Electrochemistry foundations

J. Goodisman, Electrochemistry Theoretical Foundations, Wiley-Interscience, New York, 1987, p. 132. 

Acknowledgements. The author would like to express his thanks to the National Science Foundation and Research Corporation which supported the work carried out in his laboratory. Thanks are also due to Professor Phillip J. Elving who first gave the author the opportunity to study purine electrochemistry. 

Nowadays, studies of direct electrochemistry of redox proteins at the electrodesolution interface have held more and more scientists interest. Those studies are a convenient and informative means for understanding the kinetics and thermodynamics of biological redox processes. And they may provide a model for the study of the mechanism of electron transfer between enzymes in biological systems, and establish a foundation for fabricating new kinds of biosensors or enzymatic bioreactors. 

Goodisman, J.G. Electrochemistry Theoretical Foundations John Wiley and Sons New York, 1987 p. 10. 

Fleischmann, M. Advances in Electrochemistry The Robert A. Welch Foundation Conferences on Chemical Research, 1986 No. 3-5, p. 91. 

Molecular modeling treatments of electron transfer kinetics for reactions involving bond breaking were developed much earlier than the continuum theories originated by Weiss in 1951. Gurney in 193l published a landmark paper (the foundation of quantum electrochemistry) on a molecular and quantum mechanical model of proton and electron transfer... 

We are grateful to the National Science Foundation for supporting our research efforts in the field of organic electrochemistry. 

Acknowledgments. We are grateful to the Electric Power Research Institute (EPRI) and the National Science Foundation (NSF) for a joint program supporting our efforts in organic electrochemistry. 

This book describes for the first time in a modern text the fundamental principles on which solid state electrochemistry is based. In this sense, it is distinct from other books in the field which concentrate on a description of materials. The text provides an essential foundation of understanding for postgraduates or others entering the field for the first time and may also be of value in advanced undergraduate courses. 

J. Koi3fta, Principles of Electrochemistry, Wiley, New York, 1987 J. Goodisman, Electrochemistry Theoretical Foundations, Quantum and Statistical Mechanics, Thermodynamics, the Solid State, Wiley, New York, 1987 G. Battistuzzi, M. Bellei, and M. Sola, J. Biol. Inorganic Chem. 11, 586-592 (2006) R. Heyrovska, Electroanalysis, 18, 351-361 (2006) G. Battistuzzi, M. Borsari, G. W. Ranters, E. de Waal, A. Leonard , and M. Sola, Biochemistry 41, 14293-14298 (2002). 

Because electrochemistry, as in other disciplines, has been built on the foundations established by individual scientists and their collaborators, it is important that the student know who these contributors are. These researchers are mentioned in the text, with the date of their most important work (e.g., Gumey, 1932). This will allow the student to place these leaders in electrochemistry in the development of the field. 

Gurney then collaborated with the eminent Cambridge (U.K.) physicist. Nevil Mott, to co-author a book. Electronic Processes in Crystals (1936), which provided the foundation of solid state physics. Some years later there followed Ions in Solution, the first book to treat solution J electrochemistry at a quantum level. 

We are forced to reflect that the failure of so many attempts to improve on the DH theory can be attributed to a premature rejection of the DH approach, and a tendency to include extra parameters without proper theoretical foundation. It is surprising that although ionic polarization is emphasized in studies of solvation (36), molten salts (37), and chemistry in general (38), the phenomenon has received little attention in interionic theory. In particular, our attention is drawn to the early work of Fajans and co-workers (39), who first noted the effects of concentration on the ionic molar refractivities of solutions, which were interpreted in terms of a distorting effect on the ions. For various reasons the significance of this work has not been appreciated in the field of electrochemistry. 

Financial support was provided by the National Science Foundation (Grant CHE-94-13128). Prof. Alan Bond and Mr. Richard Webster provided advance information concerning their studies on the electrochemistry of pyridine 2,6-dithioesters and related substances84. 

J. Thompson, 1893) and the development of chemical thermodynamics (G. N. Lewis, 1923). Building on this foundation, the utilization of electrochemical phenomena for thermodynamic characterization and analysis of molecules and ions (electroanalytical chemistry) began at the beginning of this century [po-tentiometry (1920) and polarography (1930)]. Relationships that describe the techniques of potentiometry and polarography derive directly from solution thermodynamics. In the case of polarography, there is a further dependence on the diffusion of ionic species in solution. The latter is the basis of conductivity measurements, another area that traces its origin to the nineteenth century. These quantitative relationships make it possible to apply electrochemistry to... 

