Pressure and Temperature Dependence of the Gas-Phase Reaction of SO₃ with H₂O and the Heterogeneous Reaction of SO₃ with H₂O/H₂SO₄ Surfaces

Abstract

The gas-phase reaction of SO3 with H2O and the heterogeneous reaction of SO3 with H2O−H2SO4 surfaces have been studied in a fast flow reactor coupled to a chemical ionization mass spectrometer (CIMS) for species detection. The gas-phase reaction was studied under turbulent flow conditions over the pressure range from 100 to 760 Torr N2 and the temperature range from 283 to 370 K. The loss rate of SO3 was measured under pseudo-first-order conditions; it exhibits a second-order dependence on water vapor concentration and has a strong negative temperature dependence. The first-order rate coefficient for the SO3 loss by gas-phase reaction shows no significant pressure dependence and can be expressed as kI(s-1) = 3.90 × 10-41 exp(6830.6/T)[H2O]2 where [H2O] is in units of molecule cm-3 and T is in Kelvin. The overall uncertainty of our experimentally determined rate coefficients is estimated to be ±20%. At sufficiently low SO3 concentrations (<1012 molecule cm-3) the rate coefficient is independent of the initial SO3 level, as expected for a gas-phase reaction mechanism involving one SO3 and two H2O molecules. However, at higher concentrations and lower temperatures, increased rate coefficients were observed, indicating a fast heterogeneous reaction after the onset of binary homogeneous nucleation of acid hydrate clusters leading to particle formation, which was verified by light-scattering experiments. The heterogeneous loss of SO3 to the reactor walls has also been investigated under low pressure (1.1−12.5 Torr) laminar flow conditions. The loss rate is highly dependent on the humidity of the surface. In the presence of excess water the reactive sticking coefficient approaches unity and the wall loss rate is gas diffusion limited; under dry conditions it approaches zero, as expected. The atmospheric implications of the homogeneous and heterogeneous SO3−water reaction are discussed.