Electron transfer reaction association

Matsue. T. Evans. D.H. Osa, T. Kobayashi, N. Electron-transfer reactions associated with host-guest complexation. Oxidation of ferrocenecarboxylic acid in the presence of 13-cyclodextrin. J. Am. Chem. Soc. 1985, 107. 3411. 

Hale in 1968 calculated the limiting electric current for an electron transfer reaction associated with the activationless process. The degenerate Fermi gas model was used to describe the electrons in the metal. 

Several processes are unique to ions. A common reaction type in which no chemical rearrangement occurs but rather an electron is transferred to a positive ion or from a negative ion is tenued charge transfer or electron transfer. Proton transfer is also conunon in both positive and negative ion reactions. Many proton- and electron-transfer reactions occur at or near the collision rate [72]. A reaction pertaining only to negative ions is associative detaclunent [73, 74],... 

Figure C3.2.1. A slice tlirough tlie intersecting potential energy curves associated witli tlie K-l-Br2 electron transfer reaction. At tlie crossing point between tlie curves (Afy, electron transfer occurs, tlius Tiarjiooning tlie species,...

The properties of electron transfer proteins that are discussed here specifically affect the electron transfer reaction and not the association or binding of the reactants. A brief overview of these properties is given here more detailed discussions may be found elsewhere (e.g.. Ref. 1). The process of electron transfer is a very simple chemical reaction, i.e., the transfer of an electron from the donor redox site to the acceptor redox site. 

Here, the relative stability of the anion radical confers to the cleavage process a special character. Thus, at a mercury cathode and in organic solvents in the presence of tetraalkylammonium salts, the mechanism is expected16 to be an ECE one in protic media or in the presence of an efficient proton donor, but of EEC type in aprotic solvents. In such a case, simple electron-transfer reactions 9 and 10 have to be associated chemical reactions and other electron transfers (at the level of the first step). Those reactions are shown below in detail ... 

The cytochromes are another group of haem proteins found in all aerobic forms of life. Cytochromes are electron carriers involving a Fe(ii)/Fe(m) redox system. They are a crucial part of the electron transfer reactions in mitochondria, in aspects of the nitrogen cycle, and in enzymic processes associated with photosynthesis. 

In this chapter we treat electron-transfer reactions from a macroscopic point of view using concepts familiar from chemical kinetics. The overall rate v of an electrochemical reaction is the difference between the rates of oxidation (the anodic reaction) and reduction (the cathodic reaction) it is customary to denote the anodic reaction, and the current associated with it, as positive ... 

For the mechanistic interpretation of activation volume data for nonsymmetrical electron-transfer reactions, it is essential to have information on the overall volume change that can occur during such a process. This can be calculated from the partial molar volumes of reactant and product species, when these are available, or can be determined from density measurements. Efforts have in recent years focused on the electrochemical determination of reaction volume data from the pressure dependence of the redox potential. Tregloan and coworkers (139, 140) have demonstrated how such techniques can reveal information on the magnitude of intrinsic and solvational volume changes associated with electron-transfer reactions of transition... 

Many electron transfer reactions are, of course, studied at quite high electrolyte concentrations, and effects of this type, even with what are usually inert electrolytes, can be important. We think this effect is due mainly to ion association, so that ion pairs, triplets, etc., are involved as reactants ... 

The theoretical modeling of electron transfer reactions at the solution/metal interface is challenging because, in addition to the difficulties associated with the quantitative treatment of the water/metal surface and of the electric double layer discussed earlier, one now needs to consider the interactions of the electron with the metal surface and the solvated ions. Most theoretical treatments have focused on electron-metal coupling, while representing the solvent using the continuum dielectric media. In keeping with the scope of this review, we limit our discussion to subjects that have been adi essed in recent years using molecular dynamics computer simulations. 

A substitution reaction involves the breaking of one bond and the formation of another one. We discuss in this section reactions in which electron transfer is associated with the breaking of a bond but in which either no bond formation occurs or, if it does, takes place in a further separated step. For such processes, a series of fundamental questions arise. Are electron... 

The rates of electron-transfer reactions can be well predicted provided that the electron transfer is a type of adiabatic outer-sphere reaction and the free-energy change of electron transfer and the reorganization energy (X) associated with the electron transfer are known [1-7]. This means that electron-transfer reactions can be designed quantitatively based on the redox potentials and the reorganization energies of molecules involved in the electron-transfer reactions. 

REDOX HALF-REACTIONS. Electron transfer reactions involve oxidation (or loss of electrons) of one component and reduction (or gain of electrons) by a second component. Therefore, a complete redox reaction can be treated as the sum of two half-reactions such that the stoichiometry and electric charge is balanced across a chemical equilibrium. For each such half-reaction, there is an associated standard potential E°. The hydrogen ion-hydrogen gas couple is ... 

If one takes a spontaneous electron-transfer reaction and separates the materials undergoing oxidation and reduction, allowing the electron transfer to occur through a good conductor such as a copper wire, a battery is created. By proper design, the electrical energy associated with reactions of this type can be harnessed. The fields of electrochemistry (e.g., batteries) and pyrotechnics (e.g., fireworks) are actually very close relatives. The reactions involved in the two areas can look strikingly similar ... 

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