Uptake of sulfur dioxide(G) by aqueous surfaces as a function of pH:  the effect of chemical reaction at the interface

Jayne, J. T.; Davidovits, P.; Worsnop, Douglas R.; Zahniser, M. S.; Kolb, C. E.

doi:10.1021/j100378a076

Cited by 157 publications

(200 citation statements)

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“…In the scientific literature similarly defined parameters have been called adsorption coefficient Turco et al, 1989;Worsnop et al, 2002), condensation coefficient (Pruppacher and Klett, 1997), sticking coefficient (Hanson, 1997), sticking probability (Clement et al, 1996;Garrett et al, 2006), trapping probability (Masel, 1996), adsorptive mass accommodation coefficient (Elliott et al, 1991), (mass) accommodation coefficient (Jayne et al, 1990;Tabazadeh and Turco, 1993;Pruppacher and Klett, 1997;Kulmala and Wagner, 2001;Huthwelker et al, 2006), and thermal accommodation coefficient (Li et al, 2001;Worsnop et al, 2002). For clarity and unambiguous distinction of the gas-to-surface mass transfer process specified above from mass transfer into the bulk, from chemical reactions, and from heat transfer (Sect.…”

Section: Gas Kinetic Fluxes and Uptake Coefficientsmentioning

confidence: 99%

“…The surface and bulk accommodation coefficients under adsorption equilibrium conditions follow from relations (32)- (33), (79), (83), (85) and (87): Jayne et al (1990) derived similar expressions to describe the dependence of SO 2 uptake into aqueous solution droplets on gas phase concentration and surface coverage. Relations equivalent to (89) have also been derived by and Hanson (1997), but they did not explicitly account for competitive adsorption and assumed α s,Xi to be the maximum value not only for α b,Xi but also for γ Xi , neglecting the possibility of gas-surface reactions (Eqs.…”

Section: Adsorption Equilibrium Conditions 441 Surface Concentratiomentioning

confidence: 99%

“…(e.g. Jayne et al, 1990;Davidovits et al, 1991;Mozurkewich, 1993;Tabazadeh and Turco, 1993;Tabor et al, 1994;Davidovits et al, 1995;Kolb et al, 1995;Nathanson et al, 1996;Atkinson et al, 1997;Carslaw and Peter, 1997;Hanson, 1997;Jayne et al, 1997;Pöschl et al, 1998;Bertram et al, 2001;Clegg and Abbatt, 2001;Grassian, 2001;Katrib et al, 2001;Vesala et al, 2001;Adams et al, 2002;Hynes et al, 2002;Remorov et al, 2002;Sander et al, 2002;Smith et al, 2002;Worsnop et al, 2002;Ammann et al, 2003;da Rosa et al, 2003;Djikaev and Tabazadeh, 2003;Folkers et al, 2003;Reid and Sayer, 2003;Strekowski et al, 2003;Frinak et al, 2004;Kwamena et al, 2004Kwamena et al, , 2006Kwamena et al, , 2007Thornberry and Abbatt, 2004;Adams et al, 2005;Al-Hosney and Grassian, 2005;Gustafsson et al, 2005;Kleffmann and Wiesen, 2005;Remorov and Bardwell, 2005;…”

Section: Introductionmentioning

confidence: 99%

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Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

2007

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Abstract. Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gasparticle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It enables a detailed description of mass transport and chemical reactions at the gas-particle interface, and it allows linking aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes.The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined and consistent rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surfacebulk transport (gas phase diffusion, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of The outlined double-layer surface concept and formalisms represent a minimum of model complexity required for a consistent description of the non-linear concentration and time dependences observed in experimental studies of atmospheric multiphase processes (competitive co-adsorption and surface saturation effects, etc.). Exemplary practical applications and model calculations illustrating the relevance of the above aspects are presented in a companion paper (Ammann and Pöschl, 2007).We expect that the presented model framework will serve as a useful tool and basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions. It shall help to end the "Babylonian confusion" that seems to inhibit scientific progress in the understanding of heterogeneous chemical reactions and other multiphase processes in aerosols and clouds. In particular, it shall support the planning and design of laboratory experiments for the elucidation and determination of fundamental kinetic parameters; the establishment, evaluation, and quality assurance of comprehensive and self-consistent collections of rate parameters; and the development of detailed master mechanisms for process mo...

