The aim of this book is to provide the reader with a modern presentation of ionic solutions at interfaces, for physical chemists, chemists and theoretically oriented experimentalists in this field. The discussion is mainly on the structural and thermodynamic properties, in relation to presently available statistical mechanical models. Some dynamic properties are also presented, at a more phenomenological level. The initial chapters are devoted to the presentation of some basic concepts for bulk properties: hydrodynamic interactions, electrostatics, van der Waals forces and thermodynamics of ionic solutions in the framework of a particular model: the mean spherical approximation (MSA). Specific features of interfaces are then discussed: experimental techniques such as in-situ X-ray diffraction, STM and AFM microscopy are described. Ions at liquid/air, liquid/metal and liquid/liquid interfaces are considered from the experimental and theoretical viewpoint. Lastly some dynamic (transport) properties are included, namely the self-diffusion and conductance of small colloids (polyelectrolytes and micelles) and the kinetics of solute transfer at free liquid/liquid interfaces.

In recent interactions with industrial companies it became quite obvious, that the search for new materials with strong anisotropic properties are of paramount importance for the development of new advanced electronic and magnetic devices. The questions concerning the tailoring of materials with large anisotropic electrical and thermal conductivity were asked over and over again. It became also quite clear that the chance to answer these questions and to find new materials which have these desired properties would demand close collaborations between scientists from different fields. Modem techniques ofcontrolled materials synthesis and advances in measurement and modeling have made clear that multiscale complexity is intrinsic to complex electronic materials, both organic and inorganic. A unified approach to classes of these materials is urgently needed, requiring interdisciplinary input from chemistry, materials science, and solid state physics. Only in this way can they be controlled and exploited for increasingly stringent demands oftechnology. The spatial and temporal complexity is driven by strong, often competing couplings between spin, charge and lattice degrees offreedom, which determine structure-function relationships. The nature of these couplings is a sensitive function of electron-electron, electron-lattice, and spin-lattice interactions; noise and disorder, external fields (magnetic, optical, pressure, etc. ), and dimensionality. In particular, these physical influences control broken-symmetry ground states (charge and spin ordered, ferroelectric, superconducting), metal-insulator transitions, and excitations with respect to broken-symmetries created by chemical- or photo-doping, especially in the form of polaronic or excitonic self-trapping.

It has been always an incentive for students to find whether his/her efforts to solve exercises give correct results, or to find tips for problems that he/she finds more difficult. These are the main reasons for the appearance of the present book. As part of the textbook Modern Electrochemistry 1: Ionics, A Guide to Problems in Modern Electrochemistry: Part 1: Ionics compiles many of the solutions to the exercises and problems presented in the text, as well as many new problems.

This long-awaited and thoroughly updated version of the classic text (Plenum Press, 1970) explains the subject of electrochemistry in clear, straightforward language for undergraduates and mature scientists who want to understand solutions. Like its predecessor, the new text presents the electrochemistry of solutions at the molecular level. The Second Edition takes full advantage of the advances in microscopy, computing power, and industrial applications in the quarter century since the publication of the First Edition. Such new techniques include scanning-tunneling microscopy, which enables us to see atoms on electrodes; and new computers capable of molecular dynamics calculations that are used in arriving at experimental values. A description of the electrochemical stage - the high field region near the interface - is the topic of Chapter 6 and involves a complete rewrite of the corresponding chapter in the First Edition, particularly the various happenings which occur with organic molecules which approach surfaces in solution. The chapter on electrode kinetics retains material describing the Butler-Volmer equation from the First Edition, but then turns to many new areas, including electrochemical theories of potential-dependent gas catalysis. Chapter 8 is a new one devoted to explaining how electrochemists deal with the fast-changing nature of the electrode surface. Quantum Mechanics as the basis to electrode kinetics is given an entirely new look - up to and including considerations of bond-breaking reactions.

