Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols
Constraints on the Role of Laplace Pressure in Multiphase Reactions and Viscosity of Organic Aerosols
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DOI：
10.1029/2022gl098959
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发表时间：
2022-06
影响因子：
5.2
通讯作者：
S. S. Petters-S.
中科院分区：
文献类型：
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作者：
S. S. Petters-S.
气溶胶化学与气候和全球公共卫生具有广泛的相关性。界面现象在凝聚相气溶胶反应中的作用仍然知之甚少。在这项工作中，液滴形式主义与高压过渡态理论相结合，制定了一个表达式，用于预测气溶胶反应速率和粘度的尺寸依赖性。来自高压合成研究的见解表明，吸积和环化反应在小于10 nm的3-10 nm颗粒中加速。过氧化物、环氧化物、呋喃类、羟醛和羰基官能团的反应被加速高达十倍。有效速率增强的排序为：环加成>>羟醛反应>环氧化物反应> Baeyer-Villiger氧化>>咪唑形成（其被抑制）。有些反应是通过粒子中的高压来实现的。有机液体的粘度增加，但粘性或固体颗粒的粘度降低。结果表明，内压是一个重要的考虑因素，在研究的物理和化学演变的纳米粒子。
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.