Surface deactivation of vibrationally excited N2 studied using infrared titration combined with quantum cascade laser absorption spectroscopy

Abstract

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 .