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Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran : Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

Andersen, Christina LU ; Nielsen, Ole John; Østerstrøm, Freja F.; Ausmeel, Stina LU ; Nilsson, Elna J K LU and Sulbaek Andersen, Mads P. (2016) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 120(37). p.7320-7326
Abstract

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10-10, kTHF+OD = (1.81 ± 0.27) × 10-11, kTHF+O3 = (6.41 ± 2.90) × 10-21, k2-MTHF+Cl = (2.65 ± 0.43) ×... (More)

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10-10, kTHF+OD = (1.81 ± 0.27) × 10-11, kTHF+O3 = (6.41 ± 2.90) × 10-21, k2-MTHF+Cl = (2.65 ± 0.43) × 10-10, k2-MTHF+OD = (2.41 ± 0.51) × 10-11, k2-MTHF+O3 = (1.87 ± 0.82) × 10-20, k2,5-DMTHF+OD = (4.56 ± 0.68) × 10-11, k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10-10, k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10-10, and kfuran+O3 = (2.60 ± 0.31) × 10-18 molecules cm-3 s-1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

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publication status
published
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in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
120
issue
37
pages
7 pages
publisher
The American Chemical Society
external identifiers
  • scopus:84988691023
  • wos:000384034300010
ISSN
1089-5639
DOI
10.1021/acs.jpca.6b06618
language
English
LU publication?
yes
id
4d68cf99-13e4-4856-9ade-b7168f8c3e58
date added to LUP
2016-10-04 10:28:51
date last changed
2017-10-04 11:06:31
@article{4d68cf99-13e4-4856-9ade-b7168f8c3e58,
  abstract     = {<p>FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O<sub>3</sub> with the five-membered ring-structured compounds tetrahydrofuran (C<sub>4</sub>H<sub>8</sub>O, THF), 2-methyltetrahydrofuran (CH<sub>3</sub>C<sub>4</sub>H<sub>7</sub>O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH<sub>3</sub>)<sub>2</sub>C<sub>4</sub>H<sub>5</sub>O, 2,5-DMTHF), and furan (C<sub>4</sub>H<sub>4</sub>O). The rate coefficients determined using relative rate methods were k<sub>THF+Cl</sub> = (1.96 ± 0.24) × 10<sup>-10</sup>, k<sub>THF+OD</sub> = (1.81 ± 0.27) × 10<sup>-11</sup>, k<sub>THF+O<sub>3</sub> </sub> = (6.41 ± 2.90) × 10<sup>-21</sup>, k<sub>2-MTHF+Cl</sub> = (2.65 ± 0.43) × 10<sup>-10</sup>, k<sub>2-MTHF+OD</sub> = (2.41 ± 0.51) × 10<sup>-11</sup>, k<sub>2-MTHF+O<sub>3</sub> </sub> = (1.87 ± 0.82) × 10<sup>-20</sup>, k<sub>2,5-DMTHF+OD</sub> = (4.56 ± 0.68) × 10<sup>-11</sup>, k<sub>2,5-DMTHF+Cl</sub> = (2.84 ± 0.34) × 10<sup>-10</sup>, k<sub>2,5-DMTHF+O<sub>3</sub> </sub> = (4.58 ± 2.18), k<sub>furan+Cl</sub> = (2.39 ± 0.27) × 10<sup>-10</sup>, and k<sub>furan+O<sub>3</sub> </sub> = (2.60 ± 0.31) × 10<sup>-18</sup> molecules cm<sup>-3</sup> s<sup>-1</sup>. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD<sub>3</sub>ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.</p>},
  author       = {Andersen, Christina and Nielsen, Ole John and Østerstrøm, Freja F. and Ausmeel, Stina and Nilsson, Elna J K and Sulbaek Andersen, Mads P.},
  issn         = {1089-5639},
  language     = {eng},
  month        = {09},
  number       = {37},
  pages        = {7320--7326},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran : Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone},
  url          = {http://dx.doi.org/10.1021/acs.jpca.6b06618},
  volume       = {120},
  year         = {2016},
}