EXPLOSIVE DECOMPOSITION OF CHLORINE DIOXIDE

The explosive decomposition of chlorine dioxide has been studied over the pressure and temperature ranges 0.2-40 torr and 54-134°. The reaction is characterized by long induction periods which were measured as a function of temperature, pressure, vessel size, irradiation, added gases, and other chlorine oxides. The explosion is of the degenerate chain-branching type, and the intermediate responsible for the delayed reaction has been identified as Cl2O3. The experimental results together with reliable enthalpy data and other studies on chlorine oxides allow a mechanism to be written. It is shown that the observed characteristics of the explosive decomposition of ClO2 are fully consistent with the reaction-kinetic equations developed on the basis of the mechanism. © Copyright, 1968, by the American Chemical Society.