Electrochemical Processes Protons

Hydrogen evolution at metal electrodes is one of the most important electrochemical processes. The mechanisms of the overall reaction depend on the nature of the electrode and solution. However, all of them involve the transfer of proton from a donor molecule in the solution to the adsorbed state on the electrode surface as the first step. The mechanism of the elementary act of proton transfer from the hydroxonium ion to the adsorbed state on the metal surface is discussed in this section. 

Lengyel, S., and B. E. Conway, Proton solvation and transfer in chemical and electrochemical processes, CTE, 5, Chap. 4. 

The several theoretical and/or simulation methods developed for modelling the solvation phenomena can be applied to the treatment of solvent effects on chemical reactivity. A variety of systems - ranging from small molecules to very large ones, such as biomolecules [236-238], biological membranes [239] and polymers [240] -and problems - mechanism of organic reactions [25, 79, 223, 241-247], chemical reactions in supercritical fluids [216, 248-250], ultrafast spectroscopy [251-255], electrochemical processes [256, 257], proton transfer [74, 75, 231], electron transfer [76, 77, 104, 258-261], charge transfer reactions and complexes [262-264], molecular and ionic spectra and excited states [24, 265-268], solvent-induced polarizability [221, 269], reaction dynamics [28, 78, 270-276], isomerization [110, 277-279], tautomeric equilibrium [280-282], conformational changes [283], dissociation reactions [199, 200, 227], stability [284] - have been treated by these techniques. Some of these... 

Of hundreds of theoretically possible pathways, the list can be trimmed to four using linear sweep voltammetry (LSV) and chemical arguments [22]. The LSV method is an exceptionally powerful one for analyzing electrochemical processes [24-27]. From LSV studies, it was concluded that a single heterogeneous electron transfer precedes the rate-determining step, cyclization is first order in substrate, and that proton transfer occurs before or in the rate-determining step. The candidates include (a) e-c-P-d-p (radical anion closure). 

Since their discovery in 1866, it has been known that sulphoxides are reducible by zinc and acid to the conesponding sulphide [63], fhe equivalent electrochemical process cannot be characterised because sulphoxides also decrease the hydrogen overpotential [64], Dialkyl sulphoxides are not reduced in absence of protons and dimethyl sulphoxide is used as a solvent for electrochemical reduction. Phenyl methyl sulphoxide gives a single two-electron wave on polarography in both ethanol (E./, = -2.17 V vs. see) and dimethylformamide (E./, = -2.32 V vs. see), forming phenyl methyl sulphide [65],... 

The biologically active relatives of folic acid and biopterin are the tetrahydro compounds with a reduced pyrazine ring. Reduction to this level occurs rapidly in vivo. The corresponding electrochemical process is well illustrated by reduction of the N-methylated analogue 28 [95], Reduction to the 5,8-dihydro stage is a reversible two-electron and two-proton process. The product rapidly tautomerises to the... 

The shape of this wave and the variation with pH are both consistent with fast equ-librium reactions In the pH region lower than the value of pK, for the hydroxyl radical, the reactions of this hydroxyl radical dominate the electrochemical process. Controlled potential reduction at the potential of this first wave indicates a IF process and the principal products are dimers of the hydroxyl radical. The second wave in this acidic region is due to addition of an electron and a proton to the neutral radical. This process competes with dimerization in the mid-pH range where the two polarographic waves merge. Over the pH range 7-9, monohydric alcohol is the principal product. At pH <3 or >12, pinacols are the main products. Unsymmet-rical carbonyl compounds afford mixtures of ( )- and meso-pinacols. Data (Table 10.3) for the ( ) / meso isomer ratio for pinacols from acetophenone and propio-phenone indicate different dimerization mechanisms in acid and in alkaline solutions. 

In the presence of excess monoalkylamine, carbonyl compounds in aqueous solution are in equilibrium with the corresponding imine. In most cases these imines cannot be isolated but they are reduced at a less negative potential than the carbonyl compound. Selective reduction of such equilibrium mixtures is a useful route to alkylamines from ketones in yields of 70-90%. The process fails with hindered ketones such as camphor and with bulky amines such as fert.-butyl amine. Overall the reaction has advantages of lower costs and simpler work-up compared to the use of cyanoborohydride reducing agents. In the electrochemical reaction, protonation of carbanion intermediates occurs from the more hindered side and where two isomeric products are fomied, the least hindered amine predominates [193]. 

