Kinetics and mechanism of the reaction of the hydroxyl radical with h8-isoprene and d8-isoprene

Isoprene absorption cross sections, rate coefficients, and the mechanism of hydroperoxyl radical production

P. Campuzano-Jost, M. B. Williams, L. D'Ottone, Anthony J Hynes

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Abstract

We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with isoprene. Three isotopomeric variants of the reaction have been studied. A rate coefficient of (8.47 ± 0.59) × 10-11 cm3 molecule-1 s-1 (±2σ) was obtained at room temperature and showed no kinetic isotope effect within the precision of the measurements. The rate coefficient was independent of pressure over the range of 60-600 Torr and showed no dependence on the nature of the buffer gas in nitrogen, air, and helium. A limited study of the temperature dependence indicated that the reaction displays a slight negative activation energy (Ea = -690 J/mol). The gas-phase ultraviolet absorption spectrum of both regular and deuterated isoprene was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross section at ∼215 nm, the absorption peak, is ∼7 × 10-17 cm2. The detailed oxidation mechanism was examined by experiments in which NO was added to the gas mixture in order to recycle product HO2 to OH. At least 20 OH temporal profiles were obtained for each of the 3 isotopomeric variants. The profiles were modeled using the current isoprene module of the master chemical mechanism (MCM) that has been developed at Leeds University. The MCM mechanism gave good fits to the experimental profiles for all three reactions. A sensitivity analysis was developed to examine the extent to which recycling experiments can constrain individual rate coefficients in the MCM reaction mechanism. We obtain a lower limit of 4 × 10-12 cm3 molecule-1 s-1 for the rate coefficient for the addition of O2 to the hydroxyalkyl radical formed by OH addition to isoprene. Our results suggest that uncertainties in the database on NO radical termination steps are a major limitation in the ability of recycling experiments to constrain the MCM mechanism.

Original languageEnglish (US)
Pages (from-to)1537-1551
Number of pages15
JournalJournal of Physical Chemistry A
Volume108
Issue number9
DOIs
StatePublished - Mar 4 2004

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hydroxyl radicals
Hydroxyl Radical
absorption cross sections
Kinetics
kinetics
coefficients
Pulsed lasers
Recycling
Gases
Helium
Molecules
Experiments
Photolysis
Gas mixtures
Isotopes
Temperature
Sensitivity analysis
recycling
Absorption spectra
Buffers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Kinetics and mechanism of the reaction of the hydroxyl radical with h8-isoprene and d8-isoprene: Isoprene absorption cross sections, rate coefficients, and the mechanism of hydroperoxyl radical production",
abstract = "We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with isoprene. Three isotopomeric variants of the reaction have been studied. A rate coefficient of (8.47 ± 0.59) × 10-11 cm3 molecule-1 s-1 (±2σ) was obtained at room temperature and showed no kinetic isotope effect within the precision of the measurements. The rate coefficient was independent of pressure over the range of 60-600 Torr and showed no dependence on the nature of the buffer gas in nitrogen, air, and helium. A limited study of the temperature dependence indicated that the reaction displays a slight negative activation energy (Ea = -690 J/mol). The gas-phase ultraviolet absorption spectrum of both regular and deuterated isoprene was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross section at ∼215 nm, the absorption peak, is ∼7 × 10-17 cm2. The detailed oxidation mechanism was examined by experiments in which NO was added to the gas mixture in order to recycle product HO2 to OH. At least 20 OH temporal profiles were obtained for each of the 3 isotopomeric variants. The profiles were modeled using the current isoprene module of the master chemical mechanism (MCM) that has been developed at Leeds University. The MCM mechanism gave good fits to the experimental profiles for all three reactions. A sensitivity analysis was developed to examine the extent to which recycling experiments can constrain individual rate coefficients in the MCM reaction mechanism. We obtain a lower limit of 4 × 10-12 cm3 molecule-1 s-1 for the rate coefficient for the addition of O2 to the hydroxyalkyl radical formed by OH addition to isoprene. Our results suggest that uncertainties in the database on NO radical termination steps are a major limitation in the ability of recycling experiments to constrain the MCM mechanism.",
author = "P. Campuzano-Jost and Williams, {M. B.} and L. D'Ottone and Hynes, {Anthony J}",
year = "2004",
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TY - JOUR

