Sulfur dioxide metal-catalyzed oxidation

The resulting products, such as sulfenic acid or sulfur dioxide, are reactive and induce an acid-catalyzed breakdown of hydroperoxides. The important role of intermediate molecular sulfur has been reported [68-72]. Zinc (or other metal) forms a precipitate composed of ZnO and ZnS04. The decomposition of ROOH by dialkyl thiophosphates is an autocata-lytic process. The interaction of ROOH with zinc dialkyl thiophosphate gives rise to free radicals, due to which this reaction accelerates oxidation of hydrocarbons, excites CL during oxidation of ethylbenzene, and intensifies the consumption of acceptors, e.g., stable nitroxyl radicals [68], The induction period is often absent because of the rapid formation of intermediates, and the kinetics of decomposition is described by a simple bimolecular kinetic equation... 

The autoxidation of aqueous solutions of sulfur dioxide (sulfite, bisulfite) is a classic problem in chemistry. Basic features of this reaction have been known since early in this century, when it was established that the reaction is trace metal ion catalyzed (1 ) and most likely involves free radicals (2). Certain chemical effects associated with sulfite autoxidation were noted also. Before the turn of the century, it was noted that sulfite would induce the oxidation of transition metal ions (3) and it was reported later that the oxidation of organic compounds was brought about during sulfite autoxidation ( 0. Conversly, organic compounds were also shown to serve as inhibitors of sulfite autoxidation (5). 

The noble metals may assist in this process, since they are well known for catalyzing the oxidation of sulfur dioxide to sulfur trioxide species in an oxygen-rich environment... 

A wide variety of interrelated homogenous gas-phase, solution-phase, and heterogenous chemistry may ultimately result in oxidation of SO2 to sulfuric acid in DUV exposure tools. The three main possible reaction pathways for the oxidation of sulfur dioxide to sulfuric acid in the exposure chamber may include (i) direct oxidation of sulfur dioxide by stable atmospheric oxygen, (ii) catalyzed oxidation of sulfur dioxide by metal ions, and (iii) photochemical oxidation of sulfur dioxide by ozone and hydroxyl radical. 

Catalyzed oxidation of sulfur dioxide by metal ions... 

Sulfur oxides and other corrosive species are brought to react with the zinc surface in two ways dry deposition and wet deposition. Sulfur dioxide has been observed to deposit on a dry surface of galvanized steel panels until a monolayer of SO2 formed (Maato, 1982). In either case, the sulfur dioxide that deposits on the surface of the zinc forms sulfurous or other strong acids, which react with the film of zinc oxide, hydroxide, or basic carbonate to form zinc sulfate. The conversion of sulfur dioxide to sulfur-based acids may be catalyzed by nitrogen compounds in the air—usually referred to collectively as NQt compounds—and it is believed that this factor may affect corrosion rates in practice. The acids partially destroy the Film of corrosion products, which will then re-form from the underlying metal, so causing continuous corrosion by an amount equivalent to the film dissolved, hence to the amount of sulfur dioxide absorbed. Above about 85% RH, corrosion rates increase further—probably as a result of the formation of basic zinc sulfates. 

Solid superacids may be made by treating ordinary solid add catalysts with strong Br0nsted or Lewis acids. For example, if freshly precipitated titanium hydroxide or zirconium hydroxide is treated with sulfuric acid and calcined in air at 500 °C. a very active solid acid catalyst results. The solids consist mainly of the metal dioxides with sulfate ions coordinated to the metal ions on the surface. Likewise, a superacid solid catalyst can be made by treating these metal oxides with antimony penlafluonde. Both catalysts contain both Br nsted and Lewis acid sites, and they arc sufficiently active to catalyze the isomerization of n-butane at room temperature.26... 

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