The overall objectives of this thesis were to investigate the potential of the peroxyoxalate chemiluminescence (POOL) reaction for the quantitative detection of target analytes in non-aqueous matrices and to compare quantitative performance with fluorescence detection. The target analytes investigated were polycyclic aromatic hydrocarbons (PAHs) and aliphatic amines. These were selected as an important class of compounds in engine exhaust emissions and a detergent additive in diesel fuel respectively. Chapter one outlines the challenges of analysing petroleum products and engine exhaust emissions and discusses the potential of luminescence techniques, particularly chemiluminescence (CL), for the quantification of trace components. The chapter also reviews the technique of flow injection (FT) as a means of sample delivery for CL detection and as a potential technique for field deployment. Liquid chromatography techniques are described as a means of separation of complex matrices, e.g. fuels and engine exhaust particulates, in the laboratory prior to CL detection. The luminescence properties of several PAHs were investigated in Chapter Two. Optimum excitation and emission wavelengths for eleven PAHs in four different solvents were determined using a batch fluorescence technique. A FI approach was used to determine PAH concentrations using fluorescence and POCL detection. Two aryl oxalates; bis(2,4-dinitophenyl)oxalate and bis(2,4,6-trichlorophenyl)oxalate were compared for their suitability for PAH determinations and an investigation of the key variables (e.g. concentration of aryl oxalate and hydrogen peroxide, mobile phase composition and pH) affecting POCL was performed. Recommendations for the optimum conditions for the determination of PAHs by POCL detection were determined, A comparison between a photodiode based detection device and a low power (12V) photomultiplier tube was also described. In Chapter Three the procedure of using POCL detection as a post column liquid chromatography (LC) detector for PAHs has been considered. The performance of the POCL detection system was compared with wavelength programmed fluorescence. Both reversed and normal phase LC was investigated and the suitability of POCL detection with each approach was discussed. Additionally the procedure for the LC separation and analysis of SRM 1649 (Urban Dust/Organics) and SRM 1650 (Diesel Particulate Matter) was described. The relative performance of fluorescence and CL detection are discussed. Chapter four describes the principles of multivariate calibration of spectrophotometric data, and three commonly applied techniques (PCR, PLSI and PLS2). Fluorescence data was obtained for synthetic mixtures of PAHs containing two, three, four and five components. A procedure whereby individual spectra were 'glued' together before undergoing data analysis has been developed and the results obtained discussed. POCL emission spectra for five PAHs were acquired using a two-dimensional charge coupled device (CCD). The sensitivity of the CCD system toward POCL detection of PAHs and a multivariate investigation using benzo[a]pyrene and benzo[k]fluoranthene has been described. The potential of the fluorescence and CL approaches used has been discussed. Chapter five describes the aryl oxalate sulphorhodamine-101 CL reaction and its application to the determination of amines. A FI optimisation of the reaction parameters is presented together with some quantitative data for the detection of a homologous series of amines and dodecylamine (a commonly added detergent compound in diesel fuels). The application of the technique toward the detection of dodecylamine in a diesel fuel matrix and the potential as a field deployable technique was also considered.

The present work is based on the need for understanding the in-cylinder flow and its subsequent effects on combustion in a valved-two-stroke spark ignition engine with fuel injection using Computational Fluid Dynamics (CFD) and experimental techniques. In this context, the CFD code KIVA-II has been modified to model the two-stroke engine gas exchange and combustion processes. A 3-D Cartesian grid generation program for complex engine geometry has been added to the KIVA code which has been modified to include intake and exhaust flow processes with valves. New and improved sub models for wall jet interaction, mixing controlled combustion and one dimensional wave action have also been incorporated. The modified version of the program has been used to simulate a fuel injected two-stroke spark ignition engine and parametric studies have been undertaken. The simulated flow, combustion and exhaust emission characteristics over a wide range of operating conditions show the expected trends in behaviour observed in actual engines. In the second phase of this study, the air-assisted-fuel-injection (AAFI) process into a cylinder has been simulated with a high resolution computational grid. The simulation results are presented and compared with experimental data obtained using the Schlieren optical technique. An approximate method based on the conservation of mass, momentum and energy of the spray jet and using a comparatively coarse grid has been suggested for simulating the AAFI process. The simulation study predicts a high degree of atomisation of fuel spray with Sauter mean diameter around 10 μm even with moderate air and fuel pressures. The penetration and width of spray are simulated within 15% of the experimental values. In the last phase of this study, the flow and combustion processes have been studied for a four-stroke spark ignition engine with the AAFI process. The simulation results obtained using this approximate method have been validated with experimental data generated for the same engine configuration.

Thesis (Ph. D.)--West Virginia University, 2010. / Title from document title page. Document formatted into pages; contains xvii, 124 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 116-124).

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (p. 205-225).

This paper presents a review of the basic thermal, chemical and radiation balances existing in the atmosphere and discusses the mechanisms by which jet engine exhaust products can disturb these balances. Possible effects of stratospheric pollution on plant and animal life are discussed. Methods for reducing harmful emissions through engine design modifications are outlined and current successful research programs are surveyed. The SST type aircraft is shown to be a greater threat to the environment than conventional jets because of differences in cruise altitudes. It is concluded that due to the existence of several potential environmental problems associated with contamination of the stratosphere, large scale deployment of the SST should be discouraged, at least until current studies are complete and more data is available.

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Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references. Available also from UMI company.

Thesis (M.S.)--West Virginia University, 2000. / Title from document title page. Document formatted into pages; contains x, 157 p. : ill. (some col.) Includes abstract. Includes bibliographical references (p. 86-87).

Thesis (Ph. D.)--University of Washington, 2005. / Vita. Includes bibliographical references (leaves 129-133).