Electrodes and electrode reactions

The electron-transfer step that takes place at each electrode is known as the electrode reaction. The substances that receive and lose electrons are called the electroactive species. 

This process takes place within the very thin interfacial region at the electrode surface, and involves quantum-mechanical tunneling of electrons between the electrode and the electroactive species. The work required to displace the H20 molecules in the hydration spheres of the ions constitutes part of the activation energy of the process. 

Z - hydration sphere of cation distorted by electron i at metal surface 

4 - water molecules Freed from farmer hydration shell 

3 - adsorbed cation now dehydrated end reedy to accept electron 

---

In the past years, the combined characterization of electrodes and electrode reactions... 

The elevated operating temperatures enable the use of non-precious metal electrodes, and electrode reaction kinetics may also be faster at these elevated temperatures. 

In many secondary school textbooks, the topic of electrochemical cells is introduced after redox reactions by demonstrating a galvanic cell, very often the Daniell cell (zinc-copper cell). But for students, this experiment is overwhelming because of this cell does not look like a battery. Moreover, the experiment is confusing for students because of the large number of new phenomena and the complexity of the explanations. We would propose to start with a more simple experiment that clarifies some basic characteristics of cells, especially the concepts of electrolyte, electrode and electrode reaction. 

In general, these points serve to illustrate the heterogeneous nature of corrosion reactions and indicate the need, whenever possible, to identify the component electrodes and electrode reactions of the corrosion cell . Furthermore, it can be seen that compositional changes in the electrolyte are always involved both in facilitating corrosion and as a result of the process. 

The treatment may be made more detailed by supposing that the rate-determining step is actually from species O in the OHP (at potential relative to the solution) to species R similarly located. The effect is to make fi dependent on the value of 2 and hence on any changes in the electrical double layer. This type of analysis has permitted some detailed interpretations to be made of kinetic schemes for electrode reactions and also connects that subject to the general one of this chapter. 

Electrode processes are a class of heterogeneous chemical reaction that involves the transfer of charge across the interface between a solid and an adjacent solution phase, either in equilibrium or under partial or total kinetic control. A simple type of electrode reaction involves electron transfer between an inert metal electrode and an ion or molecule in solution. Oxidation of an electroactive species corresponds to the transfer of electrons from the solution phase to the electrode (anodic), whereas electron transfer in the opposite direction results in the reduction of the species (cathodic). Electron transfer is only possible when the electroactive material is within molecular distances of the electrode surface thus for a simple electrode reaction involving solution species of the fonn... 

Figure Bl.28.7. Schematic shape of steady-state voltaimnograms for reversible, quasi-reversible and irreversible electrode reactions.

The chaimel-flow electrode has often been employed for analytical or detection purposes as it can easily be inserted in a flow cell, but it has also found use in the investigation of the kinetics of complex electrode reactions. In addition, chaimel-flow cells are immediately compatible with spectroelectrochemical methods, such as UV/VIS and ESR spectroscopy, pennitting detection of intennediates and products of electrolytic reactions. UV-VIS and infrared measurements have, for example, been made possible by constructing the cell from optically transparent materials. 

Similarly to the response at hydrodynamic electrodes, linear and cyclic potential sweeps for simple electrode reactions will yield steady-state voltammograms with forward and reverse scans retracing one another, provided the scan rate is slow enough to maintain the steady state [28, 35, 36, 37 and 38]. The limiting current will be detemiined by the slowest step in the overall process, but if the kinetics are fast, then the current will be under diffusion control and hence obey the above equation for a disc. The slope of the wave in the absence of IR drop will, once again, depend on the degree of reversibility of the electrode process. 

The effects of ultrasound-enlianced mass transport have been investigated by several authors [73, 74, 75 and 76]. Empirically, it was found that, in the presence of ultrasound, the limiting current for a simple reversible electrode reaction exhibits quasi-steady-state characteristics with intensities considerably higher in magnitude compared to the peak current of the response obtained under silent conditions. The current density can be... 

Sonoelectrochemistry has been employed in a number of fields such as in electroplating for the achievement of deposits and films of higher density and superior quality, in the deposition of conducting polymers, in the generation of highly active metal particles and in electroanalysis. Furtlienuore, the sonolysis of water to produce hydroxyl radicals can be exploited to initiate radical reactions in aqueous solutions coupled to electrode reactions. 

The combination of electrochemistry and photochemistry is a fonn of dual-activation process. Evidence for a photochemical effect in addition to an electrochemical one is nonnally seen m the fonn of photocurrent, which is extra current that flows in the presence of light [, 89 and 90]. In photoelectrochemistry, light is absorbed into the electrode (typically a semiconductor) and this can induce changes in the electrode s conduction properties, thus altering its electrochemical activity. Alternatively, the light is absorbed in solution by electroactive molecules or their reduced/oxidized products inducing photochemical reactions or modifications of the electrode reaction. In the latter case electrochemical cells (RDE or chaimel-flow cells) are constmcted to allow irradiation of the electrode area with UV/VIS light to excite species involved in electrochemical processes and thus promote fiirther reactions. 

Evans D FI 1991 Review of voltammetric methods for the study of electrode reactions Microelectrodes Theory and Applications (Nate ASI Series E vol 197) ed M I Montenegro, M A Queiros and J L Daschbach (Dordrecht Kluwer)... 

