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This volume comprises six chapters on aspects of fundamental and applied electrochemical science that will be of interest both to researchers in the basic areas of the subject and to those involved in aspects of electrochemical technologies. Chapter 1 is the first part of a 2-part, major contribution by Joachim Maier on Solid State Electrochemistry: Thermodynamics and Kinetics of Charge Carriers in Solids. Part 2 will follow in volume 39 to be published in year 2005. This contribution reviews modern concepts of the equilibria involving charge carriers in solids in terms of concentrations of defects in solids and at grain-boundaries, including doping effects. Complementarily, kinetics of charge transfer and ion transfer are treated in some detail in relation to conductance, kinetics of surface processes and electrode-kinetics involving solid-state processes. This chapter will be of major interest to electrochemists and physicists in the semiconductor field and that involving ionic solids. In the second chapter, Appleby presents a detailed discussion and review in modern terms of a central aspect of electrochemistry: Electron Transfer Reactions With and Without Ion Transfer. Electron transfer is the most fundamental aspect of most processes at electrode interfaces and is also involved intimately with the homogeneous chemistry of redox reactions in solutions.
This volume of Modern Aspects covers a wide spread of topics presented in an authoritative, informative and instructive manner by some internationally renowned specialists. Professors Politzer and Dr. Murray provide a comprehensive description of the various theoretical treatments of solute-solvent interactions, including ion-solvent interactions. Both continuum and discrete molecular models for the solvent molecules are discussed, including Monte Carlo and molecular dynamics simulations. The advantages and drawbacks of the resulting models and computational approaches are discussed and the impressive progress made in predicting the properties of molecular and ionic solutions is surveyed. The fundamental and applied electrochemistry of the silicon/electrolyte interface is presented in an authoritative review by Dr. Gregory Zhang, with emphasis in the preparation of porous silicon, a material of significant technological interest, via anodic dissolution of monocrystalline Si. The chapter shows eloquently how fundamental electrokinetic principles can be utilized to obtain the desired product morphology. Markov chains theory provides a powerful tool for modeling several important processes in electrochemistry and electrochemical engineering, including electrode kinetics, anodic deposit formation and deposit dissolution processes, electrolyzer and electrochemical reactors performance and even reliability of warning devices and repair of failed cells. The way this can be done using the elegant Markov chains theory is described in lucid manner by Professor Thomas Fahidy in a concise chapter which gives to the reader only the absolutely necessary mathematics and is rich in practical examples.
This volume in the acclaimed series Modern Aspects of Electrochemistry starts with a dedication to the late Professor Brian Conway who for 50 years helped to guide this series to its current prominence. The remainder of the volume is then devoted to the following topics: PEM fuel cells; the use of graphs in electrochemical reaction newtworks; nanomaterials in Lithium-ion batteries; direct methanolf fuel cells (two chapters); fuel cell catalyst layers. The book is for electrochemists, electrochemical engineers, fuel cell workers and energy generation workers.
The fourth volume of Modern Aspects of Electrochemistry is being prepared at a time of great growth of interest in electro chemistry. The situation can be summarized by saying that the realization is spreading among scientists that electrochemistry represents a broad interdisciplinary field, which has applications to many areas in physics, chemistry, metallurgy, and biology. Among the reasons for this awakening is the reorientation of what is understood under electrochemistry toward electrodics "the study of charged interfaces"-with the ionic-solution aspects of electrochemistry being regarded increasingly as aspects of physical chemistry which are helpful auxiliaries to the broad subject of charged interfaces. The pervasiveness of electrochemistry be comes clearer when one recalls that most interfaces carry a charge, or undergo local charge transfers, even though they are not con nected with a source of power. A further reason for the rapid increase in electrochemical studies arises from the technological aspects, in particular in energy conversion and storage, syntheses, extractions, devices, the stability and finishing of surfaces, the treatment of water, etc. The fact that electrodics allows the conversion of chemical to electric energy and the storage of the latter, at the same time producing fresh water as a by-product, presents an aspect of the subject which appears to have far-reaching significance.
In the last decade, the evolution of electrochemistry away from concern with the physical chemistry of solutions to its more fruitful goal in the study of the widespread consequences of the transfer of electric charges across interphases has come to fruition. The turning of technology away from an onward rush, regardless, to progress which takes into account repercussions of techno logical activity on the environment, and the consequent need for a reduction and then termination of the injection of CO into 2 the atmosphere (greenhouse effect), together with a reckoning with air and water pollution in general, ensures a long-term need for advances in a basic knowledge of electrochemical systems, an increased technological use of which seems to arise from the environmental necessities. But a mighty change in attitude needs to spread among electro chemists (indeed, among all surface chemists) concerning the terms and level in which their field is discussed. The treatment of charge transfer reactions has often been made too vaguely, in terms, it seemed, of atom transfer, with the electron-transfer step, the essence of electrochemistry, an implied accompaniment to the transfer of ions across electrical double layers. The treatment has been in terms of classical mechanics, only tenable while inadequate questions were asked concerning the behavior of the electron in the interfacial transfer. No process demands a more exclusively quantal discussion than does electron transfer.
