Kinetics of 1- and 2-methylallyl + O reaction, investigated by photoionisation using synchrotron radiation.

The reaction kinetics of the isomers of the methylallyl radical with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring. The radicals were generated by direct photodissociation of bromides or iodides at 213 nm. Experiments were conducted at room temperature and low pressures between 1 and 3 mbar using He as the buffer gas.

The Reaction NCN + H: Quantum Chemical Calculations, Role of NCN Chemistry, and NCN Absorption Cross Section.

The NCN radical plays a key role for modeling prompt-NO formation in hydrocarbon flames. Recently, in a combined shock tube and flame modeling study, the so far neglected reaction NCN + H and the related chemistry of the main product HNCN turned out to be significant for NO modeling under fuel-rich conditions. In this study, the reaction has been thoroughly revisited by detailed quantum chemical rate constant calculations both for the singlet NCN and triplet NCN pathways.

Single-tone mid-infrared frequency modulation spectroscopy for sensitive detection of transient species.

A single-tone mid-infrared frequency modulation (MIR-FM) spectrometer consisting of a cw-OPO-based laser system, a 500 MHz LiTaO electro-optical modulator (EOM), and a high-bandwidth GaAs mid-infrared detector has been developed. In order to assess the instrument's sensitivity and time resolution, FM spectra of selected CH transitions around 3070 cm were measured and the reaction Cl + CH following the 193 nm excimer laser photolysis of oxalyl chloride was investigated by recording concentration-time profiles of HCl at 2925.90 cm in a low-pressure slow-flow reactor.

The rate constant of the reaction NCN + H2 and its role in NCN and NO modeling in low pressure CH4/O2/N2-flames.

Bimolecular reactions of the NCN radical play a key role in modeling prompt-NO formation in hydrocarbon flames. The rate constant of the so-far neglected reaction NCN + H2 has been experimentally determined behind shock waves under pseudo-first order conditions with H2 as the excess component. NCN3 thermal decomposition has been used as a quantitative high temperature source of NCN radicals, which have been sensitively detected by difference UV laser absorption spectroscopy at [small nu, Greek, tilde] = 30383.

Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O2 and OCHCHO + HO2.

A detailed mechanism for the thermal decomposition and oxidation of the flame intermediate glyoxal (OCHCHO) has been assembled from available theoretical and experimental literature data. The modeling capabilities of this extensive mechanism have been tested by simulating experimental HCO profiles measured at intermediate and high temperatures in previous glyoxal photolysis and pyrolysis studies. Additionally, new experiments on glyoxal pyrolysis and oxidation have been performed with glyoxal and glyoxal/oxygen mixtures in Ar behind shock waves at temperatures of 1285-1760 K at two different total density ranges.

Direct measurements of the total rate constant of the reaction NCN + H and implications for the product branching ratio and the enthalpy of formation of NCN.

The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K < T < 2425 K behind shock waves. NCN radicals and H atoms were generated by the thermal decomposition of NCN3 and C2H5I, respectively. NCN concentration-time profiles were measured by sensitive narrow-line-width laser absorption at a wavelength of λ = 329.

Direct measurements of the high temperature rate constants of the reactions NCN + O, NCN + NCN, and NCN + M.

The rate constant of the reaction NCN + O has been directly measured for the first time. According to the revised Fenimore mechanism, which is initiated by the NCN forming reaction CH + N(2)→ NCN + H, this reaction plays a key role for prompt NO(x) formation in flames. NCN radicals and O atoms have been quantitatively generated by the pyrolysis of NCN(3) and N(2)O, respectively.