Aerosol chemistry has broad relevance for climate and global public health. The role of interfacial phenomena in condensed-phase aerosol reactions remains poorly understood. In this work, liquid drop formalisms are coupled with high-pressure transition state theory to formulate an expression for predicting the size-dependence of aerosol reaction rates. Insights from high-pressure organic synthesis studies suggest that accretion and cyclization reactions are accelerated in 3–10-nm particles smaller than 10 nm. Reactions of peroxides, epoxides, furans, aldols, and carbonyls are predicted to be accelerated by up to tenfold. Effective rate enhancements are ranked as: cycloadditions &gt;&gt; aldol reactions &gt; epoxide reactions &gt; Baeyer-Villiger oxidation &gt;&gt; imidazole formation (which is inhibited). High-pressure changes to viscosity are predicted to further perturb nanoparticle reactions. Some reactions are enabled by the elevated pressure in particles. Results suggest that internal pressure is an important consideration in studies of chemical evolution of particles during new particle formation.

Constraints on the role of Laplace pressure in multiphase reactions in organic aerosols

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.