Atmospheric Aqueous Phase Research Articles

Atmospheric chemistry and physics: from air pollution to climate change

1 The Atmosphere. 2 Atmospheric Trace Constituents. 3 Chemical Kinetics. 4 Atmospheric Radiation and Photochemistry. 5 Chemistry of the Stratosphere. 6 Chemistry of the Troposphere. 7 Chemistry of the Atmospheric Aqueous Phase. 8 Properties of the Atmospheric Aerosol. 9 Dynamics of Single Aerosol Particles. 10 Thermodynamics of Aerosols. 11 Nucleation. 12 Mass Transfer Aspects of Atmospheric Chemistry. 13 Dynamics of Aerosol Populations. 14 Organic Atmospheric Aerosols. 15 Interaction of Aerosols with Radiation. 16 Meteorology of the Local Scale. 17 Cloud Physics. 18 Atmospheric Diffusion. 19 Dry Deposition. 20 Wet Deposition. 21 General Circulation of the Atmosphere. 22 Global Cycles: Sulfur and Carbon. 23 Climate and Chemical Composition of the Atmosphere. 24 Aerosols and Climate. 25 Atmospheric Chemical Transport Models. 26 Statistical Models.

Role of chromium and vanadium in the atmospheric oxidation of sulfur(IV)

Abstract Oxidation of HSO 3 − in aqueous solution has been studied in the presence of vanadium(V), chromium(III) and chromium(VI). Based on spectrophotometric kinetics data and product analysis it is concluded that the autoxidation rate of sulfur(IV) in slightly acidic solution is unaffected by the presence of vanadium(V) and chromium(III). Chromate(VI), on the other hand, oxidizes sulfur(IV) in a direct redox process in acidic solution. The overall rate of this reaction decreases with increasing pH and it becomes relatively slow in the atmospherically relevant pH range 4–6. Moreover, chromium(III) dominates strongly over chromium(VI) in the atmospheric aqueous phase. Hence, it is concluded that cations of vanadium and chromium have no significant influence on the atmospheric aqueous-phase oxidation of sulfur(IV) under most ambient atmospheric conditions. Only in very acidic droplets, direct redox between chromium(VI) and sulfite might be of some importance.

Manganese-catalysed autoxidation of dissolved sulfur dioxide in the atmospheric aqueous phase

Autoxidation of SO 2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentrations of manganese(II) ( < 2 × 10 −5 M) and sulfur(IV) ( ≤ 10 −5 M) and 2.5 < pH < 5, the rate law for conversion of SO 2(aq) to SO 3(aq) is reduced to d[S(IV)]/d t = k[Mn(II)][S(IV)], where [S(IV)] denotes the total concentration. A value of the overall rate constant k of 1.4 × 10 3 M −1s −1 is recommended for use in atmospheric model calculations.