Ozone, reactions

The rate of aqueous ozonation reactions is affected by various factors such as the pH, temperature, and concentration of ozone, substrate, and radical scavengers. Kinetic measurements have been carried out in dilute aqueous solution on a large number of organic compounds from different classes (56,57). Some of the chemistry discussed in the foUowing sections occurs more readily at high ozone and high substrate concentrations. 

Ozonation ofAlkenes. The most common ozone reaction involves the cleavage of olefinic carbon—carbon double bonds. Electrophilic attack by ozone on carbon—carbon double bonds is concerted and stereospecific (54). The modified three-step Criegee mechanism involves a 1,3-dipolar cycloaddition of ozone to an olefinic double bond via a transitory TT-complex (3) to form an initial unstable ozonide, a 1,2,3-trioxolane or molozonide (4), where R is hydrogen or alkyl. The molozonide rearranges via a 1,3-cycloreversion to a carbonyl fragment (5) and a peroxidic dipolar ion or zwitterion (6). 

Oxidation of vinyl chloride with ozone [10028-15-6] in either the Hquid or the gas phase gives formic acid and formyl chloride. The ozone reaction with vinyl chloride can be used to remove it from gas streams in vinyl chloride production plants. 

Ozone Reaction product of VOC and nitrogen oxides Not produced directly Irritant to eyes and respiratory system... 

When the films were treated in either an oxygen plasma environment or under UV/ozone irradiation, the rates of oxidation were faster for the plasma process. Irradiation of chitosan solution showed that UV/ozone induces depolymerization. In both plasma and UV/ozone reactions, the main active component for surface modification was UV irradiation at a wavelength below 360 nm [231]. 

This process does not lead to net ozone depletion because it is rapidly followed by reaction 2, which regenerates the ozone. Reactions 2 and 3 have, however, another important function, namely the absorption of solar energy as a result, the temperature increases with altitude, and this inverted temperature profile gives rise to the stratosphere (see Figure 1). In the lower layer, the troposphere, the temperature decreases with altitude and vertical mixing occurs on a relatively short time scale. In contrast, the stratosphere is very stable towards vertical mixing because of its inverted temperature profile. 

This dry ozonation procedure is a general method for hydrox-ylation of tertiary carbon atoms in saturated compounds (Table 1). The substitution reaction occurs with predominant retention of configuration. Thus cis-decalin gives the cis-l-decalol, whereas cis- and frans-l,4-dimethylcyclohexane afford cis- and trans-1,4-dimethylcyclohexanol, respectively. The amount of epimeric alcohol formed in these ozonation reactions is usually less than 1%. The tertiary alcohols may be further oxidized to diols by repeating the ozonation however, the yields in these reactions are poorer. For instance, 1-adamantanol is oxidized to 1,3-adamantane-diol in 43% yield. Secondary alcohols are converted to the corresponding ketone. This method has been employed for the hydroxylation of tertiary positions in saturated acetates and bromides. 

The most effective antiozonants are the substituted PPDs. Their mechanism of protection against ozone is based on the scavenger-protective film mechanism [68-70]. The reaction of ozone with the antiozonant is much faster than the reaction with the C=C bond of the rubber on the rubber surface [56]. The rubber is protected from the ozone attack tUl the surface antiozonant is depleted. As the antiozonant is continuously consumed through its reaction with ozone at the mbber surface, diffusion of the antiozonant from the inner parts to the surface replenishes the surface concentration to provide the continuous protection against ozone. A thin flexible film developed from the antiozonant/ozone reaction products on the mbber surface also offers protection. 

The location of the position of double bonds in alkenes or similar compounds is a difficult process when only very small amounts of sample are available [712,713]. Hass spectrometry is often unsuited for this purpose unless the position of the double bond is fixed by derivatization. Oxidation of the double bond to either an ozonide or cis-diol, or formation of a methoxy or epoxide derivative, can be carried out on micrograms to nanograms of sample [713-716]. Single peaks can be trapped in a cooled section of a capillary tube and derivatized within the trap for reinjection. Ozonolysis is simple to carry out and occurs sufficiently rapidly that reaction temperatures of -70 C are common [436,705,707,713-717]. Several micro-ozonolysis. apparatuses are commercially available or can be readily assembled in the laboratory using standard equipment and a Tesla coil (vacuum tester) to generate the ozone. Reaction yields of ozonolysis products are typically 70 to 95t, although structures such as... 

