Experimental Determination of Rotational Temperatures and Concentrations of OH in Flames from Emission Spectra

Abstract

In order to illustate the use of two‐path experiments for correcting for self‐absorption, experimental studies to determine the rotational ``temperatures'' and concentrations of OH in flames burning at atmospheric pressure have been carried out. For mixtures of H<sub>2</sub>, C<sub>2</sub>H<sub>2</sub>, and O<sub>2</sub>, as well as for C<sub>2</sub>H<sub>2</sub>–O<sub>2</sub> flames diluted with A, ``anomalous'' rotational ``temperatures'' were observed under conditions in which strong self‐absorption was clearly indicated by the intensity ratios for the double‐path to the single‐path experiments. Unequivocal quantitative estimates of rotational temperatures and of OH concentrations cannot be carried out, even on the assumption that the emitting system is isothermal and in equilibrium. However, by using the results of theoretical studies on two‐path experiments carried out by one of us, it is possible to obtain reasonable upper limits for the temperatures and lower limits for the OH‐concentrations, based on an assumed Doppler contour for the line‐shape and utilizing Oldenberg's estimates for the f values of representative spectral lines. Our experimental studies lead to reasonable rotational temperatures at the tip of luminous cones for mixtures of H₂, C₂H₂, and O₂ and for C₂H₂–O₂ flames diluted with up to 60 percent argon. These observations do not disprove the reality of rotational temperature anomalies in the inner cones of flames. Significant improvement of experimental procedure, and quantitative interpretation of results along the lines used by us, requires additional basic studies with emphasis on the measurement of spectral line‐shape and absolute intensities.