurrently with the dominant nonpairwise one is proposed to be due to the dynamic site blocking at higher adsorbate coverages or another mechanism that would drastically limit the diffusion of H* adatoms.