Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity.

Pressure dependent product formation in the photochemically initiated allyl + allyl reaction.

Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn's largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions.

Rate coefficients for cycloalkyl + O reactions and product branching in the decomposition of chemically activated cycloalkoxy radicals: an experimental and theoretical study.

The kinetics of cycloalkyl + O reactions were studied with respect to their rate coefficients and the product branching ratios from the decomposition of the chemically activated cycloalkoxy radicals. Rate coefficients for the reactions of cyclohexyl (c-C(6)H(11)), cycloheptyl (c-C(7)H(13)) and cyclooctyl (c-C(8)H(15)) radicals with oxygen atoms were determined with an experimental setup consisting of a discharge flow reactor with molecular beam sampling and REMPI/TOF-MS detection. The following rate coefficients were obtained (units: cm(3)/mol(-1) s(-1)): k(c-C(6)H(11) + O) = (1.

Formation and decomposition of chemically activated cyclopentoxy radicals from the c-C5H9 + O reaction.

The formation and the decomposition of chemically activated cyclopentoxy radicals from the c-C5H9 + O reaction have been studied in the gas phase at room temperature. Two different experimental arrangements have been used. Arrangement A consisted of a laser-flash photolysis set up combined with quantitative Fourier transform infrared spectroscopy and allowed the determination of the stable products at 4 mbar.