Cathode reactions electrochemical equivalents

Most effort over the electrochemical reduction of benzene hydrocarbons has centred on finding a reaction medium, which is also a better solvent for the substrate than liquid ammonia. Aliphatic amines have proved useful solvents and they may be used in an undivided electrochemical cell. Base is generated at the cathode while an equivalent of acid is generated in the anode reaction so that mixing of the cel contents maintains a neutral solution. An alcohol is usually added as a proton donor to prevent the build-up of a localised highly basic environment. The simultaneous anode reaction is oxidation of the amine. Electrodes of platinum, aluminium or graphite have been used. Under these conditions, benzene [38] is converted... 

In this expression, i is current density, p is density, n is the number of electron equivalents per mole of dissolved metal, M is the atomic weight of the metal, F is Faraday s constant, r is pit radius, and t is time. The advantage of this technique is that a direct determination of the dissolution kinetics is obtained. A direct determination of this type is not possible by electrochemical methods, in which the current recorded is a net current representing the difference between the anodic and the cathodic reaction rates. In fact, a comparison of this nonelectrochemical growth rate determination with a comparable electrochemical growth rate determination shows that the partial cathodic current due to proton reduction in a growing pit in A1 is about 15% of the total anodic current (26). 

In general, metals corrode in aqueous media by an electrochemical mechanism. With iron, for example, one set of reactions occurs at anode sites of the metal surface and another set of reactions, chemically equivalent to the first, occurs at cathode sites. The over-all anode reaction is... 

At a cathodic site, the electrons react with some reducible component of the electrolyte and are themselves removed from the metal. The rates of the anodic and cathodic reactions must be equivalent according to Faraday s laws, determined by the total flow of electrons from anodes to cathodes, which is called the corrosion current 7. The most common and important electrochemical reactions in the corrosion of iron are thus [6] given as follows. 

In the particular case of lithiation or delithiation of cathode materials used in lithium secondary batteries, the calculation of the electrochemical equivalent involves an additional parameter related to the reaction of intercalation of lithium cations into the crystal lattice of the host cathode materials. Consider the theoretical reversible reaction of intercalation of lithium into a crystal lattice of a solid host material (e.g., oxide, sulfide) ... 

The smnmary equation (10) is an electrochemical equivalent of the chemical reaction (1). However, this system does not take into account the fact that for reaction (9) to occur the Cl- anions obtained in proximity to the cathode surface by reaction (8)... 

Figure 8.16 shows an equivalent electrical circuit that simulates the pipeline cathodic protection depicted in Figure 8.9. Both pipeline and sacrificial anode (galvanic anode or inert anode) are buried in the soil of uniform resistivity. The pipehne is connected to the negative terminal and the anode to the positive terminal of an external power source (battery). The arrows in Figure 8.16 indicates the direction of the ciurent flow from the anode to the pipehne. The electron flow is also toward the pipehne to support local cathodic reactions and the protechve current (Ip) flows from the pipehne to the power supply. The soil becomes the electrolyte for complehng the protective electrochemical system or cathodic protechon circmt [24].

Clemmensen reduction can be effected either using amalgamated zinc or cadmium and hydrochloric acid, or in the equivalent electrochemical reaction at cathodes of cadmium or lead in 30 % sulphuric acid (see p. 344). Where the amino function is associated with a ring system, Clemmensen reduction of a-aminoketones gives rise to three types of product ... 

In another procedure, oxidation is carried out in the presence of chloride ions and ruthenium dioxide [31]. Chlorine is generated at the anode and this oxidises ruthenium to the tetroxide level. The reaction medium is aqueous sodium chloride with an inert solvent for the alkanol. Ruthenium tetroxide dissolves in the organic layer and effects oxidation of the alkanol. An undivided cell is used so that the chlorine generated at the anode reacts with hydroxide generated at the cathode to form hypochlorite. Thus this electrochemical process is equivalent to the oxidation of alkanols by ruthenium dioxide and a stoichiometric amount of sodium hypochlorite. Secondary alcohols are oxidised to ketones in excellent yields. 1,4- and 1,5-Diols with at least one primary alcohol function, are oxidised to lactones while... 

This last electrochemical process is carried out in an undivided electrolysis cell fitted with a sacrificial magnesium anode and a nickel foam as cathode. The reaction is conducted in dimethylformamide in the presence of both NiBr2(bpy) as the catalyst and dried ZnBr2 (1.1 molar equivalents with respect to bromothiophene), which is used both as supporting electrolyte and as a zinc(II) ion source. The other conditions are the same as those described in the section concerning the aromatic halides. The yield of 3-thienylzinc bromide was roughly 80%, as determined by GC analysis after treatment with iodide (equation 34). 

