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Books > Science & Mathematics > Chemistry > Physical chemistry > Electrochemistry & magnetochemistry
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.
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.
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."
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.
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."
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.
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.
All-solid-state batteries have gained much attention as the next-generation batteries. This book is about various Li ion ceramic electrolytes and their applications to all-solid-state battery. It contains a wide range of topics from history of ceramic electrolytes and ion conduction mechanisms to recent research achievements. Here oxide-type and sulfide-type ceramic electrolytes are described in detail. Additionally, their applications to all-solid-state batteries, including Li-air battery and Li-S battery, are reviewed.Consisting of fundamentals and advanced technology, this book would be suitable for beginners in the research of ceramic electrolytes; it can also be used by scientists and research engineers for more advanced development.
This book, written by the leading experts in the field of plant electrophysiology, provides a comprehensive and up-to-date overview of the current state of knowledge on electrical signaling and responses in plant physiology. It covers a significant interdisciplinary area for a broad range of researchers, emphasizing the physical, chemical, biological, and technological aspects of plant electrophysiology, while also demonstrating the role of electrochemical processes and ion channels in plant life cycles. Separate chapters describe the electrophysiology of the Venus flytrap, the Telegraph plant, Mimosa pudica, and other interesting plant species. Subsequent sections focus on mechanisms of plant movement, the role of ion channels, morphing structures, and the effects of electrical signal transduction on photosynthesis and respiration. Further topics include the electrophysiology of plant-insect interactions, how plants sense different environmental stresses and stimuli, and how phytoactuators respond to them. All chapters analyze the generation and transmission of electrical signals in plants.
Modelling of heterogeneous processes, such as electrochemical reactions, extraction, or ion-exchange, usually requires solving the transport problem associated to the process. Since the processes at the phase boundary are described by scalar quantities and transport quantities are vectors or tensors, coupling them can take place only via conservation of mass, charge, or momentum. In this book, the transport of ionic species is addressed in a versatile manner, emphasizing the mutual coupling of fluxes in particular. Treatment is based on the formalism of irreversible thermodynamics, i.e. on linear (ionic) phenomenological equations, from which the most frequently used Nernst-Planck equation is derived. Limitations and assumptions made are thoroughly discussed. The Nernst-Planck equation is applied to selected problems at the electrodes and in membranes. Mathematical derivations are presented in detail so that the reader can learn the methodology of solving transport problems. Each chapter contains a large number of exercises, some of them more demanding than others.
The Art and Practice of Court Administration explores the context in which court administration is practiced and identifiesthe qualities and skills court administrators need. Divided into two major parts, part one covers the history of the field and how courts are organized, environmental conditions in which court administration is practiced, special impact on courts of the elected clerk of court, prosecutor, and the sheriff, the judge's administrative roles, as well as how a judge's judicial and administrative roles work with management. The second part reviews a new approach for setting and adjusting priorities among the multiple functions courts perform-the Hierarchy of Court Administration. It defines priorities, analyzes court roles that establish mission critical functions, and sets an agenda for advancing courts throughout this century. Thorough and complete, The Art and Practice of Court Administration details how courts operate, the court administrator's position and responsibilities, and approachestoissues and problems.
This book introduces readers to the preparation of metal nanocrystals and its applications. In this book, an important point highlighted is how to design noble metal nanocrystals at the atomic scale for energy conversion and storage. It also focuses on the controllable synthesis of water splitting electrode materials including anodic oxygen evolution reaction (OER) and cathode hydrogen evolution reaction (HER) at the atomic level by defect engineering and synergistic effect. In addition, in-situ technologies and theoretical calculations are utilized to reveal the catalytic mechanisms of catalysts under realistic operating condition. The findings presented not only enrich research in the nano-field, but also support the promotion of national and international cooperation.
Nanoscale electrochemistry has revolutionized electrochemical research and technologies and has made broad impacts in other fields, including nanotechnology and nanoscience, biology, and materials chemistry. Nanoelectrochemistry examines well-established concepts and principles and provides an updated overview of the field and its applications. This book covers three integral aspects of nanoelectrochemistry. The first two chapters contain theoretical background, which is essential for everyone working in the field-specifically, theories of electron transfer, transport, and double-layer processes at nanoscale electrochemical interfaces. The next chapters are dedicated to the electrochemical studies of nanomaterials and nanosystems, as well as the development and applications of nanoelectrochemical techniques. Each chapter is self-contained and can be read independently to provide readers with a compact, up-to-date critical review of the subfield of interest. At the same time, the presented collection of chapters serves as a serious introduction to nanoelectrochemistry for graduate students or scientists who wish to enter this emerging field. The applications discussed range from studies of biological systems to nanoparticles and from electrocatalysis to molecular electronics, nanopores, and membranes. The book demonstrates how electrochemistry has contributed to the advancement of nanotechnology and nanoscience. It also explores how electrochemistry has transformed itself by leading to the discovery of new phenomena, enabling unprecedented electrochemical measurements and creating novel electrochemical systems.