The present volume contains five chapters covering areas of contemporary interest in the fields of electrolyte solutions, the state of solvent molecules at electrode surfaces, charged colloid interfaces, surface chemistry of oxide electrodes and electro chemistry, and bioelectrochemistry of charge transfer complexes. The first chapter, by Barthel, Wachter, and Gores, covers the topic of conductance of nonaqueous pro tic and aprotic electro lyte solutions. This field is not only of intrinsic interest in itself, illustrating the important departures of ion-transport behavior in organic solvents from that, more well known, in water, but the information and extensive new data presented in this chapter will be of interest to those working with nonaqueous alkali-metal batteries where the conductivity and ion-association behavior of electrolytes in various solvents other than water is of great importance. The second chapter is devoted to a very fundamental and ubiquitous aspect of electrochemistry of electrodes: the state of solvent molecules, adsorbed and oriented, at their surfaces. The role of solvent adsorption and orientation in double-layer proper ties, it will be recalled, remained poorly understood until the early 1960s. This chapter, by Trasatti, gives a thorough account of the present state of knowledge of solvent orientation at electrode interfaces and of the unsuspected (until recent years) role it plays in properties of the double layer and in determining the potential profile at charged metal surfaces in solution.
Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics discussed include: A thorough and mathematical treatment of periodic phenomena, with consideration of new theories about the transition between `order' and `chaos'; Impedance spectroscopy as applied to the study of kinetics and mechanisms of electrode processes; The use of stoichiometric numbers in mechanism analysis; The electro-osmotic dewatering of clays with important implications for the processing of industrial waste and geotechnical; stabilization; Magnetic effects in electrolytic processes and the electrolytic Hall effect; and The computer analysis and modeling of mass transfer and fluid flow. These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.
As the subject of electrochemistry moves into the final quarter of the century, a number of developed areas can be assessed in depth while some new areas provide quantitatively and qualitatively novel data and results. The first chapter, by Kebarle, deals with an example of the latter type of field in which new information of the energetics and equilibria of reactions between ions and solvent molecules is studied in the gas phase and provides interesting basic information for treatments of ions in solution, i.e., ionic solvation. Chapter 2, by Hamann, discusses the behavior of electrolyte solutions under high pressures, a matter of intrinsic interest in relation to ion-solvent interaction and the structural aspects of the properties of ionic solutions, especially in water. This topic is also of current interest with regard to the physical chemistry of the marine environment, especially at great depths. In the article by Bloom and Snook (Chapter 3), models for treatments of molten salt systems are examined quantitatively in relation to the structure of molten ionic liquids and to the statistical mechanical approaches that can be meaningfully made to interpret their properties and electrochemical behavior.
Volume 41 of the prominent series Modern Aspects of Electrochemistry covers a range of topics in Electrochemistry and Electrochemical Engineering. The topics include the second chapter on the survey of experimental techniques and devices of solid state electrochemistry begun by Professor Joachim Maier in Volume 39. Chapter two contains a review of synthesis and characterization of nanoporous carbons and their electrochemical applications. The next chapter reviews and discusses the use of graphs in the study of chemical reaction network. The book also reviews and discusses mathematical models of three dimensional electrode structures.
The text Modern Electrochemistry (authored by J. O'M. Bockris and A. K. N. Reddy and published by Plenum Press in 1970) was written between 1967 and 1969. The concept for it arose in 1962 in the Energy Conversion Center at the University of Pennsylvania, and it was intended to act as a base for interdisciplinary students and mature scientists~hemists, physicists, biologists, metallurgists, and engineers-who wanted to know about electrochemical energy conversion and storage. In writing the book, the stress, therefore, was placed above all on lucidity in teaching physical electrochemistry from the beginning. Although this fundamentally undergraduate text continues to find purchasers 20 years after its birth, it has long been clear that a modernized edition should be written, and the plans to do so were the origin of the present book. However, if a new Bockris and Reddy was to be prepared and include the advances of the last 20 years, with the same degree of lucidity as characterized the first one, the depth of the development would have to be well short of that needed by professional electrochemists.