Journal of Physical Chemistry p. 3118 - 3126 (1985)
Update date:2022-08-11
Topics:
Shackelford, S. A.
Coolidge, M. B.
Goshgarian, B. B.
Loving, B. A.
Rogers, R. N.
et al.
The deuterium isotope effect was applied to condensed-phase thermodinamical reactions of HMX and HMX-d8 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 thermodinamical 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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