This volume is based on the lectures presented at the NATO Advanced Study Institute: (ASI) "Pollutants Formation from Combustion. Formation Mechanisms and Impact on th th Atmospheric Chemistry" held in Maratea, Italy, from 13 to 26 september 1998. Preservation of the environment is of increasing concern in individual countries but also at continental or world scales. The structure of a NATO ASI which involve lecturers and participants of different nationalities was thought as especially well suited to address environmental issues. As combustion is known to substantially contribute to the damaging of the atmosphere, it was natural to concentrate the ASI program on reviewing the currently available knowledge of the formation mechanisms of the main pollutants liberated by combustion systems. In most situations, pollutants are present as trace components and their formation and removal is strongly conditioned by the chemical reactions initiated by fuel consumption. Therefore specific lectures were aimed at defining precisely the general properties of combustion chemistry for gaseous, liquid and solid fuels. Physical factors can strongly affect the combustion chemistry and their influence was also considered. An interesting peculiarity of this specific ASI was to complement the program with a substantial part concerned with the impact of the main combustion pollutants: NOx, aromatics, soot, VOCs, sulphur and chlorinated compounds, on atmospheric chemistry.

This book had its nucleus in some lectures given by one of us (J. O'M. B. ) in a course on electrochemistry to students of energy conversion at the University of Pennsyl- nia. It was there that he met a number of people trained in chemistry, physics, biology, metallurgy, and materials science, all of whom wanted to know something about electrochemistry. The concept of writing a book about electrochemistry which could be understood by people with very varied backgrounds was thereby engendered. The lectures were recorded and written up by Dr. Klaus Muller as a 293-page manuscript. At a later stage, A. K. N. R. joined the effort; it was decided to make a fresh start and to write a much more comprehensive text. Of methods for direct energy conversion, the electrochemical one is the most advanced and seems the most likely to become of considerable practical importance. Thus, conversion to electrochemically powered transportation systems appears to be an important step by means of which the difficulties of air pollution and the effects of an increasing concentration in the atmosphere of carbon dioxide may be met. Cor- sion is recognized as having an electrochemical basis. The synthesis of nylon now contains an important electrochemical stage. Some central biological mechanisms have been shown to take place by means of electrochemical reactions. A number of American organizations have recently recommended greatly increased activity in training and research in electrochemistry at universities in the United States.

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.

This textbook is an accessible overview of the broad field of organic electrochemistry, covering the fundamentals and applications of contemporary organic electrochemistry. The book begins with an introduction to the fundamental aspects of electrode electron transfer and methods for the electrochemical measurement of organic molecules. It then goes on to discuss organic electrosynthesis of molecules and macromolecules, including detailed experimental information for the electrochemical synthesis of organic compounds and conducting polymers. Later chapters highlight new methodology for organic electrochemical synthesis, for example electrolysis in ionic liquids, the application to organic electronic devices such as solar cells and LEDs, and examples of commercialized organic electrode processes. Appendices present useful supplementary information including experimental examples of organic electrosynthesis, and tables of physical data (redox potentials of various organic solvents and organic compounds and physical properties of various organic solvents).

This introduction to the principles and application of electrochemistry is presented in a manner designed for undergraduates in chemistry and related fields. The author covers the essential aspects of the subject and points the way to further study, his concern being with the overall shape of electrochemistry, its coherence and its wider application. This edition differs from its predecessors in having principles and applications separated, and greater prominence is given to areas such as electrochemical sensors and electroanalytical techniques, of which a number of modern methods were not included in previous editions. A range of numerical problems and outline solutions is provided for each chapter to cover most situations that a student might encounter.

"Bioelectrochemistry: Fundamentals, Experimental Techniques and Application," covers the fundamental aspects of the chemistry, physics and biology which underlie this subject area. It describes some of the different experimental techniques that can be used to study bioelectrochemical problems and it describes various applications of biolelectrochemisty including amperometric biosensors, immunoassays, electrochemistry of DNA, biofuel cells, whole cell biosensors, "in vivo" applications and bioelectrosynthesis.

By bringing together these different aspects, this work provides a unique source of information in this area, approaching the subject from a cross-disciplinary viewpoint.

