Size-Dependent Sigmoidal Reaction Kinetics for Pyruvic Acid Condensation at the Air-Water Interface in Aqueous Microdroplets.

The chemistry of pyruvic acid (PA) under thermal dark conditions is limited in bulk solutions, but in microdroplets it is shown to readily occur. Utilizing in situ micro-Raman spectroscopy as a probe, we investigated the chemistry of PA within aqueous microdroplets in a relative humidity- and temperature-controlled environmental cell. We found that PA undergoes a condensation reaction to yield mostly zymonic acid. Interestingly, the reaction follows a size-dependent sigmoidal kinetic profile, i.e., an induction period followed by reaction and then completion. The induction time is linearly proportional to the surface area (), and the maximum apparent reaction rate is proportional to the surface-to-volume ratio (1/), showing that both the induction and reaction occur at the air-water interface. Furthermore, the droplet size is shown to be dynamic due to changes in droplet composition and re-equilibration with the relative humidity within the environmental cell as the reaction proceeds. Overall, the size-dependent sigmoidal kinetics, shown for the first time in microdroplets, demonstrates the complexity of the reaction mechanism and the importance of the air-water interface in the pyruvic acid condensation reaction.