京都大学 / 新制・課程博士 / 博士(工学) / 甲第23389号 / 工博第4881号 / 新制||工||1763(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 田中 庸裕, 教授 今堀 博, 教授 佐藤 徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第18339号 / 農博第2064号 / 新制||農||1023(附属図書館) / 学位論文||H26||N4846(農学部図書室) / 31197 / 京都大学大学院農学研究科応用生物科学専攻 / (主査)教授 左子 芳彦, 教授 澤山 茂樹, 教授 菅原 達也 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Volumetric adsorption experiments were conducted over three sorbates in Zeolitic Imidazolate Framework – 8 (ZIF-8). The sorption isotherms were measured at low temperatures. The study included carbon monoxide sorption in ZIF-8, xenon in ZIF-8, and methane sorption in ZIF-8. As a metal-organic framework that has been investigated thoroughly for its remarkable characteristics, ZIF-8 interactions with the above three sorbates has revealed some new features. Each of these systems offered a unique opportunity to study the physical properties of the sorbate and ZIF-8 and the thermodynamic responses of the system for its unique characteristics. The fundamental understating of sorbents-sorbate not only reveals some of the remarkable properties but also opens up new frontiers for researches in practical applications such as gas storage separation and other sorption-based fields of interest. The investigation into CO-ZIF-8 system has confirmed some of the predictions made on a similar system and analysis on the ZIF-8 structure. The measured adsorption isotherms have confirmed the existence of three pre-saturation subs steps, which were explained in terms of effects from the structural transition and polarity of the sorbate. The behavior of isosteric heat of adsorption and the equilibration time revealed a strong connection between steps in the isotherm and the structural changes of ZIF-8 due to organic linker rotation and volume expansion, also known as “Gate-Opening” in some cases. In both Xe-ZIF-8 and CH4 -ZIF-8 systems, the sorption isotherms revealed two substeps before the saturation. This is the first time such a feature was resolved experimentally in these systems although many previous studies have predicted the feature. The experimental observations on characteristics of the Xe -ZIF-8 system are also verified by computer simulations. Unlike the CO-ZIF-8 system, Xe-ZIF-8 interactions do not trigger the organic linker rotation of ZIF-8 structure, but it influenced the expansion of the ZIF-8 structure. In CH4 – ZIF-8 system the isotherms’ substeps were not as steep as Xe system but the loading dependence of isosteric heat of adsorption and equilibration time revealed features that are similar to CO. The lack of sorption-combined structural analysis of CH4-ZIF-8 prevent us from concluding the actual nature of the changes occurring which are related to the substeps and other thermodynamic and kinetic features. In all three systems, our measurements of the adsorption kinetics, we observed a non-monotonic behavior of the equilibration time as a function of sorbent loading. For CO the loading dependence of equilibration time exhibit peaks at loadings that correspond to the intermediate and higher loading sub-steps, and CH4 showed similar behavior at the loading corresponds to its intermediate substep region. The sharp peaks can be interpreted as packing rearrangement of adsorbed phase molecule in both cases and for CO there may be some contributions from the linker flipping and structural transition. The structural effect of kinetics is yet to be confirmed by a structural analysis for the CH4 system.

Citizens in the United States are fortunate to have an excellent system of roadways and the affluence with which to afford automobiles. The flexibility of travel on demand for most allows for a variety of lifestyles, assists with conducting business, and contributes to the feeling of freedom that most citizens enjoy. The current vehicle fleet, which is primarily powered by internal combustion engines burning fossil fuels, does however contribute to the deterioration of air quality. This effect is particularly significant in metropolitan areas. Motor vehicle exhausts contain several combustion bi-products that pose harmful effects to the environment and human health, in particular. The United States Environmental Protection Agency (EPA) and the Federal Highway Administration (FHWA) have selected carbon monoxide (CO) as the air pollutant on which it has based its guidelines for assessing potential air quality impacts from roadway construction (EPA 1992). The design of roadway networks must consider traffic flows, Level of Service (LOS), cost, and National Ambient Air Quality Standards (NAAQS) requirements. In light of the environmental standards it is necessary to model to estimate potential future near-road concentrations of CO. This modeling has two aspects, first determining the rate of pollutant emissions, and second determining how those pollutants disperse near the road. Obtaining a precise, realistic estimate of the near-road CO concentrations under a wide variety of weather and traffic patterns is a potentially huge undertaking. With budgetary constraints in mind, the development of a screening model is appropriate. CO Florida 2012 (COFL2012) is such a model that uses conservative assumptions to predict worst-case, near-road CO concentration. Projects that pass a COFL2012 model run do not require additional air quality modeling. Projects that fail a COFL2012 model run, however, may still be viable, but will require additional, detailed modeling and possibly project modifications. COFL2012 uses tables of emission factors (EFs) that were derived from numerous runs of the EPA's MOtor Vehicle Emission Simulator (MOVES2010a), which is indicated as the preferred model for near-road modeling of CO.(EPA 2009) COFL2012 then inputs the EFs, along with assumed link configurations, geographical assumptions, and user-inputted traffic information into input files that are run through CAL3QHC Version 2.0 (CAL3QHC2), the EPA's approved near-road dispersion model (EPA 1995). COFL2012 is a brand new Florida CO screening model, written from scratch. This author has written the computer code for COFL2012 in Visual Basic, using Microsoft Visual Studios 2010. Visual Studios utilizes the .net Framework 4. COFL2012 is easy to learn, quick to operate, and has been written to allow for future updates simply and easily, whenever the EPA releases updates to the databases that feed MOVES2010a.