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Section: Gas Kinetic Fluxes and Uptake Coefficientsmentioning

confidence: 99%

Section: Adsorption Equilibrium Conditions 441 Surface Concentratiomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

2007

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“…This suggests that the heterogeneous reaction of SO 2 will have an influence on the formation rate of sulfate only under dust conditions. The actual average lifetime of SO 2 is around 5 days due to cloud processing Jayne et al, 1990). In addition, the concentrations of reactants can also affect the uptake coefficients, for the uptake coefficients might be significantly higher at lower concentration.…”

Section: Atmospheric Implicationmentioning

confidence: 99%

Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

et al. 2006

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Abstract. Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO 2 by O 3 on CaCO 3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), the formation of sulfite and sulfate on the surface was identified, and the roles of O 3 and water in oxidation processes were determined. The results showed that in the presence of O 3 , SO 2 can be oxidized to sulfate on the surface of CaCO 3 particles. The reaction is first order in SO 2 and zero order in O 3 . The reactive uptake coefficient for SO 2 [(0.6-9.8)×10 14 molecule cm −3 ] oxidation by O 3 [(1.2-12)×10 14 molecule cm −3 ] was determined to be (1.4±0.3)×10 −7 using the BET area as the reactive area and (7.7±1.6)×10 −4 using the geometric area. A twostage mechanism that involves adsorption of SO 2 followed by O 3 oxidation is proposed and the adsorption of SO 2 on the CaCO 3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

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“…16 For example, for large (B10 mm) size particles, the falling droplet apparatus has been used extensively to study gas uptake and reaction. 1,3,13,17,18 FTIR studies of smaller particles have been carried out at relatively high particle concentrations; [19][20][21][22] following the particles with time using this method is complicated by continuously changing particle size distributions due to coagulation and settling of the particles. 23,24 A new technique is optical levitation of single droplets combined with Raman spectroscopy, but this has only been applied to relatively few systems to date.…”

Section: Introductionmentioning

confidence: 99%

A new approach to studying aqueous reactions using diffuse reflectance infrared Fourier transform spectrometry: application to the uptake and oxidation of SO2 on OH-processed model sea salt aerosol

Shaka

Robertson

Finlayson-Pitts

2007

Phys. Chem. Chem. Phys.

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A new approach to studying aqueous reactions using diffuse reflectance infrared Fourier transform spectrometry: application to the uptake and oxidation of SO2 on OH-processed model sea salt aerosol. Diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) is a powerful technique for analyzing solid powders and for following their reactions in real time. We demonstrate that it can also be applied to studying the uptake and reactions of gases in liquid films. Within the DRIFTS cell, a 10% (w/w) mixture of MgCl 2 Á 6H 2 O in NaCl was equilibrated with air at 50% RH, which is above the deliquescence point of the magnesium salt but below that of NaCl. This mixture of NaCl coated with an aqueous magnesium chloride solution was then reacted with gas phase OH to generate hydroxide ions via a previously identified interface reaction. This treatment, hereafter referred to as OH-processing, was sufficient to convert some of the magnesium chloride to Mg(OH) 2 and Mg 2 (OH) 3 Cl Á 4H 2 O, making the aqueous film basic and providing a reservoir of alkalinity. Subsequent addition of SO 2 to the basic processed mixture resulted in its uptake and conversion to sulfite which was measured by FTIR. The sulfite was simultaneously oxidized to sulfate by HOCl/OCl À that was formed in the initial OH-processing of the salt. Further uptake and oxidation of SO 2 in the aqueous film took place when the salt was subsequently exposed to O 3 . These studies demonstrate that DRIFTS can be used to study the chemistry in liquid films in real time, and are consistent with the hypothesis that the reaction of gaseous OH with chloride ions generates alkalinity that enhances the uptake and oxidation of SO 2 under these laboratory conditions.

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Uptake of sulfur dioxide(G) by aqueous surfaces as a function of pH: the effect of chemical reaction at the interface

Cited by 157 publications

References 1 publication

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

A new approach to studying aqueous reactions using diffuse reflectance infrared Fourier transform spectrometry: application to the uptake and oxidation of SO2 on OH-processed model sea salt aerosol

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