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Über dieses Buch

It gives us pleasure in writing the Preface to this volume, in which we tried to bring together a number of stimulating and interesting people discussing physical electrochemistry. The first chapter, by Ashok Vijh, gives a remarkable account of electrochemistry as looked at from a physicist's point of view. Among the revelations of the chapter is that in a recent survey of leading areas in Science, two out of fifteen areas chosen were electrochemical and these two were the only chemical subjects chosen. In Mikhail Vorotyntsev's chapter, one finds a very modern study of the double layer, but tenuously connected with the simpler studies made in the safe harbor of mercury. In the pioneering chapter by Pons et al., one is looking at a cutting edge of electrochemistry at this time-the use of IR spectros­ copy in modes which allow the first practical determinations of the spectra of adsorbed species at the interface-an area pioneered by Pons himself. In Chapter 4, we have reached photoelectrochemistry once more, but now Tributsch speaks about what has rapidly become the major area of that topic, photoelectrocatalysis. Close to this chapter, and indeed intellectually connected with it, is that by Schmickler and Schultze about electron transfer reac­ tions at oxide-covered metal electrodes in which theories which are still relatively dubious for metal-solution surfaces are applied to complex systems involving oxides.



1. Perspectives in Electrochemical Physics

There are many areas of chemistry that draw heavily upon and interact strongly with the corresponding advances in physics and which, together, are called chemical physics. The more common examples of these areas are quantum chemistry, statistical thermodynamics, and the myriad forms of spectroscopy, etc. Similarly, there is one prominent field of physics, namely, solid-state physics, which has a profound influence on the development and progress of electrochemistry. The research endeavor on electrochemical problems which depend heavily upon the notions of solid-state physics for their proper elucidation is best grouped under electrochemical physics, in analogy with the chemical physics mentioned above.
Ashok K. Vijh

2. Modern State of Double Layer Study of Solid Metals

Remarkable progress has been achieved during the last 20 years in the experimental study of capacitance properties for a number of solid metals. Those are polycrystalline electrodes of Pb, Bi, Tl, Sb, Cd, Sn, Ga, In, Cu, Zn, Ag, and Au in contact with aqueous electrolyte solutions as well as, in some cases, with nonaqueous ones. Interfacial characteristics have also been measured for some single-crystal faces of Ag, Au, Cu, Zn, Bi, Pb, Cd, Sn in aqueous solutions. Moreover, capacitance properties of a single-crystal face in contact with a nonaqueous electrolyte solution, (111) Bi ethanol solutions, have been determined. A major contribution to this advance was made by a group of Soviet electrochemists headed by Frumkin. Some important results for gold and silver electrodes were obtained by French and Bulgarian scientists.
Mikhail A. Vorotyntsev

3. Interfacial Infrared Vibrational Spectroscopy

The last five years have been to electrochemical infrared spectroscopy what the 1940s were to standard infrared spectroscopy. Prior to World War II, Raman spectroscopy was the most commonly used form of vibrational spectroscopy. The development of infrared technology, particularly detector technology, during World War II led to the rapid growth of infrared spectroscopy. In part owing to the relative cost advantage, the use of infrared spectroscopy rapidly overtook Raman spectroscopy for routine vibrational analyses. The advent of the laser produced a resurgence in Raman spectroscopy but it still ranks far behind infrared spectroscopy in routine use. We are today on the verge of a period in which rapid growth in electrochemical infrared spectroscopy can be expected. Furthermore, as will be discussed below, infrared methods may have greater sensitivity and versatility as a general spectroscopic probe for electrochemical systems than Raman methods. The recent development of electrochemical infrared spectroscopy resulted not from technological breakthroughs but from the marriage of well-established electrochemical and spectroscopic techniques.
Stanley Pons, John K. Foley, Joel Russell, Mark Seversen

4. Photoelectrolysis and Photoelectrochemical Catalysis

Conversion of solar energy into storable chemical energy sustains life on earth and constitutes a scientific problem of fundamental interest which might also have long-term technical importance. The most attractive reaction is the photoinduced evolution of H2 and 02 from water according to the mechanism (n = number of photons)
H. Tributsch

5. Electron Transfer Reactions on Oxide-Covered Metal Electrodes

At bare metal electrodes the rates of outer-sphere electron transfer reactions show only a small dependence on the nature of the substrate1a the exchange current densities of a particular reaction on various metals differ by no more than about one order of magnitude, and the transfer coefficients are generally close to 0.5. These experimental findings are in line with theoretical considerations.1b,2
W. Schmickler, J. W. Schultze

6. Interfacial Electrostatics and Electrodynamics in Disperse Systems

Although there are physically relevant analogies between the properties of electrical double layers on electrodes and on dispersed matter, research in these two domains has to a large extent followed disparate paths. The lack of interaction is perhaps understandable but it is also a pity.
H. P. van Leeuwen, J. Lyklema


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