The foregoing considerations can also be applied to the electrochemistry of a number of organic compounds in contact with aqueous buffers [107, 119-125]. Here, protonation/deprotonation reactions are coupled with electron transfer processes, as described for the case of indigoid-, anthraquinonic-, and flavonoid-type pigments, among others. In contact with aqueous electrolytes, the electrochemical processes can generally be described as ... 

Fig. 2.7 Schematic representation of electrochemical processes (reduction) for organic solids able to experience coupled proton transport/electron transport processes...

The electrochemical processes involving Prussian blue and organic dyes studied above can be taken as examples of solid state redox processes involving transformation of a one solid compound into another one. This kind of electrochemical reactions are able to be used for discerning between closely related organic dyes. As previously described, the electrochemistry of solids that are in contact with aqueous electrolytes involves proton exchange between the solid and the electrolyte, so that the electrochemical reaction must in principle be confined to a narrow layer in the external surface of the solid particles. Eventually, however, partial oxidative or reductive dissolution processes can produce other species in solution able to react with the dye. 

Figure 14.2 Illustration of electrochemical processes occurring in solutions with benzoquinone-hydroquinone and proton-hydrogen couples (a) processes cycling electrons through connected system, and (b) voltage measured between separated half reactions.

Proton transport in aqua solution is an electrochemical process that is important not only for numerous biochemical reactions, but it plays a fundamental role in the generation of power in fuel cells. It is connected by that a proton is the basic agent of go-ahead carry of a charge in the water solutions used in fuel cells, as it is shown on Fig. 1. 

The problem of estimating the structure of the transition state of an electrochemical process is especially important with respect to possible concerted reactions, i.e. reactions at which the electron transfer coincides with bond breaking or formation. The reduction of a protonated water molecule has been described in exactly those terms which an organic chemist would use for an ordinary concerted mechanism. 

Optimizing the rates of the electrochemical processes (Reactions 2 and 3) consti tute much of the R D focus in electrochemical or photoelectrochemical splitting of water. Two compartment cells are also employed to spatially separate the evolved gases with special attention being paid to the proton transport membranes (e.g., Na-fionR). Chapter 3 provides a summary of the progress made in water electrolyzer technologies. 

Methods for reduction of enones may be divided conveniently into four historically based classes. The earliest procedures employed dissolving metals more recent developments, such as reduction with low-valent transition metal compounds and electrochemical processes, may also be included in this category as they all proceed via sequential addition of electrons and protons to the substrate molecule. These methods are discussed in Section 3.5.2. 

Proton-coupled electron transfer (PCET) reactions play a vital role in a wide range of chemical and biological processes. For example, PCET is required for the conversion of energy in photosynthesis [1] and respiration [2], In particular, the coupling between proton motion and electron transfer is involved in the pumping of protons across biological membranes in photosynthetic reaction centers [1] and in the conduction of electrons in cytochrome c [3]. In addition to biological processes, PCET is also important in electrochemical processes [4, 5] and in solid state materials [6]. 

Until now we have mainly considered redox electrolytes comprising one-electron oxidizing or reducing agents. Multi-electron redox processes, however, are important in a variety of scenarios. Consider the reduction of protons to H2 (HER), a technologically important electrochemical process that has also been extensively studied from a mechanistic perspective on metallic electrodes. 

The general pattern of anodic behavior of para-substituted anilines (68) was established in aqueous acidic media by Bacon and Adams17,106. The postulated one-electron oxidation of the substrate to the radical cation 681 is followed by rapid head-to-tail coupling of 681 with the substrate 68 giving protonated 4 -substituted 4-aminodiphenylamine in the oxidized form (69) as the final main product. The product 69 shows reversible redox peaks at more cathodic potentials, supporting its identification beside the spectral and chemical analysis. The product formation is preceded by elimination of one para-substituent and, if it leaves as an anion (e.g. halide, methoxide or ethoxide ion), then the overall electrochemical process (equation 1) corresponds to a one-electron (two electrons per two reactant molecules) process. However, if it leaves as a neutral group (e.g. CO2 in the oxidation of p-aminobenzoic acid), a dimer is formed in the reduced form and the overall reaction is a two-electron process. 

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