Kinetics and energetics of the criegee intermediate in the gas phase. I. The criegee intermediate in ozone–alkene reactions

Abstract

The chemistry and energetics of the Criegee intermediate, a primary product of the ozonolysis of alkenes, are discussed in terms of recent ab-initio calculations and laboratory studies. The experimental observations in 03-alkene systems can be rationalized on the basis of a general mechanism:

Atmospheric photooxidation of isoprene part II: The ozone‐isoprene reaction

“…However, experimental evidence points to direct production of O(3P) from the Criegee biradical, which then reacts with isoprene to form the epoxides, as proposed by Herron et al [19];…”

“…Despite extensive mechanistic work on the breakup of the ozonide [2,3,6,7,[11][12][13][14]18,19] a mechanism has yet to be developed that can satisfactorily explain the large quantities of OH that clearly form in the 03-alkene systems, the formation of carbonyls (methacrolein and methyl vinyl ketone), propene, and epoxides (2-ethenyl 2-methyl oxirane and 2-( 1-methylethenyl) oxirane). In an effort to construct a mechanism that accounts for all of the available data, we propose the following mechanism for the ozone oxidation of isoprene: This mechanism assumes that the initial O3 attack occurs primarily at the unsubstituted double bond.…”

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

“…This acid is formed in a high energy state and may undergo dissociation if not quenched (Bunnelle, 1991;Herron et al, 1982). Numerous calculations summarized by Bunnelle (Bunnelle, 1991) indicate there is a considerable activation energy barrier between a thermally equilibrated CI and the dioxirane.…”

Mechanism and kinetics of the production of hydroxymethyl hydroperoxide in ethene/ozone/water gas-phase system

“…The reaction of ozone with alkenes, such as ethene, is initiated by cycloaddition of ozone across the double bond in ethene, forming a primary ozonide (POZ), according to Criegee [2] . POZ : CH 2 OO ≠ + M→CH 2 OO +M (R2e) The lifetime of CH 2 O 2 radicals is sufficiently long to react with numerous atmospheric species [4] , among which H 2 O has received much attention due to its ubiquitous existence on the earth and abundance in the atmosphere. The reaction of CH 2 O 2 with H 2 O was studied initially by Hatakeyama et al [5] who observed HC 18 OOH and HCO 18 OH but HC 18 O 18 OH in the product of CH 2 O 2 + H 2 18 O reaction, and therefore suggested that the reaction may have a pathway resulting in an intermediate of HMHP.…”

“…Suto [9] obtained k 3 of 1.6×10 −17 -1.6×10 −15 cm 3 ·molecule −1 ·s −1 based on the dependence between H 2 SO 4 aerosol formation rate and concentration of O 3 , SO 2 and H 2 O in C 2 H 4 /O 3 /SO 2 /H 2 O system. Herron [4] estimated k 3 ranging from 2×10 −19 -1×10 −15 cm 3 ·molecule −1 ·s −1 using a relative rate technique. Obviously, the reported k 3 are of high uncertainty.…”