Kinetic Study of the OH‐isoprene and O<sub>3</sub>‐isoprene reaction in the atmosphere simulation chamber, SAPHIR

Karl, Matthias; Brauers, T.; Dorn, Hans-Peter; Holland, F.; Komenda, M.; Poppe, D.; Rohrer, Franz; Rupp, L.; Schaub, A.; Wahner, Andreas

doi:10.1029/2003gl019189

Cited by 48 publications

(34 citation statements)

References 17 publications

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“…At the beginning, they were designed mainly to study the gas-phase reactions with ozone and the chemistry of NO x in the troposphere and the formation of aerosol from the gaseous pollutants [15][16][17]. Later research concentrated on the reactions of VOCs with OH radicals and their role in ozone formation and photochemical smog [18][19][20]. Despite intensive research on gas-phase kinetics during the last decades, comparatively little is known about the reactivity of OH radicals with VOCs below room temperature, especially for larger molecules [4,[21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

2018

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Abstract:The photochemical reaction of OH radicals with the 17 hydrocarbons n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, cyclooctane, 2,2-dimethylbutane, 2,2-dimethylpentane, 2,2-dimethylhexane, 2,2,4-trimethylpentane, 2,2,3,3-tetramethylbutane, benzene, toluene, ethylbenzene, p-xylene, and o-xylene was investigated at 288 and 248 K in a temperature controlled smog chamber. The rate constants were determined from relative rate calculations with toluene and n-pentane as reference compounds, respectively. The results from this work at 288 K show good agreement with previous literature data for the straight-chain hydrocarbons, as well as for cyclooctane, 2,2-dimethylbutane, 2,2,4-trimethylpentane, 2,2,3,3-tetramethylbutane, benzene, and toluene, indicating a convenient method to study the reaction of OH radicals with many hydrocarbons simultaneously. The data at 248 K (k in units of 10 −12 cm 3 s −1 ) for 2,2-dimethylpentane (2.97 ± 0.08), 2,2-dimethylhexane (4.30 ± 0.12), 2,2,4-trimethylpentane (3.20 ± 0.11), and ethylbenzene (7.51 ± 0.53) extend the available data range of experiments. Results from this work are useful to evaluate the atmospheric lifetime of the hydrocarbons and are essential for modeling the photochemical reactions of hydrocarbons in the real troposphere.

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Section: Introductionmentioning

confidence: 99%

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

2018

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“…If the reaction chamber is exposed to sunlight, two chemical compounds, nitrous acid (HONO) and formaldehyde (HCHO) are produced photolytically on the surface of the Teflon film (Rohrer et al, 2005;Karl et al, 2004). Although the detailed mechanism of these processes is not known, the source strengths of HONO and HCHO emissions into the chamber are well characterized by previous experiments.…”

Section: Saphir Chamber and Instrumentationmentioning

confidence: 72%

Intercomparison of peroxy radical measurements obtained at atmospheric conditions by laser-induced fluorescence and electron spin resonance spectroscopy

Fuchs

Brauers²,

Häseler³

et al. 2009

Atmos. Meas. Tech.

