Oxides oxygen adsorption

Small changes in impurity content did not affect this rate but the presence of water vapor and changes in partial pressure of oxygen were critical (61,62). Steam and various impurities and binders also affect the oxidation of siUcon carbide (63). Differences have been observed in oxygen adsorption on the different SiC crystal faces (64). 

In addition to effects on the concentration of anions, the redox potential can affect the oxidation state and solubility of the metal ion directly. The most important examples of this are the dissolution of iron and manganese under reducing conditions. The oxidized forms of these elements (Fe(III) and Mn(IV)) form very insoluble oxides and hydroxides, while the reduced forms (Fe(II) and Mn(II)) are orders of magnitude more soluble (in the absence of S( — II)). The oxidation or reduction of the metals, which can occur fairly rapidly at oxic-anoxic interfaces, has an important "domino" effect on the distribution of many other metals in the system due to the importance of iron and manganese oxides in adsorption reactions. In an interesting example of this, it has been suggested that arsenate accumulates in the upper, oxidized layers of some sediments by diffusion of As(III), Fe(II), and Mn(II) from the deeper, reduced zones. In the aerobic zone, the cations are oxidized by oxygen, and precipitate. The solids can then oxidize, as As(III) to As(V), which is subsequently immobilized by sorption onto other Fe or Mn oxyhydroxide particles (Takamatsu et al, 1985). 

SIMS Cluster Ion Characterization During Oxygen Adsorption and Oxidation. For heavy oxidation, that is essentially bulk oxide films, the oxidation state of the metal can be determined from the positive and negative SIMS intensity distributions (1 ). Though similar attempts have been made to characterize the nature of the surface during the early stages of oxygen interactions (14,15), we now know from the extensive information available from other techniques that such interpretations are incorrect. We use the by now well-characterized W(100)/O and Ni(100)/0 systems as examples. 

Shi, H. and Stampfl, C. (2007) First-principles investigations of the structure and stability of oxygen adsorption and surface oxide formation at Au(lll). Physical Review B Condensed Matter, 76, 075327-1-075327-14. 

The first step of oxide-layer formation is oxygen adsorption (chemisorption). In the case of platinum, the process stops at this stage, and depending on the conditions, an incomplete or complete monolayer of adsorbed oxygen is present on the platinum surface. In the case of other metals, layer formation continues. When its thickness 5 has attained two to three atomic diameters, the layer is converted to an individual surface phase that is crystalline (more seldom, amorphous) and has properties analogous to those of the corresponding bulk oxides. 

Check lor water splitting and oxygen adsorption (precursor to oxide formation)... 

While we have focused here on the oxygen adsorption at the electrode surface, in the following, we will discuss the part of the phase diagram shaded gray and labeled Oxide formation in Fig 5.10b. 

From the pH dependence of the peak potential (close to 60 mV/decade), it was proposed that the oxidation involves adsorption of oxygenated species, leading to the formation of either the oxide or the hydroxide ... 

Hayden BE, Murray AJ, Parsons R, Pegg DJ. 1996. UHV and electrochemical transfer studies on Pt(110)-(1 X 2) The influence of bismuth on hydrogen and oxygen adsorption, and the electro-oxidation of carbon monoxide. J Electroanal Chem 409 51-63. 

Nevertheless, there is a whole series of experimental results enabling one to propose and substantiate a sufficiently general model consistently describing the effect of oxygen adsorption on electric conductivity of partially reduced oxides observed in experiments. Let us con sider these data. 

Thus, the model proposed explains the effect of CO on electric conductivity of several oxides only in case when oxygen is present in ambient volume which was observed in numerous experiments. Accordingly, the fact of existence of relatively narrow temperature interval in which an adsorbent is sensitive to CO becomes clear. This can be linked with the fact that if the operational temperature To is small the reaction products (in case of CO this is CO2) cannot get desorbed (see expression (2.80)), i.e. regeneration of the centers of oxygen adsorption is not feasible. If Tq is very high both adsorption of oxygen and reducing gas should be ruled out. 

In surface science, work function measurements are considered to be rather sensitive towards changes of the sample surface. Work function measurements are used to follow adsorption processes and to determine the dipole established at the surface. During oxygen adsorption and oxide formation the sign of the work function change allows one to distinguish between oxygen atom adsorbed on the surface or sub-surface [30]. 

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