Search

This is the second of two papers presenting the study of vibrational energy exchanges in non-equilibrium CO2 plasmas in low-excitation conditions. The companion paper addresses a theoretical and experimental investigation of the time relaxation of ∼70 individual vibrational levels of ground-state CO molecules during the afterglow of a pulsed DC glow discharge, operating at pressures of a few Torr and discharge currents around 50 mA, where the rate coefficients for vibration-translation (V-T) and vibration-vibration (V-V) energy transfers among these levels are validated (Silva et al 2018 Plasma Sources Sci. Technol. 27 015019). Herein, the investigation is focused on the active discharge, by extending the model with the inclusion of electron impact processes for vibrational excitation and de-excitation (e-V). The time-dependent calculated densities of the different vibrational levels are compared with experimental data obtained from time-resolved in situ Fourier transform infrared spectroscopy. It is shown that the vibrational temperature of the asymmetric stretching mode is always larger than the vibrational temperatures of the bending and symmetric stretching modes along the discharge pulse - the latter two remaining very nearly the same and close to the gas temperature. The general good agreement between the model predictions and the experimental results validates the e-V rate coefficients used and provides assurance that the proposed kinetic scheme provides a solid basis to understand the vibrational energy exchanges occurring in CO2 plasmas.

The implementation of in situ rotational Raman spectroscopy is realized for a pulsed glow discharge in CO2 in the mbar range and is used to study the rotational temperature and molecular number densities of CO2, CO, and O2. The polarizability anisotropy of these molecules is required for extracting number densities from the recorded spectra and is determined for incident photons of 532 nm. The spatiotemporally-resolved measurements are performed in the same reactor and at equal discharge conditions (5-10 ms on-off cycle, 50 mA plasma current, 6.7 mbar pressure) as in recently published work employing in situ Fourier transform infrared (FTIR) spectroscopy. The rotational temperature ranges from 394 to 809 K from start to end of the discharge pulse and is constant over the length of the reactor. The discharge is demonstrated to be spatially uniform in gas composition, with a CO2 conversion factor of 0.15 ± 0.02. Rotational temperatures and molecular composition agree well with the FTIR results, while the spatial uniformity confirms the assumption made for the FTIR analysis of a homogeneous medium over the line-of-sight of absorption. Furthermore, the rotational Raman spectra of CO2 are related to vibrational temperatures through the vibrationally averaged nuclear spin degeneracy, which is expressed in the intensity ratio between even and odd numbered Raman peaks. The elevation of the odd averaged degeneracy above thermal conditions agrees well with the elevation of vibrational temperatures of CO2, acquired in the FTIR study.

Time-resolved in situ FTIR spectroscopy and spatiotemporally resolved in situ Raman spectroscopy are used to study the excitation and relaxation of the vibrations of CO 2 and the reduction of CO 2 to CO in a pulsed glow discharge.

A kinetic model describing the time evolution of ∼70 individual CO2(X1Σ+) vibrational levels during the afterglow of a pulsed DC glow discharge is developed in order to contribute to the understanding of vibrational energy transfer in CO2 plasmas. The results of the simulations are compared against in situ Fourier transform infrared spectroscopy data obtained in a pulsed DC glow discharge and its afterglow at pressures of a few Torr and discharge currents of around 50 mA. The very good agreement between the model predictions and the experimental results validates the kinetic scheme considered here and the corresponding vibration-vibration and vibration-translation rate coefficients. In this sense, it establishes a reaction mechanism for the vibrational kinetics of these CO2 energy levels and offers a firm basis to understand the vibrational relaxation in CO2 plasmas. It is shown that first-order perturbation theories, namely, the Schwartz-Slawsky-Herzfeld and Sharma-Brau methods, provide a good description of CO2 vibrations under low excitation regimes.