Photo-Oxidation of Sulfur Dioxide

Abstract

SO₂/O₂ mixtures were photolyzed at 3130 Å and in the range 2500–4000 Å at room temperature. The only product of photolysis was SO₃. Attempts to estimate ф(S0₃) using mass spectrometry, l.R. spectroscopy and pressure change measurements were unsuccessful, because it was not possible to obtain reproducible quantitative estimates of SO₃. ф(SO₂) values were determined by monitoring the 3130 Å absorption for its concentration measurements. ф(SO₂) was independent of SO₂ (11.6 to 50.4 torr) and O₂ (50.0 to 390.6 torr) pressures. At 3130 Å, ф(SO₂) varied between 1.5 × 10⁻² and 2.2 X 10⁻². Over the integrated range 2500–4000 Å ф(SO₂) values of 2.1 X 10⁻³ to 2.9 X 10⁻³ were obtained. The differences in ф(SO₂) values are explained in terms of wavelength dependence of the rate constants for the two primary reactions: ¹SO₂ + SO₂ → 2SO₂(1) and ¹SO₂ + SO₂ → ³SO₂ + SO₂(2); (k₂/k₁) _{3130 Å} ≈ 10(k₂/k₁)_{2500–4000 Å}.