Using a GC headspace measurement technique, the vapor pressure of TATP was determined over the temperature range 12 to 60 8C. As a check on the experimental method, TNT vapor pressure was likewise computed. Values for TNT are in excellent agreement with previous published ones. For TATP the vapor pressure was found to be~7 Pa at ambient conditions. This value translates to a factor of 10 4 more molecules of TATP in air than TNT at room temperature. The dependence of TATP vapor pressure on temperature can be described by the equation log 10 P(Pa) ¼ 19.791 À 5708/T(K). Its heat of sublimation has been calculated as 109 kJ/mol. ] Figure 1. Chemical structure of TATP

The decompositions of urea nitrate (UN) and guanidine nitrate (GN) are determined with isothermal heating followed by quantification of both remaining nitrate and remaining base. Activation energies determined for UN were 158 and 131 kJ=mol with the preexponential factors being 1.39 Â 10 12 s À1 and 2.66 Â 10 9 s À1 for nitrate and urea, respectively. These pairs of Arrhenius constants predict decomposition rates less than a factor of two apart. For GN the activation energies were 199 and 191 kJ=mol with the preexponential factors being 1.94 Â 10 15 s À1 and 3.20 Â 10 14 s À1 for nitrate and guanidine, respectively. These pairs of Arrhenius constants predict identical decomposition rates. Literature values for ammonium nitrate decomposition indicate that it should decompose somewhat slower than UN and faster than GN. DSC also indicates this ordering but suggested that UN is substantially less stable than was observed in the isothermal experiments. Decomposition products, both gaseous and condensed, are reported for UN and GN, and decomposition routes are suggested. Experimental results indicate that NO þ 2 is generated during the decomposition

One way being considered to destroy trinitrotoluene (TNT) land or surf mines is to exploit its reactivity using darts containing chemicals, which, upon contact with TNT, cause instantaneous decomposition, but not detonation. To determine the best candidates to fill the darts, liquids, specifically amines, which react in a hypergolic fashion with TNT were examined for both the rate of reaction and amount of energy released. Micro‐calorimetry was used to measure heat release while spectroscopy and conventional peak intensity monitoring by chromatography were used to examine the rate of reaction. Calorimetry measurements showed little variation between different amines reacting with TNT (about 110–130 kJ mol−1 TNT). TNT reaction with hydride actually produced more heat than with amines. Further, dinitrotoluene (DNT), which generates substantial heat, did not undergo a hypergolic reaction with amines suggesting that heat release is not the controlling factor for the hypergolic reactions. Rate constants, determined for the loss of TNT in dilute acetonitrile solution, clearly showed distinctions among the amines. The more primary amine functionalities in the amine compound, the faster it destroyed TNT. Hydrides or amine mixtures spiked with hydride decomposed substantially faster than the amines alone. However, a direct correlation between reaction rate and time‐to‐ignition was not observed.

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