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 expressio...
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| Language: | English |
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Wiley
2022-06-01
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| Series: | Geophysical Research Letters |
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| Online Access: | https://doi.org/10.1029/2022GL098959 |
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| author | Sarah S. Petters |
| author_facet | Sarah S. Petters |
| author_sort | Sarah S. Petters |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-11ac1e85609a4141b96d55e715a7d1f6 |
| institution | Kabale University |
| issn | 0094-8276 1944-8007 |
| language | English |
| publishDate | 2022-06-01 |
| publisher | Wiley |
| record_format | Article |
| series | Geophysical Research Letters |
| spelling | doaj-art-11ac1e85609a4141b96d55e715a7d1f62025-01-22T14:38:16ZengWileyGeophysical Research Letters0094-82761944-80072022-06-014912n/an/a10.1029/2022GL098959Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic AerosolsSarah S. Petters0Department of Environmental Sciences and Engineering Gillings School of Global Public Health The University of North Carolina at Chapel Hill Chapel Hill NC USAAbstract 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.https://doi.org/10.1029/2022GL098959new particle formationBaeyer‐Villiger oxidationhighly‐oxygenated molecules (HOMs)furansepoxidesviscosity |
| spellingShingle | Sarah S. Petters Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols Geophysical Research Letters new particle formation Baeyer‐Villiger oxidation highly‐oxygenated molecules (HOMs) furans epoxides viscosity |
| title | Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols |
| title_full | Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols |
| title_fullStr | Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols |
| title_full_unstemmed | Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols |
| title_short | Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols |
| title_sort | constraints on the role of laplace pressure in multiphase reactions and viscosity of organic aerosols |
| topic | new particle formation Baeyer‐Villiger oxidation highly‐oxygenated molecules (HOMs) furans epoxides viscosity |
| url | https://doi.org/10.1029/2022GL098959 |
| work_keys_str_mv | AT sarahspetters constraintsontheroleoflaplacepressureinmultiphasereactionsandviscosityoforganicaerosols |