Thermodynamic Properties and Detonation Characterization of 3,3-Dinitroazetidinium Hydrochloride

Abstract

The thermal behavior of 3,3-dinitroazetidinium hydrochloride (DNAZ•HCl) was studied at a nonisothermal condition by differential scanning calorimetric and thermogravimetric/differential thermogravimetric methods. The results show that there is only one intense exothermic decomposition process. Its kinetic parameters of the intense exothermic decomposition process are obtained from analysis of the DSC curves. The apparent activation energy (E a ), pre-exponential factor (A), and the mechanism function ( f(α)) are 155.72 kJ•mol −1 , 10 15.84 s −1 and 3α 2/3 , respectively. The specific heat capacity (C p ) of DNAZ•HCl was determined with a continuous C p mode of microcalorimeter. The specific molar heat capacity (C p,m ) of DNAZ•HCl was 205.10 J•mol −1 •K −1 at 298.15 K. The selfaccelerating decomposition temperature (T SADT ), thermal ignition temperature (T TIT ), and critical temperatures of thermal explosion (T b ) were obtained to evaluate the thermal stability and safety of DNAZ•HCl. The detonation velocity (D) and detonation pressure (P) of DNAZ•HCl were estimated using the nitrogen equivalent equation according to the experimental density. The stability, safety, and detonation performance of DNAZ•HCl were compared with that of 3,3-dinitroazetidinium 3,5dinitrosalicylate (DNAZ•HClO 4 ).

Thermodynamic properties of 4-amino-3-furazanecarboxamidoxime

“…Six integral methods (MacCallum-Tanner, Šatava-Še sták, Agrawal, General integral, Universal integral and FlynnWall-Ozawa) and one differential method (Kissinger) were employed [14][15][16][17][18][19][20]. The values of E a were obtained by Flynn-Wal l-Ozawa's method from the isoconversional DSC curves at the heating rates of (2.5, 5.0, 10.0 and 15.0) K Á min À1 , and the E a -a relation is shown in figure 3.…”

“…The thermal ignition temperature (T be or T TIT ) was obtained by substituting E eO and T e0 into equation (4) [14][15][16][17][18][19][20][21][22], and the critical temperatures of thermal explosion (T bp or T b ) was obtained by substituting E pO and T p0 into equation (4). The values (T TIT and T b ) are (548.89 ± 0.32) K and (564.97 ± 0.33) K, respectively.…”

Aromatic Nucleophilic Substitution of FOX‐7: Synthesis and Properties of 1‐Amino‐1‐Picrylamino‐2,2‐Dinitroethylene (APDE) and Its Potassium Salt [K(APDE)]

“…Here, we propose four reasons why the stable picryl group does not improve the thermal stability of molecular structure as we initially expected: (1) The above-mentioned strong electrostatic repulsion forces in the molecular structure of APDE can make the molecule relatively unstable, which contributes to the thermal decomposition; (2) APDE does not have a symmetrical molecular structure like its parent molecules FOX-7 and picryl chloride, which is not conducive to the stability of molecular structure; (3) Compared with the amino-NÀ C bond lengths in FOX-7 (1.319 and 1.325 Å), [2] the corresponding longer N(4)-C(7) bond length (1.364 Å) in APDE makes the CÀ N bond in APDE weaker than in FOX-7 and easier to break; (4) The energy gaps (ΔE L-H ) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) can be used to characterize the chemical stability of a compound and were calculated as 1.943 eV for APDE, 2.849 eV for FOX-7 and 2.868 eV for picryl chloride (Table 4) respectively, by the DFT method of Gaussian 09 (Revision D.01) suite of programs (Supporting Information Note 1), [37,47,48] and the value of ΔE LÀ H for APDE is the smallest indicating that APDE has the worst chemical stability among the three compounds.…”

Thermal Behavior and Detonation Characterization of 3,3‐Dinitroazetidinium Salicylate

“…The DSC curves at the heating rates of 2.5, 5.0, 10.0 and 15.0 8C min À1 were dealt with the mathematic means, and the temperature data corresponding to the conversion degrees (a) were found. Six integral methods (MacCallum-Tanner, Šatava-Šesták, Agrawal, General integral, Universal integral, and Flynn-Wall-Ozawa) and one differential method (Kissinger) were employed [14][15][16][17][18][19][20][21][22]. The values of E a were obtained by Flynn-Wall-Ozawa's method from the iso-conversional DSC curves at the heating rates of 2.5, 5.0, 10.0 and 15.0 8C min À1 , and the E a -a relation is shown in Figure 4.…”