In this work, experimental vapor pressures of the commonly used energetic plasticizers methyl-NENA, ethyl-NENA, and butyl-NENA were measured for the first time with a transpiration method. The p−T fitting equations and the corresponding molar enthalpies of phase transitions at 298.15 K are reported: the molar enthalpies of sublimation and vaporization of methyl-NENA were measured to be 104.5 ± 0.9 and 82.0 ± 1.1 kJ•mol −1 , respectively. The consistency of these results was examined by the differential scanning calorimetry experiment, which yielded the molar enthalpy of fusion at 298.15 K to be 23.8 ± 0.3 kJ•mol −1 . The molar enthalpies of vaporization at 298.15 K for ethyl-and butyl-NENAs were derived to be 79.8 ± 0.4 and 85.9 ± 0.5 kJ•mol −1 , respectively. The p−T fitting equations were extrapolated at 298.15 K, and the corresponding results were reported in this work.

Ethylene glycol dinitrate (EGDN), diethylene glycol dinitrate (DEGDN), and triethylene glycol dinitrate (TEGDN) are used as plasticizers in propellant mixtures and have been known for more than 100 years. Despite the industrial application and the long history of these compounds, the crystal structures of all three compounds, which are liquids at room temperature, have not been determined. Therefore, in this work, the crystal structures were examined by low-temperature X-ray diffraction, and thus, the bonding properties and crystal packing in the solid state could be compared and discussed for the first time. Furthermore, the compounds were characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The thermal properties were investigated by DTA (differential thermal analysis) measurements, and the experimental vapor pressures were measured with the chromatography-assisted transpiration method. The densities at room temperature (for the liquids) were measured by gas pycnometry, and the energetic properties were calculated using the EXPLO5 code. Moreover, a more in-depth analysis of the different sensitivities through discussion of the Hirshfeld surfaces, created based on their crystal structures, was performed to compare their sensitivities in the solid state.

The experimental vapor pressures of thermally modified energetic materials 2-(fluoromethyl)-1H-tetrazol-5-amine and its isomer 1-(fluoromethyl)-1H-tetrazol-5-amine were measured for the first time with the chromatography-assisted transpiration method and compared with the unsubstituted 1H-tetrazol-5-amine as well as with the methylated analogues. The resulting p–T fitting equations based on the Clausius–Clapeyron equation and the enthalpy of sublimation at the reference temperature of 298.15 K were determined for the five compounds under study, and the results are as follows: (93.8 ± 1.0) kJ·mol–1 for 2-(fluoromethyl)-1H-tetrazol-5-amine, (88.7 ± 1.3) kJ·mol–1 for 2-methyl-1H-tetrazol-5-amine, (112.6 ± 2.6) kJ·mol–1 for 1-(fluoromethyl)-1H-tetrazol-5-amine, (118.1 ± 2.0) kJ·mol–1 for 1-methyl-1H-tetrazol-5-amine, and (116.6 ± 2.2) kJ·mol–1 for 1H-tetrazol-5-amine. The p–T fitting equations were used to extrapolate to 298.15 K, and the corresponding vapor pressure results were reported in this work.

5‐Methyl‐2,4,6‐trinitrobenzene‐1,3‐diol (trinitro‐orcinol, H2TNO) as a close structural relative to the well‐known energetic materials trinitroresorcinol (styphnic acid) and trinitrotoluene (TNT) is prepared in high purity and analyzed concerning its vapor pressure using the transpiration method. Several energetic coordination compounds (ECCs) of its respective anion were produced and compared with structurally close styphnate complexes to give an insight into physiochemical trends of the ECC. The synthesized compounds were further analyzed by elemental analysis, IR spectroscopy, differential thermal analysis and low temperature X‐ray diffraction analysis. To classify the reported compounds among the energetic materials, they were tested for their sensitivities towards mechanical stimuli such as impact, friction and electrostatic discharge as well as their behavior towards flame.