ABSTRACT
The surface chemistry of the atmospheric aerosol through homogeneous and heterogeneous catalytic reactions in the bulk water and the air-water surface is reviewed. Water plays a critical role as a substrate or an actual reactant in atmospheric reactions. The atmospheric aerosol differs in shape and surface area. Many gaseous reactive species and oxidants react at the air-water surface. Different thermodynamic methods to estimate partitioning coefficients are explored. The Gibbs free energy is reduced when reactant gaseous species react with oxidant at the air-water surface; this phenomenon is explained using examples. Langmuir-Hinshelwood reaction mechanism to quantify the heterogeneous reaction rate at the air-water interface is discussed. Critical comparisons of various sampling techniques used to analyze adsorption and reaction at the water surface are presented. The heterogeneous reaction rate at the air-water surface is significantly higher than in the bulk water phase due to a cage effect, higher rate of reactions, and lower Gibbs free energy of adsorption.
