The kinetics of hydrogen abstraction by difluoroamino-radicals, from acetaldehyde, n- and iso-valeraldehyde, and their acyl radical decompositions

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Abstract
The kinetics of the aldehydic hydrogen abstraction by difluoroamino-radicals have been studied for acetaldehyde n-valeraldehyde, and isovaleraldehyde. The following Arrhenius parameters were found: [graphic omitted]. No acetyl radical decomposition was observed. The kinetics and pressure-dependence of the decompositions of the n- and iso-valeryl radicals have been studied. The limiting high-pressure rate constants for these acyl radical decompositions have been obtained by extrapolation: [graphic omitted] These parameters are based on a value of 1014 cm3mol–1s–1 for the combination of acyl and difluoroamino-radicals. The Arrhenius parameters for the acyl radical attack on difluoroimide and for n- and iso-valeryl radical formation reactions have been estimated from thermodynamic data.