Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

Ghalaieny, Mohamed; Bacak, Asan; McGillen, Max R.; Martin, Damien; Knights, A.; O’Doherty, Simon; Shallcross, Dudley E.; Percival, Carl J.

doi:10.1039/c2cp23988d

Cited by 9 publications

(18 citation statements)

References 46 publications

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“…We had found that the ozonolysis of β-C on AN:W surfaces proceeds ∼20 times faster than in the bulk liquid saturated with ozone, 30 and orders of magnitude faster than in the gas-phase. 10,44 We confirmed that 1-octanol is inert toward O 3 (g) under present conditions ( Fig. S1), in accordance with the negligibly small rate constant: k O3+1-octanol ≤ 0.8 M -1 s -1 in bulk water.…”

Section: Page 3 Of 23 Acs Paragon Plus Environmentsupporting

confidence: 85%

Reactions of Criegee Intermediates with Alcohols at Air–Aqueous Interfaces

Enami

Colussi

2017

J. Phys. Chem. A

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The fate of Criegee intermediates (CIs) from the gas-phase ozonolysis of unsaturated organic compounds in the troposphere is largely controlled by their reactions with water vapor. We recently found that against all expectations carboxylic acids compete at millimolar concentrations with water for CIs at the air-liquid interface of aqueous organic media. This outcome is consistent with both the low water concentration in the outermost interfacial layers and the enrichment of the competing acids therein. Here we show, via online electrospray mass spectrometric detection, that CIs generated in situ in the fast ozonolysis of sesquiterpenes (CH) on the surface of water:acetonitrile microjets react with n ≥ 4 linear alcohols CHOH to produce high molecular weight C ethers in one step. The OH group of 1-octanol proved to be ∼25 times less reactive than that of n-octanoic toward CIs at the same bulk molar concentration, revealing that the reactivity of hydroxylic species depends on both acidities and interfacial affinities. CI interfacial reactions with surface-active hydroxylic species, by bypassing water, represent shortcuts to molecular complexity in atmospheric aerosols.

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Section: Page 3 Of 23 Acs Paragon Plus Environmentsupporting

confidence: 85%

Reactions of Criegee Intermediates with Alcohols at Air–Aqueous Interfaces

Enami

Colussi

2017

J. Phys. Chem. A

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“…Ozonolysis is a significant pathway for ambient β-C removal; the relative contribution of O 3 reaction to tropospheric degradation is as much as 98 % (Hoffmann et al, 1997). Even though the reported reaction rate of β-C dark ozonolysis varies (Ghalaieny et al, 2012;Shu and Atkinson, 1995), aerosol is readily formed in this chamber and in other previous studies (e.g., but not limited to; Ng et al, 2006;Winterhalter et al, 2009;Chen et al, 2012).…”

Section: Introductionmentioning

confidence: 57%

Are sesquiterpenes a good source of secondary organic cloud condensation nuclei (CCN)? Revisiting β-caryophyllene CCN

2012

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Secondary organic aerosol (SOA) was formed in an environmental reaction chamber from the ozonolysis of β-caryophyllene (β-C) at low concentrations (5 ppb or 20 ppb). Experimental parameters were varied to characterize the effects of hydroxyl radicals, light and the presence of lower molecular weight terpene precursor (isoprene) for β-C SOA formation and cloud condensation nuclei (CCN) characteristics. Changes in β-C SOA chemicophysical properties (e.g., density, volatility, oxidation state) were explored with online techniques to improve our predictive understanding of β-C CCN activity. In the absence of OH scavenger, light intensity had negligible impacts on SOA oxidation state and CCN activity. In contrast, when OH reaction was effectively suppressed (> 11 ppm scavenger), SOA showed a much lower CCN activity and slightly less oxygenated state consistent with previously reported values. Though there is significant oxidized material present (O / C > 0.25), no linear correlation existed between the mass ratio ion fragment 44 in the bulk organic mass (f44) and O / C for the β-C-O3 system. No direct correlations were observed with other aerosol bulk ion fragment fraction (fx) and κ as well. A mixture of β-C and lower molecular weight terpenes (isoprene) consumed more ozone and formed SOA with distinct characteristics dependent on isoprene amounts. The addition of isoprene also improved the CCN predictive capabilities with bulk aerosol chemical information. The β-C SOA CCN activity reported here is much higher than previous studies (κ < 0.1) that use higher precursor concentration in smaller environmental chambers; similar results were only achieved with significant use of OH scavenger. Results show that aerosol formed from a mixture of low and high molecular weight terpene ozonolysis can be hygroscopic and can contribute to the global biogenic SOA CCN budget