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The aim of the present research was to gain a better understanding of the species generation and transport from enclosure fires. The species generation experiments were conducted with a half-scale ISO 9705 enclosure with three different ventilation conditions and heat release rates ranging from 50 kW to 500 kW. The transport study was conducted with a 6.1 m long hallway connected to the compartment in a head-on configuration. All measurements were performed at the compartment or hallway exit plane during the steady-state period of the fire. Measurements included species mole fractions of oxygen, carbon dioxide, carbon monoxide, and unburned hydrocarbons, along with gas pressure (used to determine gas velocities) and gas temperatures. Species mappings performed at the exit plane of the compartment indicated that the exiting species are not spatially uniform. Horizontal and vertical gradients in the species mole fractions were observed for all ventilation conditions and heat release rates examined. Predictive techniques developed previously were applied to the data obtained in the present study and were determined to be inappropriate for situations were the plume equivalence ratio was not equal to the global equivalence ratio. A new methodology for predicting species levels at the exit plane of an enclosure was developed. The proposed methodology correlates the species yields based on the combustion within the compartment as a function of a non-dimensional heat release rate. The non-dimensional heat release rate is based on the fuel load and geometrical parameters of the enclosure. The present methodology in applicable to situations where a well-mixed uniform layer is not present and the overall global conditions are of interest. Species transport to remote locations was also examined. Experiments were conducted with the baseline ventilation at x = 0 m (the compartment/hallway interface) and three different ventilation conditions at x = 6.1 m (end of hallway). The three ventilation conditions consisted of the narrow, baseline, and wide doorways. Experiments were conducted for heat release rates of 85 kW, 127 kW, and 150 kW. The results from the tests indicated that, for over-ventilated compartment fires, the hallway and hallway ventilation had no impact on the species generation within the compartment. This allows the correlations developed from the compartment study to be applied to more complex scenarios. Differences in species mole fractions between x = 0 m and x = 6.1 m were shown to be a result of air entrainment into the upper layer within the hallway, which acted as a dilutent or as a source of oxygen for further oxidation reactions. For non-dimensional heat release rates less than 1.0, the reduction in carbon monoxide levels along the hallway was a result of dilution, while for non-dimensional heat release rates greater than or equal to 1.0 the reduction in carbon monoxide levels along the hallway was a combination of dilution and further oxidation reactions. / Ph. D.

Adsorbed carbon monoxide is utilized as a double layer probe molecule because of its strong absorption in infrared region and because of the high sensitivity of the carbon-oxygen bond to changes in the environment local to the electrode surface. Potential Difference Infrared Spectroscopy was used to investigate the structural behavior of CO adsorbed on a platinum electrode. Carbon monoxide was found to be exclusively linear-bonded on platinum electrode in the presence of tetra-n alkylammonium perchlorate/acetonitrile. No bridge-bonded species were observed. It was also found that the IR peak position of adsorbed CO is linearly dependent upon applied electrode potential, in agreement with Electrochemical Stark effect. The Stark tuning rate of adsorbed CO was determined to be inversely proportional to electrolyte cation size. This quantitative relationship between the Stark tuning rate and cation size is the first time that this has been experimentally demonstrated. Statistical treatment proved that surface coverage influences the rate of infrared peak position shift. The effect of surface coverage upon the conformation of tetra-n-octylammonium cation was also observed. Data suggested that tetra-n-octylammonium cation changes its conformation with surface coverage / Master of Science

The majority of deaths and injuries in compartment fires result from inhalation of the toxic gas, carbon monoxide (CO), especially in locations remote from the burning compartment. This causes the transport and oxidation of CO in burning buildings to become an important topic. Studies have been conducted to determine the toxic environments produced inside, and in locations remote from, a burning compartment; however, no studies have investigated the composition of the exhaust gases during transport to remote locations. The goal of this study was to investigate fire exhaust gas transport through a hallway to determine the important parameters affecting the efficiency of sustained external burning in oxidizing toxic gases, including the hydrodynamic effects of different hallway configurations. Underventilated compartment fire experiments were performed with a compartment exhausting along the axis of a hallway. The design of the compartment allowed direct measurement of the global equivalence ratio which was used as a main correlating parameter. Characteristic global equivalence ratios and an ignition index concept were investigated to determine when sustained external burning would occur. Gas sampling was performed downstream of the hallway to determine the overall efficiency of sustained external burning, and in the hallway to provide detailed data on the processes occurring in the hallway. The oxidation of the exhaust gases traveling through the hallway was determined to vary among different species, and also to be very sensitive to the hydrodynamic mixing between the rich exhaust plume and the cooler ambient air in the hallway. In general, the overall oxidation of hydrocarbons was much more complete than for CO or soot. The gas temperatures in the hallway and fuel vaporization rate were also determined to affect oxidation in the hallway. Variations in the hallway inlet and exit soffits affected the hydrodynamic structure of the exhaust plume and oxidation efficiencies, with the inlet soffit exhibiting the strongest effect. / Master of Science