HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) are well known high energy density energetic materials. In this talk, we present Density Functional Theory (DFT) investigation of possible mechanisms of alkaline hydrolysis of these compounds at the PCM(Pauling)/M06-2X/6-311++G(d,p) level. Calculations show that alkaline hydrolysis of both compounds is a highly exothermic multistep process involving initial deprotonation and nitrite elimination, cycle cleavage, further transformation of cycle-opened intermediate to the end products caused by a series of C-N bonds ruptures, hydroxide attachments, and proton transfers. The computationally predicted hydrolysis products of HMX and RDX were shown to correspond to experimentally observed species. Based on the computed reaction pathways for decomposition by alkaline hydrolysis, the kinetics of the entire processes were modeled. It was revealed that higher pH significantly increases the reaction rate for hydrolysis.

In silico alkaline hydrolysis reaction kinetics of HMX and RDX

253rd National Meeting (2017)

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