J. O'M. Bockris – författare

There is no need in the 1970s to explain the writing of a book on "Environmen­ tal Chemistry. " The despoliation of the environment by man''s activities has long been clear to chemists. However, it has been the subject of public debate for a short time-since the late 1960s. Curiously, there has been little reaction in the textbook literature to reflect this concern. Apart from some brief and sketchy paperbacks for schools, there has not yet been published a substantial review of environmental chemistry. One reason for this is the breadth of the chemistry involved: it could scarcely be covered by one or two authors, for it is as wide as chemistry itself. The ideal way to write such a book would be to gather a couple of dozen authors in one place and keep them together for 6 months of discussions and writing. This not being very practical, it was decided to do the next best thing and to attempt to network a number of men together in mutual correspondence and interaction, which would lead to a book that had the advantages of the expertise of a large number of persons, and lacked many of the usual disadvan­ tages of the multi author book. Thus, synopses of the various articles were sent to each author, and they were encouraged to interact with each other in attempting to avoid repetition and in keeping their symbols uniform and their presentation style coordinated.

There is no need in the 1970s to explain the writing of a book on "Environmen­ tal Chemistry. " The despoliation of the environment by man's activities has long been clear to chemists. However, it has been the subject of public debate for a short time-since the late 1960s. Curiously, there has been little reaction in the textbook literature to reflect this concern. Apart from some brief and sketchy paperbacks for schools, there has not yet been published a substantial review of environmental chemistry. One reason for this is the breadth of the chemistry involved: it could scarcely be covered by one or two authors, for it is as wide as chemistry itself. The ideal way to write such a book would be to gather a couple of dozen authors in one place and keep them together for 6 months of discussions and writing. This not being very practical, it was decided to do the next best thing and to attempt to network a number of men together in mutual correspondence and interaction, which would lead to a book that had the advantages of the expertise of a large number of persons, and lacked many of the usual disadvan­ tages of the multi author book. Thus, synopses of the various articles were sent to each author, and they were encouraged to interact with each other in attempting to avoid repetition and in keeping their symbols uniform and their presentation style coordinated.

This volume continues the development of the Modern Aspects series in the electrochemical field. The series is now 18 years old, and it is relevant to note the degree of evolution that electro­ chemistry has undergone during this time, for it affects the character of the articles chosen. The trend is towards development of inter­ disciplinary areas of electrochemical science, with full stress upon the many directions of applications of knowledge of electrode processes. The degree of import which should be attached to electro­ chemical science arises from the changes in technology which must be made during the next few decades. These clearly involve a massive electrification and the gradual elimination of the present fossil fuel economy, for both ecological and economic reasons. Research on the fundamental aspects of the field-slow in development to a standard-must be promulgated, but its justification is the modern provisionofa basis for the needed future electrochemical technology. One vast area of potential application of electrochemical concepts is omitted by the present attitude. It is, of course, the electro biological aspect, perhaps, finally, the largest area of all for fruitful applications. These concepts are reflected in the editors'' choice of chapters. Quantum mechanical descriptions of surfaces must be bravely faced. Oscillatory aspects of electrochemical systems are often met in nature and demand attention at a fundamental level. Organic electrochemistry is in an ascending phase. With the electro biological v Preface vi article, we hope to stimulate a beginning of electrodic applications in this area.

This volume continues the development of the Modern Aspects series in the electrochemical field. The series is now 18 years old, and it is relevant to note the degree of evolution that electro­ chemistry has undergone during this time, for it affects the character of the articles chosen. The trend is towards development of inter­ disciplinary areas of electrochemical science, with full stress upon the many directions of applications of knowledge of electrode processes. The degree of import which should be attached to electro­ chemical science arises from the changes in technology which must be made during the next few decades. These clearly involve a massive electrification and the gradual elimination of the present fossil fuel economy, for both ecological and economic reasons. Research on the fundamental aspects of the field-slow in development to a standard-must be promulgated, but its justification is the modern provisionofa basis for the needed future electrochemical technology. One vast area of potential application of electrochemical concepts is omitted by the present attitude. It is, of course, the electro biological aspect, perhaps, finally, the largest area of all for fruitful applications. These concepts are reflected in the editors' choice of chapters. Quantum mechanical descriptions of surfaces must be bravely faced. Oscillatory aspects of electrochemical systems are often met in nature and demand attention at a fundamental level. Organic electrochemistry is in an ascending phase. With the electro biological v Preface vi article, we hope to stimulate a beginning of electrodic applications in this area.

