Olefins higher,.ozonization

Disharmonies in the Conception of the Direct 0 /Antiozonant Reaction Importance. Four antiozonant theories have been formulated within the last 25 years. Ozone scavenging theory suggests a preferential direct reaction of an antiozonant with ozone on the rubber surface as a decisive process (26-27). As the antiozonant is depleted via direct ozonation on the surface, fresh antiozonant diffuses rapidly from the rubber bulk to reestablish the equilibrium surface concentration. At a comparable additive concentration and migration rate, the antiozonant efficiency of an additive should be therefore dependent on its ozonation rate and the vulcanizate will be protected until the antiozonant is depleted below the lowest critical concentration. From this point of view, the ozonation rate seems to be a more important factor than the total amount of ozone scavenged by one mole of an antiozonant (this latter phenomenon may be called ozonation factor). Relations between antiozonant efficiency in vulcanizate and antiozonant ozonation rate or antiozonant surface concentration have been indeed reported in some papers and an appreciable higher ozonation rate of PD in comparison with rubber unsaturation, a preferential consumption of an antiozonant in model olefin solution or in rubber were observed. The rubber surface was not attacked by ozone until the antiozonant was almost completely consumed (28). ... 

Although higher olefins do not produce detectable chemiluminescence when reacting with ozone at atmospheric pressure (7) at pressures of about one-half torr, light is emitted by these reactions (8). Several organic sulfides also give an emission when they react with ozone at these pressures. 

Kummer et al. 8) have reported that at pressures of about 0.5 torr, the relative emission intensities of the higher olefins and of the organic sulfides were substantially greater than that of ethylene Table II summarizes the reported relative emission intensities. Since a recently developed commercial ozone monitor is based on the chemiluminescent reaction between ozone and ethylene, this suggests the possibility of using the sulfide-ozone chemiluminescent reaction to monitor the low concentration of sulfur compounds in ambient air. This possibility is being further investigated now. 

Only fluorine, atomic oxygen and FgO have higher redox potentials. The gas oxidises moist sulphur to jH2S04, raises silver(I) compounds to the 2 state and converts olefinic compounds to ozonides. The reaction 2O3 -> SOg, which is catalysed by many metals and metal oxides, is exothermic and rapid above 200°. Gaseous ozone is deeper blue than oxygen it condenses at — 112° to a dark blue liquid which freezes at —193° to a dark purple solid. Surprisingly, the liquid is not completely miscible with liquid oxygen. 

The regeneration of Y-zeolite catalysts used in isobutane alkylation with C4 olefins was studied. The coke formed on these catalysts during this reaction needs temperatures higher than 500°C to be burnt off with air. Ozone was used in this study to eliminate most of the coke at a much lower temperature. After a treatment at 125 C with ozone, the small amount of coke remaining on the catalyst can be removed with air at 250°C. The ozone not only eliminates coke from the catalyst, but also modifies its burning characteristics as measured by Temperature Programmed Oxidation, shifting the peak to lower temperatures. This allows a combined treatment with ozone at 125°C followed by air at 250°C to restore the activity and stability of Y-zeolite catalysts for isobutane alkylation. 

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