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【电化学基础书籍】electrochemistry in nonaqueous solutions
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Kosuke Izutsu (writer) Electrochemistry inNonaqueous Solutions A majority of chemical reactions are carried out in solution. The use of a solvent as reaction medium makes it easy to control reaction conditions such as tempera- ture, pressure, pH, rate of mass transfer, and concentration of reactant. Water is the most popular solvent. However, by using appropriate non-aqueous solvents, substances that are insoluble in water can be dissolved, substances that are un- stable in water remain stable, and chemical reactions that are impossible in water become possible. The reaction environments are markedly wider in non-aqueous solvents than in water. The widespread use of non-aqueous solvents, especially dipolar aprotic solvents, began in the 1950s in various fields of pure and applied chemistry and has con- tributed greatly to later advances in chemical sciences and technologies. From the very beginning, electrochemistry in non-aqueous solutions has played an impor- tant role in exploring new chemical possibilities as well as in providing the meth- ods to evaluate static solvent effects on various chemical processes. Moreover, many new electrochemical technologies have been developed using non-aqueous solvents. Recently, electrochemistry in non-aqueous solutions has made enormous progress: the dynamic solvent effects on electrochemical processes have been greatly elucidated and solvent effects are now understood much better than be- fore. On the other hand, however, it is also true that some useful solvents have properties that are problematic to human health and the environment. Today, ef- forts are being made, under the framework of ‘green chemistry’, to find environ- mentally benign media for chemical processes, including harmless non-aqueous solvents, immobilized solvents, ionic liquids, supercritical fluids, aqueous sys- tems, and even solventless reaction systems. For electrochemical purposes, replac- ing hazardous solvents by harmless solvents, ionic liquids and supercritical fluids appears to be promising. This book was written to provide readers with some knowledge of electrochem- istry in non-aqueous solutions, from its fundamentals to the latest developments, including the current situation concerning hazardous solvents. The book is di- vided into two parts. Part I (Chapters 1 to 4) contains a discussion of solvent prop- erties and then deals with solvent effects on chemical processes such as ion solva- tion, ion complexation, electrolyte dissociation, acid-base reactions and redox reac- tions. Such solvent effects are of fundamental importance in understanding chem- istry in non-aqueous solutions; furthermore, their quantitative evaluations are of- ten carried out by means of electrochemical techniques. Part II (Chapters 5 to 12) mainly deals with the use of electrochemical techniques in non-aqueous solu- tions. In Chapter 5, the fundamentals of various electrochemical techniques are outlined in preparation for the following chapters. In Chapters 6 to 9, the applica- tions of potentiometry, conductimetry, polarography, voltammetry, and other new electrochemical techniques in non-aqueous solutions are discussed by focusing on the chemical information they provide. Chapters 10 and 11 examine methods of selecting and purifying the solvents and electrolytes of electrochemical impor- tance. Finally, in Chapter 12, some practical applications of non-aqueous solvents in modern electrochemical technologies are discussed. These include their use in batteries, capacitors and display devices, and such processes as electrolytic refin- ing, plating, synthesis and polymerization. The applicability of ionic liquids and supercritical fluids as environmentally benign media for electrochemical technol- ogy is also dealt with. Most chemists are familiar with chemistry in aqueous solutions. However, the common sense in aqueous solutions is not always valid in non-aqueous solutions. This is also true for electrochemical measurements. Thus, in this book, special emphasis is placed on showing which aspects of chemistry in non-aqueous solu- tions are different from chemistry in aqueous solutions. Emphasis is also placed on showing the differences between electrochemical measurements in non-aque- ous systems and those in aqueous systems. The importance of electrochemistry in non-aqueous solutions is now widely recognized by non-electrochemical scientists – for example, organic and inorganic chemists often use cyclic voltammetry in aprotic solvents in order to determine redox properties, electronic states, and reac- tivities of electroactive species, including unstable intermediates. This book will therefore also be of use to such non-electrochemical scientists. I obtained most of the information included in this book from the publications of many scientists in this field. I would like to express my sincere thanks to all of them. I also would like to thank my coworkers for their cooperation, the editorial and production staff of Wiley-VCH for their help and support, and my wife for her assistance and patience.[ Last edited by 战国时代 on 2012-1-3 at 18:04 ] |
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