Browsing by Author "Cox, R. A."

Now showing 1 - 4 of 4
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    Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: Volume 1. Inorganic compounds
    (Katlenburg-Lindau : EGU, 2014) Tang, M. J.; Cox, R. A.; Kalberer, M.
    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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    Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: Volume 2. Diffusivities of organic compounds, pressure-normalised mean free paths, and average Knudsen numbers for gas uptake calculations
    (Katlenburg-Lindau : EGU, 2015) Tang, M. J.; Shiraiwa, M.; Pöschl, U.; Cox, R. A.; Kalberer, M.
    Diffusion of organic vapours to the surface of aerosol or cloud particles is an important step for the formation and transformation of atmospheric particles. So far, however, a database of gas phase diffusion coefficients for organic compounds of atmospheric interest has not been available. In this work we have compiled and evaluated gas phase diffusivities (pressure-independent diffusion coefficients) of organic compounds reported by previous experimental studies, and we compare the measurement data to estimates obtained with Fuller's semi-empirical method. The difference between measured and estimated diffusivities are mostly < 10%. With regard to gas-particle interactions, different gas molecules, including both organic and inorganic compounds, exhibit similar Knudsen numbers (Kn) although their gas phase diffusivities may vary over a wide range. This is because different trace gas molecules have similar mean free paths in air at a given pressure. Thus, we introduce the pressure-normalised mean free path, λP ≈ 100 nm atm, as a near-constant generic parameter that can be used for approximate calculation of Knudsen numbers as a simple function of gas pressure and particle diameter to characterise the influence of gas phase diffusion on the uptake of gases by aerosol or cloud particles. We use a kinetic multilayer model of gas-particle interaction to illustrate the effects of gas phase diffusion on the condensation of organic compounds with different volatilities. The results show that gas phase diffusion can play a major role in determining the growth of secondary organic aerosol particles by condensation of low-volatility organic vapours.
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    Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species
    (Katlenburg-Lindau : EGU, 2004) Atkinson, R.; Baulch, D. L.; Cox, R. A.; Crowley, J. N.; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; Rossi, M. J.; Troe, J.
    This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.
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    Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II - Gas phase reactions of organic species
    (Katlenburg-Lindau : EGU, 2006) Atkinson, R.; Baulch, D. L.; Cox, R. A.; Crowley, J. N.; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; Rossi, M. J.; Troe, J.
    This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Sub-committee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.