Group transfer reactions, definition

Electrochemical reactions can be broken down into two groups outer-sphere electron-transfer reactions and inner-sphere electron transfer reactions. Outer-sphere reactions are reactions that only involve electron transfer. There is no adsorption and no breaking or forming of chemical bonds. Because of their simplicity, numerous studies have been performed, many entirely theoretical.18-25 By definition, though, electrode reactions are not outer-sphere reactions. However, if charge transfer is rate limiting for an electrode reaction, it typically takes a form similar to that of an outer-sphere reaction, which is described later in this section. 

O Brien. 1235 Ohmic drop, 811, 1089, 1108 Ohmic resistance, 1175 Ohm s law, 1127. 1172 Open circuit cell, 1350 Open circuit decay method, 1412 Order of electrodic reaction, definition 1187. 1188 cathodic reaction, 1188 anodic reaction, 1188 Organic adsorption. 968. 978. 1339 additives, electrodeposition, 1339 aliphatic molecules, 978, 979 and the almost-null current test. 971 aromatic compounds, 979 charge transfer reaction, 969, 970 chemical potential, 975 as corrosion inhibitors, 968, 1192 electrode properties and, 979 electrolyte properties and, 979 forces involved in, 971, 972 977, 978 free energy, 971 functional groups in, 979 heterogeneity of the electrode, 983, 1195 hydrocarbon chains, 978, 979 hydrogen coadsorption and, 1340 hydrophilicity and, 982 importance, 968 and industrial processes, 968 irreversible. 969. 970 isotherms and, 982, 983... 

Hydrogen atoms and hydroxyl radicals react with aliphatic compounds mainly by H-abstraction from the chain, although reactions with certain substituents are also important. With hydrated electrons the functioned group is the only site of reaction and its nature determines the reactivity. The reactions of hydrated electrons are by definition electron transfer reactions. The rate of reaction of a certain substrate will depend on its ability to accommodate an additional electron. For example, in an unsaturated compound the rate may depend on the presence of a site with a partial positive charge. Thus acrylonitrile and benzonitrile are three orders of magnitude more reactive toward e q than are ethylene and benzene. On the other hand, this large difference does not exist in the case of addition of H and OH. 

Coenzyme in the narrow sense, the dissociable, low-molecular-mass active group of an enzyme which transfers chemical groups (see Group transfer) or hydrogen or electrons. C. in this sense couple two otherwise independent reactions, and can thus be regarded as transport metabolites. In a wider sense, a C. can be regarded as any catalytically active, low-molecular-mass component of an enzyme. This definition includes C. that are covalently bound to enzymes as prosthetic groups. A holoenzyme consists of a C. in combination with an apoenzyme (enzyme protein). 

The above two examples of the polymerization of styrene contrast the prototypical controlled and uncontrolled polymerizations. Controlled polymerizations offer simple molar mass control, the ability to define the polymer end groups, and give polymer samples with narrow molar mass distributions. Molar mass definition in uncontrolled polymerizations is more difficult, polymer end groups are determined by inherent termination (and transfer) reactions, and the molar mass distributions are typically broader. There is much contemporary interest in developing polymerization reactions that are controlled because of the precision with which macromolecules can be designed. Many chapters are dedicated to these endeavors with controlled radical polymerization receiving the most attention recently. 

Pericyclic reactions were defined in 1969 by R. B. Woodward and R. Hoffmann as reactions in which all first-order change.s in bonding relationships take place in concert on a closed curve that is, as concerted reactions in which all bonds are formed or brokeasimultaneously around a circle. This definition arose from the systematic study of the conservation of orbital symmetry in a series of reactions electrocyclic reactions, cycloadditions, sigmatropic shifts, cheletropic reactions, and group transfer and elimination reactions. Excellent reviews on the historical evolution of pericyclic reactions have been published. ... 

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