Electrochemistry historical development

In 1886, Wilhelm Ostwald pnblished the first detailed textbook on electrochemistry (1150 pages). In this book he gave a description of the historical development of electrochemistry and of the state of art of this branch of science at the end of the nineteenth centnry. 

The history of electrochemistry received a welcome boost in 1988 when a symposium entitled Electrochemistry Past and Present was held at the third Chemical Congress of North America at Toronto. The published proceedings contain papers describing the historical development of many electroanalytical techniques.74 Kolthoff has given an account of the state of electroanalytical chemistry prior to World War II based on personal experience.75... 

The historical development of this area is worthy of brief consideration, to place the present review in context. For more detail, there are a number of earlier reviews on the electrochemistry of the L-L interface which cover the general developments in the field up to the time of their publication [2-5]. Brief... 

Historical Development of the Understanding of Charge-Transfer Processes in Electrochemistry... 

It must first be pointed out that the idea and phenomenology of electric charge originated in the 18th century work on the physics of electrostatics, well before any of the principal developments of electrochemistry historically associated with the names of Luigi Galvani, Alessandro Volta, Sir Humphry Davy and Michael Faraday. 

In the past, it seemed fashionable to explain the mechanism with thermodynamics. As a whole, thermodynamics is always right. However, its usefulness depends on how it is applied to a particular system. In commenting on the historic development before 1947 in the treatment of electrochemical reactions across interfaces, Bockris ( ) stated that most electrochemists were still trying to do the impossible, i.e., to treat the highly thermodynamically irreversible electrode reactions by a series of misconceptions and approximations on the basis of reversible thermodynamics. This fundamental error and lack of conceptualization held a dead hand on the mode of achieving electrochemical reactions and on the electrochemical energy conversion for 4 to 5 decades. He called this period in electrochemistry... 

K. R. BuUock, "The Development and AppHcations of Storage Batteries—Historical Perspectives and Future Prospects," in Proceedings, 7th Australian Electrochemistry Conference, 1988. 

A recent book on physical chemistry,5 written by a scientist6 and aimed primarily at other scientists, contains substantial historical information on the beginnings of physical chemistry and on various topics, such as chemical spectroscopy, electrochemistry, chemical kinetics, colloid and surface chemistry, and quantum chemistry. The book also discusses more general topics, such as the development of the physical sciences and the role of scientific journals in scientific communication. The same author has written a brief account of the development of physical chemistry after 1937,7 emphasizing the application of quantum theory and the invention of new experimental methods stopped-flow techniques (1940), nuclear magnetic resonance... 

Ostwald s classic book on electrochemistry has been translated into English.86 In addition to the theory itself, the reader is presented with a host of historical details relating to the 18th and 19th centuries as well as a discussion of Ostwald s empiricist views. Another work, arising from a conference held under the auspices of the American Chemical Society, analyses the major developments and technologies of. .. electrochemistry, electrosynthesis, electroanalytical chemistry, industrial electrochemistry, electrode systems, and pH measurement. 87... 

This overpotential is an important quantity in electrochemistry—one of the central ones and it should be understood. A historical picture of how the idea of overpotential developed and what its status is today has been given by Bockris. 

This sign convention has also been widely adopted today by European electrochemists. However, the opposite convention has been in use for a long time for historical reasons electrochemistry underwent significant development in the 1950 s with studies carried out on the mercury electrode in aqueous electrolyte where only reduction reactions could be investigated. Hence, the working electrode was frequently a cathode. 

The true nature of electrolytic processes in electrochemistry took many years to be understood. An historical outline of the development of these ideas from the pre-Faraday period until the present time is given. One of the matters of outstanding importance for chemistry and electrochemistry was the eventual realization that electricity itself is "atomic in nature, with the electron as the natural unit of electric charge. Not until this concept was established experimentally, and understood in its theoretical ramifications, was it possible for the microscopic basis of electrolytic processes to be established, and developed more quantitatively with the correct qualitative basis. The final and correct perception of the nature of these processes provided one of the important bases for recognition of the electrical nature of matter itself and the foundations of physical chemistry. 

In this paper, an historical outline is given of the principal developments in electrochemistry concerning the mechanism and phenomen-ology of charge transfer in electrolytic processes. In tracing early contributions in this topic, it will be necessary to examine first the historical evolution of ideas about electricity and electric charge. 

This historical account of the development of ideas and experiments on charge transfer in electrochemistry should not conclude without reference to the Faraday Discussion(28) in 1947, held at the University of Manchester. This discussion marked an important turning point in electrode kinetics towards more modern and quantitative analyses of electrode process mechanisms and utilization of relatively new (for that time) techniques, e.g. a.c. impedance studies in the papers by.Randles (37) and by Ershler (38). it also brought together many European electrochemists, following the war years, during which little scientific intercourse had taken place on fundamental aspects of electrochemistry. 

Initially, electrochemical methods were restricted to rather conducting media (solvents with large dielectric constants, large ionic strength), because of problems related to a precise control of an electrode-solution potential difference. Since the rapid development of ultramicroelectrodes in the past decade, this is no more the case, and electrochemistry in solvents of low dielectric constants (arenes, alkanes,efo) or in the absence of deliberately added electrolytes is feasible routinely. Both the theoretical and experimental aspects of such unconventional electrochemistries are now well mastered and the techniques ready for use and application. We have no doubt that the breaking of these historical frontiers of electrochemistry will allow a rich harvest of mechanistic studies performed under conditions that may now approach those used in homogeneous reactions and in catalysis. 

After band structures of metal, insulator, and semiconductors are described and historical back-grotmd of semiconductor electrochemistry is presented, electronic structure of semiconductor/ electrolyte solution interface is discussed in relation to the unique electrochemical behavior of semiconductor electrode. Finally, effect of illumination as well as the surface modification on the electrochemical behavior of semiconductor electrode are described. Fundamental knowledge of semiconductor electrode presented here should be very important for the future development of photoelectrochemical and photocatalytic energy... 

The claims that he underestimated the historical achievements of Russian scientists did hurt Frumkin, however, and briefly he turned his attention to the history of electrochemistry in Russia in order to reevaluate Russian contributions. He rated the studies of Moritz Hermann von Jacobi (21 September 1801-10 March 1874) most highly. (The Russian version of his name is Boris Semyonovich Yakobi. ) Jacobi had discovered the maximum power theorem, and his name is also associated with the development of galvanic cells for testing electric motors. In addition, Frumkin noted the priority of Pyotr Romanovich Bagration (24 September 1818-17 January 1876), who had created the first galvanic dry cell in 1843. Finally, Frumkin drew attention to the work of Kazan professor Robert Andreyevich Colley (Kolli) (25 June 1845-2 August 1891) back in 1878. Colley was the first person to use the shift of the electrode potential in a certain period of time as a measure of the interfacial capacitance and found a value of 150 pF cm for platinum. 

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