Oxide electrodes, their thermodynamics

The ease of reduction of Q may be quantified by the reduction potential of the couple Q/Q , usually denoted by E and expressed in volts relative to the Normal Hydrogen Electrode (NHE). Only if both oxidant Q and reductant Q are in their thermodynamic standard states will the potential E equate to the standard reduction potential of the couple and symbolized as or E . In the present context, interest is focused on effective potentials under physiological conditions, i.e. in water at pH values close to 7. Reduction potentials such as polarographic half-wave potentials obtained in non-aqueous media, especially aprotic solvents such as dimethylformamide or acetonitrile and relative to a standard calomel electrode (for example), will be numerically quite different. should not be confused with a formal potential Eq, which is usually defined as the potential when the ratio of the total concentrations of oxidized and reduced... 

One of the main advantages of the optically transparent thin-layer spectroelectrochemical technique (OTTLSET) is that the oxidized and reduced forms of the analyte adsorbed on the electrode and in the bulk solution can be quickly adjusted to an equilibrium state when the appropriate potential is applied to the thin-layer cell, thereby providing a simple method for measuring the kinetics of a redox system. The formal potential E° and the electron transfer number n can be obtained from the Nernst equation by monitoring the absorbance changes in situ as a function of potential. Other thermodynamic parameters, such as AH, AS, and AG, can also be obtained. Most redox proteins do not undergo direct redox reactions on a bare metal electrode surface. However, they can undergo indirect electron transfer processes in the presence of a mediator or a promoter the determination of their thermodynamic parameters can then... 

The intercalation compounds of lithium with graphite are very different in their behavior from intercalation compounds with oxides or halcogenides. Intercalation processes in the former compounds occur in the potential region from 0 to 0.4 V vs. the potential of the lithium electrode. Thus, the thermodynamic activity of lithium in these compounds is close to that for metallic lithium. For this reason, lithium intercalation compounds of graphite can be used as negative electrodes in batteries rather than the difficultly of handling metallic lithium, which is difficult to handle. 

Anodic oxidation often involves the formation of films on the surface, i.e. of a solid phase formed of salts or complexes of the metals with solution components. They often appear in the potential region where the electrode, covered with the oxidation product, can function as an electrode of the second kind. Under these conditions the films are thermodynamically stable. On the other hand, films are sometimes formed which in view of their solubility product and the pH of the solution should not be stable. These films are stabilized by their structure or by the influence of surface forces at the interface. 

An important example is the corrosion of metals. Most metals are thermodynamically unstable with respect to their oxides. In the presence of water or moisture, they tend to form a more stable compound, a process known as wet corrosion (dry corrosion is not based on electrochemical reactions and will not be considered here). Moisture is never pure water, but contains at least dissolved oxygen, sometimes also other compounds like dissolved salt. So a corroding metal can be thought of as a single electrode in contact with an aqueous solution. The fundamental corrosion reaction is the dissolution of the metal according to ... 

In the past the electrostatic convention has often been called the European convention and the thermodynamic convention popularized by Luitmer (The Oxidation Potentials of the Elements and Their Values in Aqueous Solution Prenlicc-HBlI Englewood Cliffs. NJ, (952) the American convention. In an effort to reduce confusion, the IUPAC adopted the "Stockholm convention" in which electrode potentials refer to the electrostatic potential and end s refer to the thermodynamic quantity. Furthermore, the recommendation is that standard reduction potentials be listed as electrode potentials" to avoid the possibility of confusion over signs. 

The coordination chemist may be interested in the electrosynthesis of compounds, the generation and detection of unstable species in unusual oxidation states and the study of their mechanisms of decay or their spectroscopic properties, or in simply obtaining thermodynamic data. These, and related topics such as using electrogenerated metallo intermediates to catalyze the transformation of inert molecules, modifying the properties of an electrode surface by adsorbing or otherwise binding a coordination compound to it, or fundamental aspects of electron-transfer kinetics, are readily studied by the application of modem electrochemical techniques. 

Besides the effect of the electrode materials discussed above, each nonaqueous solution has its own inherent electrochemical stability which relates to the possible oxidation and reduction processes of the solvent,the salts, and contaminants that may be unavoidably present in polar aprotic solutions. These may include trace water, oxygen, CO, C02 protic precursor of the solvent, peroxides, etc. All of these substances, even in trace amounts, may influence the stability of these systems and, hence, their electrochemical windows. Possible electroreactions of a variety of solvents, salts, and additives are described and discussed in detail in Chapter 3. However, these reactions may depend very strongly on the cation of the electrolyte. The type of cation present determines both the thermodynamics and kinetics of the reduction processes in polar aprotic systems [59], In addition, the solubility product of solvent/salt anion/contaminant reduction products that are anions or anion radicals, with the cation, determine the possibility of surface film formation, electrode passivation, etc. For instance, as discussed in Chapter 4, the reduction of solvents such as ethers, esters, and alkyl carbonates differs considerably in Li or in tetraalkyl ammonium salt solutions [6], In the presence of the former cation, the above solvents are reduced to insoluble Li salts that passivate the electrodes due to the formation of stable surface layers. However, when the cation is TBA, all the reduction products of the above solvents are soluble. 

The thermodynamics of batteries and the kinetics of their electrodes are very complex. The purpose of this section is to introduce the reader to the basic concepts in this area in a simple manner. To achieve this goal, the concepts will be introduced using a simple electrochemical cell as an example, which uses potassium and mercuric oxide as electrodes, instead of using the lithium-ion battery described in Sect. 7.2, which is a more complex... 

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