The presence of freely moving charges gives peculiar properties to electrolyte solutions, such as electric conductance, charge transfer, and junction potentials in electrochemical systems. These charges play a dominant role in transport processes, by contrast with classical equilibrium thermodynamics which considers the electrically neutral electrolyte compounds. The present status of transport theory does not permit a first prin ciples analys1s of all transport phenomena with a detailed model of the relevant interactions. Host of the models are still unsufficient for real systems of reasonable complexity. The Liouville equation may be adapted with some Brownian approximations to problems of interact ing solute particles in a continuum (solvent>; however, keeping the Liouville level beyond the limiting laws is an unsolvable task. Some progress was made at the Pokker-Planck level; however, despite a promising start, this theory in its actual form is still unsatis factory for complex systems involving many ions and chemical reac tions. A better approach is provided by the so-called Smoluchowski level in which average velocities are used, but there the hydrodyna mic interactions produce some difficulties. The chemist or chemical engineer, or anyone working with complex electrolyte solutions in applied research wants a general representa tion of the transport phenomena which does not reduce the natural complexity of the multicomponent systems. Reduction of the natural complexity generally is connected with substantial changes of the systems."

In plating, electrochemical surface finishing, elec- trochemical reactors as well as in electrochemical energy conversion, there is an increasing demand for high speed and high efficiency processes. These ob- jectives are largely influenced by cell design. The study of such systems requires, besides know-how, a perfect scientific insight into the interaction bet- ween electrode kinetics, cell geometry and mass and charge transport. Needless to say, for that purpose, computer modelling has gained rapidly in importance over the last few years. Indeed, up to the 1960's, only problems with rather simple geometries and amenable to analytical techni- ques were treated. In 1964, Klingert et al. [60], as well as Fleck et al. [42] outlined the first computer programs for calculating current distributions by the finite dif- ference method. F~ve years later, Riggs et al. [94J presented the first electrode shape change simulations. They used also the finite difference method. In 1978, Bergh [ 12J applied at first the - nite element method to predict electrode shape changes. Since then, an increasing number of publi- cations on-computer modelling of electrochemical sys- tems, appeared. Mainly the finite difference or the finite element method were used.

Ideals are simple and able to be easily understood, but never exist in reality. In this book a theory based on the second law of thermodynamics and its applications are described. In thermodynamics there is a concept of an ideal gas which satisfies a mathematical formula PV = RT. This formula can appro- mately be applied to the real gas, so far as the gas has not an especially high pressure and low temperature. In connection with the second law of thermo- namics there is also a concept of reversible and irreversible processes. The reversible process is a phenomenon proceeding at an infinitely low velocity, while the irreversible process is that proceeding with a finite velocity. Such a process with an infinitely slow velocity can really never take place, and all processes observed are always irreversible, therefore, the reversible process is an ideal process, while the irreversible process is a real process. According to the first law of thermodynamics the energy increase dU of the thermodynamic system is a sum of the heat dQ added to the system and work dW done in the system. Practically, however, the mathematical formula of the law is often expressed by the equation , or some similar equations derived from this formula, is applied to many phenomena. Such formulae are, however, th- retically only applicable to phenomena proceeding at an infinitely low velocity, that is, reversible processes or ideal processes.

Bioelectrochemistry is a fast growing field at the interface between electrochemistry and other sciences such as biochemistry, analytical chemistry and medicinal chemistry. In the recent years, the methods and the understanding of the fundamentals have seen significant progress, which has led to rapid development in the field. Here, the expert editors have carefully selected contributions to best reflect the latest developments in this hot and rapidly growing interdisciplinary topic. The resulting excellent and timely overview of this multifaceted field covers recent methodological advances, as well as a range of new applications for analytical detection, drug screening, tumor therapy, and for energy conversion in biofuel cells. This book is a must-have for all Electrochemists, Biochemists, Analytical Chemists, and Medicinal Chemists.

This book presents a computational scheme for calculating the electronic properties of crystalline systems at an ab-ini tio Hartree-Fock level of approximation. The first chapter is devoted to discussing in general terms the limits and capabilities of this approximation in solid state studies, and to examining the various options that are open for its implementation. The second chapter illustrates in detail the algorithms adopted in one specific computer program, CRYSTAL, to be submitted to QCPE. Special care is given to illustrating the role and in: fluence of computational parameters, because a delicate compromise must always be reached between accuracy and costs. The third chapter describes a number of applications, in order to clarify the possible use of this kind of programs in solid state physics and chemistry. Appendices A, B, and C contain various standard expressions, formulae, and definitions that may be useful for reference purposes; appendix D is intended to facilitate the interpretations of symbols, conventions, and acronyms that occur in the book. Thanks are due to all those who have contributed to the implementation and test of the CRYSTAL program, especially to V.R. Saunders and M. Causal, and to F. Ricca, E. Ferrero, R. Or lando, E. Ermondi, G. Angonoa, P. Dellarole, G. Baracco

