Anodic oxides formation mechanism

Anodic oxide formation suggests itself as a passivating mechanism in aqueous electrolytes, as shown in Fig. 6.1a. However, pore formation in silicon electrodes is only observed in electrolytes that contain HF, which is known to readily dissolve Si02. For current densities in excess of JPS a thin anodic oxide layer covers the Si electrode in aqueous HF, however this oxide is not passivating, but an intermediate of the rapid dissolution reaction that leads to electropolishing, as described in Section 5.6. In addition, pore formation is only observed for current densities below JPS. Anodic oxides can therefore be excluded as a possible cause of pore wall passivation in PS layers. Early models of pore formation proposed a... 

The mechanism is determined from the competition between anodic oxide formation ... 

A quantitative description of the diverse morphological features of PS requires the integration of the aspects discussed above as well as the fundamental reaction processes involved in silicon/electrolyte interface structure, anodic dissolution, and anodic oxide formation and dissolution as detailed in Chapters 2-5. Any mathematical formulation for the mechanisms of PS formation without such a global integration would be limited in the scope of its validity and in the power to explain details. In addition, a globally and microscopically accurate model would also require the full characterization of all of the morphological features of PS in relation to all of the... 

Duncan and Frankenthal report on the effect of pH on the corrosion rate of gold in sulphate solutions in terms of the polarization curves. It was found that the rate of anodic dissolution is independent of pH in such solutions and that the rate controlling mechanism for anodic film formation and oxygen evolution are the same. For the open circuit behaviour of ferric oxide films on a gold substrate in sodium chloride solutions containing low iron concentration it is found that the film oxide is readily transformed to a lower oxidation state with a Fe /Fe ratio corresponding to that of magnetite . 

Faraday, in 1834, was the first to encounter Kolbe-electrolysis, when he studied the electrolysis of an aqueous acetate solution [1], However, it was Kolbe, in 1849, who recognized the reaction and applied it to the synthesis of a number of hydrocarbons [2]. Thereby the name of the reaction originated. Later on Wurtz demonstrated that unsymmetrical coupling products could be prepared by coelectrolysis of two different alkanoates [3]. Difficulties in the coupling of dicarboxylic acids were overcome by Crum-Brown and Walker, when they electrolysed the half esters of the diacids instead [4]. This way a simple route to useful long chain l,n-dicarboxylic acids was developed. In some cases the Kolbe dimerization failed and alkenes, alcohols or esters became the main products. The formation of alcohols by anodic oxidation of carboxylates in water was called the Hofer-Moest reaction [5]. Further applications and limitations were afterwards foimd by Fichter [6]. Weedon extensively applied the Kolbe reaction to the synthesis of rare fatty acids and similar natural products [7]. Later on key features of the mechanism were worked out by Eberson [8] and Utley [9] from the point of view of organic chemists and by Conway [10] from the point of view of a physical chemist. In Germany [11], Russia [12], and Japan [13] Kolbe electrolysis of adipic halfesters has been scaled up to a technical process. 

The mechanism of anodic oxidation of CO at polycrystalline Au remains uncertain. Several groups have reported that the voltammetry of Au in acidic electrolytes is straightforward, with a well-formed oxidation wave/peak [Stonehart, 1966 Gibbs et al., 1977 Kita et al., 1985 Sun et al., 1999]. There is, however, no voltammetric evidence for the adsorption of CO on the Au surface, and spectroscopic studies indicate only a weak interaction of CO with poly crystalline Au surfaces in acidic solutions [Kunimatsu et al., 1986 Cuesta et al., 2003]. Moreover, there is little evidence for the formation of oxidizing species at the potential where the oxidation process is observed. Certainly, the oxidation of CO occurs at a potential over 500 mV less positive than that where bulk Au oxide is formed, and, indeed, the formation of this oxide strongly... 

The electrochemical mechanism can be well explained with the mineral pyrite. The collector ion is xanthate ion (CT), a member in the anodic sulfydryl collectors group. Two electrochemical reactions occur on the surface of the pyrite. There is the formation of dixanthogen (C2) by anodic oxidation of xanthate ion (CT) on the surface of pyrite coupled with cathodic reduction of adsorbed oxygen. These reactions are shown below ... 

Various mechanisms for electret effect formation in anodic oxides have been proposed. Lobushkin and co-workers241,242 assumed that it is caused by electrons captured at deep trap levels in oxides. This point of view was supported by Zudov and Zudova.244,250 Mikho and Koleboshin272 postulated that the surface charge of anodic oxides is caused by dissociation of water molecules at the oxide-electrolyte interface and absorption of OH groups. This mechanism was put forward to explain the restoration of the electret effect by UV irradiation of depolarized samples. Parkhutik and Shershulskii62 assumed that the electret effect is caused by the accumulation of incorporated anions into the growing oxide. They based their conclusions on measurements of the kinetics of Us accumulation in anodic oxides and comparative analyses of the kinetics of chemical composition variation of growing oxides. 