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.

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.

The present collection of articles follows the arrangement used in previous volumes. Solutions are discussed first, surfaces and double­ layers second, electrode kinetics third, and then the applied subjects. The introduction of spectroscopic methods to electrochemistry is well exemplified by NMR studies of ionic solutions, as represented here in the detailed article by E. von Goldammer. Correspondingly, the spectroscopic approach can be applied to surfaces, and B. G. Baker has written an introduction to this topic for electrochemists from the point of view of gas phase measurements. One of the topics which begins to reach a degree of sophistica­ tion in electrode process chemistry is the adsorption of organic species on electrodes, and this topic is described in our volume by the well-known electrochemist M. W. Breiter. The work has much rele­ vance to the corresponding electrode kinetics and oxidation of organic materials. Much less sophisticated is the position in the electrochemistry of sulfide minerals, but it has seemed worthwhile to have the present record described by D. F. A. Koch; his chapter demonstrates the value of qualitative electrochemical studies in this field. The Hydrogen Economy is perhaps an example of straw fire in electrochemistry, for its great popularity beginning in 1973 reflects an interest which can hardly grow larger. However, much discussion of the Hydrogen Economy is concerned with its nonelectrochemical v vi Preface aspects and D. P. Gregory gives here the latest from the hydrogen front, with emphasis on the electrochemistry.

The present collection of articles follows the arrangement used in previous volumes. Solutions are discussed first, surfaces and double­ layers second, electrode kinetics third, and then the applied subjects. The introduction of spectroscopic methods to electrochemistry is well exemplified by NMR studies of ionic solutions, as represented here in the detailed article by E. von Goldammer. Correspondingly, the spectroscopic approach can be applied to surfaces, and B. G. Baker has written an introduction to this topic for electrochemists from the point of view of gas phase measurements. One of the topics which begins to reach a degree of sophistica­ tion in electrode process chemistry is the adsorption of organic species on electrodes, and this topic is described in our volume by the well-known electrochemist M. W. Breiter. The work has much rele­ vance to the corresponding electrode kinetics and oxidation of organic materials. Much less sophisticated is the position in the electrochemistry of sulfide minerals, but it has seemed worthwhile to have the present record described by D. F. A. Koch; his chapter demonstrates the value of qualitative electrochemical studies in this field. The Hydrogen Economy is perhaps an example of straw fire in electrochemistry, for its great popularity beginning in 1973 reflects an interest which can hardly grow larger. However, much discussion of the Hydrogen Economy is concerned with its nonelectrochemical v vi Preface aspects and D. P. Gregory gives here the latest from the hydrogen front, with emphasis on the electrochemistry.

The first chapter in the present volume takes up a well-known theme in modern context: the ideas concerning non-Stokesian mechanisms of ion transport. We are happy that one of the great pioneers of modern electrochemistry, T. Erdey-Gniz, in collaboration with S. Lengyel, has consented to write this article for us. Along with it is a solution-oriented article in spectroscopic vein, namely, that by A. Covington and K. E. Newman on the analysis of solution constituents by means of nuclear magnetic resonance studies. Progress in the electrochemistry of the double layer has perked up, and the advances have been triggered from critical experiments, one showing that fluoride ions are specifically adsorbed, and the other showing that the position of maximum disorder of the water molecules occurs at a charge opposite to that needed for interpreta­ tions of capacitance humps in terms of water molecules. M. A. Habib, who has contributed to the theory in this area, reviews the con­ sequences of these changes in information. The rise in the price of energy toward a situation in which sources other than the fossil fuels become economical implies much for the fuel cell and electrocatalysis. It has long been known that electrocatalysis in real situations was more than a consideration of exchange current densities, and a gap remains in the formulation of the theory of supports for such catalysts, although Boudart has stressed so much the vital nature of them. P. Stonehart and K. A. Kinoshita describe progress in this area.