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Abstract. Measurements of hydroperoxy radical (HO 2 ) and organic peroxy radical (RO 2 ) concentrations were performed by two different techniques in the atmospheric simulation chamber SAPHIR in Jülich, Germany. The first technique was the well-established Matrix Isolation Electron Spin Resonance (MIESR), which provides absolute measurements with a time resolution of 30 min and high accuracy (10%, 2 σ ). The other technique, ROxLIF, has been newly developed. It is based on the selective chemical conversion of RO x radicals (HO 2 and RO 2 ) to OH, which is detected with high sensitivity by laser-induced fluorescence (LIF). ROx-LIF is calibrated by quantitative photolysis of water vapor at 185 nm and provides ambient measurements at a temporal resolution of 1 min and accuracy of 20% (2 σ ). The measurements of HO 2 and RO 2 obtained by the two techniques were compared for two types of atmospheric simulation experiments. In one experiment, HO 2 and CH 3 O 2 radicals were produced by photooxidation of methane in air at tropospheric conditions. In the second experiment, HO 2 and C 2 H 5 O 2 were produced by ozonolysis of 1-butene in air at dark conditions. The radical concentrations were within the range of 16 to 100 pptv for HO 2 and 12 to 45 pptv for RO 2 . Good agreement was found in the comparison of the ROxLIF and MIESR measurements within their combined experimental uncertainties. Linear regressions to the combined data set yield slopes of 1.02±0.13 (1 σ ) for RO 2 and 0.98±0.08 (1 σ ) for HO 2 without significant offsets. The results confirm the calibration of the ROxLIF instrument and demonstrate that it can be applied with good accuracy for measurements of atmospheric peroxy radical concentrations.

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“…The outdoor atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich facilitates the investigation of photochemical processes under defined conditions (see Karl et al, 2004;Poppe et al, 2007). The SAPHIR chamber has a cylindrical shape (18 m length, 5 m diameter, 270 m 3 volume).…”

Section: Methodsmentioning

confidence: 99%

Atmospheric photochemistry of aromatic hydrocarbons: OH budgets during SAPHIR chamber experiments

et al. 2014

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Abstract. Current photochemical models developed to simulate the atmospheric degradation of aromatic hydrocarbons tend to underestimate OH radical concentrations. In order to analyse OH budgets, we performed experiments with benzene, toluene, p-xylene and 1,3,5-trimethylbenzene in the atmosphere simulation chamber SAPHIR. Experiments were conducted under low-NO conditions (typically 0.1-0.2 ppb) and high-NO conditions (typically 7-8 ppb), and starting concentrations of 6-250 ppb of aromatics, dependent on OH rate constants. For the OH budget analysis a steady-state approach was applied in which OH production and destruction rates (P OH and D OH ) have to be equal. The P OH were determined from measurements of HO 2 , NO, HONO, and O 3 concentrations, considering OH formation by photolysis and recycling from HO 2 . The D OH were calculated from measurements of the OH concentrations and total OH reactivities. The OH budgets were determined from D OH /P OH ratios. The accuracy and reproducibility of the approach were assessed in several experiments using CO as a reference compound where an average ratio D OH /P OH = 1.13 ± 0.19 was obtained. In experiments with aromatics, these ratios ranged within 1.1-1.6 under low-NO conditions and 0.9-1.2 under high-NO conditions. The results indicate that OH budgets during photo-oxidation experiments with aromatics are balanced within experimental accuracies. Inclusion of a further, recently proposed OH production via HO 2 + RO 2 reactions led to improvements under low-NO conditions but the differences were small and insignificant within the experimental errors.

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Kinetic Study of the OH‐isoprene and O₃‐isoprene reaction in the atmosphere simulation chamber, SAPHIR

Cited by 48 publications

References 17 publications

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

Intercomparison of peroxy radical measurements obtained at atmospheric conditions by laser-induced fluorescence and electron spin resonance spectroscopy

Atmospheric photochemistry of aromatic hydrocarbons: OH budgets during SAPHIR chamber experiments

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Kinetic Study of the OH‐isoprene and O3‐isoprene reaction in the atmosphere simulation chamber, SAPHIR

Cited by 48 publications

References 17 publications

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

Rate Constants for the Reaction of OH Radicals with Hydrocarbons in a Smog Chamber at Low Atmospheric Temperatures

Intercomparison of peroxy radical measurements obtained at atmospheric conditions by laser-induced fluorescence and electron spin resonance spectroscopy

Atmospheric photochemistry of aromatic hydrocarbons: OH budgets during SAPHIR chamber experiments

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Kinetic Study of the OH‐isoprene and O₃‐isoprene reaction in the atmosphere simulation chamber, SAPHIR