Reactive atmospheres

Atmospheric Conditions. In addition to complete combustion, wastes may be destroyed by treatment at high temperatures either without oxygen (qv) (pyrolysis), usiag limited oxygea (partial combustioa), or ia reactive atmospheres (gasiftcatioa), such as those containing steam (qv), hydrogea (qv), or carboa dioxide (qv). 

When a reactive atmosphere is present [402,1249], the reaction undergone by a solid may be changed, and perhaps complicated, by the presence of a concurrent or consecutive gas—solid reaction. When one or more of the products of the reaction in vacuum is an oxidizable metal [60] or... 

It is likely that the answers to these questions will come only from more selective and sophisticated experiments than have been done hitherto, although some useful directions have been established. The use of high-sensitivity electron spin resonance for the study in situ of anticipated radical species will likely be possible, if the background signals from other radiation-produced species are not too intense. Studies of the chemistry of implanted atoms and ions in solid organometallic substrates will make it possible to start with totally unbound atoms which suffer no Auger ionization and thus to simulate the extreme of the total recoil. Careful studies of the thermal annealing effects, especially in the presence of reactive atmospheres, will... 

The opposite behavior was observed after the treatment of the two catalysts in the steam-containing stream, at 380°C. The catalyst P/V 1.06 did not show any change of catalytic performance, whereas in the case of P/V 1.00 the treatment rendered the catalyst less active but more selective than the sample equilibrated in the reactive atmosphere at 380°C. This means that with P/V 1.00, the active layer is not fully hydrolyzed under reaction conditions, and that a hydrolyzed surface is more selective than the active surface of the equilibrated P/V 1.00 catalyst. On the contrary, the active surface of catalyst P/V 1.06 either was already hydrolyzed under... 

In situ UV-Vis Diffuse Reflectance Spectroscopy was performed under reactive atmosphere ( -butane/oxygen). These experiments confirmed that submitting the catalyst to the reaction mixture favors the development of a more oxidized active surface, and that the extent of transformation depends on the reaction temperature and on the catalyst P/V ratio. For instance, catalyst P/V 1.06 was less oxidized than catalyst P/V 1.00 at a temperature lower than 340°C. X-ray Photoelectron spectra of catalysts recorded after reaction at 380°C confirmed that catalyst P/V 1.00 was considerably more oxidized (average oxidation state for surface V 4.23) than the P/V 1.06 catalyst (average oxidation state 4.03). 

In specialized processes associated with the materials science industry, a reactive atmosphere is generated by reactions in which charged species are participants. A gaseous system wherein charged particles (electrons, ions) are important species is called a plasma, and the response of charged particles to an external field is used to increase... 

Fig. 19.10 Illustration of the fate of a vacancy in a reactive atmosphere front and side view of optimized geometry of graphene C49H1802 (M = 3).

The past five years have witnessed significant progress in the understanding and control of plasma etch processes. Nevertheless, much of the fundamental chemistry and physics occurring in these reactive atmospheres remains ill-understood, or indeed unknown. The following sections assimilate the information currently available on dry etch processes, and present a framework within which plasma etching can be viewed. 

With the ability to obtain information about the concentrations of various types of metal surface sites in complex metal nanocluster catalysts, HRTEM provides new opportunities to include nanoparticle structure and dynamics into fundamental descriptions of the catalyst properties. This chapter is a survey of recent HRTEM investigations that illustrate the possibilities for characterization of catalysts in the functioning state. This chapter is not intended to be a comprehensive review of the applications of TEM to characterize catalysts in reactive atmospheres such reviews are available elsewhere (e.g., 1,8,9 )). Rather, the aim here is to demonstrate the future potential of the technique used in combination with surface science techniques, density functional theory (DFT), other characterization techniques, and catalyst testing. 

VI. Examples of HRTEM Characterization of Catalysts in Reactive Atmospheres... 

A variety of other ceramics are prepared by pyrolysis of preceramic polymers.32,38 Some examples are silicon carbide, SC, tungsten carbide, WC, aluminum nitride, AIN, and titanium nitride, TiN. In some cases, these materials are obtained by simple pyrolysis in an inert atmosphere or under vacuum. In other cases a reactive atmosphere such as ammonia is needed to introduce some of the atoms required in the final product. Additional details are given in Chapter 9. 

The most abundant hydrocarbon in the atmosphere is methane, CH4. This gas is released from underground sources as natural gas and produced by the fermentation of organic matter. Methane is one of the least reactive atmospheric hydrocarbons and is produced by diffuse sources, so that its participation in the formation of pollutant photochemical reaction products is minimal. 

Alkaline, alkaline earth metals and aluminum are naturally covered with anodic films. The removal of these native films, even in the best glove box atmosphere, exposes the fresh metal to reactive atmospheric contaminants at a high enough concentration and quickly cover the metal with new surface films. As discussed above, even the glove box atmosphere of an inert gas containing atmospheric components at the ppm level should be considered as being quite reactive to active metals such as lithium. Therefore, anyone intending to study the intrinsic behavior of active metal electrodes in solution must prepare a fresh electrode surface in solution. 

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