| Abstract: | The use of chemiluminescence measurements to monitor a range of combustion processes has been a popular area of study due to their reliable and cost-effective nature. Electronically excited carbon dioxide (CO₂*) is known for its broadband emission, and its detection can lead to valuable information; however, due to its broadband characteristics, CO₂* is difficult to isolate experimentally, and the chemical kinetics of this species is not well known. Although numerous works have monitored CO₂* chemiluminescence, a full kinetic scheme for the species has yet to be developed. A series of shock-tube experiments was performed in H₂-N₂O-CO mixtures highly diluted in argon at conditions where emission from CO₂* could be isolated and monitored. These results were used to evaluate the kinetics of CO₂*, in particular, the main CO₂* formation reaction, CO + O + M [right arrow, left arrow] CO₂* + M (R1). Based on collision theory, the quenching chemistry of CO₂* was determined for eleven common collision partners. The final mechanism developed for CO₂* consisted of 14 reactions and 13 species. The rate for R1 was determined based on low-pressure experiments performed in two different H₂-N₂O-CO-Ar mixtures. Final mechanism predictions were compared with the experimental results at low and high pressures, with good agreement seen at both conditions. Peak CO₂* trends with temperature as well as overall CO₂* species time histories were both monitored. Comparisons were also made with previous experiments in methane-oxygen mixtures, where there was slight over-prediction of CO₂* experimental trends by the mechanism.Experimental results and mechanism predictions were also compared with past literature rates for CO₂*, with good agreement for peak CO₂* trends, and slight discrepancies in overall CO₂* species time histories. Overall, the ability of the CO₂* mechanism developed in this work to reproduce a range of experimental trends represents an improvement over existing models. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/148133 |
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