The Reaction between Ozonized Oxygen and Hydrogen Sulphide in the Gaseous Phase

Some recent measurements of H2S oxidation rates and their implications to atmospheric chemistry

“…The results of these experiments indicate that the present understanding of atmospheric sulfur chemistry and of the global sulfur balance is not so complete as had been thought previously. While deviating strongly from previously anticipated behavior and from the findings of Cadle and Ledford, these results seem to be supported qualitatively by the previous stoichiometric study of Gregor & Martin (1961) which indicated that the destruction of H,S via ozonation is slow compared to the thermal decay of ozone itself. I n addition the more recent measurements of Cox Penkett (1971) have provided further evidence that ozone oxidation of H,S is indeed too slow a process to be of large significance to the global sulfur balance.'…”

Some recent measurements of H₂S oxidation rates and their implications to atmospheric chemistry¹

“…These results, however, were thought to be complicated by competing heterogeneous reactions occurring on the reaction-vessel walls. In addition, they were in apparent qualitative disagreement with earlier stoichiometric measurements (Gregor & Martin, 1961). I n view of the apparent complication of the wall effect, expression (2) has been suggested as an "upper limit" for the rate of this reaction in the atmosphere.…”

“…While deviating strongly from previously anticipated behavior and from the findings of Cadle and Ledford, these results seem to be supported qualitatively by the previous stoichiometric study of Gregor & Martin (1961) which indicated that the destruction of H,S via ozonation is slow compared to the thermal decay of ozone itself. I n addition the more recent measurements of Cox Penkett (1971) have provided further evidence that ozone oxidation of H,S is indeed too slow a process to be of large significance to the global sulfur balance.'…”

Multichannel RRKM-TST and Direct-Dynamics CVT Study of the Reaction of Hydrogen Sulfide with Ozone

“…They reported that the half-life of sulfurous acid is only 24 h at room temperature and suggested a value of −33.8 kJ mol −1 at the G2(MP2) level of theory for the ΔE 0 of reaction R7. Li Furthermore, the produced HOSO* in reaction R8 rearranges to HSO 2 (reaction R15) or dissociates to 1 SO + OH (reaction R16) or to 3 SO + OH (reaction R16′). The total energy of 1 SO + 2OH radicals is 641.0 kJ mol −1 above the energy of sulfurous acid and 40.5 kJ mol −1 less stable than the reactants, while the total energy of 3 SO + 2OH radicals is 545.4 kJ mol −1 above the energy of sulfurous acid and 55.1 kJ mol −1 more stable than the reactants; therefore, the contribution of these channels and also stabilization process Rw8 (the stabilization process of HOSO*) are negligible in this system and in our formulation of the RRKM-TST method to calculate the rate constants for channels R1−R9 are neglected.…”