Gas‐Phase Formation of Sulfurous Acid (H₂SO₃) in the Atmosphere

Abstract

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical‐initiated gas‐phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295 ± 0.5 K and 1 bar of air with a molar yield of [[EQUATION]] %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH + CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O + H2SO3) < 3 × 10‐18 cm3 molecule‐1 s‐1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Spectroscopic Characterization and Photochemistry of the Atmospherically Relevant Methanesulfenic Acid

“…On the other hand, the ·OH-oxidation of CH 3 SOH yields methanesulfinic acid (MSIA, CH 3 S­(O)­OH), a key precursor to CH 3 SO 2 · in the ·OH + DMS reaction. Quite recently, formation of sulfurous acid (H 2 SO 3 ) from gas-phase ·OH-oxidation of CH 3 S­(O)­OH has been observed . In addition to the ·OH-addition pathway, the H-abstraction of DMS via the intermediacy of sulfur-bearing radicals CH 3 SO x · (x = 0–4) also forms H 2 SO 4 and CH 3 SO 3 H. − The addition channel contributes by about 35% at room temperature, and it becomes predominant at lower temperatures with contribution about 76% at 263 K .…”