Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase. Ethylene

Herron, John T.; Huie, Robert E.

doi:10.1021/ja00458a033

Cited by 115 publications

(115 citation statements)

References 15 publications

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“…This statement is applicable towards the ozonolysis of most unsaturated compounds. A significant fraction of gas-phase CI undergoes unimolecular decomposition and these channels have been established for the simplest CI, CH 2 OO (Horie and Moortgat, 1991;Su et al, 1980;Herron and Huie, 1977). These products include OH and other free-radicals (Martinez et al, 1981;Neeb et al, 1998;Fenske et al, 2000;Gutbrod et al, 1997;Lewin et al, 2001;Aschmann et al, 2002;Ariya et al, 2000;Atkinson et al, 1995;Gutbrod et al, 1996).…”

Section: Overview Of Ozonolysismentioning

confidence: 99%

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

2007

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Abstract. The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acidozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquidphase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics.Correspondence to: G. A. Petrucci (giuseppe.petrucci@uvm.edu) Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.

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Section: Overview Of Ozonolysismentioning

confidence: 99%

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

2007

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“…as shown by Herron et al [2,8]. Oxirane biradicals in path (10c) collapse into the epoxides or rearrange into ketones.…”

Section: Biradical Mechanism Of Ozonolysis Reactions and Geometrical mentioning

confidence: 83%

“…Homolyses of 1,2,3-trioxolane into 1,5 biradicals may occur in three different ways: (i) the C-C cleavage (·CH 2 OO [20] biradicals, four different biradical orbital configurations, σσ, σπ, πσ and ππ, are allowed in principle for ·OCH 2 CH 2 OO· 41. All the configurations are accessible from symmetry consideration since the O envelope conformation has no spatial symmetry.…”

Section: Biradical Mechanism Of Ozonolysis Reactions and Geometrical mentioning

confidence: 99%

“…Path (10c) is also conceivable theoretically. The reaction scheme in equation (10) is applicable to the complex results of gas-phase ozonolysis reactions of olefins [2]. According to O'Neal and Blumstein [5] 1,5 biradicals 42 undergo the intramolecular hydrogen abstraction, providing peroxy biradical, dioxetane and free radicals.…”

Section: Biradical Mechanism Of Ozonolysis Reactions and Geometrical mentioning

confidence: 99%

“…The Criegee mechanism [1] is now generally accepted for most reactions of ozone with alkenes in solution. On the other hand, side reactions occur in gas phase because the reactions [2] are highly exothermic. For example, biradical (BR)-type decompositions of first ozonide were proposed in relation to the gas-phase ozonolysis reactions of olefins [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study on electronic structures of oxygenated dipoles and mechanisms of ozonolysis reactions

Yoshioka

Yamaki

Kubo

et al. 1997

Elect J Theoret Chem

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SUMMARYThe different orbitals for different spins molecular orbital and complete active space SCF studies of ozone and carbonyl oxide and related ozonolysis reactions were carried out. The RHF, UHF, approximately spin-projected (AP) UHF and CASSCF calculations were performed to elucidate the covalent bond instability of the oxygenated dipoles. The correlation energies were calculated by RMP4, UMP4, APUMP4 and CASPT2 methods. The locations of concerted transition structures for ozonolysis reactions and the full geometry optimizations of 1,5 biradicals formed by the O-O cleavage of first ozonide were carried out. The implications of these results are discussed in relation to concerted and biradical mechanisms of 1,3-dipolar additions and ozonolyses in gas phases.

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Prediction of approximate transition states by Bell-Evans-Polanyi principle: II. Gas phase unimolecular decomposition of methyldioxirane

et al. 1999

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We apply a model of the Bell–Evans–Polanyi principle (BEP) proposed in the accompanying article (Part I) and CASSCF wave functions to locate approximate transition structures for the unimolecular decomposition of methyldioxirane (1) into methyldioximethane (2) and 2 into acetic acid (3), formyl acetate (4), and CO2+CH4 (5), respectively. The model provides very good starting geometries for the transition structure search except for the dissociation step into CO2+CH4. In this case, the minimum crossing point of the interaction between the two quadratic surfaces centered in 2 and CO2+CH4 is an acceptable starting point for the transition state search. The contribution weights of reactants and products to the transition structure are given in the context of this method. In addition, the relative activation energies are provided at the CASSCF and CCSD(T) levels of theory. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1130–1137, 1999

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Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase. Ethylene

Cited by 115 publications

References 15 publications

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

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

Theoretical study on electronic structures of oxygenated dipoles and mechanisms of ozonolysis reactions

Prediction of approximate transition states by Bell-Evans-Polanyi principle: II. Gas phase unimolecular decomposition of methyldioxirane

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