Cathodic process formation processes

While the metal or alloy electroless deposition reactions can be considered as cathodic processes, formation of oxides at the metallic surfaces without an external current source can be analyzed as anodic processes. This type of deposition can be illustrated in the example of chemical oxidation of aluminum in chromic acid solutions.9... 

The solution of iron represented in equation 15.1 takes place at local anodes of the steel being processed, while discharge of hydrogen ions with simultaneous dissociation and deposition of the metal phosphate takes place at the local cathodes. Thus factors which favour the cathode process will accelerate coating formation and conversely factors favouring the dissolution of iron will hinder the process. 

The first example relates dissolution of zinc metal. This pertains to Figure 5.2 (A) which provides the answer for conditions of dissolution. The dissolution of a metal is electrochemical in nature and, as the potential for the dissolution of zinc is more negative than both of the above reactions, each of them can serve as a cathodic process to support the anodic dissolution of zinc. It may be seen from Figure 5.2 (A) that solubilization is favorably disposed below a pFF of about 6.9 with the production of Zn2+ ions (cations) and beyond a pH of about 13.4 with the formation ZnO ions (anions). 

SEI formation control is the key to good performance and the safety of the whole lithium ion battery, as not only anode operation but also cathode properties are strongly affected by the SEI formation process (the cathode is the lithium cation source of lithium ion cells). Apart from control of the graphite (surface) properties, an appropriate composition of the electrolyte is usually helpful for creation of an effective SEI. 

Our investigations showed that in mixed melts of eutectic composition carbamide-NH4(K)Cl, the oxidation and reduction of melt constituents take place mainly independently of each other. The anodic process at platinum electrodes in the range of potentials below 0.9V is associated with the direct oxidation of carbamide to secondary and tertiary amide compounds, accumulation of ammonium ions in the melt, and evolution of the same gaseous products as in carbamide electrolysis [8], The cathodic process is accompanied by the formation of ammonia, CO, and C02, i.e. of the same products as in pure- carbamide electrolysis. In contrast to carbamide melt, a large amount of hydrogen appears in the cathode gases of the mixed melt, and in the anode gases of the carbamide-KCl melt, the presence of chlorine has been established at potentials above 0.9V. In the... 

The formation of S-oxides has also been observed when oxidizing a variety of 5-substituted 2-tert-butyl-l,3-dithianes in wet acetonitrile. In an undivided cell, 4-substituted 1,2-dithiolane-l-oxides were oblained (Scheme 25) [113]. A coupled cathodic process, in this case, was the reduction of protons formed in the anodic reaction. 

The reduction of a-carbonyl diphenyldi-thioacetals [212] was reported to be self-catalyzed (with formation in the course of the cathode process of the couple... 

The significance of the supporting electrolyte cation depends crucially on whether a divided or an undivided cell is used. In a divided cell, the choice of cation is of minor importance but in an undivided cell the cathode process should not lead to formation of base and thereby to buffering of the solution. Metal cations such as Li+, Na+ or Mg + are often the choice since in aprotic solvents the metal cation may be the most easily reduced component. This has been observed as deposits of metal on the surface of the cathode arising from... 

Because of the similar potentials between fully lithiated graphite and lithium metal, it has been suggested that the chemical nature of the SEIs in both cases should be similar. On the other hand, it has also been realized that for carbonaceous anodes this formation process is not expected to start until the potential of this anode is cathodically polarized (the discharge process in Figure 11) to a certain level, because the intrinsic potentials of such anode materials are much higher than the reduction potential for most of the solvents and salts. Indeed, this potential polarization process causes one of the most fundamental differences between the SEI on lithium metal and that on a carbonaceous anode. For lithium metal, the SEI forms instantaneously upon its contact with electrolytes, and the reduction of electrolyte components should be indiscriminate to all species possible,while, on a carbonaceous anode, the formation of the SEI should be stepwise and preferential reduction of certain electrolyte components is possible. 

Recent reports about the microdroplets formation in the starting periods of atmospheric corrosion [15-18] show that the idea of a thin uniform water layers is not completely in accordance with the reality. It has been observed that when a water drop is on the metallic surface, formed in the place where a salt deposit existed before, microdroplets are formed around this central drop. The cathodic process takes place in these surrounding microdroplets, meanwhile the anodic process takes place in the central drop. This idea is not consistent with the proposal of an uniform water layer on the surface and it is very probable that this situation could be obtained under indoor conditions. It has been determined that microdrops (about 1 micron diameter) clusters are formed around a central drop. An important influence of air relative humidity is reported on microdrops formation. There is a critical value of relative humidity for the formation of microdroplets. Under this value no microdroplets are formed. This value could be considered as the critical relative humidity. This situation is very similar to the process of indoor atmospheric corrosion presence of humid air, deposition of hygroscopic contaminants in the surface, formation of microdrops. Water is necessary for corrosion reaction to occur, but the reaction rate depends on the deposition rate and nature of contaminants. 

Reductive dissolution may be more complex than the two previous mechanisms in that it involves electron transfer processes. Formation of Fe" via reductive dissolution can be effected by adsorption of an electron donor, cathodic polarization of an electrode supporting the iron oxide and by transfer of an electron from within a ternary surface complex to a surface Fe ". Addition of Fe" to a system containing a ligand such as EDTA or oxalate promotes electron transfer via a surface complex and markedly accelerates dissolution. 

In contrast to the interfacial oxidative condensation polymerization, where discharge of anions occurs at the growing end through the conductive polymer, a new cathodic process of formation of unstable monomers has been developed, followed by polymerization. 

If possible, the cell should be undivided to minimize the construction cost and also the energy consumption (see goal 1). The application of a controlled reaction at the auxiliary electrode taking place at low potential allows for the use of undivided cells in many cases. For oxidations, the cathodic process at the auxiliary electrode may be a proton reduction under formation of hydrogen. For reductions, the anodic process may be the oxidation of formate or oxalate under production of carbon dioxide [68] or the dissolution of sacrificial anodes [69] (see also Sec. V.B). 

The reasons to perform electrochemistry, in particular, electrosynthesis, in a microfluidic system are the following (Rode et al., 2009) (1) reduction of ohmic resistance in the electrochemical cell, by decreasing the distance between anode and cathode, (2) enhancement of mass transport by increase of electrode surface to cell volume ratio, also realized by small interelectrode gaps, (3) performing flow chemistry to establish single-pass conversion, and (4) coupling of cathode and anode processes, permitting simultaneous formation of products at both electrodes. The latter... 

The cathode process has received much less attention than the anode process, probably because the reactions occurring at the cathode have been considered to be simple. However, the cathode reactions are important not only because of cathodic overvoltage but also because they may be connected with the formation of dissolved metal and thereby with the current efficiency of the process. 

Cathodic deposition of magnesium from various chloride melts on different substrates has been studied by several authors [288-290], In dilute solutions of Mg(II) species the cathode process has been found to be controlled by diffusion of the reactant. Alloy formation has been observed on platinum, as reported by Tunold [288] and Duan et al. [290], The rate constant of the charge transfer process on a Mg/Ni electrode in molten NaCl-CaCl2-MgCl2 was reported by Tunold to have a value of about 0.01 cm s 1. This author also reported underpotential deposition of a monolayer on iron electrodes, at potentials approximately 100 mV positive to the Mg deposition potential. 

---