Variation in the headspace of bulk hexamethylene triperoxide diamine (HMTD) with time, environment, and formulation

- Hexamethylene triperoxide diamine (HMTD) is difficult to detect in the vapor phase.
- At ambient conditions, HMTD degrades producing volatile products.
- The decomposition of HMTD was monitored over 32 weeks across a number of variables.
- Potential key components from HMTD decomposition were identified.
- Results showed that synthesis method had the greatest effect on HMTD decomposition.

Hexamethylene triperoxide diamine (HMTD) is a homemade peroxide explosive that has become of concern to homeland security due to the ease of synthesis and commercial availability of the materials required for its synthesis. Detection is a challenge because of its exceedingly low vapor pressure and high thermal lability. Though molecular HMTD vapor is essentially undetectable under most circumstances, HTMD is known to degrade under ambient conditions, producing volatile products that could aid in detection. This work studies the evolution of these volatile organic compounds over time and across a number of variables including synthesis method, precursors, storage time, and storage environment. The composition and quantity of these volatiles were compared across these variables. Analysis of the headspace of bulk HMTD was carried out using solid phase microextraction (SPME) with gas chromatography/mass spectrometry (GC/MS). Decomposition was also monitored by gravimetric analysis. Results herein reveal that formic acid is the most abundant decomposition product while formaldehyde is the most commonly detected across all variables. Synthesis method carried the greatest overall effect on decomposition rate and vapor profile composition.

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