Thesis (Ph. D.)--University of Hong Kong, 1989.

Thesis (Ph. D.)--University of Hong Kong, 1988.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (p. 96-115).

Thesis (Ph. D.)--University of Missouri--Columbia, 2002. / "December 2002." Typescript. Vita. Includes bibliographical references (leaves 109-118). Also issued on the Internet.

Thesis (Ph. D.)--University of Missouri--Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 109-118). Also issued on the Internet.

A Bayesian framework for quantification of uncertainties has been used to quantify the uncertainty introduced by chemistry models. This framework adopts a probabilistic view to describe the state of knowledge of the chemistry model parameters and simulation results. Given experimental data, this method updates the model parameters' values and uncertainties and propagates that parametric uncertainty into simulations. This study focuses on syngas, a combination in various ratios of H2 and CO, which is the product of coal gasification. Coal gasification promises to reduce emissions by replacing the burning of coal with the less polluting burning of syngas. Despite the simplicity of syngas chemistry models, they nonetheless fail to accurately predict burning rates at high pressure. Three syngas models have been calibrated using laminar flame speed measurements. After calibration the resulting uncertainty in the parameters is propagated forward into the simulation of laminar flame speeds. The model evidence is then used to compare candidate models. Sensitivity studies, in addition to Bayesian methods, can be used to assess chemistry models. Sensitivity studies provide a measure of how responsive target quantities of interest (QoIs) are to changes in the parameters. The adjoint equations have been derived for laminar, incompressible, variable density reacting flow and applied to hydrogen flame simulations. From the adjoint solution, the sensitivity of the QoI to the chemistry model parameters has been calculated. The results indicate the most sensitive parameters for flame tip temperature and NOx emission. Such information can be used in the development of new experiments by pointing out which are the critical chemistry model parameters. Finally, a broader goal for chemistry model development is set through the adjoint methodology. A new quantity, termed field sensitivity, is introduced to guide chemistry model development. Field sensitivity describes how information of perturbations in flowfields propagates to specified QoIs. The field sensitivity, mathematically shown as equivalent to finding the adjoint of the primal governing equations, is obtained for laminar hydrogen flame simulations using three different chemistry models. Results show that even when the primal solution is sufficiently close for the three mechanisms, the field sensitivity can vary. / text

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Boltzmann's equation for binary chemical reactions has been solved by the modified moment method using the equivalent of the 13-moment approximations. It was found that the transport coefficients are nonlinear in the thermodynamic forces. This nonlinearity is at least quadratic. The rate coefficient also appears to be at least quadratic in fluxes. / The stability of the solutions of two coupled equations of change for the current under the influence of an electric field is examined. These equations are deduced from the structure of dissipative terms calculated in the modified moment method. Two steady state branches in current are found to bifurcate from the primary steady state branch as a critical field value E(,c) = 4.35 V/cm is crossed. The results are in good qualitative agreement with experiment. / The dynamical behaviour of the two coupled equations used above was also studied in order to establish the influence (if any) of the entropy production surface on the trajectory followed by the system. This aspect of the study proved to be difficult since the entropy production surface associated with the two equations used did not have sufficiently distinctive features. / In order to continue studies on the relationship between dynamical behaviour and the topography of the entropy production surface, the two basic equations used before were slightly modified, and new parameters were introduced. At the critical field value E(,c) = 1.48 V/cm, no secondary steady states bifurcated out of the unstable primary steady state as in the previous model. Rather, stable oscillations in current of more or less constant amplitude occurred. This may account for some of the current fluctuations observed in experiment. The entropy production surface associated with this pair of model equations consists of two intersecting locii of minima. It turns out that the trajectory follows these minimal regions for most of the orbit, crossing from one locus of minima to another either through the intersection near to the origin or by crossing a ridge of high entropy production. The average energy dissipated over this cycle turns out to be smaller than if the system had remained with the unstable steady state. / Out of the latter studies, the useful conjecture was made. Given the topography of the entropy production surface and the stability of the steady states, it is possible to qualitatively predict the dynamics of the system provided the entropy production surface has sufficiently distinctive features.

No description available.

No description available.