Reversible chain reaction between N,N′-diphenyl-1,4-benzoquinonediimine and 2,5-dichlorohydroquinone: Kinetics, mechanism, and the rate constants of elementary steps

The kinetics of the reversible chain reaction between N,N'-diphenyl-1,4-benzoquinonediimine and 2,5-dichlorohydroquinone was studied in chlorobenzene at 298 and 343 K. Experiments in the presence of an initiator proved that the reaction proceeds via a chain mechanism with a chain length of similar to 10(4) to 10(5) units, depending on the reactant and initiator concentrations and temperature. The reaction rate first increases and then decreases with increasing concentrations of the reaction products (N,N'-diphenyl-1,4-phenylenediamine and 2,5-dichloroquinone) due to the pronounced reversibility of the chain termination and propagation steps involving the reaction products. The reaction orders with respect to the components were determined. The rate constants and activation energies of most of the elementary steps of the forward and backward chain reactions were determined or reliably estimated. Induction periods were observed for the first time in the reversible chain reactions in the quinoneimine + hydroquinone systems. The induction periods are due to the long time required for the establishment of the steady-state radical concentrations in the system.