This lecture note gives an analysis of electronic structure effects for a new class of molecular solids, i. e. one-dimensional organometal lic systems formed by transition-met. l atoms that are embedded in a matrix of macrocyclic organic ligands. These systems as well as orga nic metals have focused considerable interest due to the potential formation of high-mobility charge carriers. For the present author it is difficult to participate in this restriction on a single physical property (i. e. high electronic conductivities, technical applications, etc. ). The lecture note is hopefully a small contribution to enhance the general understanding of certain electronic properties in organo metallic polymers. Those problems have been considered in the first place that seem to form a theoretical deficit in one specific field of solid-state chemistry. For the reader it will become evident that this contribution is a compromise always guided and limited by boundaries: i) An attempt to present problems to a .chemical. audience which have their roots in solid-state physics. ii) The model calculations are limited by the currently available computational facilities. This .boundary. implies that the compu tational data a e subject to severe theoretical approximations. iii) Theorists have often a strong tendency to identify their numeri cal results and models with physical effects. Also this lecture note is not free of this almost universal trend. Nevertheless the author hopes that this text leads to some insight into a rather modern research field. M. e. B6hm I."

This book systematically describes the design and synthesis of MOF-related materials and the electrochemical energy storage-related research in the field of batteries. It starts with an introduction to the synthesis of MOF-based materials and various MOF derivatives, such as MOF-derived porous carbon and MOF-derived metal nanoparticles. This is followed by highlighting the interesting examples for electrochemical applications, illustrating recent advances in battery, supercapacitor, and water splitting. This book is interesting and useful to a wide readership in the various fields of chemical science, materials science, and engineering.

Electrochemistry is clearly an important component of the technology of many quite diverseindustries. Moreover, the future for electrochemical technology is bright and there is a general expectation that new applications of electrochemistry will become economic as the world responds to the challenge of more expensive energy, of the need to develop new materials and to exploit different chemical feedstocks and of the necessity to protect the environment. " Inthis situation, the present rather fragmentary state ofelectrochemical technology is disappointing. Whilethere are many similarities in the underlying principles and even the practices of the electrochemically based industries, they are often not fully appreciated. Certainly, the Rand D programmes in many industries are in the hands of those with little formal training and whose experience of and interest in other branches of electrochemistry is very limited. Moreover, the academic world has done little to help. Electrode processes are, too often, totally ignored in courses to both scientists and engineers and certainly electrochemical technology is almost never taught as a unified subject with an appropriate balance between fundamentals, engineering and applications. Overall, it isnot surprising that the various strands have not interwoven and that scientists and engineers do not have a proper appreciation of the importance of electrochemical technology. Inthe first half of 1979 I conducted a survey into the research and development needs of the various industries in Britain using electrochemical technology.

This is the first ever compendium of double photoionisation spectra, covering some 70 of the most important small and medium sized molecules and thus providing an essential starting point for studies of the consequences of ionisation by high energy photons in both terrestrial and astrophysical environments. It also provides a complete non-mathematical description of all the phenomena and pathways involved in molecular double photoionisation. Most spectra are presented with identification of the electronic states and leading orbital configurations. The technique of magnetic bottle time-of-flight electron spectroscopy, used for all the spectra, is fully explained and compared with other techniques. For each molecule, the book gives full references to relevant work by complementary techniques and to theoretical calculations. Written in a clear non-mathematical style, this book is accessible to students as well as more experienced researchers. The authors have designed the layout for easy retrieval of any desired spectrum through the systematic organisation and ordering of the compounds and thorough indexing. As well as being a compendium of spectra, the book is a textbook covering all the known phenomenological aspects of molecular double photoionisation. The important phenomena are first mentioned in the introductory chapters, and are discussed in more detail in connection with the groups of molecules and individual cases where they are most relevant. The most useful spectra will be available in digital form for users.

