Abstract
The effect of solvation on the rate constants of hydroperoxyl radical addition to the double bonds of 1,1-substituted ethylene vinyl compounds was studied in the medium of different polarity solvents. The values of rate constants of this process were determined in a series of experiments on the co-oxidation of diphenylethylene (was used as the source of hydroperoxyl radicals) with the studied vinyl compounds at 323 K using the method of microvolumetry in combination with ESR spectroscopy and computer kinetic modeling. The observed linear relationship between the values of rate constant logarithms and the dielectric permittivity of reaction medium in coordinates of the Kirkwood–Onsager equation allows for the conclusion that the effect of nonspecific solvation due to the electrostatic forces does take place in the studied systems.
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