This work presents the design and characterization of an optimized attenuated total reflection (ATR) microfluidic cell to assess intrinsic kinetic parameters of reactions at the liquid/solid interface under chemical control. A theoretical and computational investigation of convection, diffusion, and adsorption is presented. Transport dynamics in transient-flow experiments is characterized by a convective and diffusive mass transport of the solution species to the surface of the ATR crystal. Criteria to determine the mass transport limitations of the adsorption process are presented as a function of the Damkohler and Biot numbers. The CO adsorption on a thin film of platinum is studied in order to validate the model. (C) 2014 Elsevier B.V. All rights reserved.