Thermokinetic Combustion Oscillations as an Alternative to Thermal Explosion

Abstract A simple, exothermic reaction A → B + heat Q, with k = A exp(−E/RT) in a closed vessel may be either explosive or quiescent. Both courses have only one stationary state: that of final, chemical equilibrium. When the reaction occurs in two stages (again in a closed system): P → 0 A → 1 B , the only stationary state is again the final one but the evolution can be very different. Reaction may generate transient oscillations of considerable strength in both reactant temperature and in the concentration of species A . Neither P nor B oscillates but B rises in a succession of steps. This course of events is extremely general and may be analyzed and predicted in detail. A related experimental realization allows us to predict oscillatory behavior accompanying the admission of an exothermic reactant to a reaction vessel and to test the predictions with the gaseous reactant di- t -butyl peroxide.