The PP samples exposed to atomic oxygen show for the formation of polymer peroxy radicals (P00 ), which give almost identical ESR spectrum as in the case of ozone reaction (Fig.l). The ESCA spectra (Fig.5) indicate that atomic oxygen oxidation is more effective than ozonization. These results support our assumption that ozonization... 

Ozone Reactions with Organic Compounds, ACS 112, Washington, ACS, 1972... 

Atkinson, R., Aschmann, S.M., Carter, W.L., Pitts, Jr., J.N. (1983) Effects of ring strain on gas-phase rate constants. 1. Ozone reactions with cycloalkenes. Int. J. Chem. Kinet. 15, 721-731. 

Bufalini, J.J., Altshuller, A.P. (1965) Kinetics of vapor-phase hydrocarbon-ozone reactions. Can. J. Chem. 43, 2243-2250. 

Atkinson, R., Carter, W.P.L. (1984) Kinetics and mechanisms of gas-phase ozone reaction with organic compounds under atmospheric conditions. Chem. Rev. 84, 437 470. 

The very low yield of radicals by the reaction of ozone with cumene was found to be the result of the intensive ozone reaction with the benzene ring of cumene with molozonide formation. The values of the parameter e in other reactions are typical of the cage effect of radical pairs in solutions. The rate constants of ozone reactions with various compounds are presented in Table 3.7 and Table 3.8. 

The first term characterizes the rate of the ozone reaction with the substrate and the second term characterizes the reaction with chain propagation... 

Rate Constants of Ozone Reaction with Organic Compounds (Experimental Data)... 

The similar kinetic scheme was proposed for the ozone reaction with acetaldehyde [150], The reaction rate obeys the equation... 

Aqueous mixed salt systems, 9 36 Aqueous ozonation reactions, rate of, 17 779... 

Ozone rate constants, 27 771 Ozone reactions activation of, 27 779 kinetics and mechanism of, 27 778-779 Ozone resistance, of ethylene-propylene polymers, 10 704, 717 Ozone synthesis, energy requirements for, 27 798... 

Radical grafting, 10 206 Radical-induced decompositions, 14 280 of dialkyl peroxydicarbonates, 14 289 Radical ozone reactions, 17 774 Radical polymerization, 22 40. See also Free-radical polymerization controlling, 14 297 of methacrylic ester polymers, 16 279-290... 

The theory of particle diffusion was first advanced in 1934 by Lewis and von Elbe [5] in dealing with the ozone reaction. Tanford and Pease [6] carried this concept further by postulating that it is the diffusion of radicals that is all important, not the temperature gradient as required by the thermal theories. They proposed a diffusion theory that was quite different in physical concept from the thermal theory. However, one should recall that the equations that govern mass diffusion are the same as those that govern thermal diffusion. 

In this study, synthetic aqueous solutions of phenol were treated with ozone. The reaction of ozone with phenol was investigated at several conditions, such as different phenol and ozone concentrations, and contact times. Total Organic Carbon (TOC) and UV analysis of the aromatic by-products formed during and after the ozonation reaction were employed. The reaction rates calculated from TOC analysis were investigated. 

Seventy-five milliliters of samples were collected from reaction column upper end at different time intervals during the ozonation reaction for the determination of the by products. Ozonation of phenol was carried out at four different initial concentrations, 25, 50, 75 and 100 mg/L, with three different ozone concentrations 2, 4 and 6 g/L h. 

This initial attack of the ozone molecule leads first to the formation of ortho- and para-hydroxylated by-products. These hydroxylated compounds are highly susceptible to further ozonation. The compounds lead to the formation of quinoid and, due to the opening of the aromatic cycle, to the formation of aliphatic products with carbonyl and carboxyl functions. The nucleophilic reaction is found locally on molecular sites showing an electronic deficit and, more frequently, on carbons carrying electron acceptor groups. In summary, the molecular ozone reactions are extremely selective and limited to unsaturated aromatic and aliphatic compounds as well as to specific functional groups. 

FIGURE 3-6 Mass concentration of aerosol formation from olefin-ozone reaction as a function of olefin concentration, r, residence time in the flow reactor. Reprinted with permission from Burton et ai. 

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