Energetics of oxidation-reduction (redox) reactions in solution are conveniently studied by arranging the system in an electrochemical cell. Charge transfer from the excited molecule to a solid is equivalent to an electrode reaction, namely a redox reaction of an excited molecule. Therefore, it should be possible to study them by electrochemical techniques. A redox reaction can proceed either by electron transfer from the excited molecule in solution to the solid, an anodic process, or by electron transfer from the solid to the excited molecule, a cathodic process. Such electrode reactions of the electronically excited system are difficult to observe with metal electrodes for two reasons firstly, energy transfer to metal may act as a quenching mechanism, and secondly, electron transfer in one direction is immediately compensated by a reverse transfer. By usihg semiconductors or insulators as electrodes, both these processes can be avoided. 

A new development is that electrochemical oxidation of ferrocyanide to ferricyanide can be coupled with AD to give a very efficient electrocatalytic process [37]. Under these conditions, the amount of potassium ferricyanide needed for the reaction becomes catalytic and Eqs. 6D.6 and 7 can be added following Eq. 6D.4. Summation of Eq. 6D.1-6D.4, 6D.6, and 6D.7 gives 6D.8, showing that only water in addition to electricity is needed for the conversion of olefins to asymmetric diols and that hydrogen gas, released at the cathode, is the only byproduct of this process. In practice, sodium ferrocyanide is used in the reaction and the amount of this reagent used in comparison with the potassium ferricyanide method mentioned above has been reduced from 3.0 equiv. to 0.15 equiv. (relative to an equivalent of olefin). 

A coastal beach in California is polluted with heavy metals. Since it is a protected wildlife habitat, a minimally intrusive electrochemical method is selected for cleanup. Assume that a constant current density of 125 pA cm-2 in a 40 x 6-foot cross section is used in the contaminant pit, which is 40 x 20 x 6 feet deep, (a) What is the total current and voltage required if the pore fluid conductivity is 21.9 mS cm-1 (approx, equivalent to 0.2 M KC1) (b) If the soil is saturated and approx. 50% pore fluid and 50% solids by volume, how long would it take to pass a charge equivalent to the ionic content of the pore fluid (c) How much acid should be added to depolarize the cathode in this time in order to ensure reaction (A) below, instead of water electrolysis, reaction (B) ... 

Theoretical capacity — A calculated amount of electricity (-> charge) involved in a specific electrochemical reaction (expressed for -> battery -> discharge), and usually expressed in terms of -> ampere-hours per kg or -> coulombs per kg. The theoretical capacity for one gram-equivalent weight of material amounts to 96,487 C (see -> Faraday constant) or 26.8 Ah. The general expression for the calculation of the theoretical capacity (in Ah kg-1) for a given -> anode material and - cathode material and their combination as full cell is given by... 

The methods of coulometry are based on the measurement of the quantity of electricity involved in an electrochemical electrolysis reaction. This quantity is expressed in coulombs and it represents the product of the current in amperes by the duration of the current flow in seconds. The quantity of electricity thus determined represents, through the laws of Faraday, the equivalents of reactant associated with the electrochemical reaction taking place at the electrode of significance. In the analytical chemistry sense, the process of coulometry, carried out to the quantitative reaction of the analyte in question, either directly or indirectly, will yield the number of analyte equivalents involved in the sample under test. This will lead to a quantitative determination of the analyte in the sample. Analytical coulometry can be carried out either directly or indirectly. In the former the analyte usually reacts directly at the surface of either the anode or cathode of the electrolysis cell. In the latter, the analyte reacts indirectly with a reactant produced by electrolytic action at one of the electrodes in the electrolysis cell. In either case, the determination will hinge on the number of coulombs consumed in the analytical process. 

An electrochemical power source comprises two electrodes of different materials immersed in electrolyte, whereby electrode systems with different potentials are formed at the two electrodes. Electrochemical reactions proceed at the two interfaces which involve transfer of electrons between the electrode surface and ions from the solution. The difference between the potentials of the two electrodes generates the electromotive force of the electrochemical power source. When the two electrodes (anode and cathode) are connected to a conductor with a load, electric current which can do work flows between them, i.e., the chemical energy can be converted into an electrical one. Electric current flows due to changes of the valences of the materials at the two electrodes. Michael Faraday established that, when one gram equivalent of any substance takes part in an electrochemical reaction, the quantity of electricity that flows is always equal to 96,487 coulombs (C). This value is called Faraday constant, after the name of M. Faraday, and is denoted by the symbol F. The value of the constant is generally rounded to 96,5(X) C. 

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