Figure C2.8.2. (a) Schematic polarization curves for tire anodic and catliodic reaction of an Fe/Fe electrode. The anodic and catliodic branches of tire curve correspond to equations (C2.8.12 ) and (C2.8.13 ) respectively. The equilibrium potential of tliis electrode will adjust so tliat j = j tire corresponding potential is of Fe. (b)...

Modelling plasma chemical systems is a complex task, because these system are far from thennodynamical equilibrium. A complete model includes the external electric circuit, the various physical volume and surface reactions, the space charges and the internal electric fields, the electron kinetics, the homogeneous chemical reactions in the plasma volume as well as the heterogeneous reactions at the walls or electrodes. These reactions are initiated primarily by the electrons. In most cases, plasma chemical reactors work with a flowing gas so that the flow conditions, laminar or turbulent, must be taken into account. As discussed before, the electron gas is not in thennodynamic equilibrium... 

Potcntiomctric Biosensors Potentiometric electrodes for the analysis of molecules of biochemical importance can be constructed in a fashion similar to that used for gas-sensing electrodes. The most common class of potentiometric biosensors are the so-called enzyme electrodes, in which an enzyme is trapped or immobilized at the surface of an ion-selective electrode. Reaction of the analyte with the enzyme produces a product whose concentration is monitored by the ion-selective electrode. Potentiometric biosensors have also been designed around other biologically active species, including antibodies, bacterial particles, tissue, and hormone receptors. 

This difference is a measure of the free-energy driving force for the development reaction. If the development mechanism is treated as an electrode reaction such that the developing silver center functions as an electrode, then the electron-transfer step is first order in the concentration of D and first order in the surface area of the developing silver center (280) (Fig. 13). Phenomenologically, the rate of formation of metallic silver is given in equation 17,... 

Compounds. When nitro compounds are reduced by electrochemical methods a number of products are possible depending on such factors as the nature of the electrode, the electrode potential, and the reaction media. For the reduction of nitroben2ene these products include aniline, /)-aminopheno1,j -ch1oroani1ine, phenyUiydroxylamine, a2oxyben2ene, a2oben2ene, and hydra2oben2ene (60). 

Fig. 2. Standard potentials of battery (a) negative electrode and (b) positive electrode reactions (13). Potentials are given in volts.

On the electrode side of the double layer the excess charges are concentrated in the plane of the surface of the electronic conductor. On the electrolyte side of the double layer the charge distribution is quite complex. The potential drop occurs over several atomic dimensions and depends on the specific reactivity and atomic stmcture of the electrode surface and the electrolyte composition. The electrical double layer strongly influences the rate and pathway of electrode reactions. The reader is referred to several excellent discussions of the electrical double layer at the electrode—solution interface (26-28). 

Activation Processes. To be useful ia battery appHcations reactions must occur at a reasonable rate. The rate or abiUty of battery electrodes to produce current is determiaed by the kinetic processes of electrode operations, not by thermodynamics, which describes the characteristics of reactions at equihbrium when the forward and reverse reaction rates are equal. Electrochemical reaction kinetics (31—35) foUow the same general considerations as those of bulk chemical reactions. Two differences are a potential drop that exists between the electrode and the solution because of the electrical double layer at the electrode iaterface and the reaction that occurs at iaterfaces that are two-dimensional rather than ia the three-dimensional bulk. 

The exchange current is directiy related to the reaction rate constant, to the activities of reactants and products, and to the potential drop across the double layer. The larger the more reversible the reaction and, hence, the lower the polarization for a given net current flow. Electrode reactions having high exchange currents are favored for use in battery apphcations. 

The detailed mechanism of battery electrode reactions often involves a series of chemical and electrochemical or charge-transfer steps. Electrode reaction sequences can also include diffusion steps on the electrode surface. Because of the high activation energy required to transfer two electrons at one time, the charge-transfer reactions are beheved to occur by a series of one electron-transfer steps illustrated by the reactions of the 2inc electrode in strongly alkaline medium (41). 

In the thermodynamic treatment of electrode potentials, the assumption was made that the reactions were reversible, which implies that the reactions occur infinitely slowly. This is never the case in practice. When a battery deUvers current, the electrode reactions depart from reversible behavior and the battery voltage decreases from its open circuit or equiUbrium voltage E. Thus the voltage during battery use or discharge E is lower than the voltage measured under open circuit or reversible conditions E by a quantity called the polari2ation Tj. 

When a battery produces current, the sites of current production are not uniformly distributed on the electrodes (45). The nonuniform current distribution lowers the expected performance from a battery system, and causes excessive heat evolution and low utilization of active materials. Two types of current distribution, primary and secondary, can be distinguished. The primary distribution is related to the current production based on the geometric surface area of the battery constmction. Secondary current distribution is related to current production sites inside the porous electrode itself. Most practical battery constmctions have nonuniform current distribution across the surface of the electrodes. This primary current distribution is governed by geometric factors such as height (or length) of the electrodes, the distance between the electrodes, the resistance of the anode and cathode stmctures by the resistance of the electrolyte and by the polarization resistance or hinderance of the electrode reaction processes. 

---