Thermodynamics oxidation reactions

Relative positions between the valence (VB) and the conducting (CB) bands and the energies of two redox couples with different values (cases a-d). Oy and Red, represent the oxidized and the reduced species, respectively, of two different redox couples (1 and 2). Only for (d) are both reduction and oxidation reactions thermodynamically allowed. 

Oxides. Two oxides of xenon are known xenon trioxide [13776-58-4], XeO, and xenon tetroxide [12340-14-6], XeO (Table 1). Xenon trioxide is most efftcientiy prepared by the hydrolysis of XeE (47) or by the reaction of XeE with HOPOE2 (48). The XeO molecule has a trigonal pyramidal shape Xe—O, 176(3) pm (49), and XeO is tetrahedral with Xe—O, 173.6(2) pm (50). Xenon tetroxide is prepared by the interaction of concentrated sulfuric acid with sodium or barium perxenate, Na XeO, Ba2XeO ( )- Both oxides are thermodynamically unstable, explosive soHds which must be... 

The thermodynamic properties of sulfur trioxide, and of the oxidation reaction of sulfur dioxide are summarized in Tables 3 and 4, respectively. Thermodynamic data from Reference 49 are beheved to be more accurate than those of Reference 48 at temperatures below about 435°C. 

The exothermic oxidation reaction is carried out ia the gas phase at temperatures of 1200°C or higher. Relevant thermodynamic data are given ia Table 11. ... 

The thermodynamics of electrochemical reactions can be understood by considering the standard electrode potential, the potential of a reaction under standard conditions of temperature and pressure where all reactants and products are at unit activity. Table 1 Hsts a variety of standard electrode potentials. The standard potential is expressed relative to the standard hydrogen reference electrode potential in units of volts. A given reaction tends to proceed in the anodic direction, ie, toward the oxidation reaction, if the potential of the reaction is positive with respect to the standard potential. Conversely, a movement of the potential in the negative direction away from the standard potential encourages a cathodic or reduction reaction. 

For iron in most oxidising environments, the PBR is approximately 2.2 and the scale formed is protective. The oxidation reaction forms a compact, adherent scale, the inner and outer surfaces of which are in thermodynamic equilibrium with the metal substrate and the environment respectively, and ion mobility through the scale is diffusion controlled. 

The oxidation reactions of hydrogen, carbon monoxide, and hydrocarbons in the temperature range of 500 to 1500°F, where the catalytic reactors can be expected to operate, are all favored thermodynamically to... 

Thus indeed CH4 oxidation in a SOFC with a Ni/YSZ anode results into partial oxidation and the production of synthesis gas, instead of generation of C02 and H20 as originally believed. The latter happens only at near-complete CH4 conversion. However the partial oxidation overall reaction (3.12) is not the result of a partial oxidation electrocatalyst but rather the result of the catalytic reactions (3.9) to (3.11) coupled with the electrocatalytic reaction (3.8). From a thermodynamic viewpoint the partial oxidation reaction (3.12) is at least as attractive as complete oxidation to C02 and H20. 

Thermodynamic Disequilibrium and Microbial Catalysis of Oxidation Reactions... 

Applying the common equations for the thermodynamics of reversible cells, it is possible to extract energetic parameters for the adatom redox reaction. This approach requires the measurement of voltammograms at different temperatures. If we consider that the adatom oxidation reaction involves the formation of the hydroxide, we can write the following equation for the overall cell reaction ... 

Another method for conducting cyclizations catalytic in Cp2TiCl is shown in Scheme 14. It relies on the thermodynamically favorable ring closure of THF from 5-titanoxy radicals [81,82]. This step is mechanistically related to the oxygen rebound steps of oxidation reactions. While the scope of this transformation remains to be established, the presence of substituted THF-derivatives in many natural products renders the method potentially attractive. 

Taking sulfide oxidation (Reaction 22.19) as an example, when the fluid mixture reaches 25 °C, there are about 5 mmol of H2S(aq) and 0.6 mmol of 02(aq) in the unreacted fluid, per kg of vent water. The 02(aq) will be consumed first, after about 0.3 mmol of reaction turnover, since its reaction coefficient is two it is the limiting reactant. The thermodynamic drive for this reaction at this temperature is about 770 kJ mol-1. The energy yield, then, is (0.3 x 10-3 mol kg-1) x (770 x 103 J mol-1), or about 230 J kg-1 vent water (Fig. 22.8). In reality, of course, this entire yield would not necessarily be available at this point in the mixing. If some of the 02(aq) had been consumed earlier, or is taken up by reaction with other reduced species, less of it, and hence less energy would be available for sulfide oxidation. 

H2 production technologies based on natural gas. Operating the reaction at relatively lower temperature, between 300 and 450 °C could minimize the CO formation because the equilibria for WGS and CO oxidation reactions are thermodynamically more favorable at lower temperatures. In order to achieve this goal, highly selective catalysts that are specific for reforming via acetaldehyde formation rather than ethanol decomposition to CH4 and/or ethylene are required. The success in the development of ethanol-based H2 production technology therefore relies on the development of a highly active, selective and stable catalyst. 

Oxidation of unfunctionalized alkanes is notoriously difficult to perform selectively, because breaking of a C-H bond is required. Although oxidation is thermodynamically favourable, there are limited kinetic pathways for reaction to occur. For most alkanes, the hydrogens are not labile, and, as the carbon atom cannot expand its valence electron shell beyond eight electrons, there is no mechanism for electrophilic or nucleophilic substitution short of using extreme (superacid or superbase) conditions. Alkane oxidations are therefore normally radical processes, and thus difficult to control in terms of selectivity. Nonetheless, some oxidations of alkanes have been performed under supercritical conditions, although it is probable that these actually proceed via radical mechanisms. 

Partial wet oxidation or controlled wet oxidation is, in a sense, similar to that of catalytic oxidation. Catalytic oxidation provides a conventional catalyst in order to boost and control the oxidative reaction, whereas wet oxidation provides a favored atmosphere for the reaction to occur. More accurately, catalytic oxidation provides a surface upon which intimate contact between the reactants takes place compared to the thermodynamic (or fluid dynamic) contact provided by wet oxidation. In wet oxidation, it can be said that the supercritical water phase acts as the "catalyst for the reaction. 

Reversible redox reactions can initiate radical chemistry without a follow-up reduction or oxidation reaction. In successful reactions of this type, the redox step that produces the radical is thermodynamically disfavored. For example, Cu(I) complexes react reversibly with alkyl hahdes to give Cu(II) hahde complexes and an alkyl radical. The alkyl radical can react in, for example, an addition reaction, and the product radical will react with the Cu(II) hahde to give a new alkyl halide. This type of reaction sequence, which has been apphed in living radical polymerizations, is in the general family of nonchain radical reactions discussed earlier. ... 

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