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Über dieses Buch

This second edition of a successful and highly-accessed monograph has been extended by more than 100 pages. It includes an enlarged coverage of applications for materials characterization and analysis. Also a more detailed description of strategies for determining free energies of ion transfer between miscible liquids is provided. This is now possible with a “third-phase strategy” which the authors explain from theoretical and practical points of view. The book is still the only one detailing strategies for solid state electroanalysis. It also features the specific potential of the techniques to use immobilized particles (for studies of solid materials) and of immobilized droplets of immiscible liquids for the purpose of studying the three-phase electrochemistry of these liquids. This also includes studies of ion transfer between aqueous and immiscible non-aqueous liquids. The bibliography of all published papers in this field of research has been expanded from 318 to now 444 references in this second edition. Not only are pertinent references provided at the end of each chapter, but the complete list of the cited literature is also offered as a separate chapter for easy reference.

Inhaltsverzeichnis

Frontmatter

Chapter 1. Earlier Developed Techniques

Abstract
The first electrochemical experiments were performed with solid materials, esp. metals. However, these experiments, conducted in the eighteenth and nineteenth centuries, were directed toward the elucidation of the basic features of the electrical action of chemical substances and the chemical action of electricity. Initially, metals played the major role; only later it became obvious that many chemical compounds possess metallic or semiconducting properties that can be utilized in electrochemical cells. Parallel to the studies of new electrode materials, solid electrolytes were discovered and entire solid galvanic cells could be constructed. In this book, we will entirely neglect pure solid electrolytes because this is a field in its own and the subject of many thorough treatises.
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Chapter 2. Electrodes with Immobilized Particles and Droplets: Three-Phase Electrodes

Abstract
It is a common feature of electrodes with immobilized particles and droplets that three phases are in close contact with each other, i.e., each phase having an interface with the two other phases. This situation exists also in most of the so-called surface-modified or film electrodes, many battery and fuel cell electrodes, electrodes of the second kind, etc. In fact, the majority of surface-modified electrodes consist of arrays of particles that partially cover the electrode surface. It would be far beyond the scope of this book to include all chemical and electrochemical techniques to deposit films on electrodes. Here we shall deal only with electrodes where the particles or droplets have been mechanically attached with the aim of studying their electrochemistry. Before going into the details in Chaps. 5 and 6, we now like to outline the specificity of three-phase electrodes.
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Chapter 3. The Experiment

Abstract
Generally, all kinds of solid electrode materials can be used and have successfully been used to perform voltammetric measurements of immobilized particles and droplets. However, the suitability of an electrode material to a great deal depends on the electrode preparation, i.e., the immobilization procedure. Especially the mechanical immobilization of solid microparticles (see Sect. 3.2) requires a careful choice of electrode material.
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Chapter 4. Hyphenated Techniques

Abstract
The depth of information obtainable from a single electroanalytical technique like the voltammetry of immobilized particles and droplets is naturally limited. Consequently, the combinations of electroanalytical techniques with non-electrochemical techniques become important and attractive. In particular, in situ combinations are powerful tools for investigating electrode processes. They are based on a simultaneous recording of electrochemical and non-electrochemical signals.
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Chapter 5. Immobilized Particles

Abstract
The first prerequisite for studying the electrochemistry of particles immobilized on an electrode surface is their insolubility in the used electrolyte solution. Of course, no particle is absolutely insoluble, and so it is a matter of a practical viewpoint what solubility can be tolerated. There is no general answer to this question; however, it makes sense to discuss here only those compounds that do not dissolve to a detectable extent during their electrochemical reactions or only prompted by their electrochemical reactions. What are the general possibilities of electrochemical behavior of an immobilized particle? Figure 5.1 depicts some frequently observed cases. Case 1 illustrates the reduction of an insoluble metal salt to the metal, e.g., AgCl to Ag, the released anions diffusing into the bulk of the electrolyte solution. For the reduction of silver halides and also of lead(II) oxide, it has been shown that the solid educt is directly transformed to the solid product (see the AFM results discussed in Sect. 4.​2). Case 2 is the oxidation of a metal salt with release of metal ions into the electrolyte solution. An example would be the oxidation of copper(I) sulfide to copper(II) sulfide. Case 3 depicts the oxidation of a metal and formation of an insoluble metal compound, e.g., salt, oxide, or complex. This reaction can proceed via an oversaturated solution of the compound MX as in the case of silver oxidation to AgBr and AgI (see AFM results given in Sect. 4.​2). In case 4 the “simple” anodic oxidative dissolution of a metal particle is considered. Case 5 concerns the insertion electrochemistry of a particle where ions are exchanged between the solid particle and the electrolyte solution when electrons are exchanged between the particle and the electrode. Plenty of examples are discussed in Sects. 5.3, 5.5, and 5.6. Case 6 depicts the case where the electrochemical reaction is confined to the surface layer only. Examples are given in Sect. 5.4. In case 7 it is assumed that the electrochemical reactions occur only via a preceding dissolution of the solid particle (see the electrochemistry of metal dithiocarbamate complexes discussed in Sect. 5.6), and case 8 symbolizes the complete electrochemical dissolution of a particle resulting from its oxidation or reduction. An example of the latter type is the reductive dissolution of iron(III) oxides (see Sect. 5.7).
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Chapter 6. Immobilized Droplets

Abstract
In principle, the voltammetry of immobilized droplets is in many respects very similar to the voltammetry of immobilized microparticles. However, the fluidity of droplets in contrast to the rigidity of solids leads to specific features which have to be discussed before the details of electrochemical studies can be presented.
Fritz Scholz, Uwe Schröder, Rubin Gulaboski, Antonio Doménech-Carbó

Backmatter

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