Conformational studies of aliphatic secondary ozonides (propene, 1-butene and 1-heptene) by means of FTIR spectroscopy

Barisevičiūtė, Rūta; Čeponkus, Justinas; Gruodis, Alytis; Šablinskas, Valdas

doi:10.2478/s11532-006-0031-3

Cited by 4 publications

(3 citation statements)

References 14 publications

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“…The strong absorption in the residual spectrum at 1104 cm À1 could originate from secondary ozonides (SOZ). Typical FTIR-absorptions of SOZ from simple alkenes 45,46 and b-pinene 31 are in the range from 1050 to 1150 cm À1 .…”

Section: Ftir Measurementsmentioning

confidence: 99%

The gas-phase ozonolysis of β-caryophyllene (C15H24). Part I: an experimental study

Winterhalter

Herrmann

Kanawati

et al. 2009

Phys. Chem. Chem. Phys.

134

192

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The gas phase reaction of ozone with beta-caryophyllene was investigated in a static glass reactor at 750 Torr and 296 K under various experimental conditions. The reactants and gas phase products were monitored by FTIR-spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Aerosol formation was monitored with a scanning mobility particle sizer (SMPS) and particulate products analysed by liquid chromatography/mass spectrometry (HPLC-MS). The different reactivity of the two double bonds in beta-caryophyllene was probed by experiments with different ratios of reactants. An average rate coefficient at 295 K for the first-generation products was determined as 1.1 x 10(-16) cm(3) molecule(-1) s(-1). Using cyclohexane as scavenger, an OH-radical yield of (10.4 +/- 2.3)% was determined for the ozonolysis of the more reactive internal double bond, whereas the average OH-radical yield for the ozonolysis of the first-generation products was found to be (16.4 +/- 3.6)%. Measured gas phase products are CO, CO(2) and HCHO with average yields of (2.0 +/- 1.8)%, (3.8 +/- 2.8)% and (7.7 +/- 4.0)%, respectively for the more reactive internal double bond and (5.5 +/- 4.8)%, (8.2 +/- 2.8)% and (60 +/- 6)%, respectively from ozonolysis of the less reactive double bond of the first-generation products. The residual FTIR spectra indicate the formation of an internal secondary ozonide of beta-caryophyllene. From experiments using HCOOH as a Criegee intermediate (CI) scavenger, it was concluded that at least 60% of the formed CI are collisionally stabilized. The aerosol yield in the ozonolysis of beta-caryophyllene was estimated from the measured particle size distributions. In the absence of a CI scavenger the yield ranged between 5 and 24%, depending on the aerosol mass. The yield increases with addition of water vapour or with higher concentrations of formic acid. In the presence of HCHO, lower aerosol yields were observed. This suggests that HCOOH adds to a Criegee intermediate to form a low-volatility compound responsible for aerosol formation. The underlying reaction mechanisms are discussed and compared with the results from the accompanying theoretical paper.

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Section: Ftir Measurementsmentioning

confidence: 99%

The gas-phase ozonolysis of β-caryophyllene (C15H24). Part I: an experimental study

Winterhalter

Herrmann

Kanawati

et al. 2009

Phys. Chem. Chem. Phys.

134

192

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“…It is most probable that all three SOZ are formed. It is however suggested that the formation of SOZ 1 and SOZ 2 is favoured, because the three maxima in the relevant range of the FTIR-spectra are similar to those of the propene-SOZ 49 (having analogue DB 1 and 2). The analogue 2-butene-SOZ to SOZ 3 has only one sharp maximum in this range.…”

Section: Secondary Ozonidesmentioning

confidence: 99%

The gas-phase ozonolysis of α-humulene

Beck

Winterhalter

Herrmann

et al. 2011

Phys. Chem. Chem. Phys.

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α-Humulene contains three double bonds (DB), and after ozonolysis of the first DB the first-generation products are still reactive towards O(3) and produce second- and third-generation products. The primary aim of this study consisted of identifying the products of the three generations, focusing on the carboxylic acids, which are known to have a high aerosol formation potential. The experiments were performed in a 570 litre spherical glass reactor at 295 K and 730 Torr. Initial mixing ratios were 260-2090 ppb for O(3) and 250-600 ppb for α-humulene in synthetic air. Reactants and gas-phase products were measured by in situ FTIR spectroscopy. Particulate products were sampled on Teflon filters, extracted with methanol and analyzed by LC-MS/MS-TOF. Using cyclohexane (10-100 ppm) as an OH-radical scavenger and by monitoring the yield of cyclohexanone by PTR-MS, an OH-yield of (10.5 ± 0.7)% was determined for the ozonolysis of the first DB, and (12.9 ± 0.7)% of the first-generation products. The rate constant of the reaction of O(3) with α-humulene is known as k(0) = 1.17 × 10(-14) cm(3) molecule(-1) s(-1) [Y. Shu and R. Atkinson, Int. J. Chem. Kinet., 1994, 26, 1193-1205]. The reaction rate constants of O(3) with the first-generation products and the second-generation products were, respectively, determined as k(1) = (3.6 ± 0.9) × 10(-16) and k(2) = (3.0 ± 0.7) × 10(-17) cm(3) molecule(-1) s(-1) by Facsimile-simulation of the observed ozone decay by FTIR. A total of 37 compounds in the aerosol phase and 5 products in the gas phase were tentatively identified: 25 compounds of the first-generation products contained C13-C15 species, 9 compounds of the second-generation products contained C8-C11 species, whereas 8 compounds of the third-generation products contained C4-C6 species. The products of all three generations consisted of a variety of dicarboxylic-, hydroxy-oxocarboxylic- and oxo-carboxylic acids. The formation mechanisms of some of the products are discussed. The residual FTIR spectra indicate the formation of secondary ozonides (SOZ) in the gas phase, which are formed by the intramolecular reaction of the Criegee moiety with the carbonyl endgroup. These SOZ revealed to be stable over several hours and its formation was shown not to be affected by the addition of Criegee-radical scavengers such as HCOOH or H(2)O. This suggests that in the ozonolysis of α-humulene at atmospheric pressures the POZ will decompose rapidly, and that a large fraction of the formed exited Criegee Intermediate will be stabilized to form stable SOZ, while the formation of OH-radicals via the hydroperoxide channel will be a minor process.

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“…Reaction products evaporated at 190 -210 K temperature interval were transferred to the coolable infrared gas cell equipped with White optics [16,17]. The spectra were recorded on BRUKER IFS 120 HR spectrometer.…”

Section: Methodsmentioning

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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Conformational studies of aliphatic secondary ozonides (propene, 1-butene and 1-heptene) by means of FTIR spectroscopy

Cited by 4 publications

References 14 publications

The gas-phase ozonolysis of β-caryophyllene (C15H24). Part I: an experimental study

The gas-phase ozonolysis of β-caryophyllene (C15H24). Part I: an experimental study

The gas-phase ozonolysis of α-humulene

Matrix isolation FTIR spectroscopical study of ethene secondary ozonide

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