Statistical models like Transition State Theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) Theory have generally been successful in predicting the rates and selectivities of chemical reactions. However, these statistical models can fail to explain experimental results of ordinary organic reactions. For these reactions, consideration of nonstatistical dynamic effects or the detailed motion and momenta of the atoms is necessary to account for the experimental observations. Dynamic effects have been found to be important in a growing number of reactions and the nature of these effects can be varied. One of the most interesting reactions investigated is the ozonolysis of vinyl ethers. Ozonolysis of a homologous series of vinyl ethers in solution exhibit experimental product ratios wherein the selectivity among cleavage pathways increases with the size of the alkyl group to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. A recent theoretical study from our group predicted that a highly asynchronous organocatalytic Diels-Alder (DA) reaction, which is concerted in the potential energy surface, is stepwise in the free energy surface. Kinetic isotope effects (KIEs) were measured for three DA reactions. We envision that the entropic barrier may have several experimental consequences such as unusual isotope effects due to extensive recrossing. Preliminary results for the organocatalytic reaction show an intramolecular KIE close to unity that cannot be reconciled with statistical theories. This is in contrast with Lewis-acid catalyzed and thermal DA reactions, which exhibit substantial "normal" intramolecular KIEs that are in accord with TST predictions. Finally, the Baeyer-Villiger oxidation of cylohexanone in water was investigated. KIEs were measured for the oxidation of cyclohexanone with peracetic acid and trifluoroperacetic acid. When using peracetic acid as the oxidant, the alkyl migration was determined to be the rate-determining step based on significant intermolecular KIEs on the carbonyl and alpha-methylene carbons. A change in the rate-determining step is seen when trifluoroperacetic acid is used. Only the carbonyl carbon exhibits a significant isotope effect. Theoretical predictions provide an experimental picture of the transition states and qualitatively support these conclusions.

The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.

Aerosols play important roles in atmospheric and environmental processes. Not only do they impact human health, they also affect visibility and climate. Despite recent advances made to under their sources and fate, there remains a limited understanding of the mechanisms that lead to the formation of aerosols and their ultimate fate in the atmosphere. These knowledge gaps provide the crux of the research reported herein, which has focused on identifying novel sources of atmospheric aerosol, characterizing its physical and optical properties, and rationalizing these properties using an in-depth knowledge of the molecular level mechanisms that led to its formation. Upon mowing, turfgrasses emit large amounts of green leaf volatiles which can then be oxidized by ozone to form SOA. Overall, the mowing of lawns has the potential to contribute nearly 50 µg SOA per square meter of lawn mowed. This SOA contribution is on the same order of magnitude as other predominant SOA sources (isoprene, monoterpenes, sesquiterpenes). Turfgrasses represent an interesting and potentially meaningful SOA source because they contribute to SOA and also because they cover large land areas in close proximity to oxidant sources. Another related SOA precursor is sugarcane, which is in the same family as turfgrass and is among the largest agricultural crops worldwide. Globally, the ozonolysis of sugarcane has the potential to contribute 16 Mg SOA to the atmosphere, compared to global estimates of SOA loading that range from 12-70 Tg SOA. In order to fully understand the role of atmospheric SOA on the radiative budget (and therefore climate), it is also important to understand its optical properties; its ability to absorb vs scatter light. Turfgrass and sugarcane produced SOA that was weakly absorbing while its scatter efficiency was wavelength and size-dependent. Interestingly, SOA formed under both dry (10% RH) and wet (70% RH) conditions had the same bulk chemical properties (O:C), yet significantly different optical properties, which was attributed to differences in molecular-level composition. The work presented herein represents a unique, inclusive study of SOA precursors. A complete understanding of the chemistry leading to SOA formation is used to understand its physical and optical properties and evaluate these large-scale effects of SOA from these precursors.

