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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]

Quantum cascade lasers (QCLs) have attracted considerable interest as an alternative tuneable narrow bandwidth light source in the mid-infrared spectral range for chemical sensing. Pulsed QCL spectrometers are often used with short laser pulses and a bias current ramp similar to diode laser spectroscopy. Artefacts in the recorded spectra such as disturbed line shapes or underestimated absorption coefficients have been reported. A detailed time-resolved high-bandwidth analysis of individual pulses during a laser sweep has been performed. Quantitative results for CH absorption features around 1347 cm (7.42 μm) fell short of the expected values for reasonable operating conditions of the QCL. The origin of the artefacts using short pulses was identified to be partly of the same nature as in the case of long laser pulses. A complex combination with the tuning principle was found, leading to an apparently increased instrumental broadening (effective line width) and underestimated concentrations at low-pressure conditions. [ABSTRACT FROM AUTHOR]

Within the last decade mid-infrared absorption spectroscopy between 3 and 20 μm, known as infrared laser absorption spectroscopy (IRLAS) and based on tuneable semiconductor lasers, namely lead salt diode lasers, often called tuneable diode lasers (TDL), and quantum cascade lasers (QCL) has progressed considerably as a powerful diagnostic technique for in situ studies of the fundamental physics and chemistry of molecular plasmas. The increasing interest in processing plasmas containing hydrocarbons, fluorocarbons, organo-silicon and boron compounds has lead to further applications of IRLAS because most of these compounds and their decomposition products are infrared active. IRLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species, which is of particular importance for the investigation of reaction kinetics. Since plasmas with molecular feed gases are used in many applications such as thin film deposition, semiconductor processing, surface activation and cleaning, and materials and waste treatment, this has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. The recent development of QCLs offers an attractive new option for the monitoring and control of industrial plasma processes as well as for highly time-resolved studies on the kinetics of plasma processes. The aim of the present article is twofold: (i) to review recent achievements in our understanding of molecular phenomena in plasmas using TDLs and (ii) to report on selected new applications of QCLs in the mid-infrared. [ABSTRACT FROM AUTHOR]

The absorption spectra of the fundamental bands of the free radicals 10B16O and 11B16O in their ground 2Σ+ states have been measured in natural abundance and at Doppler limited resolution using diode laser spectroscopy. The band origins are found to be 1915.30674(14) and 1861.92409(13) cm−1, respectively. The rotational constants for the lower states are 1.877680(22) and 1.773421(10) cm−1, which are in excellent agreement with the microwave values for B0. Assuming a linear dependence of Bv on (v+1/2) the derived value of re is 1.204552(5) A˚. [Copyright &y& Elsevier]

Many P- and R-branch lines of the fundamental bands of the 12 C 14 N and 13 C 14 N radicals in their ground ( 2 Σ + ) electronic state have been measured at high resolution by diode laser absorption spectroscopy. The radicals were generated in a 2.45 GHz planar microwave plasma in methane with varying proportions of N 2 and H 2 . From a fit to the spectra the origins of the fundamental bands of the two isotopomers were determined to be 2042.421 04(84) cm -1 and 2000.084 70(30) cm -1 . The main product detected in the plasma by diode laser spectroscopy is HCN, with concentrations about three orders of magnitude higher than CN. [ABSTRACT FROM AUTHOR]

Infrared laser absorption spectroscopy (IRLAS) and laser-induced fluorescence spectroscopy (LIF) are applied in the present study for online in-situ characterization of volatiles products in the close vicinity of a single pyrolysing wood sphere. These advanced analytical techniques are combined with online measurements of temperature and mass evolutions in order to gain further insight into the complex processes occurring during slow pyrolysis of thermally thick wood particles. Three different heating rates (5, 10, 20 °C/min) and two wood types (beech, pine) were used. Time-resolved absolute concentrations of the main permanent gases CO 2 , CO, CH 4 and H 2 O were measured applying IRLAS. From the LIF measurements the qualitative temporal release of polycyclic aromatic hydrocarbons (PAHs) could be deduced. Different behaviors regarding the release of volatiles, temperature evolution and conversion rates were observed for both wood species, which could not be ascribed only to the different content of cellulose, hemicellulose and lignin. According to the measured volatiles evolution an enhancement of heterogeneous catalytic tar cracking seemed to be present with higher heating rates for both wood types. However, the evolution of exothermicity and PAH release differed for both wood types indicating different reaction pathways. An analysis of possible reaction pathways including secondary reactions is performed taking into account all experimental findings about the in-situ composition of the volatiles and the evolution of the PAHs as well as the exothermicity. The differences in the pyrolytic behavior of both species can be related to both the chemical and physical properties of the raw materials. [ABSTRACT FROM AUTHOR]