Chemiluminescence from the OH(A-X) transition near 307 nm is a commonly used diagnostic in combustion applications such as flame chemistry, shock-tube experiments, and reacting-flow visualization. Measurements of the chemiluminescent intensity provide a simple, cost-effective, non-intrusive look at the combustion environment. The presence of the ultra-violet emission is often used as an indicator of the flame zone in practical combustion systems, and its intensity may be correlated to the temperature distribution or other parameters of interest. While absolute measurements of the ground-state OH(X) concentrations are well-defined, there is no elementary relation between emission from the electronically excited state (OH*) and its absolute concentration. Thus, to enable quantitative emission measurements, a kinetics model has been assembled and optimized to predict OH* formation and quenching at combustion conditions. Shock-tube experiments were conducted in mixtures of H2/O2/Ar, CH4/O2/Ar and CH4/H2/O2/Ar with high levels of argon dilution (> 98%). Elementary reactions to model OH*, along with initial estimates of their rate coefficients, were taken from the literature. The important formation steps follow. CH + O2 = OH* + CO (R0) H + O + M = OH* + M (R1) H + OH + OH = OH* + H2O (R2) Sensitivity analyses were performed to design experiments at conditions most sensitive to the formation reactions. A fitting routine was developed to express the key rate parameters as a function of a single rate, k1 at the reference temperature (1490 K). With all rates so expressed, H2/CH4 mixtures were designed to uniquely determine the value of k1 at the reference temperature, from which the remaining rate parameters were calculated. Quenching rates were fixed at their literature values. Comparisons to predictions of previously available models show marked improvement relative to the new shock-tube data. An approach for using this work in the calibration of further measurements is outlined taking examples from a recent ethane oxidation study. The new model qualitatively matches the experimental data over the range of conditions studied and provides quantitative results applicable to real combustion environments, containing higher-order hydrocarbon fuels and lower levels of dilution in air.

Flame chemiluminescence has received increasing attention for its potential sensor and diagnostic applications in combustors. A number of studies have used flame chemiluminescence to monitor flame status, and combustor performance. While most of these studies have been empirical in nature, chemiluminescence modeling has the potential to provide a better understanding of the chemiluminescence processes and their dependence on various combustion operating conditions. The primary objective of this research was to identify and validate the important chemiluminescence reaction mechanisms for OH*, CH* and CO2*. To this end, measurements were performed at various operating conditions, primarily in laminar, premixed flames, fueled with methane, syngas (H2/CO) and Jet-A. The results are compared to 1-d laminar flame simulations employing the chemiluminescence mechanisms. The secondary objective was to use the experiments and validated chemiluminescence reaction mechanisms to evaluate the usefulness of flame chemiluminescence as a combustion diagnostic, particularly for heat release rate and equivalence ratio. The validation studies were able to identify specific mechanisms for OH*, CH* and CO2* that produced excellent agreement with the experimental data in most cases. The mechanisms were able to predict the variation of the chemiluminescence signals with equivalence ratio but not with pressure and reactant preheat. The possible reasons causing this disagreement could be due to the inaccuracies in the basic chemical mechanism used in the simulations, lack of accurate quenching data (for CH*), thermal excitation (for OH*) and radiative trapping (for OH* and CO2*) and interference from the emissions of other species (such as HCO and H2O), for CO2*. Regarding the utility of chemiluminescence for sensing, a number of observations can be made. In syngas-air flames, CO2* is a reasonable heat release rate marker, at least for very lean conditions. OH* shows some advantage in atmospheric-pressure methane and Jet-A flames in general, while CH* is advantageous at high pressure and very lean conditions at atmospheric pressure. The CO2*/OH* intensity ratio is not useful for sensing equivalence ratio in syngas flames, except maybe at very lean conditions. However, the CH*/OH* signal ratio is a promising approach for sensing equivalence ratio at low or very high pressure conditions in hydrocarbon flames. Thermal excitation and self-absorption processes for OH* chemiluminescence can become important for combustors operating at high pressure, high preheat and near stoichiometric conditions. Background subtracted chemiluminescence signals are recommended for sensing purposes.