Dynamic electrochemistry

All the discussions of electrochemistry so far in this chapter concern current - the flow of charged electrons. We call this branch of electrochemistry dynamic, implying that compositions change in response to the flow of electrons. Much of the time, however, we wish to perform electrochemical experiments at equilibrium. 

As on previous occasions, the reader is reminded that no very extensive coverage of the literature is possible in a textbook such as this one and that the emphasis is primarily on principles and their illustration. Several monographs are available for more detailed information (see General References). Useful reviews are on future directions and anunonia synthesis [2], surface analysis [3], surface mechanisms [4], dynamics of surface reactions [5], single-crystal versus actual catalysts [6], oscillatory kinetics [7], fractals [8], surface electrochemistry [9], particle size effects [10], and supported metals [11, 12]. 

K. Heinzinger. Molecular dynamics of water at interfaces. In J. Lipkowski, P. N. Ross, eds. Structure of Electrified Interfaces, Erontiers of Electrochemistry. New York VCH 1993, Chap 7, p. 239. 

M. L. Berkowitz, I.-C. Yeh, E. Spohr. Structure of water at the water/metal interface. Molecular dynamics computer simulations. In A. Wieckowski, ed. Interfacial Electrochemistry. New York Marcel Dekker, 1999, (in press). 

Benjamin, I. Molecular Dynamic Simulations in Interfacial Electrochemistry 31... 

Adsorbed CO on a metal surface is one of the simplest adsorbates and has attracted significant interest within the areas of fundamental surface science, catalysis, and electrochemistry. An understanding of the oxidation mechanism of adsorbed CO is important to design and develop electrocatalysts for fuel cells [69-73] and the surface dynamics of adsorbed CO on electrode surfaces in electrolyte solutions is, therefore, very important. 

The purpose is manifold, mainly to provide a modern reference for graduate instruction and for active researchers in the two disciplines, as well as to document that electrocatalysis and electrochemistry are dynamic fields that expand rapidly and likewise rapidly change in their scientific profiles. 

In dynamic electrochemistry (when currents flow) we need to be careful not to mistake ionic strength and current, since both have the symbol I. 

Also, try Electrode Dynamics, by A. C. Fisher, Oxford University Press, Oxford, 1996, which is another title in the Oxford primer series. Its early chapters discuss the transport of analyte through solution and the various rates inherent in a dynamic electrochemistry measurement. It is a readily affordable and readable introduction and highly recommended. 

Before discussing the voltammogram obtained with the triangular waveform of figure 16.3, which is simply a plot of the observed current intensity versus the applied potential, it is useful to describe some experimental details of a cyclic voltammetry experiment [335-337] and to recall some basic theory of dynamic electrochemistry [180,332], A typical cell (figure 16.4) consists of... 

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