The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews.
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