Use of the potential of a galvanic cell to measure the concentration of an electroactive species developed later than a number of other electrochemical methods. In part this was because a rational relation between the electrode potential and the concentration of an electroactive species required the development of thermodynamics, and in particular its application to electrochemical phenomena. The work of J. Willard Gibbs1 in the 1870s provided the foundation for the Nemst equation.2 The latter provides a quantitative relationship between potential and the ratio of concentrations for a redox couple [ox l[red ), and is the basis for potentiometry and potentiometric titrations.3 The utility of potentiometric measurements for the characterization of ionic solutions was established with the invention of the glass electrode in 1909 for a selective potentiometric response to hydronium ion concentrations.4 Another milestone in the development of potentiometric measurements was the introduction of the hydrogen electrode for the measurement of hydronium ion concentrations 5 one of many important contributions by Professor Joel Hildebrand. Subsequent development of special glass formulations has made possible electrodes that are selective to different monovalent cations.6"8 The idea is so attractive that intense effort has led to the development of electrodes that are selective for many cations and anions, as well as several gas- and bioselective electrodes.9 The use of these electrodes and the potentiometric measurement of pH continue to be among the most important applications of electrochemistry. 

For chemists, the second important application of electrochemistry (beyond potentiometry) is the measurement of species-specific [e.g., iron(III) and iron(II)] concentrations. This is accomplished by an experiment in which the electrolysis current for a specific species is independent of applied potential (within narrow limits) and controlled by mass transfer across a concentration gradient, such that it is directly proportional to concentration (/ = kC). Although the contemporary methodology of choice is cyclic voltammetry, the foundation for all voltammetric techniques is polarography (discovered in 1922 by Professor Jaroslov Heyrovsky awarded the Nobel Prize for Chemistry in 1959). Hence, we have adopted a historical approach with a recognition that cyclic voltammetry will be the primary methodology for most chemists. 

Overview The English chemist Humphrey Davy wrote in 1812 If a piece of zinc and a piece of copper be brought in contact with each other, they will form a weak electrical combination, of which the zinc will be positive, and the copper negative. . . so initiating the history of the electrochemical cell. But it was Michael Faraday who, in 1834, laid the foundations of quantitative electrochemistry by relating the quantity of a substance electrolysed to the amount of electrical charge involved. 

It is from these foundations that electrochemistry has evolved and which now provides the scientific basis to the technology of electrochemical cells. 

This book consists of nine chapters. The second chapter provides an overview of the important thermodynamic and kinetic parameters of relevance to corrosion electrochemistry. This foundation is used in the third chapter to focus on what might be viewed as an aberration from normal dissolution kinetics, passivity. This aberration, or peculiar condition as Faraday called it, is critical to the use of stainless steels, aluminum alloys, and all of the so-called corrosion resistant alloys (CRAs). The spatially discrete failure of passivity leads to localized corrosion, one of the most insidious and expensive forms of environmental attack. Chapter 4 explores the use of the electrical nature of corrosion reactions to model the interface as an electrical circuit, allowing measurement methods originating in electrical engineering to be applied to nondestructive corrosion evaluation and... 

Refi. [i] Hunter RJ (2004) Foundations of colloid science, 2"d edn. Oxford University Press, Oxford, pp 317 [ii] Bockris J OM, Reddy AKN (1998) Modern electrochemistry, vol. 1. Plenum Press, p 230... 

Refs. [i] Bard AJ, Faulkner LR (2001) Electrochemical methods. Wiley, New York [ii] BardAJ, Stratmann M, GileadiE, Urbakh M (eds) (2002) Thermodynamics and electrified interfaces. Encyclopedia of electrochemistry, vol. 1. Wiley-VCH, Weinheim [in] Goodrich EC, Rusanov AI (eds) (1981) The modern theory of capillarity. Akademie-Verlag, Berlin [iv] Hunter RJ (2004) Foundations of colloid science. Oxford University Press, Oxford, pp 84... 

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