| Carbon monoxide - hydrogen - oxygen chemistry is studied experimentally (via flow reactor, 800 - 1250 K, 1 atm), modeled numerically, and subsequently used as a diagnostic tool for studying hydrocarbon inhibition chemistry and elementary reaction rates. Newly developed sensitivity analysis techniques are used extensively to guide and analyze both the experiment and modeling calculations.;A comprehensive, elementary reaction mechanism for carbon monoxide - hydrogen - oxygen chemistry is developed. Validation of the reaction mechanism is obtained with reproduction of experimental results by model predictions and from sensitivity analysis calculations. The validations are made over a combined temperature range of 800 - 3000 K, fuel-air equivalence ratios between 0.025 and 6.0, and pressures between 0.3 and 3 atmospheres.;The carbon monoxide - hydrogen - oxygen reaction is further employed to study the inhibition chemistry of various alkyl compound hydrocarbons on the carbon monoxide reaction, and also to provide a controllable source of reactive radicals for studying hydrocarbon-radical (OH, H, and O) reactions. Inhibition of the carbon monoxide reaction by propane, propylene, ethane, ethylene, acetylene, and methane is studied between 960 and 1250 K and at one atmosphere. From these results, rate constants are obtained for the elementary reactions of CH(,4) + OH and C(,3)H(,6) + OH.;Furthermore, a methodology is presented for evaluating the uncertainties in measured rate constants using the combined experimental/modeling data and specialized sensitivity coefficients. The developed methodology is then applied to obtain the rate constant, product branching ratio, and corresponding uncertainties for the elementary reaction between formaldehyde and hydroxyl radical.;The present work provides for the most complete documentation on the applications and interpretations of sensitivity gradient analysis in the chemical kinetics field. Interpretations and usage of the following gradients are given; elementary first and second order gradients, "derived" first and second order gradients, standard and reduced Green's function gradients, feature sensitivity gradients, and experimental sensitivity gradients. After describing and demonstrating these gradients, they are used as an integral part of the research on the carbon monoxide - hydrogen - oxygen reaction.;Finally, novel procedures on how the comprehensive, elementary reaction mechanism for the carbon monoxide - hydrogen - oxygen system may be simplified to a lumped model are described and demonstrated. (Abstract shortened with permission of author.)... |
