Skip to main content
SpringerLink
Log in

Thermal decomposition mechanisms of nitro-1,2,4-triazoles: A theoretical study

  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Possible decomposition mechanisms of C-nitro-and N-nitro-1,2,4-triazoles were simulated. We showed that in addition to the experimentally detected thermolysis products including N2, N2O, NO, CO2, HCN, HNCO, 1,2,4-triazole, 3(5)-nitroso-1,2,4-triazole, and 1,2,4-triazolone, some other decompositon products (H2O, CO, NO2, cyanamide, cyanuric acid, and melamine) can be formed. Using the density functional approach (B3LYP/6-31G* approximation), we assessed the most favorable thermal decomposition pathways of nitrotriazoles and studied the relationships between the thermolysis pathways of these substances and their molecular and electronic structures. We found a correlation between the energy gap width (energy difference between the frontier molecular orbitals) and the stabilities of the C-nitro-1,2,4-triazole tautomers to thermal decomposition.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. G. B. Manelis, G. M. Nazin, Yu. I. Rubtsov, and V. A. Strunin, Termicheskoe razlozhenie i gorenie vzryvchatykh veshchestv i porokhov [Thermal Decomposition and Combustion of Explosives and Powders], Nauka, Moscow, 1996, 223 pp. (in Russian).

    Google Scholar 

  2. Yu. Shu, B. L. Korsunskii, and G. M. Nazin, Usp. Khim., 2004, 73, 320 [Russ. Chem. Rev., 2004, 73 (Engl. Transl.)].

    Google Scholar 

  3. G. A. Olah and R. Squire, in Chemistry of Energetic Materials, Ed. G. A. Olah, Academic Press, San Diego, 1991, p. 212.

    Google Scholar 

  4. P. L. Marinkas, in Organic Energetic Compounds, Ed. P. L. Marinkas, Nova Science Publishers, Inc., New York, 1996, p. 425.

    Google Scholar 

  5. V. F. Sopin and G. A. Marchenko, Sovremennye problemy tekhnicheskoi khimii. Materialy dokl. Vseros. nauchnotekhnicheskoi konf. [Modern Problems of Technical Chemistry. Proc. All-Russia Res. and Technol. Conf.] (Kazan’, November 21–22, 2003), Kazan’, 2003, 40 (in Russian).

  6. L. P. Smirnov, Usp. Khim., 2004, 73, 1210 [Russ. Chem. Rev., 2004, 73 (Engl. Transl.)].

    Google Scholar 

  7. M. S. Pevzner, Ros. Khim. Zh., 1997, 41, 73 [Mendeleev Chem. J., 1997, 41 (Engl. Transl.)].

    CAS  Google Scholar 

  8. H. H. Licht, H. Ritter, and B. Wanders, Proc. 25 Intern. Ann. Conf. of ICT (Energetic Materials), Karlsruhe (Germany), 1994, 45(1).

  9. H. H. Licht, S. Braun, M. Wanders, and H. Ritter, Proc. 29 Intern. Ann. Conf. of ICT (Energetic Materials), Karlsruhe (Germany), 1998, 47(1).

  10. H. H. Licht and H. Ritter, Propellants, Explosives, Pyrotechnics, 1997, 22, 333.

    Article  CAS  Google Scholar 

  11. US Pat. 5889161; Chem. Abstr., 1999, 130, 239630.

    Google Scholar 

  12. C. L. Habraken and P. Cohen-Fernandez, Chem. Commun., 1972, 2, 37.

    Google Scholar 

  13. M. S. Pevzner, T. N. Kulibabina, S. L. Ioffe, I. A. Maslina, B. V. Gidaspov, and V. A. Tartakovsky, Khim. Geterotsikl. Soedin., 1979, 550 [Chem. Heterocycl. Compd., 1979 (Engl. Transl.)].

  14. M. S. Pevzner, T. N. Kulibabina, N. A. Povarova, and L. V. Kilina, Khim. Geterotsikl. Soedin., 1979, 1132 [Chem. Heterocycl. Compd., 1979 (Engl. Transl.)].

