Publisher Summary The chapter focuses on the measurements of kinetic parameters of heterogeneous electron transfer (ET) processes and homogeneous rate constants of coupled chemical reactions. A typical electrochemical process comprises three consecutive steps: diffusion of a reactant to the electrode surface, heterogeneous ET, and diffusion of the product into the bulk solution. Electrons can be transferred across the electrode interface through two parallel pathways: the faradaic process, which can be represented by the charge transfer resistance and the diffusion impedance connected in series, and the charging or discharging of the electrical double layer. The second pathway is important only if the electrode potential changes rapidly. The charge transfer resistance can be measured accurately only if it is larger than the solution resistance. There are many ways by which mass transfer rate can be increased. One is by employing fast convection in hydrodynamic techniques and another is by applying high-frequency perturbation in impedance measurements. The kinetic parameters of a coupled homogeneous chemical reaction can be determined electrochemically as long as they affect the magnitude of the measured signal.
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