Dynamics and mass accommodation of HCl molecules on sulfuric acid–water surfaces

Abstract

A molecular beam technique has been used to study the dynamics and mass accommodation of HCl molecules in collision with sulfuric acid–water surfaces. The experiments were performed by directing a nearly mono-energetic beam of HCl molecules onto a continuously renewed liquid film of 54–76 wt% sulfuric acid at temperatures between 213 K and 243 K. Deuterated sulfuric acid was used to separate sticking but non-reactive collisions from those that involved penetration through the phase boundary followed by dissociation and recombination with D⁺. The results indicate that the mass accommodation of HCl on sulfuric acid–water surfaces decreases sharply with increasing acidity over the concentration range 54–76 wt%. Using the capillary wave theory of mass accommodation this effect is explained by a change of the surface dynamics. Regarding the temperature dependence it is found that the mass accommodation of HCl increases with increasing temperature and is limited by the bulk phase viscosity and driven by the restoring forces of the surface tension. These findings imply that under atmospheric conditions the uptake of HCl from the gas phase depends crucially on the bulk phase parameters of the sulfuric acid aerosol.