Enhanced condensation kinetics in aqueous microdroplets driven by coupled surface reactions and gas-phase...

Although aqueous microdroplets have been shown to exhibit enhanced chemical reactivity compared to bulk solutions, mechanisms for these enhancements are not completely understood. Here we combine experimental measurements and kinetic modeling to show the strong coupling of interfacial reactions and gas/droplet partitioning in the condensation reaction of pyruvic acid (PA) to yield zymonic acid (ZA) in acidic aqueous microdroplets. Experimental analysis of single microdroplets reveals the substantial influence of evaporation of PA and partitioning of water on the size-, relative humidity (RH)- and temperature-dependent sigmoidal reaction kinetics for the condensation reaction. A newly developed diffusion-reaction-partitioning model is used to simulate the complex kinetics observed in the microdroplets. The model can quantitatively predict the size and compositional changes as the reaction proceeds under different environmental conditions, and provides insights into how microdroplet reactivity is controlled by coupled interfacial reactions and the gas-phase partitioning of PA and water. Importantly, the kinetic model best fits the data when an autocatalytic step is included in the mechanism, i.e. a reaction step where the product, ZA, catalyzes the interfacial condensation reaction. Overall, the dynamic nature of aqueous microdroplet chemistry and the coupling of interfacial chemistry with gas-phase partitioning are demonstrated. Furthermore, autocatalysis of small organic molecules at the air-water interface for aqueous microdroplets, shown here for the first time, has implications for several fields including prebiotic chemistry, atmospheric chemistry and chemical synthesis.