Aerosols are either emitted directly into the atmosphere or are generated in the atmosphere; the latter process forms secondary organic aerosol (SOA). One of the important sources for SOA is the oxidation of volatile organic compounds (VOCs) by OH radicals, NOx, and O3. Aerosol can be visualized as suspended solid or liquid particle which is in equilibrium with surrounding gases. The products of SOA formation is a mixture of semi volatile organic compounds and a fraction of the products are condensable under atmospheric conditions. The condensable portion of aerosol is called particulate matter (PM) and these suspended particles can range in diameter from a few nanometers to microns. PM can impact climate through direct and indirect radiative forcing and can degrade air quality by reducing visibility and causing detrimental health effects. SOA can also form indoors, which also contributes to the health risk of PM. The severe impact of PM on human health and climate drives the scientific community to investigate the volatile organic compounds (VOCs) and their potential to form SOA, as well as the factors that alter the efficiency of SOA generation and the type of products. In a similar pursuit, the focus of this dissertation is the investigation of the SOA precursors that are emitted from trees and how they vary as a function of insect infestation. Also, the role of mixtures of VOCs as SOA precursors are investigated; commercial and lab made VOC mixtures are studied for SOA generation, product analysis, and absorption characteristics of aged SOA. Chapter 1 introduces PM, VOCs present in atmosphere, SOA generation, and speciation of products generated from the ozonolysis of VOCs. The impact of PM on human health and climate are summarized. A literature survey on the VOCs that are precursors to SOA and present in the outdoor and indoor environment is presented along with factors that may lead to variability in amount of VOCs. SOA generation from direct plant emissions and consumer products is surveyed. These studies show that VOC oxidation generate SOA which is important in the atmosphere due to climate and health effects and indoors due to health effects. A summary of SOA phase partitioning theories, the reaction mechanism for the formation of products from ozonolysis of the dominant biogenic SOA precursors (monoterpenes), and the factors that affect SOA generation is presented. Chapter 2 summarizes the results obtained from a field study assessing the impact of bark beetle infestation on SOA precursor emissions from forests in the Western United States. Samples of VOCs were collected by our collaborators from healthy and bark beetle infested trees using scent traps. We solvent extracted and analyzed by gas chromatography/mass spectrometry (GC/MS) nearly four hundred scent traps. An increase in the total and the individual VOCs emitted by infested trees was measured. A statistical analysis shows significant differences between the emissions from infested and healthy trees. A perspective is provided on potential impact of bark beetle infestation on regional SOA. The majority of the laboratory experiments for SOA generation have focused on individual VOCs as the single SOA precursor. However, as demonstrated in Chapter 2 for example, in a real environment multiple VOCs co-exist. Multiple SOA precursors undergo concurrent oxidation reactions, and it is not known if the products from concurrent oxidation of multiple precursors are the same as the sum of the products from individual SOA precursors. Mass closure analysis of field samples show that a significant fraction of the chemical identity of organic PM is unknown, but the chemistry impacts the toxicity of PM. Hence, it is important to understand SOA formation from realistic SOA mixtures. Chapter 3 describes the results of the SOA generation by ozonolysis of limonene and VOC mixtures containing limonene. We use an additive approach for building a surrogate VOC mixture close in composition to a commercially-available mixture. The yield of PM as a function of VOC precursor mixture was measured with respect to VOC composition using smog chamber SOA generation and scanning mobility particle sizing. PM in the chamber was collected onto filters and extracted, and the individual products of SOA were identified and quantified by GC/MS. The condensed-phase SOA products generated during these experiments for different VOC mixtures are compared. In Chapter 4, condensed-phase products sampled from SOA generated by the ozonolysis of α pinene and VOC mixtures containing α pinene, including two fir needle essential oils, are studied by extracting filter samples and analyzing the extracts by GC/MS. The products generated from VOC mixtures are characteristic of the most dominant VOC present in the mixture i.e. either limonene or α pinene. Some mixtures show the generation of new products which are not observed for corresponding individual VOC ozonolysis and hence can be used as marker for the corresponding VOC mixture. The distribution of α-pinene SOA products changes as the composition of the SOA precursor mixture changes. In Chapter 5, the UV visible absorption characteristics of ammonium ion aged SOA are discussed. Ammonium ion aging of aerosol leads impacts the radiative properties of aerosol and has the potential to impact aerosol's role in climate change. Filter samples containing SOA generated from two mixtures with different dominant monoterpenes (α-pinene-based Siberian fir needle oil and a limonene-based air freshener) were extracted. The absorption coefficients of the extracts were measured as a function of ammonium ion aging time using UV-visible absorption spectrometry. The conclusions from all above chapters are summarized in Chapter 6.

