Hypergolic Reactions of TNT

Abstract

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.

Plasticization of a polymer layer harnessed to a silicon microcantilever as a highly sensitive and selective means to detect nitroaromatic derivatives

“…In the cases of TNT and 1,3-DNB one could clearly observe the formation of the characteristic color of the Meisenheimer complex formed between the nitro aromatic system and the APS nucleophile, Figure 1. 8 As can be clearly appreciated from Figure 6, analytes that are unable of forming a Meisenheimer complex vary in their bending response from noninteracting (toluene) through moderately interacting (water and benzaldehyde) to strongly interacting (ethanol) analytes. All these analytes yield reversible and negligible to positive bending curves with respect to the reference.…”

“…For example, Engel et al demonstrated binding TNT using a layer of nucleophiles residing atop a nanotube, Figure 1. 8 The potential of such approach was demonstrated in the detection of TNT in water using amino modified silicon nanowire FET devices, showing subfemtomolar detection limits. 6 While this approach often makes the sensing element suitable only for single use, as it destroyed upon exposure to the analyte, it renders the sensing element an integrator, overcoming the loss of analyte molecules through the dissociative pathways of dynamic equilibrium.…”

Determination of gas phase triacetone triperoxide with aspiration ion mobility spectrometry and gas chromatography–mass spectrometry

“…At room temperature, synthesized TATP exists as a solid crystalline compound but it sublimes easily [1]. Oxley et al determined that the vapor pressure of TATP at 25 • C is ∼7 Pa which is much higher than the vapor pressure of most of the nitrogen-based explosives such as trinitrotoluene (∼5 × 10 −4 Pa) [2]. Dubnikova et al have theoretically calculated that the main decomposition product of TATP is acetone [3] which was also the main degradation product when Oxley et al studied the reaction pathways of thermolysis of TATP with slow heating [4].…”

“…Oxley et al determined that the vapor pressure of TATP at 25 • C is ∼7 Pa which is much higher than the vapor pressure of most of the nitrogen-based explosives such as trinitrotoluene (∼5 × 10 −4 Pa) [2]. Dubnikova et al have theoretically calculated that the main decomposition product of TATP is acetone [3] which was also the main degradation product when Oxley et al studied the reaction pathways of thermolysis of TATP with slow heating [4]. Hiyoshi and Nakamura have shown that the degradation of TATP takes place mainly in the gas phase and the degradation with rapid heating produces mainly carbon dioxide and water [5].…”

A Colorimetric Sensor Array for Detection of Triacetone Triperoxide Vapor

“…An extrapolated limit of detection based on 3 × S/N of the three largest color changes was 2 ppb after 10 min of exposure, i.e., <0.02% of its saturated vapor concentration at room temperature (∼69 ppm at 25°C). 16 As shown in SI Figure S5, one may also use hierarchical cluster analysis (HCA) to analyze the color change patterns of the array. Dendrograms are based on the clustering of the array response data in the 48 dimensional ∆RGB color space (i.e., 16 changes in red, green, and blue values).…”