Atmospheric Chemistry of alpha-Diketones: Kinetics of C-5 and C-6 Compounds with Cl Atoms and OH Radicals.

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F17%3A00507141" target="_blank" >RIV/67985858:_____/17:00507141 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0298198" target="_blank" >http://hdl.handle.net/11104/0298198</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/kin.21060" target="_blank" >10.1002/kin.21060</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Atmospheric Chemistry of alpha-Diketones: Kinetics of C-5 and C-6 Compounds with Cl Atoms and OH Radicals.

Popis výsledku v původním jazyce

Carbonyls play an important role in atmospheric chemistry due to their formation in the photooxidation of biogenic and anthropogenic volatile organic compounds and their high atmospheric reactivity. The Cl-initiated kinetics of two alpha-diketones (2,3-pentanedione (PTD) and 2,3-hexanedione (HEX)) have been determined as well as the OH + HEX rate constant using atmospheric simulation chamber experiments and the relative rate method. Up to three different reference compounds were used to assess robust results. The following rate constants (in cm(3) molecule(-1) s(-1)) have been obtained at 298 K: k(Cl + PTD) = (1.6 +/- 0.2) x 10(-11), k(Cl + HEX) = (8.8 +/- 0.4) x 10(-11), and k(OH + HEX) = (3.6 +/- 0.7) x 10(-12) with a global uncertainty of 30%. The present determinations of Cl-and OH-reaction rate constants for HEX constitute first measurements. Using the present measurements, a recently improved structure-activity relationship for Cl + ketone reactions has been updated by introducing an F(-COCO-) factor of 8.33 x 10(-4). Atmospheric lifetime calculations indicate that chlorine-initiated oxidation may be a significant alpha-diketone sink in the marine-boundary layer or in places where high Cl concentrations may be found.

Název v anglickém jazyce

Atmospheric Chemistry of alpha-Diketones: Kinetics of C-5 and C-6 Compounds with Cl Atoms and OH Radicals.

Popis výsledku anglicky

Carbonyls play an important role in atmospheric chemistry due to their formation in the photooxidation of biogenic and anthropogenic volatile organic compounds and their high atmospheric reactivity. The Cl-initiated kinetics of two alpha-diketones (2,3-pentanedione (PTD) and 2,3-hexanedione (HEX)) have been determined as well as the OH + HEX rate constant using atmospheric simulation chamber experiments and the relative rate method. Up to three different reference compounds were used to assess robust results. The following rate constants (in cm(3) molecule(-1) s(-1)) have been obtained at 298 K: k(Cl + PTD) = (1.6 +/- 0.2) x 10(-11), k(Cl + HEX) = (8.8 +/- 0.4) x 10(-11), and k(OH + HEX) = (3.6 +/- 0.7) x 10(-12) with a global uncertainty of 30%. The present determinations of Cl-and OH-reaction rate constants for HEX constitute first measurements. Using the present measurements, a recently improved structure-activity relationship for Cl + ketone reactions has been updated by introducing an F(-COCO-) factor of 8.33 x 10(-4). Atmospheric lifetime calculations indicate that chlorine-initiated oxidation may be a significant alpha-diketone sink in the marine-boundary layer or in places where high Cl concentrations may be found.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

International Journal of Chemical Kinetics

ISSN

0538-8066

e-ISSN

—

Svazek periodika

49

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

112-118

Kód UT WoS článku

000393876500004

EID výsledku v databázi Scopus

2-s2.0-85006659993