京都大学 / 0048 / 新制・課程博士 / 博士(地球環境学) / 甲第18704号 / 地環博第127号 / 新制||地環||26(附属図書館) / 31637 / 京都大学大学院地球環境学舎地球環境学専攻 / (主査)教授 梶井 克純, 教授 杉山 雅人, 准教授 清中 茂樹 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

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Constructing a detailed understanding of the heterogeneous oxidation of atmospheric organic aerosols, both from a mechanistic and kinetic perspective, will enable researchers to predict the fate and lifetime of atmospheric gases and the particles with which they interact. In an effort to develop a more complete understanding of the interfacial reactions of ozone with vinyl-containing organic thin films, self-assembled monolayers that contain vinyl groups positioned precisely at the gas/surface interface were synthesized as model systems for atmospheric organic aerosols. To isolate the reactions of background gases with ozone or surface products, an ultrahigh vacuum surface analysis instrument was designed and constructed to explore the reactions of ozone with the atmospheric model systems. The surface reactions can be monitored in real-time with reflection absorption infrared spectroscopy (RAIRS) and mass spectrometry. The chemical identity of adsorbates on a surface can also be determined before or after a reaction with X-ray photoelectron spectroscopy (XPS). Disordering of the monolayers concurrent with the disappearance of the vinyl group was observed with RAIRS. New bands within the RAIR spectra were observed and assigned to carbonyl or carboxylic acids bound to the surface. Little oxidation of the sulfur head groups and no significant loss of carbon during the reaction was observed with XPS. A mechanism is proposed that includes the cross linking of the hydrocarbon chains within the monolayer, which impedes further oxidation of the sulfur head group and limits desorption of the chains. By RAIRS, the kinetics of the oxidation of the vinyl groups were tracked and an observed rate constant was determined by monitoring the changes in IR absorbance of the C=C bond. With the aid of the rate constant, an initial reaction probability for the collisions of ozone with vinyl groups positioned precisely at an interface was determined. The reaction probability is approximately three orders of magnitude greater than the reaction probability for an analogous gas-phase reaction, which demonstrates that the gas/surface interface plays an important role in this reaction. The results presented in this thesis should help develop a more detailed understanding of the interfacial reactions of pure ozone at surfaces. / Ph. D.

<p>Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. </p><p>In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings.</p><p>To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of >95% for all monoterpenes and formed products included in the investigation.</p><p>Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆³-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation.</p><p>Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene. </p>

Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings. To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of &gt;95% for all monoterpenes and formed products included in the investigation. Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆3-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation. Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene.

Accurate measurements of ammonia, nitric acid and formic acid are important for achieving a complete understanding of their atmospheric role. Models and measurements of formic acid in the atmosphere continue to show disagreements. Also, the contributions of NMHCs and reactive nitrogen (HNO3 and NH3) to organic and inorganic aerosol formation are important to quantify as gaps in the knowledge of atmospheric aerosols are a source of uncertainty in climate science. In this thesis, concentrations of ammonia were measured in the atmosphere and the production of formic acid from the ozonolysis of isoprene was measured in the EXTRA (EXTreme RAnge) chamber. Both gases were studied using chemical ionisation mass spectrometry (CIMS). The kinetics of the reactions of sesquiterpenes and terminal alkenes with ozone were studied in theEXTRA chamber using the relative rates technique and GC-FID. The ozonolysis rate coefficients of a homologous series of terminal alkenes were measured at elevated temperatures and found to be invariant with the carbon number. This led to the conclusion that previous measurements of these rate coefficients were subject to experimental artefacts. The elevated temperature protocol was employed to study the ozonolysis of sesquiterpenes, leading to revisions in ko3 for β-caryophyllene and α-humulene of 3 orders of magnitude. It was thus concluded that ozonolysis only accounts for 9-15% of sesquiterpeneoxidation in the atmosphere. A field intercomparison of CIMS for measuring ammonia was conducted wherein CIMS was found to perform well alongside instruments of comparable time response and limits of detection. This thesis also characterised inlet materials used in atmospheric measurements in the first systematic study on the uptake onto inlet walls in a flow tube system coupled to CIMS. It was found that PFA is the preferable material for atmospheric measurements, both for its kinetic qualities and its ready availability and ease of use. Finally, CIMS was used to measure the yield of formic acid from isoprene ozonolysis as a function of relative humidity. Formic acid yield was found to increase between 0-40% RH to a maximum of 0.18. Using the measured formic acid yields in a global chemistry model leads to an estimate that formic acid production from isoprene ozonolysis is ~9.5 Tg yr-1.