Reaction ozone-olefin

Hanst, P.L., Stephens, E.R., Scott, W.E., Doerr, R.C. (1958) Atmospheric Ozone-Olefin Reactions. Franklin Institute, Philadelphia, Pa. 

Furthermore, it has been noted that when the rate of the oxygen atom-olelin reaction and the rate of the ozone-olefin reaction are totaled, they do not give the complete hydrocarbon consumption. This anomaly is also an indication of an additional process. 

Atkinson, R., B. J. Finlayson, and J. N. Pitts, Jr. Photoionization mass spectrometer studies of gas phase ozone-olefin reactions. J. Amer. Chem. Soc. 95 7592-7599, 1973. 

McAfee, J. M., A. M. Winer, and J. N. Pitts, Jr. Infrared Product Analysis of Ozone-Olefin Reaction by Fourier Interferometry. Paper Presented at CODATA... 

Much evidence has been accumulated that the ozone-olefin reaction has a predominant role in aerosol formation from alkenes, cyclic olefins, diolefins, and other unsaturated compounds. Free radicals are formed in the reaction and can react further, along with nitric oxide and nitrogen dioxide, either with the various intermediates or with the olefin itself (see the recent review by Pitts and Finlayson ). 

A mechanism has been proposed recently by O Neal and Blumstein for the gas-phase ozone-olefin reaction. This mechanism postulates that molozonide-biradical equilibrium is reached fast and postulates a competition between a-, 8-, and y-hydrogen abstraction reactions and the classical mechanism proposed by Criegee for the liquid-phase reaction. The main features of the Criegee mechanism (Figure 3-9) are the formation, from the initial molozonide, of the major carbonyl products and a second biradical intermediate, the zwitterion. The decomposition pathways of the zwitterion comprise unimolecular re-... 

FIGURE 3-10 Gas-phase ozone-olefin reaction the O Neal and Blumstein mechanism J... 

Reactions with intermediates of the ozone-olefin reaction ... 

Becker, K. H., U. Schurath, and H. Seitz. Ozone-olefin reactions in the gas phase. 

Burton. C. S., E. Franzblau, and G. M. Hidy. Aerospl Formation from Ozone-Olefin Reactions, Abstract COLL 128. In Abstracts of Papers. 167th National Meeting, American Chemical Society, Los Angeles, Califomb, March 31-April 5, 1974. 

Becker, K. H., U. Schurath, and H. Seitz. Ozone-olefin reactions in the gas phase. 1. Rate constants and activation energies. Int. J. Chem. Kinetics 6 725-739, 1974. 

Acroldn concentration, 186,187 Adenosine triphosphate, effect of ozone on lung concentration of, 354 Aerosol carbon balance, 50 Aerosol formation, 4, 14, 674-76 ability index, 61 diemical medianisms of, 72 hydrox]4 radical-aromatic hydrocar> bon reaction, 76-81 ozone-olefin reaction, 72-76 condensable species vapor pressure and, 86-90,101... 

Cotton, effect of oxidants on, 462,687 Cotton fiber, ozone damage to, 665 Coulombmetry. See Amperometric analyzers <>i ee mechanism, for liquid-phase ozone-olefin reaction, 72-74, 76 Cydic olefins, 4,60,76 aerosols from, 70-72,83,88 importance of, 104... 

Finlayson, B. J., J. N. Pitts, Jr., and H. Akimoto, Production of Vibrationally Excited OH in Chemiluminescent Ozone-Olefin Reactions, Chem. Phys. Lett., 12, 495-498 (1972). 

Pryor WA, Prier DG, Church DF. Detection of free radicals from low-temperature ozone-olefin reaction by ESR spin trapping evidence that the radical precursor is a trioxide. J Am Chem Soc 1983 105 2883-2888. 

Niki, H., Maker, P.D., Savage, C M., Breitenbach, L.P. (1983) Atmospheric ozone-olefin reactions. Environ. Sci. Technol. 17, 312A. 

Similar conclusions are drawn by Cvetanovic et al. from their results of ozonization of alkenes in the gas phase (9) and in CC14 solution (10). The rate constants for the ozonolysis of chloroethylenes and allyl chloride, in CC14 solution, indicate (11) that the rate of ozone attack decreases rapidly as the number of chlorine atoms in the olefin molecules is increased. However, to explain the departures from simple correlations, in some cases steric effects and the dipolar character of ozone had to be invoked (10). The relevance of the dipolar character of ozone in its reactions has also been stressed by Huisgen (12), who provided evidence that the ozone—olefin reaction is usually a 1,3-dipolar cycloaddition. 

On the basis of the evidence (10) that, in solution, the ozone—olefin reaction takes place with a 1 1 stoichiometry, the consumption of olefin i may be written... 

Table II presents a summary of the values of kreY which were obtained in the way just indicated, for p-methylstyrene, in CC14 solution, with respect to styrene. These results indicate that kTei is invariant with respect to the ozone flow rate, the temperature of ozonolysis, and the olefin initial concentration. The fact that kreA is independent of temperature in this case is readily understood when it is considered that the experimental activation energies for the ozone-olefin reaction are likely to be very similar for p-methylstyrene and styrene.

Perhaps the most interesting point which emerges from the results is that in ethylenes bearing electron-releasing alkyl substituents the ratedetermining step appears to be a nucleophilic process, as indicated by the positive p values. This does not contradict the assumption that the first step in the ozone—olefin reaction is an electrophilic attack of ozone on the carbon-carbon double bond. The present observations also agree with some of the results obtained recently by Pritzkow et al. (16) for alkyl mono-substituted ethylenes in ethanol solution at — 60 °C. 

Spectra from the chemiluminescent gas phase reactions at 0,5 torr, of ozone with ethylene, tetramethylethylene, trans-2-hutene, and methyl mercaptan at room temperature are presented, and a summary of the general features of the emissions obtained from reaction in the gas phase of ozone with fourteen different olefins is given. The emitting species in the ozone-olefin reactions have been tentatively identified as electronically excited aldehydes, ketones, and a-dicarbonyl compounds. The reaction of ozone with hydrogen sulfide, methyl mercaptan, and dimethylsulfide produces sulfur dioxide in its singlet excited state. 

Lovas, F. J., and R. D. Suenram (1977). Identification of Dioxirane H2COO in ozone-olefin reactions via microwave spectroscopy. Chem. Phys. Lett. 51, 453-456. 

The effect of ozone is both greatly delayed and reduced when various antiozonants, such as NJ -di-alkyl-p-phenylene-diamines (X) or similar compounds, are incorporated in the rubber. They may react directly with ozone or with the ozone-olefin reaction products in such a way as to prevent chain scission. SBR is much more receptive to protection than either the nitrile or natural rubbers. Of the latter two the nitrile is more readily inhibited. If a wax is also added in small quantities with the antiozonant, the retardation of the attack of ozone is in certain instances enhanced several fold. 

Becker, K. H., Schurath, U. Seitz, H. (1974). Ozone-Olefin Reactions in the Gas Phase. 1. Rate Constants and Activation Eneigies. Int J. Chem. Kinet, (6), 725-739. 

Amongst the evidence that the Criegee proposals can account for at least some ozone-olefin reactions may be cited the following ... 

Hatakeyama, S., Kobayashi, H., Akimoto, H. Gas-phase oxidation of sulfur dioxide in the ozone-olefin reactions. J. Phys. Chem. 88, 4736-4739 (1984)... 

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