Transient Techniques in Electrochemistry

1. Front Matter

   Pages i-xii

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2. Introduction

   • Digby D. Macdonald

   Pages 1-13

3. Experimental Methods

   • Digby D. Macdonald

   Pages 15-46

4. The Mathematics of Diffusion

   • Digby D. Macdonald

   Pages 47-67

5. Potential Step Chronoamperometry and Chronocoulometry

   • Digby D. Macdonald

   Pages 69-118

6. Chronopotentiometry

   • Digby D. Macdonald

   Pages 119-184

7. Linear Potential Sweep and Cyclic Voltammetry

   • Digby D. Macdonald

   Pages 185-228

8. AC Impedance Techniques

   • Digby D. Macdonald

   Pages 229-272

9. Surface Processes

   • Digby D. Macdonald

   Pages 273-307

10. Back Matter

    Pages 309-329

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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.

• Ion
• chemical reaction
• electrochemistry

• Stanford Research Institute (SRI International), Menlo Park, USA

  Digby D. Macdonald

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