Introduction electrochemical principles

For a pair of excellent discussions of electrochemical principles see H. Lund, O. Hammerich, Eds., Organic Electrochemistry An Introduction and a Guide, 4th ed., Marcel Dekker, New York, 2001. 

Lead references to more comprehensive review articles are included here [2-4] and in most sections, as I have endeavored to provide a concise introduction to the broad array of technologies commercially available and under development, and to introduce and explain certain key chemical and electrochemical principles underlying this field. 

A number of excellent texts are available that provide a thorough discussion of electrochemical principles. Newman provides a comprehensive and mathematically detailed treatment of electrochemical engineering. Prentice provides slightly greater emphasis on applications. Bard and Faulkner emphasize analytical methods, and Bockris and Reddy provide a very approachable introduction to electrochemical processes. Gileadi provides an excellent treatment of electrode kinetics, and Brett and Brett provide a treatment that includes fundamentals as well as applications, including impedance spectroscopy. 

Scanning electrochemical microscopy-introduction and principles. Analytical Chemistry, 61 (2), 132-138. 

R.G. Compton and G.H.W. Sanders (1996) Electrode Potentials, Oxford University Press, Oxford - A useful introduction to electrochemical equilibria and electrochemical principles. 

Bard, A. J. 2012. Introduction and principles. In Scanning Electrochemical Microscopy. Second edition, Bard, A. J. and Mirkin, M. V. (eds.), pp. 1—14. Boca Raton, FL Taylor Francis. 

Bard AJ, Fan FRF, Kwak J, Lev O (1989) Scanning electrochemical microscopy. Introduction and principles. Anal Chem 61 132-138... 

If the relevant literature is surveyed for the keywords etch stops and silicon, a confusing multiplicity of methods is found using different electrolytes, different bias and differently doped silicon substrates. This section does not aim to be a comprehensive review of all these techniques [Co2], but an introduction to the basic principles of electrochemical etch stops, which will be illustrated by a few typical examples. 

Chapter 1 serves as an introduction to both volumes and is a survey of the fundamental principles of electrode kinetics. Chapter 2 deals with mass transport — how material gets to and from an electrode. Chapter 3 provides a review of linear sweep and cyclic voltammetry which constitutes an extensively used experimental technique in the field. Chapter 4 discusses a.c. and pulse methods which are a rich source of electrochemical information. Finally, Chapter 5 discusses the use of electrodes in which there is forced convection, the so-called hydrodynamic electrodes . 

Field-Effect Transistors (FETs) are part of all modern pH meters. With the introduction of ion-sensitive field-effect transistors, they have both been brought to the attention of chemists. In order to understand the principles of operation of these new electrochemical devices, it is necessary to include the FET in the overall discussion of the electrochemical cell. The outline of the operation of an insulated gate field-effect transistor is given in Appendix C. 

The goal of this volume is to provide (1) an introduction to the basic principles of electrochemistry (Chapter 1), potentiometry (Chapter 2), voltammetry (Chapter 3), and electrochemical titrations (Chapter 4) (2) a practical, up-to-date summary of indicator electrodes (Chapter 5), electrochemical cells and instrumentation (Chapter 6), and solvents and electrolytes (Chapter 7) and (3) illustrative examples of molecular characterization (via electrochemical measurements) of hydronium ion, Br0nsted acids, and H2 (Chapter 8) dioxygen species (02, OJ/HOO-, HOOH) and H20/H0 (Chapter 9) metals, metal compounds, and metal complexes (Chapter 10) nonmetals (Chapter 11) carbon compounds (Chapter 12) and organometallic compounds and metallopor-phyrins (Chapter 13). The later chapters contain specific characterizations of representative molecules within a class, which we hope will reduce the barriers of unfamiliarity and encourage the reader to make use of electrochemistry for related chemical systems. 

Scanning electrochemical microscopy (SECM the same abbreviation is also used for the device, i.e., the microscope) is often compared (and sometimes confused) with scanning tunneling microscopy (STM), which was pioneered by Binning and Rohrer in the early 1980s [1]. While both techniques make use of a mobile conductive microprobe, their principles and capabilities are totally different. The most widely used SECM probes are micrometer-sized ampero-metric ultramicroelectrodes (UMEs), which were introduced by Wightman and co-workers 1980 [2]. They are suitable for quantitative electrochemical experiments, and the well-developed theory is available for data analysis. Several groups employed small and mobile electrochemical probes to make measurements within the diffusion layer [3], to examine and modify electrode surfaces [4, 5], However, the SECM technique, as we know it, only became possible after the introduction of the feedback concept [6, 7],... 

Bioelectrochemistry is hardly a new area—it led to a Nobel prize in the 1950s—but its theory has hitherto been based on older Nernstian principles, and this type of thinking in electrophysiology involves a conservation that slows the introduction of interfacial electrode kinetics in newer treatments. Metabolism, nerve conduction, brain electrochemistry—these areas are where the mechanism of the processes, as yet poorly understood, certainly involve electric currents and are most probably electrochemical. 

Refs. [i] Hassel AW, Diesingb D (2002) Thin Solid Films 414 296 [ii] Strehblow HH (2003) Passivity of metals. In AlkireRC and Kolb DM (eds) Advances in electrochemical science and engineering, vol. 8. Wiley-VCH, Weinheim, pp 271-374 [iii] Kern W, Schuegraf KK (2002) Deposition technologies and applications introduction and overview. In Seshan K (ed) Handbook of thin film deposition techniques principles, methods, equipment and applications. William Andrew, Noyes, p 19... 

In the present chapter, the main focus will be on the most common electrochemical techniques and methods used in the elucidation of reaction mechanisms. In general, it is possible from a quantitative analysis of the relation between current and potential to formulate even complex reaction mechanisms that incorporate preceding and/or follow-up reactions. A part of this text is devoted specifically to the description of the procedures used in the extraction of standard potentials and rate constants once the mechanism is known. However, before a discussion of the individual techniques can be accomplished, an introduction to the basic concepts in electrochemistry seems appropriate. For obvious reasons, this part can only be of limited length in a chapter, and for the reader who would appreciate a more detailed description of the basic principles, we recommend the book of Bard and Faulkner [1]. 

The methods described in this chapter and this book apply to electrochemical impedance spectroscopy. Impedance spectroscopy should be viewed as being a specialized case of a transfer-function analysis. The principles apply to a wide variety of frequency-domain measurements, including non-electrochemical measurements. The application to generalized transfer-function methods is described briefly with an introduction to other sections of the text where these methods are described in greater detail. Local impedance spectroscopy, a relatively new and powerful electrochemical approach, is described in detail. 

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