Download PDF by Marvin Antelman: Encyclopedia of Electrochemistry. Organic Electrochemistry

By Marvin Antelman

This e-book is an try and bring together the main finished directory of chemical electrode potentials up to now. In compiling this encyclopedia, many papers, articles, and publi­ cations-often with contradictory data-were consulted. Of all of the par­ released fabric on hand, the authors came upon the next of ticular curiosity: G. Milazzo and S. Caroli, Tables of ordinary Electrode Poten­ tials, John Wiley and Sons, Inc. (1978). A. J. deBethune and N. A. Swendeman Loud, ordinary Aque­ ous Electrode Potentials and Temperature Coefficients at 25°C, Clifford A. Hempel (1964). W. Mansfield Clark, Oxidation-Reduction Potentials of - ganic platforms, The Williams and Wilkins Co. (1960). although, it used to be our rationale additionally to incorporate unpublished advanced forma­ tion EMF info. additionally, after we consulted released EMF info, we stumbled on that the compilations usually paid no realization to disparate stipulations and ranging pressures and electrolyte concentrations. to accomplish an invaluable compilation, we resorted to Nernst equation thermodynamic calculations to reconcile disparate facts. We additionally uti­ lized the following relationships to calculate EMF values for inclusion in our tables from organization constants: In ok = nFE log ok = -nE(16. nine) RT As a realistic instance, reflect on the response three Ca + Nta- - 2e = Ca(Ntar We may possibly write 2 Ca - 2e = Ca+ EO = -2. 87 2 three Ca+ + Nta- = Ca(Ntar E, = ? three Ca - 2e + Nta- = Ca(Ntar E2 = ? xl xII advent Given log okay Ca(Ntaf = 6. forty-one, 6. forty-one = -(2)(16.

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Extra info for Encyclopedia of Electrochemistry. Organic Electrochemistry

Example text

If a computer data acquisition system is used, the current integration is possible by software. In principle, a further inexpensive method is to work at constant cell voltage. But here the potentials of the working and of the counter electrode, and all voltage drops of the electrolytes and of the cell separator are included (see Fig. 2). Thus, in most cases, clearly defined conditions at the working electrode cannot be adjusted using this operation mode (nevertheless, because of its uncomplicated realization, it is applied in most technical electrolyses to achieve approximately the desired cell current).

7 potentials and overvoltages and of the ohmic voltage drops in the electrodes (electron conductors) and in the electrolytes, including cell separators (ion conductors). Operation with Constant Cell Current (Galvanostatic Operation) Constant current electrolysis is an easy way to operate an electrochemical cell. Usually, it is also applied in industrial scale electrolysis. For laboratory scale experiments, inexpensive power supplies for constant current operation are available (also a potentiostat normally can work in galvanostatic operation).

In practice, electroorganic conversions mostly are not simple reversible reactions. Often, they will include, for example, energy-rich intermediates, complicated reaction mechanisms, and irreversible steps. In this case, it is difficult to define E and it has only poor practical relevance. Then, a suitable value of the ‘‘redox potential’’ is used as a base for the design of an electroorganic synthesis. It can be estimated from measurements of the ‘‘peak potential’’ in cyclovoltammetry or of the ‘‘half-wave potential’’ in polarography (see Chapter 1).

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Encyclopedia of Electrochemistry. Organic Electrochemistry by Marvin Antelman

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