Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters br

Energetic materials undergo hundreds of chemical reactions during exothermic runaway, generally beginning with the breaking of the weakest chemical bond, the trigger linkage. Herein we report the syntheses of a series of pentaerythritol tetranitrate (PETN) derivatives in which the energetic nitrate ester groups are systematically substituted by hydroxyl groups. Because all the PETN derivatives have the simulations show very similar Arrhenius kinetics for the first reactions. However, handling sensitivity testing conducted using drop weight impact indicates that sensitivity decreases precipitously as nitrate esters are replaced by hydroxyl groups. These experimental results are supported by QMD simulations that show systematic decreases in the final temperatures of the products and the energy release as the nitrate ester functional groups are removed. To better interpret these results, we derive a simple model based only on the specific enthalpy of explosion and the kinetics of trigger linkage rupture that accounts qualitatively for the decrease in sensitivity as nitrate ester groups are removed.

Automated summary

This study reports the synthesis of a series of pentaerythritol tetranitrate (PETN) derivatives in which the energetic nitrate ester groups are systematically replaced by hydroxyl groups. Simulations and experimental testing show that the sensitivity of these derivatives decreases as nitrate ester groups are removed.