Study of vibrational kinetics of CO2 and CO in CO2-O2 plasmas under non-equilibrium conditions

This work explores the effect of O2 addition on CO2 dissociation and on the vibrational kinetics of CO2 and CO under various non-equilibrium plasma conditions. A self-consistent model, previously validated for pure CO2 discharges, is further extended by adding the vibrational kinetics of CO, including electron impact excitation and de-excitation (e-V), vibration-to-translation relaxation (V-T) and vibration-to-vibration energy exchange (V-V) processes. The vibrational kinetics considered include levels up to v = 10 for CO and up to v1=2 and v2=v3=5, respectively for the symmetric stretch, bending and asymmetric stretch modes of CO2, and accounts for e-V, V-T in collisions between CO, CO2 and O2 molecules and O atoms and V-V processes involving all possible transfers involving CO2 and CO molecules. The kinetic scheme is validated by comparing the model predictions with recent experimental data measured in a DC glow discharge, operating at pressures in the range 0.4 - 5 Torr (53.33 - 666.66 Pa). The experimental results show a lower vibrational temperature of the different modes of CO2 and a decreased dissociation fraction of CO2 when O2 is added to the plasma but an increase of the vibrational temperature of CO. On the one hand, the simulations suggest that the former effect is the result of the stronger V-T energy-transfer collisions with O atoms which leads to an increase of the relaxation of the CO2 vibrational modes; On the other hand, the back reactions with O2 contribute to the lower CO2 dissociation fraction with increased O2 content in the mixture.Comment: 34 pages 15 figure

Electron impact dissociation of CO<SUB>2</SUB>

International audienceSeveral CO&lt;SUB&gt;2&lt;/SUB&gt; electron impact dissociation cross sections are available in the literature, different in magnitude and threshold, hindering the understanding of CO&lt;SUB&gt;2&lt;/SUB&gt; dissociation mechanisms under gas discharges. This work reports the experimental validation of the electron impact CO&lt;SUB&gt;2&lt;/SUB&gt; dissociation cross section using two complementary methods: through the comparison of the measured rate coefficients with those derived from cross sections available in literature; and through the comparison of the experimental time evolution of the dissociation fraction with the simulations of a 0D model. A careful experimental approach was designed to avoid any influence from other dissociation mechanisms or chemical reactions. The experimental results match remarkably well the theoretical predictions from Polak and Slovetsky and establish the validity of the dissociation rate coefficients derived from their cross section. This validation supports the use of Polak and Slovetsky's cross section in any theoretical or modelling approach involving CO&lt;SUB&gt;2&lt;/SUB&gt; molecules under electrical discharges

A reaction mechanism for vibrationally-cold low-pressure CO<SUB>2</SUB> plasmas

International audienceThe use of plasmas for CO2 utilization has been under investigation in recent years following a wave of environmental awareness. In this work, previously published experimental results on vibrationally cold CO2 plasmas are modelled to define a reaction mechanism, i.e. a set of reactions and rate coefficients validated against benchmark experiments. The model couples self-consistently the electron and heavy particle kinetics. In turn, the simulated results are validated against measurements taken in CO2 DC glow discharges in a relatively large range of experimental conditions: at pressures from 0.4 to 5 Torr, reduced electric fields ranging from 50 to 100 Td and gas flowing from 2 to 8 sccm. The model predicts the measured values of product formation (CO and O) as well as discharge power and electric field. After validation, a thorough analysis of the model's results is presented, including: electron properties, species densities, power distribution into different excitation channels and main creation and destruction mechanisms of the main species. It is shown that, although vibrational populations are low, they have a significant effect on the electron properties and thus on the electric field and conversion. Moreover, the shape of the EEDF is significantly dependent on the dissociation degree. The role of electronically excited states on CO2 dissociation is also analyzed, showing that the first electronic excited state of CO can have a beneficial or detrimental effect in further producing CO and O in the discharge

Oxygen atom kinetics in CO₂ plasmas ignited in a DC glow discharge

International audienceOxygen atom densities were measured in situ in a CO2 glow discharge, at pressures between 0.2 and 5 Torr (26.7?666.6 Pa). Two measurement techniques were compared, namely optical emission actinometry (using Ar as the actinometer) and high-resolution two-photon absorption laser induced fluorescence normalised to Xe, and were found to give consistent results. The variation of the atomic oxygen density with gas pressure shows two different regimes with a transition around 1 Torr. Measurements of the O atom loss frequency under plasma exposure showed that this behaviour is caused by a change in the O atom loss mechanisms, which are dominated by surface processes in our experimental conditions. The corresponding recombination probabilities on Pyrex ? O are found to vary with the gas temperature near the wall for a constant surface temperature, similarly to what has recently been obtained in pure O2. However, the measured values are more than two times lower than ? O obtained in a O2 plasma in similar conditions. The O atom densities are also compared to the dissociation fraction of CO2 determined by infra-red absorption. The obtained CO and O densities show different behaviour as a function of the energy input. The simultaneous measurement of gas temperature, electric field, O, CO and CO2 densities and O atoms loss frequency in the same conditions provides an ideal set of constraints for validating CO2 plasma kinetic models