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The time-dependent evolution of the energy transfer into gas heating in the afterglow of pulsed CO2 and CO2–N2 glow discharges produced in cylindrical tubes at low pressures (1–5 Torr) is theoretically investigated, by developing a self-consistent model that couples the time-dependent gas thermal balance equation with the vibrational kinetics. The modelling predictions are in good agreement with recently published experimental data on gas temperature, obtained via time-resolved in situ Fourier transform infrared spectroscopy. The cooling of the gas in the afterglow is found to be strongly dependent on the thermal conductivity and the wall temperature. It is verified that wall and volume deactivation of CO2 vibrationally excited species influences the gas heating along the afterglow, in different proportions depending on the pressure of the gas. The time-resolved contributions of each of these cooling and heating mechanisms are discussed in detail. The new results bring an additional validation of a set of mechanisms and rate coefficients for vibrationally-energy transfers previously proposed.

International audience; This work employs in situ rotational Raman spectroscopy to study the effect of N2 and O2 addition to CO2 in pulsed glow discharges in the mbar range. The spatiotemporally resolved measurements are performed in CO2 and 25%, 50% and 75% of N2 or O2 admixture, in a 5–10 ms on-off cycle, 50 mA plasma current and 6.7 mbar total pressure. The rotational temperature profile is not affected by adding N2, ranging from 400 to 850 K from start to end of the discharge pulse, while the addition of O2 decreases the temperature at corresponding time points. Molecular number densities of CO2, CO, O2 and N2 are determined, showing the spatial homogeneity along the axis of the reactor and uniformity during the cycle. The measurements in the N2 containing mixtures show that CO2 conversion factor α increases from 0.15 to 0.33 when the content of N2 is increased from 0% to 75%, demonstrating the potential of N2 addition to enhance the vibrational pumping of CO2 and its beneficial effect on CO2 dissociation. Furthermore, the influence of admixtures on CO2 vibrations is examined by analysing the vibrationally averaged nuclear spin degeneracy. The difference between the fitted odd averaged degeneracy and the calculated odd degeneracy assuming thermal conditions increases with the addition of N2, demonstrating the growth of vibrational temperatures in CO2. On the other hand, the addition of O2 leads to a decrease of α, which might be attributed to quenched vibrations of CO2, and/or to the influence of the back reaction in the presence of O2.

International audience; The excitation and relaxation of the vibrations of CO2 as well as the reduction of CO2 to CO are studied in a pulsed glow discharge. Two diagnostics are employed, being (1) time-resolved in situ Fourier transform infrared (FTIR) spectroscopy and (2) spatiotemporally resolved in situ rotational Raman spectroscopy. Experiments are conducted within a pressure range of 1.3-6.7 mbar and a current range of 10-50 mA. In the afterglow, the rate of exponential decay from the asymmetric stretch temperature (T3) to the rotational temperature (Trot) is found to be only dependent on Trot, in the conditions under study. The decay rate ρT3-Trot follows the relation ρT3-Trot = 388 s-1 exp((Trot - 273 K)/(154 K)). Pressure and varying concentrations of CO and (presumably) atomic oxygen did not show to be of significant influence. In the active part of the discharge the excitation of T3 showed to be positively related to current and negatively to pressure. However, the contribution of current to vibrational excitation is ambiguous: the conversion of CO2 and therefore the fraction of CO in the discharge, is found to be strongly dependent on the current, with a conversion factor of 0.05 to 0.18 for 10 mA to 50 mA, while CO can contribute to the excitation through near-resonant collisions. A clear relation between the elevation of T3 and the dissociation of CO2 could not be confirmed, though conversion peaks are observed in the near afterglow, which motivate future experiments on vibrational ladder-climbing directly after termination of the discharge.

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.

International audience; Herein, it is argued that Mars has nearly ideal conditions for CO 2 decomposition by non-equilibrium plasmas. It is shown that the pressure and temperature ranges in the ##IMG## [http://ej.iop.org/images/0963-0252/26/11/11LT01/psstaa8dccieqn1.gif] ∼ 96 % CO 2 Martian atmosphere favour the vibrational excitation and subsequent up-pumping of the asymmetric stretching mode, which is believed to be a key factor for an efficient plasma dissociation, at the expense of the excitation of the other modes. Therefore, gas discharges operating at atmospheric pressure on Mars are extremely strong candidates to produce O 2 efficiently from the locally available resources.