Aqueous oxidation of sulfur dioxide by hydrogen peroxide at low pH

Abstract We have measured the rate of oxidation of aqueous sulfur dioxide species to sulfate and bisulfate by aqueous hydrogen peroxide over the pH range 0–3. The rate of formation of oxidized sulfur is given by: d(S VI ) d t = (8±2) × 10 4 ( H 2 O 2 )(SO 2 .aq ) 0.1+(H + ) mole l −1 s −1 Comparison with the literature shows that this expression describes the data from pH 0 to 5. We show that the expression is consistent with a mechanism suggested by Hoffmann and Edwards [ J. phys. Chem , 79 , 2096–2098 (1975)]. The expression gives atmospheric oxidation rates that are comparable to the rate at which SO 2 can dissolve in aerosols for ppb levels of hydrogen peroxide in the gas phase.

[1]  M. Trinite,et al.  Transfer resistances to SO2 capture by some plane surfaces, water and leaves , 1977 .

[2]  G. Kok.  Measurements of hydrogen peroxide in rainwater , 1980 .

[3]  J. Bufalini,et al.  Hydrogen peroxide formation from the photooxidation of formaldehyde and its presence in rainwater , 1979 .

[4]  P. Mader.  Kinetics of the Hydrogen Peroxide-Sulfite Reaction in Alkaline Solution , 1958 .

[5]  D. Stedman,et al.  Measurements of H2O2 and HNO3in rural air , 1979 .

[6]  D. Powell,et al.  Estimation of transformation rate of SO2 to SO4 from atmospheric concentration data , 1977 .

[7]  J. Bottenheim,et al.  Mechanism of the homogeneous oxidation of sulfur dioxide in the troposphere , 1978 .

[8]  Rudolf B. Husar,et al.  Sulfur budget of a power plant plume , 1978 .

[9]  M. Hoffmann,et al.  Kinetics of the oxidation of sulfite by hydrogen peroxide in acidic solution , 1975 .

[10]  Stuart A. Penkett,et al.  The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater , 1979 .

[11]  A. P. Altshuller.  Model predictions of the rates of homogeneous oxidation of sulfur dioxide to sulfate in the troposphere , 1979 .

[12]  P. Hobbs,et al.  Measurements of gas-to-particle conversion in the plumes from five coal-fired electric power plants , 1980 .

[13]  Rudolf B. Husar,et al.  Project mistt: Kinetics of particulate sulfur formation in a power plant plume out to 300 km , 1978 .

[14]  L. Martin,et al.  The reactions of nitrogen oxides with SO2 in aqueous aerosols , 1981 .

[15]  A. Winer,et al.  Ambient air measurements of hydrogen peroxide in the California South Coast Air Basin , 1978 .

[16]  G. Gravenhorst,et al.  Heterogeneous SO2-oxidation in the droplet phase , 1978 .

[17]  J. A. Garland,et al.  Oxidation of sulphur dioxide in artificial fogs by ozone , 1974 .

[18]  G. Scatchard,et al.  Vapor-Liquid Equilibrium. VIII. Hydrogen Peroxide—Water Mixtures1 , 1952 .

[19]  R. L. Clark,et al.  The reaction of sulfur dioxide with ozone in water and its possible atmospheric significance , 1977 .

[20]  D D Wagman,et al.  Selected values of chemical thermodynamic properties , 1952 .

[21]  Purnendu K. Dasgupta,et al.  The importance of atmospheric ozone and hydrogen peroxide in oxidizing sulphur dioxide in cloud and rainwater , 1980 .

[22]  H. Judeikis,et al.  Particle-catalyzed oxidation of atmospheric pollutants , 1973 .

[23]  R. A. Cox,et al.  Homogeneous oxidation of sulphur compounds in the atmosphere , 1978 .

[24]  R. A. Cox.  Photochemical oxidation of atmospheric sulphur dioxide , 1979, Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences.