Kinetics of the gas phase reaction of chlorine atoms with a series of alkenes, alkynes and aromatic species at 295 K

Wallington, Timothy J.; Skewes, Loretta M.; Siegl, Walter O.

doi:10.1016/1010-6030(88)80126-6

Cited by 81 publications

(76 citation statements)

References 31 publications

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“…The chlorine mechanism introduced in the present study further extends the one proposed by Sarwar et al (2012), which was based on CB05, and includes more chlorine species and reactions. It consists of six photolysis reactions (photolysis of Cl 2 , HOCl, ClNO 2 , ClONO 2 , and FMCl) and 30 gas-phase reactions (Reactions R7-R36 as listed in Ta- Wallington et al (1988); f the units for first-order rate constants are s −1 and those for second-order rate constants are cm 3 molecule −1 s −1 .…”

Section: Heterogeneous N 2 O 5 Chemistry and Chlorine Chemistrymentioning

confidence: 99%

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

Zhang

Wang

et al. 2017

Atmos. Chem. Phys.

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Abstract. Nitrous acid (HONO) and nitryl chloride (ClNO 2 ) -through their photolysis -can have profound effects on the nitrogen cycle and oxidation capacity of the lower troposphere. Previous numerical studies have separately considered and investigated the sources/processes of these compounds and their roles in the fate of reactive nitrogen and the production of ozone (O 3 ), but their combined impact on the chemistry of the lower part of the troposphere has not been addressed yet. In this study, we updated the WRFChem model with the currently known sources and chemistry of HONO and chlorine in a new chemical mechanism (CBMZ_ReNOM), and applied it to a study of the combined effects of HONO and ClNO 2 on summertime O 3 in the boundary layer over China. We simulated the spatial distributions of HONO, ClNO 2 , and related compounds at the surface and within the lower troposphere. The results showed that the modeled HONO levels reached up to 800-1800 ppt at the surface (0-30 m) over the North China Plain (NCP), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD) regions and that HONO was concentrated within a 0-200 m layer. In comparison, the simulated surface ClNO 2 mixing ratio was around 800-1500 ppt over the NCP, YRD, and central China regions and was predominantly present in a 0-600 m layer. HONO enhanced daytime RO x (OH + HO 2 + RO 2 ) and O 3 at the surface (0-30 m) by 2.8-4.6 ppt (28-37 %) and 2.9-6.2 ppb (6-13 %), respectively, over the three most developed regions, whereas ClNO 2 increased surface O 3 in the NCP and YRD regions by 2.4-3.3 ppb (or 5-6 %) and it also had a significant impact (3-6 %) on above-surface O 3 within 200-500 m. The combined effects increased surface O 3 by 11.5, 13.5, and 13.3 % in the NCP, YRD, and PRD regions, respectively. Over the boundary layer (0-1000 m), the HONO and ClNO 2 enhanced O 3 by up to 5.1 and 3.2 %, respectively, and their combined effect increased O 3 by 7.1-8.9 % in the three regions. The new module noticeably improved O 3 predictions at ∼ 900 monitoring stations throughout China by reducing the mean bias from −4.3 to 0.1 ppb. Our study suggests the importance of considering these reactive nitrogen species simultaneously into chemical transport models to better simulate the formation of summertime O 3 in polluted regions.

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Section: Heterogeneous N 2 O 5 Chemistry and Chlorine Chemistrymentioning

confidence: 99%

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

Zhang

Wang

et al. 2017

Atmos. Chem. Phys.

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“…The reaction of ground-state chlorine atoms with acetylene has previously been studied at low to moderate temperatures, in the context of a potential sink for Cl and/or C 2 H 2 in the atmosphere [1][2][3][4][5][6][7][8]. That work revealed a pressure dependence of the effective second order rate constant k 1 so that the reaction can be written as Cl + C 2 H 2 → C 2 H 2 Cl (1) where C 2 H 2 Cl is an adduct, presumably the β-chlorovinyl radical.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and thermochemistry of the addition of atomic chlorine to acetylene

Gao

Alecu

Hsieh

et al. 2007

Proceedings of the Combustion Institute

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“…38,46,47 An estimate for k C=C can be obtained from the chlorine atom reaction with propene, where the rate constant [39][40][41][42][43][44][45] for the addition portion of the reaction at 1 atm is 2.3 Â 10…”

mentioning

confidence: 99%

“…29,41,44 Based on studies of the propene and isoprene reactions, the net abstraction at 1 atm pressure typically contributes $10-15% of the total reaction. [39][40][41][42][43][44][45][50][51][52] In the case of propene, this corresponds to an abstraction rate constant of 0. s À1 and our measured rate constant for ACR. This suggests that abstraction from the methyl group, separated from the double bond by a carbonyl group, does not contribute significantly to the reaction.…”

mentioning

confidence: 99%

Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity

Wang

Ezell

et al. 2002

Phys. Chem. Chem. Phys.

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Kinetics of the gas phase reaction of chlorine atoms with a series of alkenes, alkynes and aromatic species at 295 K

Cited by 81 publications

References 31 publications

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

Kinetics and thermochemistry of the addition of atomic chlorine to acetylene

Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity

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