a b s t r a c tHexamethylene 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.Published by Elsevier B.V.
This study was undertaken to address the need for an improved analytical method to detect and quantify hindered phenolic antioxidant additives in Navy mobility fuels that overcomes the limitations of currently available methods. It was demonstrated that hindered phenols in fuels can be accurately quantified using capillary gas chromatography−mass spectrometry with selected ion monitoring (GC−MS/SIM) of mass fragments unique to each analyte. Using this approach, three methods were developed for the analysis of antioxidants in fuels: (1) a single-column GC−MS/SIM method that, because of co-elution of fuel constituents, is only suitable for quantifying tri-tert-butylphenol, (2) a two-column heart-cutting method that overcomes the problem of co-eluting fuel components but requires modification of the instrument, and (3) a GC−MS/MS method that does not require modification of the instrument. The heart-cutting method was developed as a practical method for the routine determination of each of the five hindered phenolic antioxidants in any type of fuel, with a method quantitation limit (MQL) of 0.5 mg/L, with minimal interference from fuel. The GC−MS/MS method provides a lower MQL of 0.05 mg/L. Both methods offer a significant advantage over traditional high-performance liquid chromatography with electrochemical detection (HPLC− ECD) methods, which are more labor-intensive and not capable of separating each of the individual phenolic antioxidants.
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