Chemical reaction and equilibration mechanisms in detonation waves

Experimental and theoretical evidence for the nonequilibrium Zeldovich-von Neumann-Doring (NEZND) theory of self-sustaining detonation is presented. High density, high temperature transition state theory is used to calculate unimolecular reaction rate constants for the initial decomposition of gaseous norbornene, liquid nitromethane, and solid, single crystal pentaerythritol tetranitrate as functions of shock temperature. The calculated rate constants are compared to those derived from experimental induction time measurements at various shock and detonation states. Uncertainties in the calculated shock and von Neumann spike temperatures are the main drawbacks to calculating these reaction rates. Nanosecond measurements of the shock temperatures of unreacted explosives are necessary to reduce these uncertainties