title: The gas-phase ozonolysis of beta-caryophyllene (C(15)H(24)). Part I: an experimental study.
abstract: 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.
authors.affiliation: Max Planck Institute for Chemistry, Atmospheric Chemistry Department, P.O. Box 3060, D-55020, Mainz, Germany. winterha@mpch-mainz.mpg.de
authors.forename: Richard
authors.initials: R
authors.lastname: Winterhalter
authors.forename: Frank
authors.initials: F
authors.lastname: Herrmann
authors.forename: Basem
authors.initials: B
authors.lastname: Kanawati
authors.forename: Thanh Lam
authors.initials: TL
authors.lastname: Nguyen
authors.forename: Jozef
authors.initials: J
authors.lastname: Peeters
authors.forename: Luc
authors.initials: L
authors.lastname: Vereecken
authors.forename: Geert K
authors.initials: GK
authors.lastname: Moortgat
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D003510:Cyclohexanes / Q000737:chemistry; D005557:Formaldehyde / Q000737:chemistry; D016166:Free Radical Scavengers / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry; D013058:Mass Spectrometry; D010126:Ozone / Q000737:chemistry*; D000081223:Polycyclic Sesquiterpenes; D011522:Protons; D012717:Sesquiterpenes / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D003510:Cyclohexanes; D016166:Free Radical Scavengers; D000081223:Polycyclic Sesquiterpenes; D011522:Protons; D012717:Sesquiterpenes; D002245:Carbon Dioxide; D005557:Formaldehyde; D017665:Hydroxyl Radical; C506365:Cyclohexane; D010126:Ozone; D002248:Carbon Monoxide; D006861:Hydrogen Peroxide; C024714:caryophyllene