  15. A. M. Astakhov, V. A. Revenko, and E. S. Buka, Sovremennye problemy tekhnicheskoi khimii. Materialy dokl. Vseros. nauchno-tekhnicheskoi konf. [Modern Problems of Technical Chemistry. Proc. All-Russia Res. and Technol. Conf.] (Kazan’, November 21–22, 2003), Kazan’, 2003, 209 (in Russian).

  16. A. M. Astachov, V. A. Revenko, and E. S. Buka, Proc. Seventh Seminar “New Trends in Research of Energetic Materials”, Pardubice (the Czech Republic), 2004, 424.

  17. J. C. Oxley, J. L. Smith, Z. L. Zhou, and R. L. McKenney, J. Phys. Chem., 1995, 99, 10383.

    Google Scholar 

  18. R. S. Stepanov, L. A. Kruglyakova, and M. A. Stepanova, Tez. dokl. mezhinstitutskogo kollokviuma “ Khimiya azotistykh geterotsiklov” [Abstrs Inter-Institute Colloq. “Chemistry of Nitrous Heterocycles”], Chernogolovka, 1995, 38 (in Russian).

  19. R. S. Stepanov and L. A. Kruglyakova, Kinet. Katal., 1996, 37, 339 [Kinet. Catal., 1996, 37 (Engl. Transl.)].

    Google Scholar 

  20. R. S. Stepanov, L. A. Kruglyakova, and M. A. Stepanova, Zh. Obshch. Khim., 1997, 67, 324 [Russ. J. Gen. Chem., 1997, 67 (Engl. Transl.)].

    Google Scholar 

  21. A. K. Sikder, M. Geetha, D. B. Sarwade, and J. P. Agrawal, J. Hazardous Materials, 2001, A82, 1.

    Google Scholar 

  22. R. S. Stepanov, L. A. Kruglyakova, O. A. Golubtsova, and A. M. Astakhov, Khim. Geterotsikl. Soedin., 2003, 699 [Chem. Heterocycl. Compd., 2003 (Engl. Transl.)].

  23. Wai-Leung Yim and Zhi-Feng Liu, J. Am. Chem. Soc., 2001, 123, 2243.

    Article  CAS  Google Scholar 

  24. A. A. Porollo, D. E. Lushnikov, T. S. Pivina, and V. P. Ivshin, J. Mol. Struc. (THEOCHEM), 1997, 391, 117.

    Article  CAS  Google Scholar 

  25. A. A. Porollo, D. E. Lushnikov, T. S. Pivina, V. P. Ivshin, and N. S. Zefirov, Izv. Akad. Nauk, Ser. Khim., 1999, 1869 [Russ. Chem. Bull., 1999, 48, 1845 (Engl. Transl.)].

    Google Scholar 

  26. A. A. Porollo, T. V. Petukhova, V. P. Ivshin, T. S. Pivina, and D. E. Lushnikov, Proc. “Energetic Materials” of the 30th Intern. Ann. Conf. of ICT, Karlsruhe (Germany), 1999, 15(1).

  27. T. S. Pivina, A. A. Porollo, T. V. Petukhova, and V. P. Ivshin, Proc. 26th Intern. Pyrotechnics Seminar, Nanjing (China), 1999, 438.

  28. T. S. Pivina, A. A. Porollo, T. V. Petukhova, and V. P. Ivshin, Proc. 5th Intern. Symp. on Special Topics in Chemical Propulsion (5-ISICP), Stresa (Italy), 2000, 343.

  29. A. A. Porollo, T. V. Petukhova, V. P. Ivshin, T. S. Pivina, and E. A. Smolenskii, Tez. dokl. 2-j Vseros. konf. “Molekulyarnoe modelirovanie” [Abstrs 2nd All-Russia Conf. “Molecular Modeling”], Moscow, 2001, 94 (in Russian).

  30. A. Porollo, T. Petukhova, V. Ivshin, T. Pivina, B. Korsunskii, and O. Golovanov, Proc. 32nd Intern. Ann. Conf. of ICT, Karlsruhe (Germany), 2001, 87(1).

