$\mathrm{CO}_{2}^{*}$ chemiluminescence study at low and elevated pressures

Abstract

Chemiluminescence experiments have been performed to assess the state of current $\mathrm{CO}_{2}^{*}$ kinetics modeling. The difficulty with modeling $\mathrm{CO}_{2}^{*}$ lies in its broad emission spectrum, making it a challenge to isolate it from background emission of species such as CH^∗ and CH₂O^∗. Experiments were performed in a mixture of 0.0005H₂+0.01N₂O+0.03CO+0.9595Ar in an attempt to isolate $\mathrm{CO}_{2}^{*}$ emission. Temperatures ranged from 1654 K to 2221 K at two average pressures, 1.4 and 10.4 atm. The unique time histories of the various chemiluminescence species in the unconventional mixture employed at these conditions allow for easy identification of the $\mathrm{CO}_{2}^{*}$ concentration. Two different wavelengths to capture $\mathrm{CO}_{2}^{*}$ were used; one optical filter was centered at 415 nm and the other at 458 nm. The use of these two different wavelengths was done to verify that broadband $\mathrm{CO}_{2}^{*}$ was in fact being captured, and not emission from other species such as CH^∗ and CH₂O^∗. As a baseline for time history and peak magnitude comparison, OH^∗ emission was captured at 307 nm simultaneously with the two $\mathrm{CO}_{2}^{*}$ filters. The results from the two $\mathrm{CO}_{2}^{*}$ filters were consistent with each other, implying that indeed the same species (i.e., $\mathrm{CO}_{2}^{*}$) was being measured at both wavelengths. A first-generation kinetics model for $\mathrm{CO}_{2}^{*}$ and CH₂O^∗ was developed, since no comprehensively validated one exists to date. CH₂O^∗ and CH^∗ were ruled out as being present in the experiments at any measurable level, based on calculations and comparisons with the data. Agreement with the $\mathrm{CO}_{2}^{*}$ model was only fair, which necessitates future improvements for a better understanding of $\mathrm{CO}_{2}^{*}$ chemiluminescence as well as the kinetics of the ground state species.