A fundamental kinetic model for the catalytic hydrogenation of benzene over Pt(111) has been constructed based on periodic DFT calculations using the PW91 and optPBE vdW-DF functional. In contrast to traditional quantum chemical calculations at low to medium surface coverage, the calculations have been performed at a hydrogen coverage of 0.44 in order to account for the strong lateral interactions between the surface intermediates at industrial hydrogenation conditions (p(B) = 0.1-0.6 bar; p(H2) = 0.5-6 bar; T = 400-500 K). The destabilization of the surface species at increased hydrogen coverage results in rate coefficients that are several orders of magnitude larger than at low hydrogen coverage, caused by not only reduced activation barriers, but also a one-order of magnitude increase of the pre-exponential factors. Accounting for coverages representative for industrial conditions in the ab initio calculations is crucial for a correct modeling of the hydrogenation kinetics. Using the given methodology, the turnover frequency (TOF), temperature dependence of the TOF, and the partial reaction orders of benzene and hydrogen are in quantitative agreement with experimental results. (C) 2015 Elsevier Inc. All rights reserved.