Electron transfer reactions redox potentials

Both the thermodynamics and kinetics of electron transfer reactions (redox potentials and electron transfer rates) have steric contributions, and molecular mechanics calculations have been used to identity them. A large amount of data have been assembled on Co3+/Co2+ couples, and the majority of the molecular mechanics calculations reported so far have dealt with hexaaminecobalt (III/II) complexes. 

The course of electron transfer reactions (redox reactions, see p. 14) also follows the law of mass action. For a single redox system (see p.32), the Nernst equation applies (top). The electron transfer potential of a redox system (i. e., its tendency to give off or take up electrons) is given by its redox potential E (in standard conditions, E° or E° ). The lower the... 

In the dark, the junction between an extrinsic (doped) semiconductor and a redox electrolyte behaves as a diode because only one type of charge carrier (electrons for n-type and holes for p-type) is available to take part in electron transfer reactions. The potential distribution across the semiconductor/electrolyte interface differs substantially from that across... 

The electron-transfer chemiexcitation is shown schematically in molecular orbital terms in Fig. 2. Although other electron-transfer reactions are potentially chemiluminescent (Tokel-Takvoryan et al., 1973), the charge annihilation reaction of oppositely charged aromatic radical ions is the prototypical case and has been most extensively studied. This is due to the convenient preparation of the radical ions by electrochemical means, the large range of redox potentials which are available, and the high fluorescence... 

Many of transition metal ions, especially Zn(ll), Ni(II), Cu(Il), and Pb(ll), are common ions used in the core of the Pc ring. MPcs-RIAM gives very similar redox reactions with H2PCS [22]. They also have possibility to exhibit four reductions and two oxidation reactions. The only difference between the redox properties of MPcs-RIAM is the corresponding potentials of the electron transfer reactions. Peak potentials of MPcs-RIAM shift toward the negative potentials due to the small... 

For a simple electron transfer reaction containing low concentrations of a redox couple in an excess of electrolyte, the potential established at an inert electrode under equilibrium conditions will be governed by the Nemst equation and the electrode will take up the equilibrium potential for the couple 0/R. In temis of... 

Determining Equilibrium Constants for Coupled Chemical Reactions Another important application of voltammetry is the determination of equilibrium constants for solution reactions that are coupled to a redox reaction occurring at the electrode. The presence of the solution reaction affects the ease of electron transfer, shifting the potential to more negative or more positive potentials. Consider, for example, the reduction of O to R... 

Electron Transport Between Photosystem I and Photosystem II Inhibitors. The interaction between PSI and PSII reaction centers (Fig. 1) depends on the thermodynamically favored transfer of electrons from low redox potential carriers to carriers of higher redox potential. This process serves to communicate reducing equivalents between the two photosystem complexes. Photosynthetic and respiratory membranes of both eukaryotes and prokaryotes contain stmctures that serve to oxidize low potential quinols while reducing high potential metaHoproteins (40). In plant thylakoid membranes, this complex is usually referred to as the cytochrome b /f complex, or plastoquinolplastocyanin oxidoreductase, which oxidizes plastoquinol reduced in PSII and reduces plastocyanin oxidized in PSI (25,41). Some diphenyl ethers, eg, 2,4-dinitrophenyl 2 -iodo-3 -methyl-4 -nitro-6 -isopropylphenyl ether [69311-70-2] (DNP-INT), and the quinone analogues,... 

A further important feature of HMPA is its stabilizing effect on the Redox potential of [Fe(CO)4]2 by ion solvation. In less polar solvents, electron-transfer reactions take place and [Fe(CO)4]2 is oxidized to [HFe3(CO)iThis redox reaction is suppressed in HMPA. 

Cyclic voltammetry is the most widely used technique for acquiring qualitative information about electrochemical reactions. The power of cyclic voltammetry results from its ability to rapidly provide considerable information on the thermodynamics of redox processes, on the kinetics of heterogeneous electron-transfer reactions, and on coupled chemical reactions or adsorption processes. Cyclic voltammetry is often the first experiment performed in an electroanalytical study. In particular, it offers a rapid location of redox potentials of the electroactive species, and convenient evaluation of the effect of media upon the redox process. 

