Ultraviolet/Visible Spectroelectrochemistry

Abstract This article reviews the field of solution‐phase ultraviolet/visible (UV/VIS) absorption spectroelectrochemistry and its application to problems in thermodynamics, kinetics, and mass transport, with emphasis on both experimental and theoretical aspects. Examples are provided for transmission in thin layer and semi‐infinite media, using optically transparent electrodes, and external and internal reflection in quiescent media. Also illustrated is the coupling of UV/VIS spectroscopy to systems under forced convection, such as rotating disk and channel electrodes, under steady state and transient conditions. Attention is also focused on spatially resolved spectroelectrochemistry for the imaging of diffusion and reaction layers. The last section is devoted to the more complex and particularly powerful modulation techniques involving diffraction, refraction and absorption in stagnant media and in the presence of convective flow. Factors that limit the sensitivity and spatial and temporal resolution of UV/VIS absorption spectroelectrochemistry, as well as its future prospects in analytical chemistry are briefly discussed.