Transient Techniques in Electrochemistry

The study of electrochemical reactions by relaxation or transient techniques has expanded rapidly over the last two decades. The impetus for the develop­ ment of these techniques has been the desire to obtain quantitative data on the rates of "fast" electrochemical processes, including those coupled to homogeneous chemical reactions in solution. This has necessarily meant the development of techniques that are capable of delineating the effects of mass transport and charge transfer at very short times. The purpose of this book is to describe how the various transient techniques may be used to obtain the desired information. Emphasis is placed upon the detailed mathematical development of the subject, since this aspect is the most frequently ignored in other texts in this field. In any relaxation or transient technique for the study of rate processes, it is necessary to disturb the reaction from equilibrium or the steady state by applying a perturbing impulse to the system. The system is then allowed to relax to a new equilibrium or steady-state position, and. the transient (i. e. , the response as a function of time) is analyzed to extract the desired kinetic information. In electrochemical studies the heterogeneous rate constants are, in general, dependent upon the potential difference across the interface, so that the perturbing impulse frequently takes the form of a known variation in potential as a function of time.