Electrochemical Analysis of Proteins and Cells presents the remarkable progress made over the years in the electrochemical analysis of proteins and cells, due to the rapid development of protein electrochemistry together with related technologies such as surface modification, molecular recognition, molecular assembly, and nanotechnology. As an interdisciplinary field combining electrochemistry, analytical chemistry, biochemistry, biophysics, biomedicine and material science, the electrochemical analysis of proteins and cells has attracted broad and extensive research interest. The main emphasis of this book is on the principles of electrochemical strategies and the practical utility of related detection systems, which is of great importance in all biological sciences, such as cell biology and molecular biology, as well as in biomedical fields like cancer research. This brief offers an up-to-date, easy-to-follow presentation of recent advances on the subject and can serve as a supplement for graduate-level courses in analytical chemistry, biochemistry, biophysics, biotechnology, biomedical engineering, etc. It may also help young scientists get an overview of this topic.
Transition metal oxides form a series of compounds with a uniquely wide range of electronic properties. They have important applications as dielectrics, semiconductors and metals, and as materials for magnetic and optical uses. The discovery of high temperature superconductors has brought the attention of a wide scientific community to this area and has highlighted the problems involved in trying to understand transition metal oxides. The present book is not primarily about Tc superconductors, although their main properties are discussed in the final sections. The main aim is to describe the varied electronic behaviour shown by transition metal oxides, and to discuss the different types of theoretical models that have been proposed to interpret this behaviour.
Modelling of heterogeneous processes, such as electrochemical
reactions, extraction or ion-exchange, usually requires solving the
transport problem associated to the process. Since the processes at
the phase boundary are described by scalar quantities and transport
quantities are vectors or tensors, coupling of them can take place
only via conservation of mass, charge or momentum. In this book,
transport of ionic species is addressed in a versatile manner,
emphasizing the mutual coupling of fluxes in particular. Treatment
is based on the formalism of irreversible thermodynamics, i.e. on
linear (ionic) phenomenological equations, from which the most
frequently used Nernst-Planck equation is derived. Limitations and
assumptions made are thoroughly discussed.
The renowned Oxford Chemistry Primers series, which provides focused introductions to a range of important topics in chemistry, has been refreshed and updated to suit the needs of today's students, lecturers, and postgraduate researchers. The rigorous, yet accessible, treatment of each subject area is ideal for those wanting a primer in a given topic to prepare them for more advanced study or research. Moreover, cutting-edge examples and applications throughout the texts show the relevance of the chemistry being described to current research and industry. The learning features provided, including questions at the end of every chapter and online multiple-choice questions, encourage active learning and promote understanding. Furthermore, frequent diagrams, margin notes, further reading, and glossary definitions all help to enhance a student's understanding of these essential areas of chemistry. This brand new addition to the series provides the most accessible first introduction to electrochemistry, combining explanation of the fundamental concepts with practical examples of how they are applied in a range of real-world situations. Online resources The online resources that accompany Electrochemistry include: For students: - Multiple-choice questions for self-directed learning - Online tutorials to explain difficult concepts For registered adopters of the text: - Figures from the book available to download
This brief book introduces the Poisson-Boltzmann equation in three chapters that build upon one another, offering a systematic entry to advanced students and researchers. Chapter one formulates the equation and develops the linearized version of Debye-Hückel theory as well as exact solutions to the nonlinear equation in simple geometries and generalizations to higher-order equations.   Chapter two introduces the statistical physics approach to the Poisson-Boltzmann equation. It allows the treatment of fluctuation effects, treated in the loop expansion, and in a variational approach. First applications are treated in detail: the problem of the surface tension under the addition of salt, a classic problem discussed by Onsager and Samaras in the 1930s, which is developed in modern terms within the loop expansion, and the adsorption of a charged polymer on a like-charged surface within the variational approach. Chapter three finally discusses the extension of Poisson-Boltzmann theory to explicit solvent. This is done in two ways: on the phenomenological level of nonlocal electrostatics and with a statistical physics model that treats the solvent molecules as molecular dipoles. This model is then treated in the mean-field approximation and with the variational method introduced in Chapter two, rounding up the development of the mathematical approaches of Poisson-Boltzmann theory. After studying this book, a graduate student will be able to access the research literature on the Poisson-Boltzmann equation with a solid background.Â
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. Chapter 10 starts with a detailed description of what happens when light strikes semi-conductor electrodes and splits water, thus providing in hydrogen a clean fuel. There have of course been revolutionary advances here since the First Edition was written. The book also discusses electrochemical methods that may provide the most economical path to many new syntheses - for example, the synthesis of the textile, nylon. The broad area of the breakdown of material in moist air, and its electrochemistry is taken up in the substantial Chapter 12. Another exciting topic covered is the evolution of energy conversion and storage which lie at the cutting edge of clean automobile development. Chapter 14 presents from a fresh perspective a discussion of electrochemical mechanisms in Biology, and Chapter 15 shows how new electrochemical approaches may potentially alleviate many environmental problems. |
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