Carbon standard potential

Several significant electrode potentials of interest in aqueous batteries are listed in Table 2 these include the oxidation of carbon, and oxygen evolution/reduction reactions in acid and alkaline electrolytes. For example, for the oxidation of carbon in alkaline electrolyte, E° at 25 °C is -0.780 V vs. SHE or -0.682 V (vs. Hg/HgO reference electrode) in 0.1 molL IC0 2 at pH [14]. Based on the standard potentials for carbon in aqueous electrolytes, it is thermodynamically stable in water and other aqueous solutions at a pH less than about 13, provided no oxidizing agents are present. 

Table 2. Standard potentials for reactions of carbon materials in batteries containing aqueous electrolytes...

In Figure 2 the solubility and speciation of plutonium have been calculated, using stability data for the hydroxy and carbonate complexes in Table III and standard potentials from Table IV, for the waters indicted in Figure 2. Here, the various carbonate concentrations would correspond to an open system in equilibrium with air (b) and closed systems with a total carbonate concentration of 30 mg/liter (c,e) and 485 mg/liter (d,f), respectively. The two redox potentials would roughly correspond to water in equilibrium wit air (a-d cf 50) and systems buffered by an Fe(III)(s)/Fe(II)(s)-equilibrium (e,f), respectively. Thus, the natural span of carbonate concentrations and redox conditions is illustrated. 

Galus Z. 1985. Carbon, sihcon, germanium, tin, and lead. In Bard AJ, Parsons R, Jordan J, editors. Standard Potentials in Aqueous Solution. New York Marcel Dekker. 

In spite of the high effort focused on the carbon electrochemistry, very little is known about the electrochemical preparation of carbon itself. This challenging idea appeared in the early 1970s in connection with the cathodic reduction of poly(tetrafluoroethylene) (PTFE) and some other perfluorin-ated polymers. The standard potential of the hypothetical reduction of PTFE to elemental carbon ... 

FIGURE 4.3. Redox and chemical homogeneous catalysis of trans-1,2 dibromocyclohexane. a cyclic voltammetry in DMF of the direct electrochemical reduction at a glassy carbon electrode (top), of redox catalysis by fhiorenone (middle), of chemical catalysis by an iron(I) porphyrin, b catalysis rate constant as a function of the standard potential of the catalyst couple aromatic anion radicals, Fe(I), a Fe(0), Co(I), Ni(I) porphyrins. Adapted from Figures 3 and 4 of reference lb, with permission from the American Chemical Society. 

The actual potential for the reduction half-reaction is less than the standard potential (1.23 V) because the water droplet is not 1 M in H+ ions. (In fact, the water is only slightly acidic because the main source of H+ ions is the reaction of water with dissolved atmospheric carbon dioxide.) Even at pH 7, however, the potential for the reduction half-reaction is 0.81 V, which means that the cell potential is highly positive, indicative of a spontaneous reaction. 

In another study, the reductive C-F bond cleavage of fluoromethylarenes has been investigated in liquid ammonia and DMF by CV and/or redox catalysis [299]. Within a series of 4-cyanotoluenes where the a-carbon bears one, two or three fluorine atoms, the rate of radical anion cleavage increases on going from the trifluoro to the monofluoro derivative, a behavior which reflects the decrease in both C-F BDE and standard potential, °rx/rx.-, as the number of fluorine atoms is diminished (Table 14). 

Figure 8.18. Measured redox potentials in a deep groundwater. Experimental values of the measured redox potentials (recalculated to the standard hydrogen electrode scale) versus (3pH + log[Fe ]). The concentration of [Fe J has been obtained from the analytical determinations by correction for the complex formation with carbonate. The notation refers to the different test sites. The full-drawn line has been calculated using the selected value of the standard potential E. The straight line has the theoretical Nemstian slope of +0.056 V, at the temperature of measurements. (Adapted from Grenthe et al., 1992.)...

The computational procedures now used in the application of density functional theory and molecular simulation for the prediction and analysis of physisorption isotherms are based on the statistical mechanics of confined fluids [14]. These important advances are described in several chapters of this book and therefore the present introductory remarks are confined to a few general comments. Whichever computational procedure is adopted [39, 40], it is first necessary to define a 3-D model of the pore structure within a sohd of known and uniform composition [14]. It has been customary to assume that the pores of different width are aU of the same shape (e.g., slits in activated carbons). Further assumptions made by many investigators are that the filling or emptying of each group of pores can occur independently and reversibly, that the internal surface is uniform and that the solid-fluid and fluid-fluid interactions can be expressed in terms of standard potential functions [14],... 

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