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“…Up to now, only three literature studies exist that investigated the rate coefficient of the reaction of ozone with these SQTs. [20][21][22] Reported rate coefficients differ by more than two orders of magnitude for the two atmospherically most important SQTs, b-caryophyllene and a-humulene, apparently strongly motivating a reinvestigation.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, Ghalaieny et al 21 carried out relative rate experiments in the EXTRA chamber (volume: 123 liter, Teflon-coated) at 366 AE 3 K and 780 Torr of a N 2 -O 2 mixture. GC-FID analysis served for the detection of the SQT and the reference substance applying a gas loop for sampling.…”

Section: Introductionmentioning

confidence: 99%

“…The measured relative rate coefficients of SQTs at 366 K (TME as the reference substance) were set on an absolute scale using k (O 3 +TME, 366K) = 2.89 Â 10 À17 cm 3 molecule À1 s À1 as determined in this study 21 as well. It is to be noted that the k (O 3 +TME, 366K) value by Ghalaieny et al 21 is about a factor of 45 smaller than the literature value by Huie and Herron.…”

Section: Introductionmentioning

confidence: 99%

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Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K

Richters

Herrmann

Berndt

2015

Phys. Chem. Chem. Phys.

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The rate coefficients of the reaction of ozone with the four atmospherically relevant sesquiterpenes β-caryophyllene, α-humulene, α-cedrene and isolongifolene were investigated at 295 ± 2 K and atmospheric pressure by at least two independent experimental investigations for each reaction. Relative rate experiments were carried out in a flow tube using two different experimental approaches with GC-MS detection (RR 1) and PTR-MS analysis (RR 2) as the analytical techniques. Absolute rate coefficients were determined in a stopped-flow experiment following the ozone depletion by means of UV spectroscopy. The average rate coefficients from the combined investigations representing the mean values of the different experimental methods are (unit: cm(3) molecule(-1) s(-1)): k(O3+β-caryophyllene) = (1.1 ± 0.3) × 10(-14) (methods: RR 1, RR 2, absolute), k(O3+α-humulene) = (1.2 ± 0.3) × 10(-14) (RR 1, RR 2), k(O3+α-cedrene) = (1.7 ± 0.5) × 10(-16) (RR 2, absolute) and k(O3+isolongifolene) = (1.1 ± 0.5) × 10(-17) (RR 2, absolute). The high ozonolysis rate coefficients for β-caryophyllene and α-humulene agree well with the results by Shu and Atkinson (Int. J. Chem. Kinet., 1994, 26) and lead to short atmospheric lifetimes of about two minutes with respect to the ozone reaction. The relatively small rate coefficients for α-cedrene and isolongifolene differ from the available literature values by a factor of about 2.5-6. Possible reasons for the deviations are discussed. Finally, calibrated sesquiterpene FT-IR spectra were recorded for the first time.

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Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

Cited by 9 publications

References 46 publications

Reactions of Criegee Intermediates with Alcohols at Air–Aqueous Interfaces

Reactions of Criegee Intermediates with Alcohols at Air–Aqueous Interfaces

Are sesquiterpenes a good source of secondary organic cloud condensation nuclei (CCN)? Revisiting β-caryophyllene CCN

Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K

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