title: Factors affecting the intramolecular decomposition of hexamethylene triperoxide diamine and implications for detection.
abstract: Hexamethylene triperoxide diamine (HMTD) is an easily synthesized and highly sensitive organic peroxide frequently used as a primary explosive. The vapor pressure of HMTD is very low, impeding vapor detection, especially when compared to other peroxide explosives, such as triacetone triperoxide (TATP) or diacetone diperoxide (DADP). Despite this fact, HMTD has a perceptible odor that could be utilized in the indirect detection of HMTD vapor. Headspace measurements above solid HMTD samples confirm that HMTD readily decomposes under ambient conditions to form highly volatile products that include formic acid, ammonia, trimethylamine and formamides. The presence and quantity of these compounds are affected by storage condition, time, and synthetic method, with synthetic method having the most significant effect on the content of the headspace. A kinetic study of HMTD decomposition in solution indicated a correlation between degradation rate and the presence of decomposition species identified in the headspace, and provided further insight into the mechanism of decomposition. The study provided evidence for a proton assisted decomposition reaction with water, as well as an intramolecular decomposition process facilitated by the presence of water.
authors.affiliation: Former National Research Council post-doctoral fellow at U.S. Naval Research Laboratory, 4555 Overlook Ave. SW, Washington, DC 20375, United States. Electronic address: frank.steinkamp.ctr@navy.mil.
authors.forename: Frank Lucus
authors.initials: FL
authors.lastname: Steinkamp
authors.affiliation: U.S. Naval Research Laboratory, 4555 Overlook Ave. SW, Washington, DC 20375, United States. Electronic address: lauryn.degreeff@nrl.navy.mil.
authors.forename: Lauryn E
authors.initials: LE
authors.lastname: DeGreeff
authors.affiliation: U.S. Naval Research Laboratory, 4555 Overlook Ave. SW, Washington, DC 20375, United States. Electronic address: greg.collins@nrl.navy.mil.
authors.forename: Greg E
authors.initials: GE
authors.lastname: Collins
authors.affiliation: U.S. Naval Research Laboratory, 4555 Overlook Ave. SW, Washington, DC 20375, United States. Electronic address: susan.rosepehrsson@nrl.navy.mil.
authors.forename: Susan L
authors.initials: SL
authors.lastname: Rose-Pehrsson
mesh_terms: D000641:Ammonia / Q000032:analysis; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000032:analysis* / Q000737:chemistry*; D004356:Drug Storage; D053834:Explosive Agents / Q000032:analysis* / Q000737:chemistry*; D005559:Formamides / Q000032:analysis; D005561:Formates / Q000032:analysis; D007700:Kinetics; D008744:Methylamines / Q000032:analysis; D011522:Protons; D013997:Time Factors; D055548:Vapor Pressure; D014835:Volatilization; D014867:Water / Q000737:chemistry*
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D053834:Explosive Agents; D005559:Formamides; D005561:Formates; D008744:Methylamines; D011522:Protons; D014867:Water; C030544:formic acid; C058103:hexamethylenetriperoxidediamine; D000641:Ammonia; C023336:trimethylamine
keywords: Decomposition pathway; Explosives detection; Hexamethylene triperoxide diamine; Peroxide explosives