Oxygen, atomic, exposure

Figure XVIII-2 shows how a surface reaction may be followed by STM, in this case the reaction on a Ni(llO) surface O(surface) + H2S(g) = H20(g) + S(surface). Figure XVIII-2a shows the oxygen atom covered surface before any reaction, and Fig. XVIII-2h, the surface after exposure to 3 of H2S during which Ni islands and troughs have formed on which sulfur chemisorbs. The technique is powerful in the wealth of detail provided on the other hand, there is so much detail that it is difficult to relate it to macroscopic observation (such as the kinetics of the reaction).

Fig. XVni-2. Successive STM images of (a) Ni(llO) with a chemisorbed layer of oxygen atoms and (b) after exposure to 3 1 of H2S. The area shown in 85 x 91 A. [From F. Besenbacher, P. T. Sprunger, L. Ruan, L. Olesen, I. Stensgaard, and E. Lcegsgaard, Tap. Catal., 1, 325 (1994).]...

Another important catalytic reaction that has been most extensively studied is CO oxidation catalyzed by noble metals. In situ STM studies of CO oxidation have focused on measuring the kinetic parameters of this surface reaction. Similar to the above study of hydrogen oxidation, in situ STM studies of CO oxidation are often conducted as a titration experiment. Metal surfaces are precovered with oxygen atoms that are then removed by exposure to a constant CO pressure. In the titration experiment, the kinetics of surface reaction can be simplified and the reaction rate directly measured from STM images. 

Exposure of the clean stepped platinum surface to oxygen caused saturation of the step and kink sites (no adsorption occurred on a 111 surface under identical conditions). The oxygen atom-saturated surface was then exposed to varying amounts of carbon monoxide. Both carbide carbon and CO carbon C Is peaks formed, with a one-to-one correspondence between the growth of carbide and the decrease of surface oxygen atoms. These data are consistent with threee possible reaction schemes ... 

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. 

A rather different allene cyclization that takes place in tandem with an alkylative process has been described by Trost and Urabe [66] (Eq. 13.52). Exposure of ketoal-lene 169 to divinylmethylaluminum 170 in dichloromethane solution leads to 171 in 60% yield. The mechanism of this alkylative cyclization involves complexation of the Lewis acidic aluminum to the carbonyl oxygen atom, followed by ring closure, leading to zwitterion 172. Intramolecular transfer of a vinyl group from aluminum to carbon completes the process. 

The latter compound results from loss of two hydrogen atoms by metabolic oxidation at each of two of the carbon atoms of hexane, and their replacement by oxygen atoms. Schaumburg and Spencer not only demonstrated this, but also showed that the identical neurotoxic events result from direct exposure to compound II and also another common solvent called methyl-n-butyl ketone (III). Chemical III is, like hexane, readily metabolized to the active toxicant, molecule II. Because both I and III yield the same metabolite (II), and because this metabolite is the source of toxicity, then exposure to both of these chemicals produces the identical type of neuropathy. 

In the presence of oxygen atoms, 02 is not formed on rutile but subsequent exposure of the sample to molecular oxygen gives 02 with gzz = 2.019 (203). 

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