T1 - Kinetics and mechanism of the reaction of the hydroxyl radical with h8-isoprene and d8-isoprene

T2 - Isoprene absorption cross sections, rate coefficients, and the mechanism of hydroperoxyl radical production

AU - Campuzano-Jost, P.

AU - Williams, M. B.

AU - D'Ottone, L.

AU - Hynes, Anthony J

PY - 2004/3/4

Y1 - 2004/3/4

N2 - We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with isoprene. Three isotopomeric variants of the reaction have been studied. A rate coefficient of (8.47 ± 0.59) × 10-11 cm3 molecule-1 s-1 (±2σ) was obtained at room temperature and showed no kinetic isotope effect within the precision of the measurements. The rate coefficient was independent of pressure over the range of 60-600 Torr and showed no dependence on the nature of the buffer gas in nitrogen, air, and helium. A limited study of the temperature dependence indicated that the reaction displays a slight negative activation energy (Ea = -690 J/mol). The gas-phase ultraviolet absorption spectrum of both regular and deuterated isoprene was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross section at ∼215 nm, the absorption peak, is ∼7 × 10-17 cm2. The detailed oxidation mechanism was examined by experiments in which NO was added to the gas mixture in order to recycle product HO2 to OH. At least 20 OH temporal profiles were obtained for each of the 3 isotopomeric variants. The profiles were modeled using the current isoprene module of the master chemical mechanism (MCM) that has been developed at Leeds University. The MCM mechanism gave good fits to the experimental profiles for all three reactions. A sensitivity analysis was developed to examine the extent to which recycling experiments can constrain individual rate coefficients in the MCM reaction mechanism. We obtain a lower limit of 4 × 10-12 cm3 molecule-1 s-1 for the rate coefficient for the addition of O2 to the hydroxyalkyl radical formed by OH addition to isoprene. Our results suggest that uncertainties in the database on NO radical termination steps are a major limitation in the ability of recycling experiments to constrain the MCM mechanism.

AB - We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with isoprene. Three isotopomeric variants of the reaction have been studied. A rate coefficient of (8.47 ± 0.59) × 10-11 cm3 molecule-1 s-1 (±2σ) was obtained at room temperature and showed no kinetic isotope effect within the precision of the measurements. The rate coefficient was independent of pressure over the range of 60-600 Torr and showed no dependence on the nature of the buffer gas in nitrogen, air, and helium. A limited study of the temperature dependence indicated that the reaction displays a slight negative activation energy (Ea = -690 J/mol). The gas-phase ultraviolet absorption spectrum of both regular and deuterated isoprene was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross section at ∼215 nm, the absorption peak, is ∼7 × 10-17 cm2. The detailed oxidation mechanism was examined by experiments in which NO was added to the gas mixture in order to recycle product HO2 to OH. At least 20 OH temporal profiles were obtained for each of the 3 isotopomeric variants. The profiles were modeled using the current isoprene module of the master chemical mechanism (MCM) that has been developed at Leeds University. The MCM mechanism gave good fits to the experimental profiles for all three reactions. A sensitivity analysis was developed to examine the extent to which recycling experiments can constrain individual rate coefficients in the MCM reaction mechanism. We obtain a lower limit of 4 × 10-12 cm3 molecule-1 s-1 for the rate coefficient for the addition of O2 to the hydroxyalkyl radical formed by OH addition to isoprene. Our results suggest that uncertainties in the database on NO radical termination steps are a major limitation in the ability of recycling experiments to constrain the MCM mechanism.

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SN - 1089-5639

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