Journal of Thermal Analysis and Calorimetry

, Volume 116, Issue 1, pp 259–263 | Cite as

Thermal behavior of several stable hydrazyl free radicals and of their parent hydrazines

  • Maria Marinescu
  • Christina Zalaru
  • Mihaela Florea
  • Petre Ionita


A thermal analysis study has been performed for the stable free radical 2,2-diphenyl-1-picrylhydrazyl and other ten free radical congeners, together with their corresponding parent hydrazines. Qualitative studies on the decomposition products showed that nitrogen dioxide plays a key role. A mechanistic decomposition pathway is also proposed.


DPPH Hydrazyl Free radical DTA TG 



This work was supported by a Grant of the Romanian National Authority for Scientific Research, CNCS—UEFISCDI, Project Number PN-II-ID-PCE-2011-3-0408.

Supplementary material

10973_2013_3448_MOESM1_ESM.doc (13.5 mb)
ESM—DTA and TG of the hydrazyl free radicals 14a, 7a, 9a, and 10a and of the corresponding hydrazines 14b, 7b, 9b, and 10b. (DOC 13868 kb)


  1. 1.
    Goldschmidt S. Uber zweiwertigen Stickstoff: das Triphenyl-hydrazyl. Ber. 1920;53:44.CrossRefGoogle Scholar
  2. 2.
    Goldschmidt S, Renn K. Zweiwertiger Stickstoff: Über das α, α-Diphenyl-β-trinitro-phenyl-hydrazyl. Ber. 1922;55B:628–43.CrossRefGoogle Scholar
  3. 3.
    Chen O, Zhuang J, Guzzetta F, Lynch J, Angerhofer A, Cao YC. Synthesis of water-soluble 2,2′-diphenyl-1-picrylhydrazyl nanoparticles: a new standard for electron paramagnetic resonance spectroscopy. J Am Chem Soc. 2009;131:12542–3.CrossRefGoogle Scholar
  4. 4.
    Ionita P. Is DPPH stable free radical a good scavenger for oxygen active species? Chem Papers. 2005;59:11–6.Google Scholar
  5. 5.
    Sanchez-Moreno C. Methods used to evaluate the free radical scavenging activity in foods and biological systems. Food Sci Technol Int. 2002;8:121–37.CrossRefGoogle Scholar
  6. 6.
    Balaban AT, Frangopol PT, Frangopol M, Negoita N. Stability and equilibria of free radicals—III: preparation of stable, sterically shielded, diarylnitrogen radicals with donor and acceptor aryl groups in the same molecule. Tetrahedron. 1967;23:4661–76.CrossRefGoogle Scholar
  7. 7.
    Balaban AT, Frangopol PT, Marculescu M, Bally J. Factors affecting stability and equilibria of free radicals: steric factors in hydrazyls. Tetrahedron. 1961;13:258–67.CrossRefGoogle Scholar
  8. 8.
    Brill TB, James KJ. Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives. Chem Rev. 1993;93:2667–92.CrossRefGoogle Scholar
  9. 9.
    Ionita P. An enhanced colorimetric chemosensor for the detection of various nitro-explosives. Tetrahedron Let. 2012;53:7143–6.CrossRefGoogle Scholar
  10. 10.
    Tudose M, Angelescu D, Ionita G, Caproiu MT, Ionita P. New hydrazyl derivatives with multiple properties. Lett Org Chem. 2010;7:182–5.CrossRefGoogle Scholar
  11. 11.
    Ionita P, Tuna F, Andruh M, Constantinescu T, Balaban AT. Synthesis and characterization of some novel homo- and hetero-diradicals of hydrazyl and nitroxide type. Aust J Chem. 2007;60:173–9.CrossRefGoogle Scholar
  12. 12.
    Ionita P, Caproiu MT, Balaban AT. New sulfonyl derivatives of 2,2-diphenyl-1-picrylhydrazyl and their supramolecular complexes with crown ethers or kryptands. Rev Roum Chim. 2000;45:935–41.Google Scholar
  13. 13.
    Zeman S. Thermogravimetric analysis of polynitroarenes. J Therm Anal Calorim. 2001;65:919–33.CrossRefGoogle Scholar
  14. 14.
    Keshavarz MH, Moradi S, Saatluo BE, Rahimi H, Madram AR. A simple accurate model for prediction of deflagration temperature of energetic compounds. J Therm Anal Calorim. 2013;112:1453–63.CrossRefGoogle Scholar
  15. 15.
    Hung-Low F, Peterson GR, Hope-Weeks LJ. Controllable thermal degradation of 2,4,6-trinitrotoluene (TNT) by absorption and confinement into mixed metal sponges. J Therm Anal Calorim. 2013;113:475–80.CrossRefGoogle Scholar
  16. 16.
    Matsunaga H, Habu H, Miyake A. Thermal behavior of new oxidizer ammonium dinitramide. J Therm Anal Calorim. 2013;111:1183–8.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2013

Authors and Affiliations

  • Maria Marinescu
    • 1
  • Christina Zalaru
    • 1
  • Mihaela Florea
    • 1
  • Petre Ionita
    • 1
  1. 1.Department of Organic Chemistry, Biochemistry and CatalysisUniversity of BucharestBucharestRomania

Personalised recommendations