  31. T. V. Petukhova, A. A. Porollo, V. L. Korolev, V. P. Ivshin, Y. N. Surikova, and T. S. Pivina, Proc. 33rd Intern. Ann. Conf. of ICT, Karlsruhe (Germany), 2002, 60(1).

  32. G. M. Khrapkovskii, G. N. Marchenko, and A. G. Shamov, Vliyanie molekulyarnoi struktury na kineticheskie parametry monomolekulyarnogo raspada S-i O-nitrosoedinenii [Effect of Molecular Structure on Kinetic Parameters of Monomolecular Decomposition], FEN, Kazan’, 1997 (in Russian).

    Google Scholar 

  33. E. V. Sokerina, D. E. Lushnikov, T. S. Pivina, A. A. Porollo, and V. P. Ivshin, Proc. 21st Intern. Pyrotechnics Seminar, Moscow, 1995, 849.

  34. A. A. Porollo, Ph.D. (Chem.) Thesis, Mari State University, Yoshkar-Ola, 1999, 135 pp. (in Russian).

  35. D. C. Nonhebel and J. Walton, Free-Radical Chemistry; Structure and Mechanism, University Press, Cambridge, 1974.

    Google Scholar 

  36. A. L. Fridman, V. P. Ivshin, and S. S. Novikov, Usp. Khim., 1969, 38, 1448 [Russ. Chem. Rev., 1969, 38 (Engl. Transl.)].

    CAS  Google Scholar 

  37. A. M. Astakhov, Ph.D. (Chem.) Thesis, Sibirskii State Technological University, Krasnoyarsk, 1999, 118 pp. (in Russian).

  38. J. C. Oxlye, M. Hiskey, D. Naud, and R. Szekeres, J. Phys. Chem., 1992, 96, 2505.

    Article  Google Scholar 

  39. J. March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, J. Wiley and Sons, New York, 1985.

    Google Scholar 

  40. A. N. Nesmeyanov and N. A. Nesmeyanov, Nachala organicheskoi khimii [The Foundations of Organic Chemistry], Khimiya, Moscow, 1977, 1, 624 pp. (in Russian).

    Google Scholar 

  41. E. N. Zil’berman, Reaktsii nitrilov [Reactions of Nitriles], Khimiya, Moscow, 1972, 445 pp. (in Russian).

    Google Scholar 

  42. T. Brill, Mat. Res. Soc. Symp. Proc., 1993, 296, 269.

    CAS  Google Scholar 

  43. T. Brill, J. Propulsion and Power, 1995, 11, 740.

    Article  CAS  Google Scholar 

  44. V. I. Avdeev, S. F. Ruzankin, and G. M. Zhidomirov, Kinet. Katal., 2005, 46, 191 [Kinet. Catal., 2005, 46 (Engl. Transl.)].

    Google Scholar 

  45. Fiziko-khimicheskie i teplofizicheskie svoistva rastvorov na osnove chetyrekhokisi azota [Physicochemical and Thermal-Physical Properties of Solutions Based on Nitrogen Tetroxide], Ed. V. B. Nesterenko, Nauka i Tekhnika, Minsk, 1981, 303 pp. (in Russian).

    Google Scholar 

  46. W. Koch and M. C. Holthausen, A Chemists’s Guide to Density Functional Theory, Wiley-VCH, Weinheim, 2001, 300 p.

    Google Scholar 

  47. T. Clark, A Handbook of Computational Chemistry, J. Wiley and Sons, New York, 1985.

    Google Scholar 

  48. E. V. Nikolaeva, Ph.D. (Chem.) Thesis, Kazan’ State Technological University, Kazan’, 2002, 203 pp. (in Russian).

  49. M. J. Frish, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komazomi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzales, M. Head-Gordon, E. S. Replogle, and J. A. Pople, GAUSSIAN 98. Revision A.9, Gaussian, Inc., Pittsburgh (PA), 1998.

