The acceleratory effect of potassium perchlorate on the reactivity of the red lead-silicon system has been studied by employing DTA and DSC. Supporting investigations on pure potassium perchlorate and the binary system red lead-potassium perchlorate suggest that the complex decomposition kinetics of potassium perchlorate drastically influences the oxidation of silicon. Further, the ternary system also undergoes a transition from exothermic smooth decomposition to ignition at a certain critical mass, as noted in the red lead-silicon and iron(III) oxide system. The criticality should be a result of the rise in temperature expressed as a perturbation of the steady-state energy conservation conditions, as postulated by Gray.