Date of Award
Doctor of Philosophy in Chemistry
Jimmie C. Oxley
Factors Influencing Safety of Unconventional Explosives
This dissertation details three studies regarding safety aspects for the formation, decomposition and use of unconventional explosives. The first study is a mechanistic study for the formation and decomposition of triacetone triperoxide (TATP). Using GC-MS, LC-MS, and NMR, the mechanism for the formation of TATP was elucidated detailing how experimental conditions affect the product composition. The presence of water had a significant impact on the distribution of the products TATP and diacetone diperoxide (DADP), a common contaminant in the synthesis. Water also had an impact on the decomposition of TATP resulting in a slower and more complete decomposition. The second study pertains to copper acetylide, a primary explosive sensitive towards initiation by impact, friction or spark. Copper acetylide is regarded as a safety risk in the petrochemical industry due to the presence of copper catalysts in refinery gas streams contaminated with acetylene. Analysis of the products formed after catalyst samples were exposed to acetylene gas suggested that acetylene readily reacts with many copper catalysts, likely via a copper acetylide intermediate, to form an amorphous phase of carbon. It was found that proprietary catalyst compositions inhibit the reaction significantly, reducing the potential risk of acetylide formation and subsequent accidental explosion. The third study is aimed at mitigating potential failure of direct borohydride fuel cells. The incompatibility of sodium borohydride and hydrogen peroxide poses a serious safety risk for electrochemical cells using these substances. The hydrolysis kinetics of sodium borohydride in dilute hydrogen peroxide solutions was studied to obtain fundamental information regarding the reaction. Hydrolysis by water is slow and yields hydrogen gas while hydrolysis by hydrogen peroxide is fast and yields a potentially combustible mixture of hydrogen and oxygen gases.
Steinkamp, F. Lucus, "Factors Influence the Safety of Unconventional Explosives" (2013). Open Access Dissertations. Paper 59.