Deutsch
 
Benutzerhandbuch Datenschutzhinweis Impressum Kontakt
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT

Freigegeben

Zeitschriftenartikel

Temperature-dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, alpha-pinene and delta-3-carene

MPG-Autoren
/persons/resource/persons100909

Dillon,  T. J.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

/persons/resource/persons100915

Dulitz,  K.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

/persons/resource/persons100966

Groß,  C. B. M.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

/persons/resource/persons100898

Crowley,  J. N.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

Externe Ressourcen
Es sind keine Externen Ressourcen verfügbar
Volltexte (frei zugänglich)
Es sind keine frei zugänglichen Volltexte verfügbar
Ergänzendes Material (frei zugänglich)
Es sind keine frei zugänglichen Ergänzenden Materialien verfügbar
Zitation

Dillon, T. J., Dulitz, K., Groß, C. B. M., & Crowley, J. N. (2017). Temperature-dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, alpha-pinene and delta-3-carene. Atmospheric Chemistry and Physics, 17(24), 15137-15150. doi:10.5194/acp-17-15137-2017.


Zitierlink: http://hdl.handle.net/21.11116/0000-0001-5656-E
Zusammenfassung
Pulsed laser methods for OH generation and de- tection were used to study atmospheric degradation reac- tions for three important biogenic gases: OH + isoprene (Reaction R1), OH + α -pinene (Reaction R2) and OH + 1 - 3-carene (Reaction R3). Gas-phase rate coefficients were characterized by non-Arrhenius kinetics for all three reactions. For (R1), k 1 (241–356 K) = ( 1 . 93 ± 0 . 08 ) × 10 − 11 exp { ( 466 ± 12 )/T } cm 3 molecule − 1 s − 1 was deter- mined, with a room temperature value of k 1 (297 K) = ( 9 . 3 ± 0 . 4 ) × 10 − 11 cm 3 molecule − 1 s − 1 , independent of bath-gas pressure (5–200 Torr) and composition (M = N 2 or air). Ac- curacy and precision were enhanced by online optical mon- itoring of isoprene, with absolute concentrations obtained via an absorption cross section, σ isoprene = ( 1 . 28 ± 0 . 06 ) × 10 − 17 cm 2 molecule − 1 at λ = 184 . 95 nm, determined in this work. These results indicate that significant discrepancies be- tween previous absolute and relative-rate determinations of k 1 result in part from σ values used to derive the isoprene concentration in high-precision absolute determinations. Similar methods were used to determine rate coefficients (in 10 − 11 cm 3 molecule − 1 s − 1 ) for (R2)–(R3): k 2 (238– 357 K) = ( 1 . 83 ± 0 . 04 ) × exp { ( 330 ± 6 )/T } and k 3 (235– 357 K) = ( 2 . 48 ± 0 . 14 ) × exp { ( 357 ± 17 )/T } . This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime condi- tions. Room temperature values of k 2 (296 K) = ( 5 . 4 ± 0 . 2 ) × 10 − 11 cm 3 molecule − 1 s − 1 and k 3 (297 K) = ( 8 . 1 ± 0 . 3 ) × 10 − 11 cm 3 molecule − 1 s − 1 were independent of bath- gas pressure (7–200 Torr, N 2 or air) and in good agree- ment with previously reported values. In the course of this work, 184.95 nm absorption cross sections were determined: σ = ( 1 . 54 ± 0 . 08 ) × 10 − 17 cm 2 molecule − 1 for α -pinene and ( 2 . 40 ± 0 . 12 ) × 10 − 17 cm 2 molecule − 1 for 1 -3-carene.