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This book provides up-to-date discussion of modern polarographic methods, with examples and experimental details. It is designed for the practicing analyst and a factor in bringing the reincarnated area of analytical chemistry into a new and healthy maturity.
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.
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.
In order to use rare earths successfully in various applications, a good understanding of the chemistry of these elements is of paramount importance. Nearly three to four decades have passed since titles such as The Rare Earths edited by F.H. Spedding and A.H. Daane, The chemistry of the Rare Earth Elements by N.E. Topp and Complexes of the Rare Earths by S.P. Sinha were published. There have been many international conferences and symposia on rare earths, as well as the series of volumes entitled Handbook of Physics and Chemistry of Rare Earths edited by K.A. Gschneidner and L. Eyring. Thus, there is a need for a new title covering modern aspects of rare earth complexes along with the applications. The present title consists of twelve chapters. 1. Introduction2. General aspects3. Stability of complexes4. Lanthanide complexes5. Structural chemistry of lanthanide compounds6. Organometallic complexes7. Kinetics and mechanisms of rare earths complexation8. Spectroscopy of lanthanide complexes9. Photoelectron spectroscopy of rare earths10. Lanthanide NMR shift reagents11. Environmental ecological biological aspects12. Applications The authors studied in schools headed by pioneers in rare earth chemistry, have a combined experience of one hundred and fifty years in inorganic chemistry, rare earth complex chemistry, nuclear and radiochemistry of rare earths and supramolecular chemistry. The present monograph is a product of this rich experience.
Principles of Polarography is a revised and extended version of an original Czech edition that appeared in 1962 at the Publishing House of the Czechoslovak Academy of Sciences in Prague. Based on a one-term course of lectures for third-year students of chemistry at the Charles University it brings the fundamental results of more than forty years' research in the field of polarography. The book contains 22 chapters and opens with a discussion of the principles of polarography. This is followed by separate chapters on polarizable electrodes used in polarography; charging current; influence of the resistance of the electrolyte on polarographic curves; migration and diffusion-controlled currents; and equation of a reversible polarographic wave. Subsequent chapters deal with reversible processes controlled by diffusion of complex ions; reversible reduction of organic substances; deposition of mercury ions; irreversible electrode processes; applications of limiting currents; polarographic curves for the formation of semiquinones and dimers; and catalytic hydrogen currents.
Starts with the most fundamental aspects of the subject and work to the more complex. Topics treated include the electron overlap contribution to the double layer potential difference; the electron transfer theory; farzdaic rectification; photoelectrochemical reduction of CO 2; aluminum in aqueous s
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.
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.
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.