Redox reactions principles

In principle at least, any spontaneous redox reaction can serve as a source of energy in a voltaic cell. The cell must be designed in such a way that oxidation occurs at one electrode (anode) with reduction at the other electrode (cathode). The electrons produced at the anode must be transferred to the cathode, where they are consumed. To do this, the electrons move through an external circuit, where they do electrical work. 

To determine whether a given redox reaction is spontaneous, apply a simple principle ... 

The stoichiometry of the redox reactions of conducting polymers (n and m in reactions 1 and 2) is quite variable. Under the most widely used conditions, polypyrroles and polythiophenes can be reversibly oxidized to a level of one hole per ca. 3 monomer units (i.e., a degree of oxidation, n, of ca. 0.3).7 However, this limit is dictated by the stability of the oxidized film under the conditions employed (Section V). With particularly dry and unreactive solvents, degrees of oxidation of 0.5 can be reversibly attained,37 and for poly-(4,4 -dimethoxybithiophene), a value of n = 1 has been reported.38 Although much fewer data are available for n-doping, it appears to involve similar stoichiometries [i.e., m in Eq. (2) is typically ca. 0.3].34,39"41 Polyanilines can in principle be reversibly p-doped to one... 

Although this section provides only a brief introduction to equilibrium, the principles presented here arc critically important, because the tendency of reactions to proceed toward equilibrium is the basis of much of chemistry. The material in this section lays the foundation for the next five chapters, including phase changes, the reactions of acids and bases, and redox reactions. 

We begin this chapter with a discussion of the principles of redox reactions, including redox stoichiometry. Then we introduce the principles of electrochemishy. Practical examples of redox chemistry, including corrosion, batteries, and metallurgy, appear throughout the chapter. 

The elementary act of an electrochemical redox reaction is the transition of an electron from the electrode to the electrolyte or conversely. Snch transitions obey the Franck-Condon principle, which says that the electron transition probability is highest when the energies of the electron in the initial and final states are identical. 

It follows from the Franck-Condon principle that in electrochemical redox reactions at metal electrodes, practically only the electrons residing at the highest occupied level of the metal s valence band are involved (i.e., the electrons at the Fermi level). At semiconductor electrodes, the electrons from the bottom of the condnc-tion band or holes from the top of the valence band are involved in the reactions. Under equilibrium conditions, the electrochemical potential of these carriers is eqnal to the electrochemical potential of the electrons in the solution. Hence, mntnal exchange of electrons (an exchange cnrrent) is realized between levels having the same energies. 

The present technique enables light-induced redox reaction UV light-induced oxidative dissolution and visible light-induced reductive deposition of silver nanoparticles. Reversible control of the particle size is therefore possible in principle. The reversible redox process can be applied to surface patterning and a photoelectrochemical actuator, besides the multicolor photochromism. 

Trager WF (2006) Principles of drug metabolism 1 redox reactions. In Taylor JB, Triggle DJ (eds) Comprehensive medicinal chemistry II. Elsevier, Oxford, Sect 5.05... 

The principle of this method is quite simple The electrode is kept at the equilibrium potential at times t < 0 at t = 0 a potential step of magnitude r) is applied with the aid of a potentiostat (a device that keeps the potential constant at a preset value), and the current transient is recorded. Since the surface concentrations of the reactants change as the reaction proceeds, the current varies with time, and will generally decrease. Transport to and from the electrode is by diffusion. In the case of a simple redox reaction obeying the Butler-Volmer law, the diffusion equation can be solved explicitly, and the transient of the current density j(t) is (see Fig. 13.1) ... 

Topics discussed above are some basic principles and techniques in voltammetry. Voltammetry in the frequency domain where i-E response is obtained at different frequencies from a single experiment known as AC voltammetry or impedance spectroscopy is well established. The use of ultramicroelectrodes in scanning electrochemical microscopy to scan surface redox sites is becoming useful in nanoresearch. There have been extensive efforts made to modify electrodes with enzymes for biosensor development. Wherever an analyte undergoes a redox reaction, voltammetry can be used as the primary sensing technique. Microsensor design and development has recently received... 

The principle of electrochemistry is to replace the direct electron transfer between atoms or molecules of a conventional redox reaction by separating... 

In equilibrium of redox reactions, the Fermi level of the electrode equals the Fermi level of the redox particles (ckm) = panodic reaction current equals, but in the opposite direction, the cathodic reaction current (io = io = io). It follows from the principle of micro-reversibility that the forward and backward reaction currents equal each other not only as a whole current but also as a differential current at constant energy level e io(e) = tS(e) = io(e). Referring to Eqns. 8-7 and 8-8, we then obtain the exchange reaction ciurent as shown in Eqn. 8-18 ... 

The transmission coefficient k is approximately 1 for reactions in which there is substantial (>4kJ) electronic coupling between the reactants (adiabatic reactions). Ar is calculable if necessary but is usually approximated by Z, the effective collision frequency in solution, and assumed to be 10" M s. Thus it is possible in principle to calculate the rate constant of an outer-sphere redox reaction from a set of nonkinetic parameters, including molecular size, bond length, vibration frequency and solvent parameters (see inset). This represents a remarkable step. Not surprisingly, exchange reactions of the type... 

The basic theory of the kinetics of charge-transfer reactions is that the electron transfer is most probable when the energy levels of the initial and final states of the system coincide [5] following the Franck-Condon principle. Thus, the efficiency of the redox reaction processes is primarily controlled by the energy overlap between the quantum states in the energy bands of the semiconductor and the donor and acceptor levels of the reactants in the electrolyte (Fig. 1). In the ideal case, the anodic current density is given by the... 

The concept of oxidation has been expanded from a simple combination with oxygen to a process in which electrons are transferred. Oxidation cannot take place without reduction, and oxidation numbers can be used to summarize the transfer of electrons in redox reactions. These basic concepts can be applied to the principles of electrochemical cells, electrolysis, and applications of electrochemistry. 

When you balance a chemical reaction equation, the primary concern is to obey the principle of conservation of mass The total mass of the reactants must equal the total mass of the products. (See Chapter 8 if you need to review this process.) In redox reactions, you must obey a second principle as well the conservation of charge. The total number of electrons lost must equal the total number of electrons gained. In other words, you can t just leave electrons lying around. The universe is finicky about that type of thing. 

Among chemistry students, redox reactions have a bad reputation because of perceptions that they re difficult to understand and even more difficult to balance. But the perception is only a perception. The whole process boils down to the following principles ... 

Maetal ions are known to catalyze many organic reactions in solution. Some ex-m amples of metal ion catalysis are discussed here and an attempt is made to point out the underlying principles concerning metal ion catalysis of organic reactions. Since the field is very large, it is necessary to limit discussion and to omit the topics of metal ion-catalyzed redox reactions and metal ion-catalyzed polymerization reactions, although the latter are extremely important. 

Organic photoeleclrochemistry is that field of investigation in which redox reactions of carbon-based compounds are initiated or assisted by the absorption of a photon at or near the surface of an electrode The principles of photoelectrochemistry have been well described elsewhere and only a very brief discussion of their salient features is given here. 

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