    Google Scholar 

  50. Cambridge Structural Database, Version 5.26, November, 2004.

  51. B. D. T. Cromer, K.-Y. Lee, and R. R. Ryan, Acta Crystallogr., 1988, C44, 1673.

    CAS  Google Scholar 

  52. J. Janssen, C. L. Habraken, and R. Louw, J. Org. Chem., 1976, 41, 1758; M. I. Kanishchev, N. V. Korneeva, S. A. Shevelev, and A. A. Fainzil’berg, Khim. Geterotsikl. Soedin., 1988, 435 [Chem. Heterocycl. Compd., 1988 (Engl. Transl.)].

    Article  CAS  Google Scholar 

  53. G. Evrard, F. Durant, A. Michel, J. G. Fripiat, J. L. Closset, and A. Copin, Bull. Soc. Chim. Belg., 1984, 93, 233.

    Article  CAS  Google Scholar 

  54. H. H. Licht, H. Ritter, H. R. Bircher, and P. Bigler, Magn. Reson. Chem., 1998, 36, 343.

    Article  CAS  Google Scholar 

  55. M. S. Pevzner, E. Ya. Fedorova, I. N. Shokhor, and L. I. Bagal, Khim. Geterotsikl. Soedin., 1971, 275 [Chem. Heterocycl. Compd., 1971 (Engl. Transl.)].

  56. M. S. Pevzner and R. E. Trifonov, Zh. Org. Khim., 1998, 34, 784 [Russ. J. Org. Chem., 1998, 34, 748 (Engl. Transl.)].

    Google Scholar 

  57. P. Politzer, M. E. Grice, and J. M. Seminario, J. Quantum Chem., 1997, 61, 389.

    Article  CAS  Google Scholar 

  58. R. F. W. Bader, Atoms in Molecules. A Quantum Theory, Clarendron Press, Oxford, 1990.

    Google Scholar 

  59. A. Gao, A. L. Reingold, and T. B. Brill, Propellants, Explosives, Pyrotechnics, 1991, 16, 97.

    Article  CAS  Google Scholar 

  60. A. Gao, Y. Oyumi, and T. V. Brill, Comb. and Flame, 1991, 83, 345.

    Article  CAS  Google Scholar 

  61. T. V. Brill, Prog. Energy Combast. Sci., 1992, 18, 91.

    Article  CAS  Google Scholar 

  62. T. V. Brill and H. Ramanathan, Comb. and Flame, 2000, 122, 165.

    Article  CAS  Google Scholar 

  63. V. M. Karlik, V. I. Zagranichnyi, and L. N. Al’tshuler, Khimicheskaya promyshlennost’ [Chem. Industry], 1981, 8, 16 (464) (in Russian).

    Google Scholar 

  64. A. I. Finkel’shtein and N. V. Spiridonova, Usp. Khim., 1964, 33, 900 [Russ. Chem. Rev., 1964, 33 (Engl. Transl.)].

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991, Moscow, Russian Federation

    V. L. Korolev, T. S. Pivina & A. B. Sheremetev

  2. Mari State University, 1 Lenin Sq., 424000, Yoshkar-Ola, Mari El Republic, Russian Federation

    T. V. Petukhova & V. P. Ivshin

  3. Biomedical Informatics, Children’s Hospital Research Foundation, 3333 Burnet Av., Cincinnati, OH, 45229, USA

    A. A. Porollo

  4. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    K. Yu. Suponitskii

Authors
  1. V. L. Korolev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. T. V. Petukhova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. T. S. Pivina
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. A. Porollo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. B. Sheremetev
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. K. Yu. Suponitskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. V. P. Ivshin
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1338–1358, August, 2006.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Korolev, V.L., Petukhova, T.V., Pivina, T.S. et al. Thermal decomposition mechanisms of nitro-1,2,4-triazoles: A theoretical study. Russ Chem Bull 55, 1388–1410 (2006). https://doi.org/10.1007/s11172-006-0430-9

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11172-006-0430-9

Key words

Search

Navigation