The oxidation or reduction of a substrate suffering from sluggish electron transfer kinetics at the electrode surface is mediated by a redox system that can exchange electrons rapidly with the electrode and the substrate. The situation is clear when the half-wave potential of the mediator is equal to or more positive than that of the substrate (for oxidations, and vice versa for reductions). The mediated reaction path is favored over direct electrochemistry of the substrate at the electrode because, by the diffusion/reaction layer of the redox mediator, the electron transfer step takes place in a three-dimensional reaction zone rather than at the surface Mediation can also occur when the half-wave potential of the mediator is on the thermodynamically less favorable side, in cases where the redox equilibrium between mediator and substrate is disturbed by an irreversible follow-up reaction of the latter. The requirement of sufficiently fast electron transfer reactions of the mediator is usually fulfilled by such revemible redox couples PjQ in which bond and solvate... 

Figure 2.9 Schematic structures of Fe-S redox centres, their electron-transfer reactions and approximate range of potentials. See text for details. Individual iron atom oxidation states are not specified for delocalized cluster spin states are indicated. Reprinted with permission from Holm et al., 1996. Copyright (1996) American Chemical Society.

The NO/NO+ and NO/NO- self-exchange rates are quite slow (42). Therefore, the kinetics of nitric oxide electron transfer reactions are strongly affected by transition metal complexes, particularly by those that are labile and redox active which can serve to promote these reactions. Although iron is the most important metal target for nitric oxide in mammalian biology, other metal centers might also react with NO. For example, both cobalt (in the form of cobalamin) (43,44) and copper (in the form of different types of copper proteins) (45) have been identified as potential NO targets. In addition, a substantial fraction of the bacterial nitrite reductases (which catalyze reduction of NO2 to NO) are copper enzymes (46). The interactions of NO with such metal centers continue to be rich for further exploration. 

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... 

Back electron transfer is at the diffusion limit because the homogeneous electron transfer reaction is uphill, owing to the fact that the standard potential of the redox catalyst is necessarily chosen as positive of the reduction potential of the substrate. 

Since k2/k 2 corresponds to the equilibrium constant of the redox reaction (redox potential), Eq. (9.12) suggests that the dissolution reaction may depend both on the tendency to bind the reductant to the Fe(III)(hydr)oxide surface and (even if the electron transfer is not overall rate determining), on the redox equilibrium (see Fig. 9.4b). 

The thermodynamic feasibility of redox reactions at the semiconductor-electrolyte interface can be assessed from thermodynamic considerations. Since typical redox potentials for many redox couples encountered in electrolytes of natural or technical systems often lie between the band potentials of typical semiconductors, many electron transfer reactions are (thermodynamically) feasible (Pichat and Fox, 1988). With the right choice of semiconductor material and pH the redox potential of the cb can be varied from 0.5 to 1.5 V and that of the vb from 1 to more than 3.5 V (see Fig. 10.4). 

AG° for the single electron-transfer reaction can be obtained from the redox potentials of the systems involved in the process and is given by ... 

In this review, wherever electrochemistry is concerned, the reversibility of a reaction refers firstly to the chemical reversibility. It also requires that the electron transfer reaction occurs at such a rate that the rate of the whole electrodic process, which is measured by the output current of the electrode, is controlled by the diffusion of the redox species towards the electrode surface. Furthermore, the surface concentrations of O and R at a given potential should be governed by the Nemst equation. 

Fig. 8-14. Electron state density for a redox electron transfer reaction and profile of electrostatic inner potential, across an electrode interface = potential...

Fig. 8-16. Electron state density in a semiconductor electrode and in hjrdrated redox partides, rate constant of electron tunneling, and exchange redox current in equilibrium with a redox electron transfer reaction for which the Fermi level is close to the conduction band edge eF(sc) = Fermi level of intrinsic semiconductor at the flat band potential 1. 0 (tp.o) = exchange reaction current of electrons (holes) (hvp)) - tunneling rate constant of electrons (holes).

TABLE 8-1. Preference for the conduction band mechanism (CB) and the valence band mechanism (VB) in outer sphere electron transfer reactions of hydrated redox particles at semiconductor electrodes (SC) Eo = standard redox potential referred to NHE c, = band gap of semiconductors. [From Memming, 1983.]... 

A simple reaction of the former molecule with H2 would reduce its two clusters again. The final level of reduction of the Ee-S clusters would then only depend on the effective redox potential in the system. Under 1 per cent H2 at pH 6, where the redox potential is about —295 mV, part of the Fe-S clusters are oxidized. At this pH they only reduce under f 00 per cent H2. At pH 8 or higher, however, the redox potential of both fOO per cent H2 and 1 per cent H2 is low enough to keep all clusters fully reduced. So via intermolecular, one-electron transfer reactions the Fe-S clusters can presumably follow the current potential imposed upon the system by H2 even in the absence of redox mediators. Of course, the presence of such mediators facilitates electron (re)distribution. 

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