Technical note: Entrainment-limited kinetics of bimolecular reactions in clouds

Abstract

The method of entrainment-limited kinetics enables atmospheric chemistry models that do not resolve clouds to simulate heterogeneous (surface and multiphase) cloud chemistry more accurately and efficiently than previous numerical methods. The method, which was previously described for reactions with first-order kinetics in clouds, incorporates cloud entrainment into the kinetic rate coefficient. This technical note shows how bimolecular reactions with second-order kinetics in clouds can also be treated with entrainment-limited kinetics, enabling efficient simulations of a wider range of cloud chemistry reactions. Accuracy is demonstrated using oxidation of SO2 to S(VI) – a key step in the formation of acid rain – as an example. Over a large range of reaction rates, cloud fractions, and initial reactant concentrations, the numerical errors in the entrainment-limited bimolecular reaction rates are typically ≪1 % and always <4 %; thus, they are far smaller than the errors found in several commonly used methods of simulating cloud chemistry with fractional cloud cover.