In the last fifty years. computational chemistry has made impressive strides. Huckel NO computations were rapidly succeeded by semiempirical monodeterminantal Self Consistent Field (SCF) MO calculations which now give way to high quality ab initio calculations of the poly-determinantal SCF-MO and Generalized VB variety. By contrast. no analogous progress has been made in the area of the qualitative theo~ of chemical bonding. In fact. more than a half-centu~ after the exposition of HUckel MO theory the conceptual superstructure of chemist~ is still founded on it. This is made glaringly evident by the fact that highly sophisticated computations are still interpreted with primitive HUckel MO theory. despite the fact that most chemists are well aware of its formal deficiencies. The current popularity Qf qual1tati. ve MO theory among experimental i sts is not the resul t ~f fonnai -advances ~Wt, rather the consequence of stimulating application of old MO theoreti~a. 1 ~oncepts. : . . " This work attemps to improve this situation by outlining a~t. iJlitative theory of chemical bonding which operates at a high level of theoretical sophistication. It was first presented at the NATO Advanced Study Institute on "Topics in Theoretical Organic Chemistry" in Gargnano. Italy. in June 1979. and in other international meetings and conferences. colloquia. and informal gatherings in the period of time follOWing the Gargnano meeting. It was also presented in a seminar given at the University of Washington in October 1980.

This book introduces the synthesis and modification of 3D hierarchical porous graphene materials and presents various applications of it. By directly constructing a 3D graphene framework with sp2 hybridization and hierarchical porosity, this book is aimed to bridge the gap between 2D ideal nanostructure and 3D practical materials by systematically studying the growth mechanism, synthetic methodology, customized application, and system promotion of 3D hierarchical porous graphene (hpG) materials. The achievements presented offer a valuable contribution to the fundamental research and the industrial development of graphene with significantly improved performance and also inspire further research into various nanomaterials beyond graphene.

This comprehensive handbook covers all fundamentals of electrochemistry for contemporary applications. It provides a rich presentation of related topics of electrochemistry with a clear focus on energy technologies. It covers all aspects of electrochemistry starting with theoretical concepts and basic laws of thermodynamics, non-equilibrium thermodynamics and multiscale modeling. It further gathers the basic experimental methods such as potentiometry, reference electrodes, ion-sensitive electrodes, voltammetry and amperometry. The contents cover subjects related to mass transport, the electric double layer, ohmic losses and experimentation affecting electrochemical reactions. These aspects of electrochemistry are especially examined in view of specific energy technologies including batteries, polymer electrolyte and biological fuel cells, electrochemical capacitors, electrochemical hydrogen production and photoelectrochemistry. Organized in six parts, the overall complexity of electrochemistry is presented and makes this handbook an authoritative reference and definitive source for advanced students, professionals and scientists particularly interested in industrial and energy applications.

Electrochemical processes play an increasingly large role in our daily lives; whether in producing or saving energy, rust protection or nerve stimuli in our bodies. This 11-volume encyclopedia provides both an easy introduction to all topics related to modern electrochemistry as well as a comprehensive overview of the subject. Unrivalled in its breadth and depth, this first-class reference work has been created and written by renowned scientists, covering everything from fundamental research to areas of application. Editors-in-Chief: Allen Bard, Martin Stratmann Volume 1: Thermodynamics and Electrified Interfaces (Editors: Eliezer Gileadi, Micheal Urbakh) Volume 2: Interfacial Kinetics and Mass Transport (Editor: Ernesto Julio Calvo) Volume 3: Instrumentation and Electroanalytical Chemistry (Editor: Pat Unwin) Volume 4: Corrosion and Oxide Films (Editors: Martin Stratmann, Gerald S. Frankel) Volume 5: Electrochemical Engineering (Editor: Digby D. Macdonald) Volume 6: Semiconductor Electrodes and Photoelectrochemistry (Editor: Stuart Licht) Volume 7: Inorganic Electrochemistry (Editors: William E. Geiger, Chris Pickett) Volume 8: Organic Electrochemistry (Editor: Hans J. Schafer) Volume 9: Bioelectrochemistry (Editor: George S. Wilson) Volume 10: Modified Electrodes (Editors: Israel Rubinstein, Masamichi Fujihira) Volume 11: Index