Dynamic in situ spectroscopic ellipsometry studies of the chemical reaction between ferrous ion and 2,2'-bipyridine (bpy) in a thin Nafion film are presented. A simple prototype system composed of a thin Nafion film on a glass substrate was used throughout the work. The reaction was detected by optically monitoring the formation of the strongly absorbing complex ion, Fe(bpy)(3)(2+) (epsilon(520) = 7.70 x 10(3) M-1 cm(-1) in 0.1 M NaCl). The changes in film optical constants, n and k, and the thickness upon exposure of it to various solutions were monitored in a flow cell with the film on the backside of the substrate relative to the interrogation by light. A "step-by-step" approach was used to isolate the component parts of the system in which the film was consecutively exposed to solutions in the following order: supporting electrolyte, bpy, and, last, ferrous iron solution. The optical properties of the materials were quantitatively described before and during mass transport within the film by modeling using the appropriate multilayer optical models, i.e., the Cauchy equation for nonabsorbing media and the Urbach and Tauc-Lorentz (oscillator) functions for a film that absorbed. The experiments done allowed study of the diffusion in the film and the chemical reactions that are important in the sensing scheme for ferrous iron. Ligand (bpy) diffusion followed a two-stage diffusion mechanism described by a Berens-Hopfenberg model for incremental sorption (D-25 = 7.04 x 10(-13) cm(2) s(-1)). The stabilities of the appropriate systems, i.e., Nafion film with bpy, iron, and iron complex, were studied by exposing equilibrated films to circulating supporting electrolyte solutions. The measurements gave important insights into a set of film chemical reactions and, in turn, selective film dynamics. This work exemplifies the usefulness of spectroscopic ellipsometry in monitoring the kinetics of a chemical reaction in situ, as well as the changes in the film physical properties under dynamic conditions.