Kinetics of CH2OO reactions with SO2, NO2, NO, H2O and CH3CHO as a function of pressure

Abstract

Kinetics of CH₂OO Criegee intermediate reactions with SO₂, NO₂, NO, H₂O and CH₃CHO and CH₂I radical reactions with NO₂ are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH₂I₂–O₂–N₂ gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO₂, direct detection of CH₂OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH₂OO + SO₂ and CH₂OO + NO₂ are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10⁻¹¹ cm³ s⁻¹ (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10⁻¹² cm³ s⁻¹ (measured between 25 and 300 Torr), respectively. The rate coefficient for CH₂OO + CH₃CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10⁻¹³ cm³ s⁻¹ and 9 × 10⁻¹⁷ cm³ s⁻¹ are placed on the rate coefficients for CH₂OO + NO and CH₂OO + H₂O, respectively. The upper limit for the rate coefficient for CH₂OO + H₂O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH₂OO chemistry.