Uptake of Nitrosyl Chloride (NOCl) by Aqueous Solutions

Scheer, Volker; Frenzel, Andreas; Behnke, Wolfgang; Zetzsch, Cornelius; Magi, Laurent; George, Christian; Mirabel, Philippe

doi:10.1021/jp972143m

Cited by 24 publications

(25 citation statements)

References 33 publications

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“…This heterogeneous activation mechanism was originally proposed and investigated by Finlayson-Pitts et al (1989) and confirmed in an aerosol smog chamber by Zetzsch and Behnke (1992) and Behnke et al (1993Behnke et al ( , 1997 Thornton et al (2010) and over continental Europe (Phillips et al, 2012). A further important class of heterogeneous reactions provides chloride to the aqueous phase example such as the well-known conversion of molecular chlorine to bromine on halide 5 surfaces: One example is the well-known conversion of molecular chlorine to bromine on halide surfaces:…”

Section: Interactive Discussionsupporting

confidence: 55%

“…Br 2 Cl − (aq) → Br 2 + Cl − (aq) (R22) 10 and the formation of HONO from an uptake of NOCl into the aqueous phase (Scheer et al, 1997):…”

Section: Interactive Discussionmentioning

confidence: 99%

“…Uptake of ClNO 2 is possible as well (Behnke et al, 1997), but at a slower rate compared to NOCl (Frenzel et al,1998). The most important source of NOCl is the reaction of 2 15 NO 2 + NaCl → NOCl + NaNO 3 (Finlayson-Pitts, 1983).…”

Section: Interactive Discussionmentioning

confidence: 99%

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The influence of nitrogen oxides on the activation of bromide and chloride in salt aerosol

Bleicher

Buxmann

Sander

et al. 2014

Preprint

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Experiments on salt aerosol with different salt contents were performed in a Teflon chamber under tropospheric light conditions with various initial contents of nitrogen oxides (NO x = NO + NO 2 ). A strong activation of halogens was found at high NO x mixing ratios, even in samples with lower bromide contents such as road salts. The 5 ozone depletion by reactive halogen species released from the aerosol, was found to be a function of the initial NO x mixing ratio. Besides bromine, large amounts of chlorine have been released in our smog chamber. Time profiles of the halogen species Cl 2 , Br 2 , ClNO 2 , BrNO 2 and BrO, ClO, OClO and Cl atoms were simultaneously measured by various techniques (chemical ionization mass spectrometry, differential op-10 tical absorption spectrometry coupled with a multi-reflection cell and gas chromatography of hydrocarbon tracers for Cl and OH, employing cryogenic preconcentration and flame ionization detection). Measurements are compared to calculations by the CAABA/MECCA 0-D box model, which was adapted to the chamber conditions and took the aerosol liquid water content and composition into account. The model results 15 agree reasonably with the observations and provide important information about the prerequisites for halogen release, such as the time profiles of the aerosol bromide and chloride contents as well as the aerosol pH. 2010). Although the mechanisms of halide activation, namely the conversion of inactive 10136 Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables 25 ClNO2 has been observed by Osthoff et al. (2008) in the polluted subtropical marine boundary layer. It alters. The production of ClNO 2 alters the NO x and Cl budgets, both 10139 Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables Abstract Introduction Conclusions References Tables

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Section: Interactive Discussionsupporting

confidence: 55%

“…Br 2 Cl − (aq) → Br 2 + Cl − (aq) (R22) 10 and the formation of HONO from an uptake of NOCl into the aqueous phase (Scheer et al, 1997):…”

Section: Interactive Discussionmentioning

confidence: 99%

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The influence of nitrogen oxides on the activation of bromide and chloride in salt aerosol

Bleicher

Buxmann

Sander

et al. 2014

Preprint

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“…It is also notable that separate experiments (see SI Text) show that water vapor does not enhance the heterogeneous hydrolysis of ClNO in this system. This suggests that under some conditions, loss of ClNO to aerosol particles and surfaces at the terrestrial-air interface may be much slower than what is expected to occur in bulk water (28,29). Fig.…”

Section: ]mentioning

confidence: 94%

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Raff

Njegic

Chang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

113

182

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Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO y ) are also globally distributed, because NO formed in combustion processes is oxidized to NO 2 , HNO 3 , N 2 O 5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NO y onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO 2 or N 2 O 5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO 2 ), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO 2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

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“…54 In the presence of O 3 (leading to N 2 O 5 from NO X ), ClNO 2 could be formed 53 that is more stable against hydrolysis 18 and can be photolyzed to form Cl and NO 2 (J ClNO2 = 2 × 10 −4 s −1 ). This summarizes the activation of Cl via uptake of, for example, NO 2 , N 2 O 5 , and O 3 on the deliquesced salt, and concomitant release of photolyzable precursors.…”

Section: Resultsmentioning

confidence: 99%

Iron(III)-Induced Activation of Chloride and Bromide from Modeled Salt Pans

2014

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The photochemistry of halides in sea spray aerosol, on salt pans, and on other salty surfaces leads to a formation of reactive halogen species. We investigated the photochemical formation of atomic chlorine (Cl) and bromine (Br) in the gas phase in the presence of laboratory-modeled salt pans consisting of sodium chloride doped with iron(III) chloride hexahydrate (0.5 and 2 wt %). The samples were spread on a Teflon sheet and exposed to simulated sunlight in a Teflon smog chamber in purified, humidified air in the presence of a test mixture of hydrocarbons at the ppb level to determine Cl, Br, and OH formation by the radical clock method. Driven by the photolytic reduction of Fe(III) to Fe(II), the production rates of the Fe(III)-doped NaCl salt samples (up to10(7) atoms cm(-3) s(-1)) exceeded the release of Cl above a pure NaCl sample by more than an order of magnitude in an initially O3-free environment at low NOX. In bromide-doped samples (0.5 wt % NaBr), a part of the Cl release was replaced by Br when Fe(III) was present. Additions of sodium sulfate, sodium oxalate, oxalic acid, and catechol to NaCl/FeCl3 samples were found to restrain the activation of chloride.

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Uptake of Nitrosyl Chloride (NOCl) by Aqueous Solutions

Cited by 24 publications

References 33 publications

The influence of nitrogen oxides on the activation of bromide and chloride in salt aerosol

The influence of nitrogen oxides on the activation of bromide and chloride in salt aerosol

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Iron(III)-Induced Activation of Chloride and Bromide from Modeled Salt Pans

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