Electron transfer reactions Self-exchanges

A. Insights into the Mechanism of the Tl3+/ Tl+ Self-Exchange Reaction VII. Electrochemical Electron-Transfer Reactions... 

The theoretical results obtained for outer-sphere electron transfer based on self-exchange reactions provide the essential background for discussing the interplay between theory and experiment in a variety of electron transfer processes. The next topic considered is outer-sphere electron transfer for net reactions where AG O and application of the Marcus cross reaction equation for correlating experimental data. A consideration of reactions for which AG is highly favorable leads to some peculiar features and the concept of electron transfer in the inverted region and, also, excited state decay. 

In equation (23), a and a2 are the molecular radii of the reactants and r the internuclear separation between them. For a self-exchange reaction where there is no change in coordination number, ai a2 = a, and if it is assumed that electron transfer occurs between the reactants in close contact, a1 + a2 = r which leads to equation (24). Equations (23) and (24) neglect specific contributions from individual solvent molecules such as hydrogen bonding and, also, possible dielectric saturation effects that may arise because of restricted rotations of solvent dipoles in the near vicinity of the electrostatic fields of the ions. 

Most of the redox centers in a polymer film cannot rapidly come into direct contact with the electrode surface. The widely accepted mechanism proposed for electron transport is one in which the electroactive sites become oxidized or reduced by a succession of electron-transfer self-exchange reactions between neighboring redox sites [22]. However, control of the overall rate is a more complex problem. To maintain electroneutrality within the film, a flow of counterions and associated solvent is necessary during electron transport. There is also motion of the polymer chains and the attached redox centers which provides an additional diffusive process for transport. The rate-determining step in the electron site-site hopping is still in question and is likely to be different in different materials. 

The Marcus therory provides an appropriate formalism for calculating the rate constant of an outer-sphere redox reaction from a set of nonkinetic parameters1139"1425. The simplest possible process is a self-exchange reaction, where AG = 0. In an outer-sphere electron self-exchange reaction the electron is transferred within the precursor complex (Eq. 10.4). 

The simplest outer-sphere electron transfer reaction is the so-called self-exchange reaction, where the two reactants are converted one into the other by electron transfer. For example ... 

The simplest elementary act in homogeneous solution chemistry is the exchange of an electron between two chemical entities. No bonds need to be formed or broken in the process, and if the two species are identical, except for a difference in oxidation state, no net chemical change takes place (1). Such self-exchange reactions, although of no chemical consequence, constitute the basis of theoretical treatments of electron transfer. 

Thus the Marcus theory gives rise to a free energy relationship of a type similar to those commonly used in physical organic chemistry. It can be transformed into other relationships (see below) which can easily be subjected to experimental tests. Foremost among these are the remarkably simple relationships that were developed (Marcus, 1963) for what have been denoted cross reactions. All non-bonded electron-transfer processes between two different species can actually be formulated as cross reactions of two self-exchange reactions. Thus the cross reaction of (59) and (60) is (61), and, neglecting a small electrostatic effect, the relationship between kn, k22 and kl2... 

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