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Reaction kinetics of Cl atoms with limonene: An experimental and theoretical study
Published in Elsevier Ltd
2014
Volume: 99
   
Pages: 183 - 195
Abstract
Rate coefficients for the reaction of Cl atoms with limonene (C10H16) were measured between 278-350K and 800Torr of N2, using the relative rate technique, with 1,3-butadiene (C4H6), n-nonane (C9H20), and 1-pentene (C5H10) as reference compounds. Cl atoms were generated by UV photolysis of oxalyl chloride ((COCl)2) at 254nm. A gas chromatograph equipped with a flame ionization detector (GC-FID) was used for quantitative analysis of the organics. The rate coefficient for the reaction of Cl atoms with limonene at 298K was measured to be (8.65±2.44)×10-10cm3molecule-1s-1. The rate coefficient is an average value of the measurements, with two standard deviations as the quoted error, including uncertainties in the reference rate coefficients. The kinetic data obtained over the temperature range of 278-350K were used to derive the following Arrhenius expression: k(T)=(9.75±4.1)×10-11exp[(655±133)/T]cm3molecule-1s-1. Theoretical kinetic calculations were also performed for the title reaction using conventional transition state theory (CTST) in combination with G3(MP2) theory between 275 and 400K. The kinetic data obtained over the temperature range of 275-400K were used to derive an Arrhenius expression: k(T)=(7.92±0.82)×10-13exp[(2310±34)/T]cm3molecule-1s-1. The addition channels contributes maximum to the total reaction and H-abstraction channels can be neglected in the range of studied pressures. The Atmospheric lifetime (τ) of limonene due to its reaction with Cl atoms was estimated and concluded that the reaction with chlorine atoms can be an effective tropospheric loss pathway in the marine boundary layer and in coastal urban areas. © 2014.
About the journal
JournalData powered by TypesetAtmospheric Environment
PublisherData powered by TypesetElsevier Ltd
ISSN13522310
Open AccessNo
Concepts (39)
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    ATMOSPHERIC LIFETIME
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    CL ATOMS
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    LIMONENE
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    Rate coefficients
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    RELATIVE RATE TECHNIQUES
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    Transition state theories
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    1 PENTENE
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    1,3 butadiene
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    Chloride
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    Chlorine
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    LIMONENE
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    NONANE
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    Organic compound
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    OXALYL CHLORIDE
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    Unclassified drug
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    Error analysis
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    Estimation method
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    Hydrocarbon
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    Reaction kinetics
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    Theoretical study
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    Uncertainty analysis
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    Ab initio calculation
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    ANALYTICAL EQUIPMENT
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    ANALYTICAL ERROR
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    Article
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    Atom
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    Chemical reaction kinetics
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    Controlled study
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    CONVENTIONAL TRANSITION STATE THEORY
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    Experimental study
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    FLAME IONIZATION DETECTOR
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    GAS CHROMATOGRAPH
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    Molecular size
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    Molecule
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    Photolysis
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    Quantitative analysis
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    Temperature
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    Theory
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    Ultraviolet radiation