Journal
GEOPHYSICAL RESEARCH LETTERS
Volume 49, Issue 12, Pages -Publisher
AMER GEOPHYSICAL UNION
DOI: 10.1029/2022GL098959
Keywords
new particle formation; Baeyer-Villiger oxidation; highly-oxygenated molecules (HOMs); furans; epoxides; viscosity
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Funding
- U.S. National Science Foundation Postdoctoral Fellowship Award [AGS-1624696]
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In this study, a formalism combining liquid drop formalisms and high-pressure transition state theory is used to predict the size-dependence of aerosol reaction rates and viscosity. The results show that accretion and cyclization reactions are accelerated in particles smaller than 10 nm, while reactions of peroxide, epoxide, furanoid, aldol, and carbonyl functional groups are accelerated by up to tenfold. Some reactions are enabled by the elevated pressure in particles. The study highlights the importance of internal pressure in the physics and chemical evolution of nanoparticles.
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.
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