Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub>
Rate coefficients (<i>k</i><sub>5</sub>) for the title reaction were obtained using pulsed laser photolytic generation of OH coupled to its detection by laser-induced fluorescence (PLP–LIF). More than 80 determinations of <i>k</i><sub>5</sub>...
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2018-02-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/18/2381/2018/acp-18-2381-2018.pdf |
| _version_ | 1818887504405725184 |
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| author | K. Dulitz K. Dulitz D. Amedro T. J. Dillon T. J. Dillon A. Pozzer J. N. Crowley |
| author_facet | K. Dulitz K. Dulitz D. Amedro T. J. Dillon T. J. Dillon A. Pozzer J. N. Crowley |
| author_sort | K. Dulitz |
| collection | DOAJ |
| description | Rate coefficients (<i>k</i><sub>5</sub>) for the title reaction were obtained using pulsed laser photolytic generation of OH coupled to its detection by laser-induced fluorescence (PLP–LIF). More than 80 determinations of <i>k</i><sub>5</sub> were carried out in nitrogen or air bath gas at various temperatures and pressures. The accuracy of the rate coefficients obtained was enhanced by in situ measurement of the concentrations of both HNO<sub>3</sub> reactant and NO<sub>2</sub> impurity. The rate coefficients show both temperature and pressure dependence with a rapid increase in <i>k</i><sub>5</sub> at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire data set was combined with selected literature values of <i>k</i><sub>5</sub> and parameterised using a combination of pressure-dependent and -independent terms to give an expression that covers the relevant pressure and temperature range for the atmosphere. A global model, using the new parameterisation for <i>k</i><sub>5</sub> rather than those presently accepted, indicated small but significant latitude- and altitude-dependent changes in the
HNO<sub>3</sub> ∕ NO<sub><i>x</i></sub> ratio of between −6 and +6 %. Effective
HNO<sub>3</sub> absorption cross sections (184.95 and 213.86 nm, units of
cm<sup>2</sup> molecule<sup>−1</sup>) were obtained as part of this work:
<i>σ</i><sub>213.86</sub> = 4.52<sub>−0.12</sub><sup>+0.23</sup> × 10<sup>−19</sup> and <i>σ</i><sub>184.95</sub> = 1.61<sub>−0.04</sub><sup>+0.08</sup> × 10<sup>−17</sup>. |
| first_indexed | 2024-12-19T16:38:17Z |
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| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-19T16:38:17Z |
| publishDate | 2018-02-01 |
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| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-10cbc780290248828f5eb9ae53b77f3a2022-12-21T20:13:54ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242018-02-01182381239410.5194/acp-18-2381-2018Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub>K. Dulitz0K. Dulitz1D. Amedro2T. J. Dillon3T. J. Dillon4A. Pozzer5J. N. Crowley6Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, Germanynow at: Institute of Physics, University of Freiburg, 79104 Freiburg, GermanyDivision of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, GermanyDivision of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, Germanynow at: Department of Chemistry, University of York, York, UKDivision of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, GermanyDivision of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, GermanyRate coefficients (<i>k</i><sub>5</sub>) for the title reaction were obtained using pulsed laser photolytic generation of OH coupled to its detection by laser-induced fluorescence (PLP–LIF). More than 80 determinations of <i>k</i><sub>5</sub> were carried out in nitrogen or air bath gas at various temperatures and pressures. The accuracy of the rate coefficients obtained was enhanced by in situ measurement of the concentrations of both HNO<sub>3</sub> reactant and NO<sub>2</sub> impurity. The rate coefficients show both temperature and pressure dependence with a rapid increase in <i>k</i><sub>5</sub> at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire data set was combined with selected literature values of <i>k</i><sub>5</sub> and parameterised using a combination of pressure-dependent and -independent terms to give an expression that covers the relevant pressure and temperature range for the atmosphere. A global model, using the new parameterisation for <i>k</i><sub>5</sub> rather than those presently accepted, indicated small but significant latitude- and altitude-dependent changes in the HNO<sub>3</sub> ∕ NO<sub><i>x</i></sub> ratio of between −6 and +6 %. Effective HNO<sub>3</sub> absorption cross sections (184.95 and 213.86 nm, units of cm<sup>2</sup> molecule<sup>−1</sup>) were obtained as part of this work: <i>σ</i><sub>213.86</sub> = 4.52<sub>−0.12</sub><sup>+0.23</sup> × 10<sup>−19</sup> and <i>σ</i><sub>184.95</sub> = 1.61<sub>−0.04</sub><sup>+0.08</sup> × 10<sup>−17</sup>.https://www.atmos-chem-phys.net/18/2381/2018/acp-18-2381-2018.pdf |
| spellingShingle | K. Dulitz K. Dulitz D. Amedro T. J. Dillon T. J. Dillon A. Pozzer J. N. Crowley Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> Atmospheric Chemistry and Physics |
| title | Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> |
| title_full | Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> |
| title_fullStr | Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> |
| title_full_unstemmed | Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> |
| title_short | Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub> |
| title_sort | temperature 208 ndash 318 k and pressure 18 ndash 696 torr dependent rate coefficients for the reaction between oh and hno sub 3 sub |
| url | https://www.atmos-chem-phys.net/18/2381/2018/acp-18-2381-2018.pdf |
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