Formation of secondary ozonides in the gas phase low-temperature ozonation of primary and secondary alkenes

Fajgаr, Radek; Vítek, Josef; Haas, Yehuda; Pola, J.

doi:10.1039/a807208f

Cited by 25 publications

(27 citation statements)

References 61 publications

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“…50 New product peaks also appear at 2950, 2880, 1385, and 1110 cm À1 , and are assigned to a secondary ozonide (SOZ). 28,50,54,[67][68][69][70][71][72][73] The band at 1110 cm À1 in the Instant Ocean spectra (Fig. 2a) is largely obscured by small changes in the strong sulfate band in that region (Fig.…”

Section: Resultsmentioning

confidence: 99%

Heterogeneous oxidation of a phosphocholine on synthetic sea salt by ozone at room temperature

Dilbeck

Finlayson-Pitts

2013

Phys. Chem. Chem. Phys.

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The ozonolysis of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) adsorbed on salt mixtures as models for sea-salt particles was studied in real time using diffuse reflection infrared Fourier transform spectrometry (DRIFTS) at room temperature with and without added water vapor. The salt substrates were a mixture of MgCl 2 Á6H 2 O with NaCl or a commercially available synthetic sea salt. Ozone concentrations ranged from (0.25 to 3.9) Â 10 13 molecules cm À3 (0.1-1.6 ppm). The major products identified by FTIR and confirmed using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry were the secondary ozonide (SOZ) and a phospholipid aldehyde and carboxylic acid formed by scission of the double bond. The reaction probabilities for the two substrates were similar, g = (6-7) Â 10 À7 , with an estimated overall uncertainty of a factor of two. The presence of water vapor decreased the yield of SOZ relative to the products formed by CQC scission, but also increased the availability of the double bond for reaction, particularly on the less hygroscopic commercial sea-salt substrate. Thus, water not only affects the mechanisms and products, but also the structure of the phospholipid on the salt in a manner that affects its reactivity. The results of these studies suggest that the reactivity and products of oxidation of unsaturated phospholipids on sea-salt particles in air will be very sensitive to the nature and phase of the substrate, the amount of water present, and whether there is phase separation between the organics and the inorganic salt mixture.

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Section: Resultsmentioning

confidence: 99%

Heterogeneous oxidation of a phosphocholine on synthetic sea salt by ozone at room temperature

Dilbeck

Finlayson-Pitts

2013

Phys. Chem. Chem. Phys.

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“…The production of gas phase secondary ozonide (gSOZ) from the reaction between formaldehyde and Criegee intermediate (III) is also possible, and there have been several reports of gas phase SOZ formation from ozonation of alkenes in various pressure ranges. [21][22][23] As the SAM oxidation proceeds and surface products accumulate, new reaction channels open up due to the close proximity of surface bound molecules in SAM. For example, the association reaction of surface aldehyde (II) with surface Criegee intermediate (I) can form surface SOZ dimer (V) shown in Fig.…”

Section: Discussion (A) Ozonolysismentioning

confidence: 99%

Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles

Park

Gomez

Walser

et al. 2006

Phys. Chem. Chem. Phys.

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Photolysis of alkene-terminated self assembled monolayers (SAM) deposited on Degussa SiO(2) nanoparticles is studied following oxidation of SAM with a gaseous ozone/oxygen mixture. Infrared cavity ring-down spectroscopy is used to observe gas-phase products generated during ozonolysis and subsequent photolysis of SAM in real time. Reactions taking place during ozonolysis transform alkene-terminated SAM into a photochemically active state capable of photolysis in the tropospheric actinic window (lambda > 295 nm). Formaldehyde and formic acid are the observed photolysis products. Photodissociation action spectra of oxidized SAM and the observed pattern of gas-phase products are consistent with the well-established Criegee mechanism of ozonolysis of terminal alkenes. There is strong evidence for the presence of secondary ozonides (1,3,4-trioxalones) and other peroxides on the oxidized SAM surface. The data imply that photolysis plays a role in atmospheric aging of primary and secondary organic aerosol particles.

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“…Despite numerous studies of this reaction by different spectroscopic techniques the precise mechanism of the reaction is still unknown [2][3][4][5][6][7][8][9][10]. This is also true for the dissociation of the secondary ozonide.…”

Section: IImentioning

confidence: 99%

Matrix isolation FTIR spectroscopical study of ethene secondary ozonide

2007

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Abstract:A new method is used for the separation of ethene secondary ozonide (SOZ) from the other products of ethene ozonization reaction. The reaction was performed in the neat films of the reactants at 77 K. Ethene SOZ was separated from other products of the reaction by vacuum distillation at 190-210 K and analyzed by means of the matrix isolation IR absorption spectroscopy. Spectroscopic data from photolysis of the matrix isolated ozonide was used as an argument for assignment of the infrared spectral bands either to ethene SOZ or to other products of the reaction. The spectra of ethene SOZ isolated in the Ar matrix were analyzed by combining experimental results with the theoretical calculations performed at the MP2 6-311+G (3df, 3pd) level. A new assignment of some experimental fundamental bands is proposed taking in to account the Fermi resonance between CH stretch and the five membered ring vibrations. For the first time more than 30 weak infrared absorption bands were observed and assigned to various combination vibrations and overtones. By using new spectral information concerning the overtones and the combination bands it is concluded that the dissociation of unstable ethene SOZ involving breaking of any of the four CO bonds of the five membered ring of ethene SOZ has low probability. Dissociation of the ring starts from breaking of the OO bond.

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Formation of secondary ozonides in the gas phase low-temperature ozonation of primary and secondary alkenes

Cited by 25 publications

References 61 publications

Heterogeneous oxidation of a phosphocholine on synthetic sea salt by ozone at room temperature

Heterogeneous oxidation of a phosphocholine on synthetic sea salt by ozone at room temperature

Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles

Matrix isolation FTIR spectroscopical study of ethene secondary ozonide

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