Update 1 of: Mass Accommodation and Chemical Reactions at Gas−Liquid Interfaces

Davidovits, P.; Kolb, C. E.; Williams, Leah R.; Jayne, John T.; Worsnop, Douglas R.

doi:10.1021/cr100360b

Cited by 72 publications

(116 citation statements)

References 284 publications

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“…The location of a reaction is Journal Name ARTICLE determined by the accessible thickness of liquid for the reacting system. 59 A key question emerges: What determines the accessible liquid thickness for OH reacting with squalane? The simplest measure of this thickness is the reacto-diffusion length calculated using the diffusion coefficient (DOH) for OH in the liquid particle, and its pseudo-first order abstraction rate constant as a time interval Δtabs for the mean distance that OH diffuses prior to reaction, D OH Δ t |¿| L OH =√¿ .…”

Section: Discussionmentioning

confidence: 99%

Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake

Houle

Hinsberg

Wilson

2015

Phys. Chem. Chem. Phys.

155

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An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

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Section: Discussionmentioning

confidence: 99%

Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake

Houle

Hinsberg

Wilson

2015

Phys. Chem. Chem. Phys.

155

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“…The most recent evaluation of experimental and theoretical results within the atmospheric science community on this subject has been compiled by , Garrett et al (2006) and updated by Kolb et al (2010) and Davidovits et al (2011). This debate has been initiated by the conflicting results between H 2 O uptake experiments to a train of droplets (Li et al, 2001) and one cloud droplet growth experiment and involved consideration of mass transfer aspects in the gas phase but also questions around energy dissipation in the condensed phase.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

“…The data of Zientara et al (2008) obtained on a stationary droplet are consistent with a negative T dependence of α b and α t = 1. Other evaporation rate measurements were inconclusive about the temperature dependence (Smith et al, 2006;Drisdell et al, 2008). Although the emphasis of the work of Cappa et al (2005) was placed on obtaining (H/D) isotope fractionation ratios, the cooling of the microjet along the axis was used to derive E a = 55 kJ mol −1 for the evaporation rate of H 2 O which is approximately 10 kJ mol −1 larger than H vap .…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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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“…Heterogeneous interactions of trace gases with particles in the atmosphere (and with all surfaces) are very complex and usually consist of several steps (Davidovits et al, 2011;Pöschl et al, 2007): (1) gas molecules diffuse towards the surface; (2) gas molecules collide with the surface, and some are then accommodated on the surface; (3) molecules adsorbed on the surface can desorb from the surface, undergo reactions on the surface or diffuse into the bulk, and get dissolved and/or react with other species in the bulk; (4) gaseous products formed in the heterogeneous reactions can diffuse towards the surface, desorb from the surface, and finally diffuse into the gas phase. The overall kinetics of a heterogeneous reaction can be described by the uptake coefficient, γ , which is the net probability that a molecule X undergoing collision with a surface is actually taken up by the surface.…”

Section: Introductionmentioning

confidence: 99%

“…The uptake of a trace gas onto the surface can cause depletion of the trace gas close to the surface, leading to an effective uptake coefficient, γ eff , which is smaller than the true uptake coefficient, γ . The relation between γ eff and γ , under appropriate steady-state assumptions, can be described by the following equation (Davidovits et al, 1995(Davidovits et al, , 2011:…”

Section: Introductionmentioning

confidence: 99%

Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: volume 1. Inorganic compounds

2014

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Abstract. Diffusion of gas molecules to the surface is the first step for all gas-surface reactions. Gas phase diffusion can influence and sometimes even limit the overall rates of these reactions; however, there is no database of the gas phase diffusion coefficients of atmospheric reactive trace gases. Here we compile and evaluate, for the first time, the diffusivities (pressure-independent diffusion coefficients) of atmospheric inorganic reactive trace gases reported in the literature. The measured diffusivities are then compared with estimated values using a semi-empirical method developed by Fuller et al. (1966). The diffusivities estimated using Fuller's method are typically found to be in good agreement with the measured values within ±30 %, and therefore Fuller's method can be used to estimate the diffusivities of trace gases for which experimental data are not available. The two experimental methods used in the atmospheric chemistry community to measure the gas phase diffusion coefficients are also discussed. A different version of this compilation/evaluation, which will be updated when new data become available, is uploaded online (https://sites.google.com/ site/mingjintang/home/diffusion).

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Update 1 of: Mass Accommodation and Chemical Reactions at Gas−Liquid Interfaces

Cited by 72 publications

References 284 publications

Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake

Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake

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

Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: volume 1. Inorganic compounds

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