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The wall de-excitation probability of vibrationally excited nitrogen molecules was determined using infrared (IR) titration with CO, CO2 and N2O. Gas mixtures of N2 with 0.05–0.5% of CO (CO2 or N2O) were excited by a pulsed dc discharge at p = 133 Pa in a cylindrical discharge tube. During the afterglow, the vibrational relaxation of titrating molecules was monitored in situ with quantum cascade laser absorption spectroscopy. The value of was deduced from measured vibrational relaxation times using a model of vibrational kinetics in N2. It was found that adsorption of IR tracers on the surface may increase the value of by a factor up to two, depending on the molecule and the surface material. It was demonstrated that N2O is the most inert and reliable tracer and it was used for the determination of on silica, Pyrex, TiO2, Al2O3 and anodized aluminum. Pretreatment of the silica surface by low-pressure plasma was found to have a strong effect on the vibrational de-excitation. Values of measured after O2, Ar and N2 plasma pretreatment of the same silica discharge tube were 5.7 × 10−4, 8.2 × 10−4 and 11 × 10−4, respectively. This study clearly demonstrates that the presence of adsorbed atoms and molecules on the surface may significantly alter the value of . [ABSTRACT FROM AUTHOR]

The objective of this study is to understand fundamental aspects of interactions of plasmas with catalytic surfaces. Based on this approach the reactivity of plasma treated and stimulated catalytic surfaces of TiO2 is studied by analysing the oxidation (i) of C2H2 to CO and CO2 and (ii) of CO to CO2. The inner surface of a Pyrex discharge tube is coated with TiO2 films impregnated with TiO2 nanoparticles, which provides a surface area of about 4m². In addition to the exposure of the TiO2 surface by low-pressure radio-frequency plasmas using O2, Ar or N2 (f = 13.56 MHz, p = 0.53 mbar, P = 17 W) the surfaces are stimulated by heating and UV radiation treatment. The temporal development of the concentrations of the precursor gases C2H2 or CO and of the reaction products is monitored using quantum cascade laser absorption spectroscopy, which provides multi-component detection in the mid-infrared spectral range. The C2H2 concentration was found to be nearly constant over time after a pre-treatment with Ar or N2 discharges using an initial gas mixture of 1% C2H2 in Ar. However, a strong decay of the concentration of C2H2 is observed for pure O2 plasma pre-treatment. In general, the decay is found to be nearly exponential with time constant in the order of about 10 min. The reactive adsorption of C2H2 molecules on the inner surface of the tube reactor showed a density of about 7.5 × 1012 C2H2 molecules cm-2. This behaviour demonstrates that the reaction (Oads +C2H2)TiO2 produces some adsorbed intermediates, which can be thermally or photo-catalytically oxidized to CO2. In contrast, when 1% CO in Ar is used as an initial gas mixture no adsorption processes on the TiO2 surface could be detected. An effective destruction of CO took part via photo-catalytic oxidation. [ABSTRACT FROM AUTHOR]

A new method for determination of the wall de-excitation probability of vibrationally excited N2 on different surfaces exposed to low-pressure plasmas has been developed. A short dc discharge pulse of only a few milliseconds was applied to a mixture containing 0.05–1% of CO2 in N2 at a pressure of 133 Pa. Due to a nearly resonant fast vibrational transfer between N2(v) and the asymmetric ν3 mode of CO2 the vibrational excitation of these titrating molecules is an image of the degree of vibrational excitation of N2. In the afterglow, the vibrational relaxation of CO2 was monitored in situ using quantum cascade laser absorption spectroscopy. The experimental results were interpreted in terms of a numerical model of non-equilibrium vibrational kinetics in CO2–N2 mixtures. Heterogeneous relaxation was the main quenching process of N2(v) under the conditions of this study, which allowed determination of the value of from the best agreement between the experiment and the model. The new method is suitable for determination in a single plasma pulse with the discharge tube surface pretreated by a low-pressure plasma. The relaxation probability of the first vibrational level of nitrogen γ1 = (1.1 ± 0.15) × 10−3 found for Pyrex and silica is in reasonable agreement with the literature data. Using the new technique the N2(v = 1) quenching probability was measured on TiO2 surface, γ1 = (9 ± 1) × 10−3. A linear enhancement of the N2(v) wall deactivation probability with an increase in the admixture of CO2 was observed for all studied materials. In order to explain this effect, a vibrational energy transfer mechanism between N2(v) and adsorbed CO2 is proposed. [ABSTRACT FROM AUTHOR]