Plasma activation of N₂, CH₄ and CO₂: an assessment of the vibrational non-equilibrium time window

Vibrational excitation potentially enhances the energy efficiency of plasma dissociation of stable molecules and may open new routes for energy storage and process electrification. Electron, vibrational and rotational temperatures were measured by in situ Thomson and Raman scattering in order to assess the opportunities and limitations of the essential vibration-translation non-equilibria in N₂, CO₂ and CH₄ plasma. Electron temperatures of 1.1–2.8 eV were measured in N₂ and CH₄. These are used to confirm predominant energy transfer to vibrations after an initial phase of significant electronic excitation and ionization. The vibrational temperatures initially exceed rotational temperatures by almost 8000 K in N₂, by 900 K in CO₂, and by 300 K in CH₄. Equilibration is observed at the 0.1 ms timescale. Based on the vibrational temperatures, the vibrational loss rates for different channels are estimated. In N₂, vibrational quenching via N atoms is identified as the dominant equilibration mechanism. Atomic nitrogen population reaches a mole fraction of more than 1%, as inferred from the afterglow emission decay, and explains a gas heating rate of 25 K μs⁻¹. CH₄ equilibration at 1200 K is predominantly caused by vibrational-translational relaxation in CH₄–CH₄ collisions. As for CO2, vibrational-translational relaxation via parent molecules is responsible for a large fraction of the observed heating, whereas product-mediated VT relaxation is not significantly contributing. It is suggested that electronic excitation, followed by dissociation or quenching contributes to the remaining heat generation. In conclusion, the time window to profit from vibrational excitation under the present conditions is limiting practical application.