Evidence for Adsorbed SO2 at the Aqueous-Air Interface

Donaldson, D. J.; Guest, J. A.; Goh, M. Cynthia

doi:10.1021/j100023a002

Cited by 83 publications

(99 citation statements)

References 4 publications

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“…k I is the pseudo first order rate constant for reaction of SO 2 with H 2 O. Taking into account the surface complex, the pressure dependent uptake kinetics over a range of pH can be described well with the above expression for γ and with the value of k I in bulk aqueous solution measured by Eigen et al (1961) …”

Section: Comments On Preferred Valuesmentioning

confidence: 69%

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

et al. 2013

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Abstract. This article, the sixth in the ACP journal series, presents data evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the heterogeneous processes involving liquid particles present in the atmosphere with an emphasis on those relevant for the upper troposphere/lower stratosphere and the marine boundary layer, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website since 2009. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. The experimental data on which the recommendations are based are provided in data sheets in separate appendices for the four surfaces considered: liquid water, deliquesced halide salts, other aqueous electrolytes and sulfuric acid.

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Section: Comments On Preferred Valuesmentioning

confidence: 69%

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

et al. 2013

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“…41 This complex has a measurable effect on the uptake only in the low-pH region where γ 0 is relatively small (<0.002). The SO 2 uptake at higher pH and the uptake of H 2 S and CO 2 do not show evidence for interfacial reactions and are entirely in accord with bulk-phase processes.…”

Section: Discussionmentioning

confidence: 99%

Uptake of Gas-Phase SO₂, H₂S, and CO₂ by Aqueous Solutions

Boniface¹,

Qiu²,

Li³

et al. 2000

J. Phys. Chem. A

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The uptake of gas-phase SO 2 , H 2 S, and CO 2 by aqueous solutions was studied as a function of pH and temperature using droplet train flow reactor and bubble train reactor apparatuses. All three atmospheric species react with H 2 O and OH -, acidifying aqueous solutions. Studies yielded the reaction rates of SO 2 , H 2 S, and CO 2 with OH -and the mass accommodation coefficient (R) of SO 2 on water as a function of temperature. The second-order aqueous-phase rate coefficients at 291 K for SO 2 , H 2 S and CO 2 reaction with OH -are (1.1 ( 0.2) × 10 10 , (1.7 ( 0.2) × 10 9 , and (4.0 ( 0.7) × 10 3 M -1 s -1 , respectively. As far as we can determine, the rate coefficients for SO 2 and H 2 S have been determined here for the first time. At 291 K, for SO 2 , R ) 0.175 ( 0.015, and as in previous studies, the temperature dependence of R is well represented by the relationship R /(1 -R) ) exp(-∆G obs /RT) with ∆H obs ) -7.6 ( 0.6 kcal mol -1 and ∆S obs ) -29.2 ( 2.1 cal mol -1 K -1 . IntroductionIn this work, we describe uptake studies of gas-phase SO 2 , H 2 S, and CO 2 by aqueous solutions as a function of pH and temperature. These three atmospheric species exhibit similar chemical behaviors that contribute to the acidification of aqueous media in the atmosphere. Sulfur dioxide oxidation is responsible for about 90% of atmospheric H 2 SO 4 , and an estimated 50% of this oxidation occurs via heterogeneous reactions. 1 Hydrogen sulfide is a major biogenic reduced sulfur species, emitted into the atmosphere by vegetation, soils, and marine waters, 2 that is oxidized by the OH radical in the gas phase to produce SO 2 . 3 H 2 S may also be important to O 3 chemistry, as in the aqueous phase, H 2 S dissociates readily to HS -, which, in turn, reacts rapidly with O 3 . 4 Of the three gas-phase species, CO 2 is the least reactive but perhaps the most atmospherically important. Because of its high atmospheric abundance (∼370 ppm) and its infrared absorption properties, CO 2 plays an important role in the global warming process.The pH-dependent reactions of SO 2 and CO 2 in aqueous solution are (R ) SO 2 or CO 2 )The pH-dependent reactions of H 2 S are Here, k 1 is the pseudo-first-order reaction-rate coefficient of the species with H 2 O, and k 2 is the second-order reaction-rate coefficient of the species with OH -. As the current study makes evident, the forward reaction rates for SO 2 , H 2 S, and CO 2 with OH -vary over nearly 6 orders of magnitude. The uptake coefficients vary over a similar range. Two complementary apparatuses were used to span this range of uptake coefficients: a droplet train flow reactor apparatus and a horizontal bubble train reactor apparatus. The uptake measurements yielded rate coefficients for the reaction of SO 2 , H 2 S, and CO 2 with OH -, and the mass accommodation coefficient for SO 2 on water as a function of temperature.In several previous uptake studies, the measured uptake was larger than predicted by bulk-phase parameters. Such enhanced uptake was observed among others in the follow...

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“…Atmospheric species may react at the interface without actually being taken up into the bulk (FinlaysonPitts and Pitts, 2000). The uptake and oxidation of SO 2 cannot be explained by liquid-phase chemistry alone (Jayne et al, 1990;Donaldson, et al, 1995;Finlayson-Pitts and Pitts, 2000;Knipping et al, 2000) and it proceeds via the formation of a bound complex at the air-water interface (Jayne et al, 1990;Donaldson et al, 1995;Finlayson-Pitts and Pitts, 2000). Similarly, the atmospheric uptake of acetaldehyde (Jayne et al, 1992;Davidovits et al, 1995) and glyoxal (Schweitzer et al, 1998) cannot be described solely by liquid-phase chemistry and are best explained in terms of enhanced reactivity at the gas-liquid interface.…”

Section: Gas-liquid Interactions Leading To Soa Productionmentioning

confidence: 99%

The formation, properties and impact of secondary organic aerosol: current and emerging issues

et al. 2009

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Abstract. Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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Evidence for Adsorbed SO2 at the Aqueous-Air Interface

Cited by 83 publications

References 4 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Uptake of Gas-Phase SO₂, H₂S, and CO₂ by Aqueous Solutions

The formation, properties and impact of secondary organic aerosol: current and emerging issues

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Evidence for Adsorbed SO2 at the Aqueous-Air Interface

Cited by 83 publications

References 4 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Uptake of Gas-Phase SO2, H2S, and CO2 by Aqueous Solutions

The formation, properties and impact of secondary organic aerosol: current and emerging issues

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Uptake of Gas-Phase SO₂, H₂S, and CO₂ by Aqueous Solutions