Constraints on the role of Laplace pressure in multiphase reactions and
viscosity of organic aerosols
Abstract
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 and viscosity. Insights from high-pressure synthesis
studies suggest that accretion and cyclization reactions are accelerated
in 3-10-nm particles smaller than 10 nm. Reactions of peroxide, epoxide,
furanoid, aldol, and carbonyl functional groups are accelerated by up to
tenfold. Effective rate enhancements are ranked as: cycloadditions
>> aldol reactions > epoxide
reactions > Baeyer-Villiger oxidation
>> imidazole formation (which is inhibited).
Some reactions are enabled by the elevated pressure in particles.
Viscosity increases for organic liquids but decreases for viscous or
solid particles. Results suggest that internal pressure is an important
consideration in studies of the physics and chemical evolution of
nanoparticles.