chemiluminescence modeling shock tube kinetics diagnostics


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.


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Graduation Date





Petersen, Eric


Master of Science in Mechanical Engineering (M.S.M.E.)


College of Engineering and Computer Science


Mechanical, Materials and Aerospace Engineering

Degree Program

Mechanical Engineering








Release Date

January 2015

Length of Campus-only Access


Access Status

Masters Thesis (Open Access)