Gas‐phase ozonolysis: Rate coefficients for a series of terpenes and rate coefficients and OH yields for 2‐methyl‐2‐butene and 2,3‐dimethyl‐2‐butene

Witter, M.; Berndt, Torsten; Böge, Olaf; Stratmann, Frank; Heintzenberg, Jost

doi:10.1002/kin.10063

Cited by 39 publications

(38 citation statements)

References 32 publications

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“…Here, the exposure is calculated directly from the measured loss of the gas‐phase reference compound, MB, using the integrated rate law for its reaction with O 3 : where k is the second‐order rate constant for the reaction of O 3 with MB and is 4.1 (±0.5) × 10 −16 cm 3 /molecule/sec. [ Witter et al , 2002]. The slope of the fit to the initial data can then be used to calculate the rate of reaction of methyl oleate, γ MO , as shown previously [ Smith et al , 2002; Katrib et al , 2005]: Here, R is the gas constant, T is the temperature, is the mean speed of O 3 , and V / S A (= d /6) is the volume‐to‐surface area ratio of the particles.…”

Section: Resultsmentioning

confidence: 99%

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

Hearn

Smith

2006

Geophysical Research Letters

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[1] A mixed-phase relative rates approach for measuring rates of reaction in aerosols is presented. Using this method the rate of reaction of methyl oleate (MO) particles, normalized to the gas-particle collision rate, was measured to be g MO = 1.12 (±0.36) Â 10 À3 with 2-methyl-2-butene as the gas-phase reference. This value compares favorably with our previously published value of 1.23 Â 10 À3 measured using an absolute technique. Reaction of bis(2-ethylhexyl) sebacate (BES) particles with Cl and OH radicals was also studied using acetone and hexanal, respectively, as the gas-phase references. The rates of reaction of BES, normalized to the gas-particle collision rate, were measured to be g BES = 1.8 ( À0.3 +0.8 ) and g BES = 2.0 ( À0.1 +0.6 ) with Cl and OH, respectively. These fast rates of reaction (g BES > 1) imply that secondary reactions, perhaps involving radical chain mechanisms, could impact the rate at which organic particles are oxidized in the atmosphere. Citation: Hearn, J. D., and G. D. Smith (2006), A mixed-phase relative rates technique for measuring aerosol reaction kinetics, Geophys. Res. Lett., 33, L17805,

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Section: Resultsmentioning

confidence: 99%

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

Hearn

Smith

2006

Geophysical Research Letters

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“…In the present study, the stated purity of 3-carene was ≥ 98.5% (more details in supplementary), and the impurities at this level would not significantly affect our absolute and relative rates. Witter, et al [19] reported k(O 3 +3-carene) = 5.6 × 10 -17 cm 3 molecule -1 s -1 using relative method in a flow reactor. It is ~50% higher than the other values, for which the reason is unknown.…”

Section: Discussionmentioning

confidence: 99%

Rate coefficients for the reaction of ozone with 2- and 3-carene

Chen

Ren

Cazaunau

et al. 2015

Chemical Physics Letters

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International audienceThe rate coefficients for the reactions of ozone with 2-carene and 3-carene have been measured at760 Torr of air and 299 ± 6 K using both absolute and relative methods. The data obtained are (in unitsof ×10−17cm3molecule−1s−1): k(2-carene) = 23.8 ± 1.0, k(3-carene) = 3.7 ± 0.2. The present work supple-ments the kinetic database of 2-carene and 3-carene using varied conventional experimental methods.The results are compared with the literature data and discussed with respect to atmospheric chemistry

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“…The needed rate coefficients k 1 − k 4 were taken from the literature (unit: cm 3 molecule −1 s −1 ; TME: tetramethylethylene; MCM: 1-methyl-cyclohexene): k 1,TME = 1.0 × 10 −15 (Witter et al, 2002); k 1,MCH = 1.65 × 10 −16 (Treacy et al, 1997); k 1,α−pinene = 1.1 × 10 −16 and k 1,limonene = 2.5 × 10 −16 (Witter et al, 2002); k 2,TME = 1.1 × 10 −10 (Atkinson, 1986); k 2,MCH = 9.6 × 10 −11 (Darnall et al, 1976); k 2,α−pinene = 5.3 × 10 −11 (Atkinson, 1986); k 2,limonene = 1.6 × 10 −10 ; k 3 = 6.7 × 10 −15 (DeMore et al, 1997) and k 4 = 1.2 × 10 −12 (Zellner, 1978). A diffusion controlled process is assumed for the H 2 SO 4 wall loss in the flow tube, k 5 = 3.65 · D(H 2 SO 4 )/r 2 .…”

Section: Simple Mechanismmentioning

confidence: 99%

Enhancement of atmospheric H2SO4 / H2O nucleation: organic oxidation products versus amines

et al. 2014

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Abstract. Atmospheric H 2 SO 4 / H 2 O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research -Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 10 7 -10 8 molecule cm −3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H 2 SO 4 formation starting from SO 2 . The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H 2 SO 4 concentrations higher than ∼ 10 7 molecule cm −3 . Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H 2 SO 4 -independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H 2 SO 4 concentrations smaller than ∼ 10 7 molecule cm −3 . Furthermore, the findings confirm the appearance of an additional oxidant for SO 2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 10 7 -10 10 molecule cm −3 applying photolytic OH radical generation for H 2 SO 4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine < aniline < dimethylamine < trimethylamine. This result supports the idea of H 2 SO 4 cluster stabilization by amines due to strong H 2 SO 4 ↔ amine interactions. On the other hand, this study indicates that for organic oxidation products (in presence of the possible amine background as stated) a distinct H 2 SO 4 / H 2 O nucleation enhancement can be due to increased H 2 SO 4 formation caused by additional organic oxidant production (sCI) rather than by stabilization of H 2 SO 4 clusters due to H 2 SO 4 ↔ organics interactions.

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Gas‐phase ozonolysis: Rate coefficients for a series of terpenes and rate coefficients and OH yields for 2‐methyl‐2‐butene and 2,3‐dimethyl‐2‐butene

Cited by 39 publications

References 32 publications

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

Rate coefficients for the reaction of ozone with 2- and 3-carene

Enhancement of atmospheric H<sub>2</sub>SO<sub>4</sub> / H<sub>2</sub>O nucleation: organic oxidation products versus amines

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Gas‐phase ozonolysis: Rate coefficients for a series of terpenes and rate coefficients and OH yields for 2‐methyl‐2‐butene and 2,3‐dimethyl‐2‐butene

Cited by 39 publications

References 32 publications

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

A mixed‐phase relative rates technique for measuring aerosol reaction kinetics

Rate coefficients for the reaction of ozone with 2- and 3-carene

Enhancement of atmospheric H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; / H&lt;sub&gt;2&lt;/sub&gt;O nucleation: organic oxidation products versus amines

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Enhancement of atmospheric H<sub>2</sub>SO<sub>4</sub> / H<sub>2</sub>O nucleation: organic oxidation products versus amines