Oxygen atom, diffusion

Fig. XVIII-15. Oxygen atom diffusion on a W(IOO) surface (a) variation of the activation energy for diffusion with d and (b) variation of o- (From Ref. 136. Reprinted with kind permission of Elsevier Science-NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)...

The continued oxidation of the metal substrate beneath the protective oxide layer must become a diffusion-controlled process for thick enough oxide films in which either metal atoms or oxygen atoms diffuse through the metal oxide layer to the appropriate interface where reaction proceeds. Let us assume a thick enough oxide layer on a plane metal surface where a steady state has been achieved. Then we can write for the rate of formation of metal oxide, MO, per unit area (assuming metal ion diffusion) ... 

From the oxygen 32 line included in the Figure we might infer that during oxidation first are consumed oxygen atoms diffusing to the catalyst surface fh)m the deeper oxide layer of the catalyst, and later oxygen from the gas feed. 

Some of the oxygen atoms diffuse into the anodic layer and on reaching the metal they oxidize it to tet-PbO [17]. 

When the sensor is exposed to a test gas environment, the oxygen molecules get adsorbed onto the porous eleetrode, commonly made of platinum, and dissociate into atomic oxygen. Then the oxygen atoms diffuse into the boundary of the eleetrode (Pt), eleetrolyte (YSZ), and the gas called the triple phase boundary (TPB), where electron transfer takes place from the electrode to the atomic oxygen forming O " ions (reduction). The overall electrode reaetions are as follows (Robertson and Michaels 1990 Mitterdorfer and Gauckler 1999) ... 

A number of chemiluminescent reactions have been studied by producing key reactants through pulsed electric discharge, by microwave dissociation, or by observing the reactions of atoms and free radicals produced in the inner cone of a laminar flame as they diffuse into the flame s cool outer cone (182,183). These are either combination reactions or atom-transfer reactions involving transfer of chlorine (184) or oxygen atoms (181,185—187), the latter giving excited oxides. 

The kinetics of this Uansport, virtually of oxygen atoms tlrrough the solid, is determined by the diffusion coefficient of the less mobile oxide ions, and local... 

The measurement of oxygen diffusion is usually made by the use of as die labelling isotope. If a gas containing an initial concentration C, of in O , and Co is the initial conceiiuation of in a right cylinder oxide sample of thickness 21, and a is the ratio of oxygen atoms in the original gas phase compared widi that in the solid, dieii after a time t, when the concentration in the gas phase is C/... 

Either the and the two e s diffuse outward through the film to meet the 0 at the outer surface, or the oxygen diffuses inwards (with two electron holes) to meet the at the inner surface. The concentration gradient of oxygen is simply the concentration in the gas, c, divided by the film thickness, x and the rate of growth of the film dx/dt is obviously proportional to the flux of atoms diffusing through the film. So, from Pick s Law (eqn. (18.1)) ... 

Lateral density fluctuations are mostly confined to the adsorbed water layer. The lateral density distributions are conveniently characterized by scatter plots of oxygen coordinates in the surface plane. Fig. 6 shows such scatter plots of water molecules in the first (left) and second layer (right) near the Hg(l 11) surface. Here, a dot is plotted at the oxygen atom position at intervals of 0.1 ps. In the first layer, the oxygen distribution clearly shows the structure of the substrate lattice. In the second layer, the distribution is almost isotropic. In the first layer, the oxygen motion is predominantly oscillatory rather than diffusive. The self-diffusion coefficient in the adsorbate layer is strongly reduced compared to the second or third layer [127]. The data in Fig. 6 are qualitatively similar to those obtained in the group of Berkowitz and coworkers [62,128-130]. These authors compared the structure near Pt(lOO) and Pt(lll) in detail and also noted that the motion of water in the first layer is oscillatory about equilibrium positions and thus characteristic of a solid phase, while the motion in the second layer has more... 

Figure 5. Cartoon models of the reaction of methanol with oxygen on Cu(llO). 1 A methanol molecule arrives from the gas phase onto the surface with islands of p(2xl) CuO (the open circles represent oxygen, cross-hatched are Cu). 2,3 Methanol diffuses on the surface in a weakly bound molecular state and reacts with a terminal oxygen atom, which deprotonates the molecule in 4 to form a terminal hydroxy group and a methoxy group. Another molecule can react with this to produce water, which desorbs (5-7). Panel 8 shows decomposition of the methoxy to produce a hydrogen atom (small filled circle) and formaldehyde (large filled circle), which desorbs in panel 9. The active site lost in panel 6 is proposed to be regenerated by the diffusion of the terminal Cu atom away from the island in panel 7.

In addition to enhancing surface reactions, water can also facilitate surface transport processes. First-principles ab initio molecular dynamics simulations of the aqueous/ metal interface for Rh(l 11) [Vassilev et al., 2002] and PtRu(OOOl) alloy [Desai et al., 2003b] surfaces showed that the aqueous interface enhanced the apparent transport or diffusion of OH intermediates across the metal surface. Adsorbed OH and H2O molecules engage in fast proton transfer, such that OH appears to diffuse across the surface. The oxygen atoms, however, remained fixed at the same positions, and it is only the proton that transfers. Transport occurs via the symmetric reaction... 

Fig. 5.9. Distribution of oxygen atoms (/) and 02 molecules (2) concentration during their diffusion along glass tube [71]...

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