ISSN:
1573-0662
Keywords:
ozone
;
1,1-disubstituted alkenes
;
carbonyl products
;
ozone-alkene reaction mechanism
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
,
Geosciences
Notes:
Abstract Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O3+R1R2C=CH2→ α(HCHO+R1R2COO)+(1−α)(R1COR2+H2COO) where formaldehyde and the ketone R1 COR2 are the primary carbonyls and R1R2COO and H2COO are the corresponding biradicals. Measured values of α were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H2COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R1R2COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00162408
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