Fig. 5.4 Voltage-time curve for a p-type silicon electrode anodized galvanostatically at 0.1 mA cm"2 in 10% acetic acid. Silicon electrodes were removed from the electrolyte after various anodization times (filled circles) and the thickness of the anodic oxide was measured by ellipsometry (open circles). The curvature of the sample was monitored in situ and is plotted as the value of stress times oxide thickness (filled triangles). The bar graph below the V(t) curve shows a proposed formation mechanism. Galvanostatically a...

Oxidations of heterocycles can afford formations of double bonds. This is illustrated by the anodic oxidation of dihydropy-ridines (Scheme 11) [16] for which pyri-dinium cations are produced according to an ECE mechanism. Unsubstituted dihy-dropyridines at carbon 4 give pyridines. 

The formation of a double bond during anodic oxidations can result from eliminations of protons, carbon dioxide or acylium cations. The electrooxi dative aromatization of dihydropyridine derivatives and heterocycles containing nitrogen atom (di-hydroquinoxalines, tetrahydrocinnolines) involves an ECE mechanism as previously... 

In the absence of more easily oxidized substrates, residual water in aprotic solvents will undergo oxidation at platinum anodes. However, the mechanism of proton formation is not necessarily by simple water oxidation with the evolution of O2 but may involve radical reactions of the solvent or oxidation of supporting electrolyte anions [6, 7]. The protons produced, together with the most basic species in solution, form... 

Anodic oxidation of 45 in dry acetonitrile at 60 °C and at low current density provided a quantitative yield of 46, while oxidation of 45 in aqueous acetonitrile at 0 °C provided a high yield of 47. It has been shown that quinoneimine 47 can be transformed to 46 in 93% yield, through BF3Et20 catalyzed cyclization [75]. The reaction pathways leading to the formation of 46 or 47 are summarized in Scheme 25. Two-electron oxidation of 45 leads to the cation 45a through an ECE or e-p-e mechanism. It seems that the cyclization of 45a is the ratedetermining step in the overall intramolecular cyclization of 45 to 46. The high... 

Hoar, T. P. and N. F. Mott. 1959. Mechanism for the formation of porous anodic oxide films on aluminum. J. Phys. Chem. Solids 9 97-99. 

Electrolytic or anodic oxidation is fast, uniform and best suited to mass production. This process is most widely used for treatment of commercial carbon fibers. The oxidation mechanism of most carbon fibers is characterized by simultaneous formation of CO2 and degradation products that are dissolved in the electrolyte of alkaline solution or adhere onto the carbon fiber surface in nitric acid. Only minor changes in the surface topography and the surface area of the fiber are obtained with a small weight loss, say, normally less than 2%. 

We are still further from being able to explain the anodic activity of the CoTAA complex. The cobalt phthalocyanine, which is structurally identical with CoTAA in the inner coordination sphere, is completely inactive in the catalysis of anodic reactions. It therefore looks as if the central region is not exclusively responsible for the anodic activity. On the other hand, the fact that CoTAA is inactive for the oxidation of H2 points to n orbitals of the fuel participating in the formation of the chelate-fuel complex. A redox mechanism (cf. Section 5.2) can be ruled out because anodic oxidation proceeds only in the region below the redox potential of CoTAA (i.e. at about 600—650 mV). 

On the basis of oxidation potentials, current-potential relationships, and isotope effects, an electron-transfer mechanism is suggested for the anodic oxidation of methyl N,N-dialkyl substituted carbamates, which can reasonably explain the formation of all three types of products. Also, N-acylazacycloalkanes are converted anodically at a platinum electrode in R0H-Et4NBF4 into a-monoalkoxy or a,a -dialkoxy derivatives depending on the electrolysis conditions employed.198... 

The anodic oxidation of 10-phenylphenothiazine in CH3CN-Et4NC104 solution of pyridine gives rise to the formation of JV-[3-(10-phenylphenothia-zinyl)]pyridinium perchlorate, the parent compound, and pyridinium perchlorate.274 On the basis of kinetic determinations a half-regeneration mechanism was proposed. 

The anodic oxidation of 2-amino-5-ethoxycarbonyl-4-methylthiazole (268) has been studied in CH3CN-LiC104.425 The mechanism of the formation of azo (273) and hydrazo (271) dimeric compounds as the main oxidation products is shown in Eq. (141). 

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