On the rate and activation parameters for the primary decomposition of a quaternary ammonium persulfate in moderately polar organic solvents

The activation energy for the primary decomposition of ionpaired trioctylmethylammonium persulfate in moderately polar organic solvents was found to be about one half the value for the persulfate ion decomposition in aqueous alkaline media. However, its effect on the primary decompostion rate of the former is largely offset by the lowered entropy of activation, which adopts a negative value. The results indicate that the activated state is more ionic than the ground state. A tentative structure of the activated state which involves an intra‐ionic triple ion is proposed to account for the observed results.