Browsing by Subject "nucleation"
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Item Experimental and theoretical investigation of nucleation and growth of atmospheric aerosols(2009-05-15) Zhao, JunAerosol particles have profound impacts on human health, atmospheric radiation, and cloud microphysics and these impacts are strongly dependent on particle sizes. However, formation and growth of atmospheric particles are currently not well understood. In this work, laboratory and theoretical studies have been performed to investigate the formation and growth of atmospheric particles. The first two parts of the dissertation are a laboratory investigation of new particle formation and growth, and a theoretical study of atmospheric molecular complexes and clusters. The nucleation rate was considerably enhanced in the presence of cis-pinonic acid and ammonia. The composition of the critical cluster was estimated from the dependence of the nucleation rate on the precursor concentration and the time evolution of the clusters was then simulated using molecular dynamic simulations. Results from quantum chemical calculations and quantum theory of atoms in molecules (QTAIM) reveal that formation of strong hydrogen bonding between an organic acid and sulfuric acid is likely responsible for a reduction of the nucleation barrier by modifying the hydrophobic properties of the organic acid and allowing further addition of hydrophilic species (e.g., H2SO4, H2O, and possibly NH3) to the hydrophilic side of the clusters. This promotes growth of the nascent cluster to overcome the nucleation barrier and thus enhances the nucleation in the atmosphere. The last part of this dissertation is the laboratory investigation of heterogeneous interactions of atmospheric carbonyls with sulfuric acid. Direct measurement has been performed to investigate the heterogeneous uptake of atmospheric carbonyls on sulfuric acid. Important parameters have been obtained from the time-dependent or timeindependent uptake profiles. The results indicated that the acid-catalyzed reactions of larger aldehydes (e.g. octanal and 2, 4-hexadienal) in sulfuric acid solution were attributed to aldol condensation in high acidity. However such reactions do not contribute much to secondary organic aerosol (SOA) formation due to the low acidity under tropospheric conditions. On the other hand, heterogeneous reactions of light dicarbonyl such as methylglyoxal likely contribute to SOA formation in slightly acidic media. The reactions of methylglyoxal in the atmospheric aerosol-phase involve hydration and subsequent polymerization, which are dependent on the hygroscopicity, rather than the acidity of the aerosols.Item Photochemistry of aromatic hydrocarbons: implications for ozone and secondary organic aerosol formation(Texas A&M University, 2006-08-16) Suh, InseonAromatic hydrocarbons constitute an important fraction (~20%) of total volatile organic compounds (VOCs) in the urban atmosphere. A better understanding of the aromatic oxidation and its association in urban and regional ozone and organic aerosol formation is essential to assess the urban air pollution. This dissertation consists of two parts: (1) theoretical investigation of the toluene oxidation initiated by OH radical using quantum chemical and kinetic calculations to understand the mechanism of O3 and SOA precursors and (2) experimental investigation of atmospheric new particle formation from aromatic acids. Density functional theory (DFT) and ab initio multiconfigurational calculations have been performed to investigate the OH-toluene reaction. The branching ratios of OH addition to ortho, para, meta, and ipso positions are predicted to be 0.52, 0.34, 0.11, and 0.03, respectively, significantly different from a recent theoretical study of the same reaction system. Aromatic peroxy radicals arising from initial OH and subsequent O2 additions to the toluene ring are shown to cyclize to form bicyclic radicals rather than undergoing reaction with NO under atmospheric conditions.Isomerization of bicyclic radicals to more stable epoxide radicals possesses significantly higher barriers and hence has slower rates than O2 addition to form bicyclic peroxy radicals. At each OH attachment site, only one isomeric pathway via the bicyclic peroxy radical is accessible to lead to ring cleavage. Decomposition of the bicyclic alkoxy radicals leads primarily to formation of glyoxal and methyl glyoxal along with other dicarbonyl compounds. Atmospheric aerosols often contain a considerable fraction of organic matter, but the role of organic compounds in new nanometer-sized particle formation is highly uncertain. Laboratory experiments show that nucleation of sulfuric acid is considerably enhanced in the presence of aromatic acids. Theoretical calculations identify the formation of an unusually stable aromatic acid-sulfuric acid complex, which likely leads to a reduced nucleation barrier. The results imply that the interaction between organic and sulfuric acids promotes efficient formation of organic and sulfate aerosols in the polluted atmosphere because of emissions from burning of fossil fuels, which strongly impact human health and global climate.