New Insights into the Actual H-Abstraction Activities of Important Oxygen and Nitrogen Free Radicals: Thermodynamics and Kinetics in Acetonitrile.

The H-abstraction activity of a free radical is a research hotspot and has been extensively studied. In this article, the second-order rate constants of 21 HAT reactions in acetonitrile at 298 K were chosen from several published literature. A kinetic study on the H-abstraction reaction from TEMPOH by a DPPH radical was carried out. This reaction was researched as an insertion point. By combining this reaction with the 21 HAT reactions in this paper, the thermokinetic parameters of 28 free radicals X and their corresponding antioxidants XH were obtained by the cross-HAT reaction method. The scales of the H-abstraction activities of these 28 oxygen and nitrogen free radicals were determined by using the thermokinetic parameters Δ (X). Applications of the thermokinetic parameter Δ (X) in assessing the actual H-abstraction activity of a free radical quantitatively and selecting a suitable free radical in scientific research and chemical production were discussed. Predictions of the rate constants by using thermokinetic parameters of reactants were researched, and the reliabilities of the predicted activation free energies of XH/Y reactions were also examined.