Surface oxygen effect

A typical oxidation is conducted at 700°C (113). Methyl radicals generated on the surface are effectively injected into the vapor space before further reaction occurs (114). Under these conditions, methyl radicals are not very reactive with oxygen and tend to dimerize. Ethane and its oxidation product ethylene can be produced in good efficiencies but maximum yield is limited to ca 20%. This limitation is imposed by the susceptibiUty of the intermediates to further oxidation (see Figs. 2 and 3). A conservative estimate of the lower limit of the oxidation rate constant ratio for ethane and ethylene with respect to methane is one, and the ratio for methanol may be at least 20 (115). 

Paraffin wax additives are effective in overcoming surface inhibition by forming a monomolecular wax layer at the curing surface. Although effective in excluding oxygen, this waxy layer must be removed for subsequent lamination or bonding processes (see Waxes). 

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

For the silica gel (Figure 3A), the solution was removed slightly less effectively, and more Cs was left (ca. 0.0020 atoms/A2). The spectral behavior is quite similar to that of boehmite, except that there is a peak due to surface Cs coordinated by only water molecules and not in contact with the surface oxygens (so-called outer sphere complexes)at 30% RH. Complete dynamical averaging among sites at frequencies greater than ca. 10 kHz occurs at 70% RH and greater. 

Firstly, they might be expected to have an effect when corrosion occurs under conditions of active (film-free) anodic dissolution and is not limited by the diffusion of oxygen or some other species in the environment. However, if the rate of active dissolution is controlled by the rate of oxygen diffusion, or if, in general terms, the rate-controlling process does not take place at the metal surface, the effect of crystal defects might be expected to be minimal. 

Figure 9. Effect of burnoff on surface oxygen content natural graphite NG7 [391.

Figure 8.4 shows the steady-state effect of po2 and imposed catalyst potential Uwr on the rate of C2H4 oxidation and compares the results with the open-circuit kinetics. The sharp rate decline for high po2 values is due to the formation of surface Rh oxide.13 Increasing UWr causes a significant increase in the oxygen partial pressure, po2, where oxide forms and thus causes a dramatic increase in r for intermediate (1 to 2.5 kPa) Po2 values. For low P02 values (reduced surface) the effect of Uwr is moderate with p values up to 2. For highp02 values (po2>Po2 > oxidized surface) Uwr has practically no effect on the rate. 

Stamenkovic V, Schmidt TJ, Markovic NM, Ross PN Jr. 2002. Surface composition effects in electrocatalysis Kinetics of oxygen reaction on well defined PtsNi and PtsCo alloy surfaces. J Phys Chem B 106 11970-11979. 

In above sections the main attention has been paid to adsorption-caused change in electrophysical characteristics of semiconductor adsorbent caused by surface charging effects. However, as it was mentioned in section 1.6, the change in electrophysical characteristics of such adsorbents can be caused by other mechanisms, e.g. by direct interaction of absorbate with the surface defects provided (as in the case of oxide adsorbents) by superstoichiometric atoms of metals and oxygen... 

In order to find the relationship between the stationary concentration of current carriers in semiconductor film and concentration of dissolved oxygen in polar liquid, it is essential to examine the expression for rate of chemisorbtion of dissolved oxygen molecules on ZnO film and its chemical desorbtion from the surface under effect of solvent... 

FIGURE 3.4 Measured effective surface oxygen exchange coefficient of the LSM/YSZ composites as a function of the LSM content. (From Ji, Y. et al., Solid State Ionics, 176 937-943, 2005. With permission.)... 

The first scheme was ruled out by showing that, at room temperature, a surface formed by very brief exposure of the oxygen-saturated surface to carbon monoxide is stable after removal of the carbon monoxide from the reaction chamber. In other words, no further surface carbide formed by lateral reactions of adsorbed carbon monoxide with surface oxygen atoms. The second scheme was ruled out by showing that exposure of the surface formed in the latter experiment to oxygen had no effect. Consequently the third scheme is believed to represent the mechanism of oxidation of carbon monoxide at the step and kink sites of platinum. 

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