In order to meet the stricter NO, and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO2. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 degrees C the reaction was in the intrinsic kinetic regime (E-A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH3 and NO2, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO2 were most effective in blocking cations and anions of TiO2. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO2 forms Ti-N=C=O and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH3 and NO, retards hydrolysis leading to the appearance of isocyanate species on the surface. (c) 2006 Elsevier B.V. All fights reserved.