Digital Simulation In Electrochemistry

This book is the result of frustration. When I first became interested in digi tal simulation in 1967 (I didn't know the name then), there were no texts to tell one the how of it. This has not changed greatly since then; it is significant that just about all publications about the technique refer to a chapter by Feldberg in an electrochemical series, written in 1969. When I ran a course on the method recently, it became evident that this chapter is not enough for the raw beginner. Neither does he/she get much help from the mathematical textbooks which, at best, leave the special electrochemical aspects (if not a lot else) to one's imagination. This book, then, is written for practical digital simulators who do not have a friend who will tell them how to do it. The beauty of the digital approach is that one can separate out various dynamic processes taking place simultaneously. I have structured the book in this way. The major computing usually lies in the diffusion of substance, while the major program ming effort (and preparatory paper work) goes into the boundary conditions. These are treated separately.

This book explains how the partial differential equations (pdes) in electroanalytical chemistry can be solved numerically. It guides the reader through the topic in a very didactic way, by first introducing and discussing the basic equations along with some model systems as test cases systematically. Then it outlines basic numerical approximations for derivatives and techniques for the numerical solution of ordinary differential equations. Finally, more complicated methods for approaching the pdes are derived. The authors describe major implicit methods in detail and show how to handle homogeneous chemical reactions, even including coupled and nonlinear cases. On this basis, more advanced techniques are briefly sketched and some of the commercially available programs are discussed. In this way the reader is systematically guided and can learn the tools for approaching his own electrochemical simulation problems. This new fourth edition has been carefully revised, updated and extended compared to the previous edition (Lecture Notes in Physics Vol. 666). It contains new material describing migration effects, as well as arrays of ultramicroelectrodes. It is thus the most comprehensive and didactic introduction to the topic of electrochemical simulation.

Preface to the second edition -- Preface to the first edition - Introduction -- Mathematical model of an electrochemical system -- Numerical solution of the model system -- Diffusion-only electrochemical problems in one-dimensional systems -- First-order chemical kinetic mechanisms -- Second-order chemical kinetic mechanisms -- Electrochemical simulation in weakly supported media -- Hydrodynamic voltammetry -- Two-dimensional systems: microdisc electrodes -- Heterogeneous surfaces -- Stochastic electrochemistry.

This volume is meant as an introductory resource aimed at practitioners of electrochemistry research, technology and development mainly at the atomic, molecular or macromolecular levels. Emphasis is placed at length scales in the 1-100 nm range. The aim of the volume is to help provide understanding of electrochemical phenomena and materials at the nanoscale through modeling and numeric simulations. It is also designed to serve as a means to create and use structures.

This book describes the electrochemical behavior of supramolecular systems. Special emphasis will be given to the electrochemistry of host-guest complexes, monolayer and multilayer assemblies, dendrimers, and other supramolecular assemblies. A fundamental theme throughout the book is to explore the effects that supramolecular structure exerts on the thermodynamics and kinetics of electrochemical reactions. Conversely, attention will be placed to the various ways in which electrochemical or redox conversions can be utilized to control or affect the structure or properties of supramolecular systems. This first book on this topic will be of value for graduate students and advanced researchers in both electrochemistry and supramolecular chemistry.

It has been fashionable to describe electrochemistry as a discipline at the interface between the branches of chemistry and many other sciences. A perusal of the table of contents will affirm that view. Electrochemistry finds applications in all branches of chemistry as well as in biology, biochemistry, and engineering; electrochemistry gives us batteries and fuel cells, electroplating and electrosynthesis, and a host of industrial and technological applications which are barely touched on in this book. However, I will maintain that electrochemistry is really a branch of physical chemistry. Electrochemistry grew out of the same tradition which gave physics the study of electricity and magnetism. The reputed founders of physical chemistry-Arrhenius, Ostwald, and van't Hoff-made many of their contributions in areas which would now be regarded as electrochemistry. With the post-World War II capture of physical chemistry by chemical physicists, electrochemists have tended to retreat into analytical chemistry, thus defining themselves out of a great tradition. G. N. Lewis defined physical chemistry as "the study of that which is interesting." I hope that the readers of this book will find that electrochemistry qualifies.

Electrochemistry is a discipline of wide scientific and technological interest. Scientifically, it explores the electrical properties of materials and especially the interfaces between different kinds of matter. Technologically, electrochemistry touches our lives in many ways that few fully appreciate; for example, materials as diverse as aluminum, nylon, and bleach are manufactured electrochemically, while the batteries that power all manner of appliances, vehicles, and devices are the products of electrochemical research. Other realms in which electrochemical science plays a crucial role include corrosion, the disinfection of water, neurophysiology, sensors, energy storage, semiconductors, the physics of thunderstorms, biomedical analysis, and so on. This book treats electrochemistry as a science in its own right, albeit resting firmly on foundations provided by chemistry, physics, and mathematics. Early chapters discuss the electrical and chemical properties of materials from which electrochemical cells are constructed. The behavior of such cells is addressed in later chapters, with emphasis on the electrodes and the reactions that occur on their surfaces. The role of transport to and from electrodes is a topic that commands attention, because it crucially determines cell efficiency. Final chapters deal with voltammetry, the methodology used to investigate electrode behavior. Interspersed among the more fundamental chapters are chapters devoted to applications of electrochemistry: electrosynthesis, power sources, “green electrochemistry”, and corrosion. Electrochemical Science and Technology is addressed to all who have a need to come to grips with the fundamentals of electrochemistry and to learn about some of its applications. It will constitute a text for a senior undergraduate or graduate course in electrochemistry. It also serves as a source of material of interest to scientists and technologists in various fields throughout academia, industry, and government – chemists, physicists, engineers, environmentalists, materials scientists, biologists, and those in related endeavors. This book: Provides a background to electrochemistry, as well as treating the topic itself. Is accessible to all with a foundation in physical science, not solely to chemists. Is addressed both to students and those later in their careers. Features web links (through www.wiley.com/go/EST) to extensive material that is of a more tangential, specialized, or mathematical nature. Includes questions as footnotes to support the reader’s evolving comprehension of the material, with fully worked answers provided on the web. Provides web access to Excel® spreadsheets which allow the reader to model electrochemical events. Has a copious Appendix of relevant data.