Analysis of the reactivities of organic compounds in hydrogen atom abstraction from their C-H bonds by the sulfate radical anion SO 4 ·−

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An experimental rate constant data array (>50 values) for the reactions of the sulfate radical anion with the C-H bonds of various organic compounds is analyzed by Denisov’s intersecting parabolas method. The data array is divided into the following four groups according to the type of the C-H bond attacked and the bre value: compounds with primary C-H bonds (bre = 13.14 ± 0.17), compounds with secondary C-H bonds remote from the polar groups (bre = 12.64 ± 0.34), compounds with secondary α-C-H bonds (bre = 13.28 ± 0.24), and compounds with tertiary C-H bonds. It is demonstrated by DFT calculations that the rate constant of the reaction SO4·− + RH is determined by nonspecific solvation and by the ion-dipole interaction in the transition state of the reaction.