Abstract
3,3-Dinitroazetidinium (DNAZ) salt of perchloric acid (DNAZ·HClO4) was prepared, it was characterized by the elemental analysis, IR, NMR, and a X-ray diffractometer. The thermal behavior and decomposition reaction kinetics of DNAZ·HClO4 were investigated under a non-isothermal condition by DSC and TG/DTG techniques. The results show that the thermal decomposition process of DNAZ·HClO4 has two mass loss stages. The kinetic model function in differential form, the value of apparent activation energy (E a) and pre-exponential factor (A) of the exothermic decomposition reaction of DNAZ·HClO4 are f(α) = (1 − α)−1/2, 156.47 kJ mol−1, and 1015.12 s−1, respectively. The critical temperature of thermal explosion is 188.5 °C. The values of ΔS ≠, ΔH ≠, and ΔG ≠of this reaction are 42.26 J mol−1 K−1, 154.44 kJ mol−1, and 135.42 kJ mol−1, respectively. The specific heat capacity of DNAZ·HClO4 was determined with a continuous C p mode of microcalorimeter. Using the relationship between C p and T and the thermal decomposition parameters, the time of the thermal decomposition from initiation to thermal explosion (adiabatic time-to-explosion) was evaluated as 14.2 s.
Similar content being viewed by others
References
Frumkin AE, Churakov AM, Strelenko YA, Kachala VV, Tartakkovsky VA. Synthesis of 1,2,3,4-tetrazino[5,6-f]benzo-1,2,3,4-tetrazine 1,3,7,9-tetra-N-oxides. Org Lett. 1999;1:721–4.
Archibald TG, Gilardi R, Baum K, George C. Synthesis and X-ray crystal structure of 1,3,3-trinitroazetidine. J Org Chem. 1990;55:2920–4.
Hiskey MA, Coburn MD, Mitchell MA, Benicewicz BC. Synthesis of 3,3-dinitroazetidine from 1-t-butyl-3,3-dinitroazetidine. J Heterocycl Chem. 1992;29:1855–6.
Hiskey MA, Stincipher MM, Brown JE. Synthesis and initial characterization of some energetic salts of 3,3-dinitroazetidine. J Energy Mater. 1993;11:157–65.
Ma HX, Yan B, Li ZN, Song JR, Hu RZ. Synthesis, molecular structure, non-isothermal decomposition kinetics and adiabatic time to explosion of 3,3-dinitroazetidinium 3,5-dinitrosalicylate. J Therm Anal Calorim. 2009;95:437–44.
Gao R, Ma HX, Yan B, Song JR, Wang YH. Structure–property investigation on TDNAZ·HNO3 and DNAZ·HCl. Chem J Chin U. 2009;30:577–82 (in Chinese).
Ma HX, Yan B, Song JR, Lü XQ, Wang LJ. Molecular structure and quantum chemical investigation of acyl derivatives of DNAZ. Chem J Chin U. 2009;30:377–81 (in Chinese).
Ma HX, Yan B, Li ZN, Guan YL, Song JR, Xu KZ, Hu RZ. Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to-explosion of NTO·DNAZ. J Hazard Mater. 2009;169:1068–73.
Li ZN, Ma HX, Yan B, Guan YL, Song JR. Synthesis, crystal structure, theoretical calculation and thermal behavior of DNAZ·NTO. Chin J Chem. 2009;27:2284–90.
Yan B, Ma HX, Hu Y, Guan YL, Song JR. 1-(2,4-Dinitrophenyl)-3,3-dinitroazetidine. Acta Crystallogr E. 2009;65:o3215.
Yan B, Ma HX, Li JF, Guan YL, Song JR. 1-Benzoyl-3,3-dinitroazetidine. Acta Crystallogr E. 2010;66:o57.
Ditmars DA, Ishihara S, Chang SS, Bernstein G. Enthalpy and heat-capacity standard reference material: sapphire (a-Al2O3) from 10 to 2250 K. J Res Natl Bur Stand. 1982;87:159–63.
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29:1702–6.
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.
Vyazovkin S, Dollimore D. Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids. J Chem Inf Comput Sci. 1996;36:42–5.
Hu RZ, Yang ZQ, Liang YJ. The determination of the most probable mechanism function and three kinetic parameters of exothermic decomposition reaction of energetic materials by a single non-isothermal DSC curve. Thermochim Acta. 1988;123:135–51.
Hu RZ, Shi QZ. Thermal analysis kinetics. 2nd ed. Beijing: Science Press; 2001 (in Chinese).
Zhang TL, Hu RZ, Xie Y, Li FP. The estimation of critical temperatures of thermal explosion for energetic materials using non-isothermal DSC. Thermochim Acta. 1994;244:171–6.
Smith LC. An approximate solution of the adiabatic explosion problem. Thermochim Acta. 1975;13:1–6.
Zhao HA, Hu RZ, Wang XJ, Zhao FQ, Gao HX, Zhang H, Zhang XL, Feng Y, Ma HX. Thermal safety of 1,3,3-trinitroazetidine (TNAZ). Acta Chim Sinica. 2009;67:2536–40 (in Chinese).
Acknowledgements
This study is supported by the National Natural Science Foundation of China (20603026), the Provincial Natural Foundation of Shaanxi (2009JQ2002) and NWU Graduate Experimental Research Funds (09YSY23).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ma, H.X., Yan, B., Ren, Y.H. et al. Thermal behavior and thermal safety on 3,3-dinitroazetidinium salt of perchloric acid. J Therm Anal Calorim 103, 569–575 (2011). https://doi.org/10.1007/s10973-010-0950-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-010-0950-2