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By Bard A.J., Stratmann M., Schafer H.J.

Writing for pros in addition to scholars, editors Schafer (chemistry, U. of Munster), Bard (chemistry, U. of Texas at Austin), Stratmann (corrosive technology and floor engineering, U, of Erlangen) and participants research a variety of themes in the box of natural electrochemistry, together with examine on purposes in different fields comparable to inorganic and natural compounds and organic structures. Article themes comprise the right way to examine mechanisms of electroorganic reactions; functional points of preparative scale electrolysis; comparisons of chemical and electrochemical equipment in natural synthesis; catholic reactions of hydrocarbons, olefins, and fragrant compounds; anodic reactions of alkanes, alkenes, and fragrant compounds; oxidation (and aid) of oxygen-containing compounds, and of halogen-containing compounds; electrochemistry of nitrogen-containing compounds; electrosynthesis of typical items, fantastic chemical substances, and prescription drugs; electrochemistry of heterocycles; selectivity in electrochemical reactions; electrogenerated acids and bases; oblique electrochemical reactions; and accomplishing polymers.

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If the anode is the working electrode and a strong oxidation power is desired, special materials with a high oxygen overvoltage are needed in order to reduce concurrent oxygen production. If the anode is the oxygen evolving counter electrode it is mostly difficult to avoid disadvantageous oxidation reactions, due to the high potential of the oxygen formation, further increased by the oxygen overvoltage. There are no anode materials with a real low oxygen overvoltage. Thus, in most cases, the anode as counter electrode has to work in a divided cell within a separate compartment, unless a depolarized anode can be used (see Sect.

Dimensions and structures of pores in electrode materials will vary in an extremely wide range. The influence of the porosity on the electrode properties includes also mass-transfer effects. In order to extend the effective electrode area in principle three-dimensional electrodes are possible, for example, by using a packed particle bed, a sintered or foamed metal, or a graphite fiber felt. But the depth of the working electrode volume usually is only small (it is dependent on the ratio of the electrode and electrolyte conductivity, for example, [45]).

2 Gas Evolving Electrodes Gases, for example, hydrogen, oxygen, or carbon dioxide, are often formed in the main reaction or as a by-product (caution: the possibility of explosive gas mixtures and of an ignition by a shortcut between the electrodes has to be taken into consideration). An advantageous effect of the moving gas bubbles is the increase of the mass transfer at the electrode surface [46]. On the other hand, the gas has to be removed as fast as possible from the current path in front of the electrode, in order to prevent a too large decrease of the electrolyte conductivity and a perturbation of the uniform current density on the electrodes, up to a (temporarily) blocking of the electrode surface.

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