The first chapter in the present volume takes up a well-known theme in modern context: the ideas concerning non-Stokesian mechanisms of ion transport. We are happy that one of the great pioneers of modern electrochemistry, T. Erdey-Gniz, in collaboration with S. Lengyel, has consented to write this article for us. Along with it is a solution-oriented article in spectroscopic vein, namely, that by A. Covington and K. E. Newman on the analysis of solution constituents by means of nuclear magnetic resonance studies. Progress in the electrochemistry of the double layer has perked up, and the advances have been triggered from critical experiments, one showing that fluoride ions are specifically adsorbed, and the other showing that the position of maximum disorder of the water molecules occurs at a charge opposite to that needed for interpreta­ tions of capacitance humps in terms of water molecules. M. A. Habib, who has contributed to the theory in this area, reviews the con­ sequences of these changes in information. The rise in the price of energy toward a situation in which sources other than the fossil fuels become economical implies much for the fuel cell and electrocatalysis. It has long been known that electrocatalysis in real situations was more than a consideration of exchange current densities, and a gap remains in the formulation of the theory of supports for such catalysts, although Boudart has stressed so much the vital nature of them. P. Stonehart and K. A. Kinoshita describe progress in this area.

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.

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.

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.

Despite reductions in the level of research activity in most fields which, for reasons of economic decline, have taken place in the U.S. during the last year or two, world progress in the fundamental aspects has continued actively. An important aspect of such recent work has been the use of nonaqueous solvents in studies on the constitution of the double-layer and electrochemical reactions. Interpretation of the behavior of electrode interfaces in such solvents demands more knowledge of the solvation properties of ions in nonaqueous media. Chapter 1 by Pad ova on "Ionic Solvation in Nonaqueous and Mixed Solvents" gives an up to date review of the present state of knowledge in this field, together with tabulations of data that are likely to be of quantitative value in further investigations of both homogeneous and heterogeneous electrochemistry in such media. Electrochemical studies of cathodic processes in nonaqueous solvents have, in recent years, revealed the role of solvated electrons. These are of interest in new approaches to reductive electro-organic synthesis. Similarly, the generation of hydrated electrons in photo­ cathodic processes is of great interest. In Chapter 2, by Conway, the conditions under which solvated electrons can arise in electrode processes are critically examined and the electro-organic reactions that hwe been investigated are reviewed. The supposed electro­ generation of hydrated electrons in the water solvent and as inter­ mediates in cathodic hydrogen evolution is shown to be unlikely.

Despite reductions in the level of research activity in most fields which, for reasons of economic decline, have taken place in the U.S. during the last year or two, world progress in the fundamental aspects has continued actively. An important aspect of such recent work has been the use of nonaqueous solvents in studies on the constitution of the double-layer and electrochemical reactions. Interpretation of the behavior of electrode interfaces in such solvents demands more knowledge of the solvation properties of ions in nonaqueous media. Chapter 1 by Pad ova on "Ionic Solvation in Nonaqueous and Mixed Solvents" gives an up to date review of the present state of knowledge in this field, together with tabulations of data that are likely to be of quantitative value in further investigations of both homogeneous and heterogeneous electrochemistry in such media. Electrochemical studies of cathodic processes in nonaqueous solvents have, in recent years, revealed the role of solvated electrons. These are of interest in new approaches to reductive electro-organic synthesis. Similarly, the generation of hydrated electrons in photo­ cathodic processes is of great interest. In Chapter 2, by Conway, the conditions under which solvated electrons can arise in electrode processes are critically examined and the electro-organic reactions that hwe been investigated are reviewed. The supposed electro­ generation of hydrated electrons in the water solvent and as inter­ mediates in cathodic hydrogen evolution is shown to be unlikely.

En la redacción del texto de este libro se ha procurado empezar cada capítulo a un nivel muy simple e ir incrementando hasta llegar a un nivel que permita la conexión con las monografías especializadas. El nivel a que se presentan las diferentes materias ha sido intencionadamente variable, dependiendo en particular del grado en que parece haberse extendido el conocimiento del material.