Carbon electrodes thermodynamics

Recent studies describe the use of cyclic voltammetry in conjunction with controlled-potential coulometry to study the oxidative reaction mechanisms of benzofuran derivatives [115] and bamipine hydrochloride [116]. The use of fast-scan cyclic voltammetry and linear sweep voltammetry to study the reduction kinetic and thermodynamic parameters of cefazolin and cefmetazole has also been described [117]. Determinations of vitamins have been studied with voltammetric techniques, such as differential pulse voltammetry for vitamin D3 with a rotating glassy carbon electrode [118,119], and cyclic voltammetry and square-wave adsorptive stripping voltammetry for vitamin K3 (menadione) [120]. 

Twenty years ago the main applications of electrochemistry were trace-metal analysis (polarography and anodic stripping voltammetry) and selective-ion assay (pH, pNa, pK via potentiometry). A secondary focus was the use of voltammetry to characterize transition-metal coordination complexes (metal-ligand stoichiometry, stability constants, and oxidation-reduction thermodynamics). With the commercial development of (1) low-cost, reliable poten-tiostats (2) pure, inert glassy-carbon electrodes and (3) ultrapure, dry aptotic solvents, molecular characterization via electrochemical methodologies has become accessible to nonspecialists (analogous to carbon-13 NMR and GC/MS). 

Carbon is generally used as catalyst support material because of its high electric and thermal conductivity, chemical stability, and porous structure [11]. The catalytic activity of the catalyst layer increases with increasing carbon surface area due to better platinum dispersion. High surface area carbon blacks such as Ketjenblack and Vulcan are therefore preferred in PEMFC application. However, carbon is thermodynamically unstable at normal cathode potentials between 0.5 and 1V. As shown in Figure 20.1a, carbon is oxidized to carbon dioxide (CO2) or carbon monoxide (CO) at high electrode potentials whereas it is reduced to methane (CH4) at low electrode potentials. The following reactions are relevant for fuel-cell operation ... 

Taraszewska, J.,and Roslonek,G., "Effect of solvent on the kinetic and thermodynamic redox properties of Ni(III)/ Ni(II) in tetraazamacrocyclic complexes with pendant amino group and cyclam studied on the glassy carbon electrodes", J.Electroanal.Chem.,(in press). 

The standard potential for the Ru(II/III) redox transformation is 712 mV in aqueous perchlorate media, whereas the standard potential for the ferrocyanide/ferricyanide couple is 375 mV. Hence the driving force for the mediation is some 337 mV, which corresponds to an equilibrium constant of 5 X 10 at 298 K. Thus we see that equilibrium lies very much on the rhs. Typical RDE voltammograms for the oxidation of Fe(CN)e in 0.1 M HCIO4 at uncoated glass carbon and metallopolymer-coated glassy carbon electrodes are shown in Fig. 2.24. Note that the reduction of Fe(CN) is quite sluggish. This is to be expected due to the unfavorable thermodynamics. Two anodic oxidation waves are observed at the metallopolymer-coated electrode. The first occurs at a potential where Fe(CN)6 is oxidized at the bare electrode, so it corresponds to the direct unmediated oxidation of substrate at the inner electrode/polymer interface. The second wave is due to the mediated oxidation via the Ru(II) redox sites, as just discussed. This mediated wave exhibits linear Koutecky-Levich behavior. It is clear that we are dealing with Case C here, since the direct unmediated oxidation of substrate occurs at a less positive potential than the mediated oxidation via the Ru(III) sites in the film. 

The diagram for carbon in Fig. 83 displays a very small domain of stability. It is thermodynamically possible for carbons to be easily oxidized to carbon dioxide, carbonic acid, and carbonates. Reduction of carbon may lead to the formation of methane, methyl alcohol and other organic substances. However, the energetically possible reactions are strongly irreversible [2] and do not occur under normal conditions of pressure and temperature. Schmidt [24] reported a corrosive destruction of carbon electrodes when a critical potential was exceeded during the reduction of O2. The carbon electrodes were not impregnated with metallic electrocatalysts. The critical potential depended upon the extent to which an oxygen layer was present (compare section 5 in chapter VIII). 

The thermodynamic and kinetics of the adsorption of a redox couple of quinone nature produced by the anodic oxidation of OTA has been studied at glassy carbon electrodes in 10 % acetonitrile + 90 % 1 M HCIO4 aqueous solution (Ramirez, Zon, Jara Ulloa, Squella, Nunez Vergara Fernandez, 2010). The surface quasi-reversible redox couple was studied by CV and SWV. The Frumkin adsorption isotherm (Adamson, 1990 Bard Faulkner, 2001) resulted in being the best one to describe the specific interaction of the surface redox couple with carbon electrodes. 

Several parameters can govern the storage mechanism in the EDLC for PILs according to the electrolytes/material couple. First, a reduction of the ammonium cation in the presence of an activated carbon electrode is presumably linked to electronic transfer kinetics. Reactions in which electron and proton transfer is performed have been described either by two distinct steps. Electron Proton Transfer or Proton Electron Transfer (EPT or PET), or in the same concerted step. Concerted Proton Electron Transfer (CPET) [140-142]. Contrary to simple proton or electron transfer, CPET is more complicated and the coupling at the activated carbon /molecule (cation) interface influences the process both thermodynamically and kinetically. 

These equations are based on the thermodynamically stable species. Further research is needed to clarify the actual intermediate formed during overcharge. In reahty, the oxygen cycle can not be fully balanced because of other side reactions, that include gtid corrosion, formation of residual lead oxides in the positive electrode, and oxidation of organic materials in the cell. As a result, some gases, primarily hydrogen and carbon dioxide (53), are vented. 

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