Relationship Between Electronic Charges at Nitrogen Atoms of Nitro Groups and Onsets of Thermal Decomposition of Polynitro Arenes

• Autorzy: Zeman S. , Friedl Z.
• Języki publikacji: EN

Abstrakty

EN

Thermal stability of twenty-five polynitro arenes has been examined by means of non-isothermal differential thermal analysis (DTA), and it was expressed as an onset of thermal decomposition, TD. Electronic charges, qN, at nitrogen atoms of the polynitro arene molecules were calculated by means of the ab initio DFT B3LYP/6-31G** method. The relationship was confirmed between the onsets TD and squares of the qN values for the nitro groups that are primarily split off. In the sense of this relationship, the compounds studied fall into five groups. The reason of this diversification and principle of the relationship existence are discussed. It is stated that stabilising influence of the crystal lattice of the studied polynitro arenes can be evaluated by DTA of solutions of these compounds in 1,3,5-trinitrobenzene (TNB).

Słowa kluczowe

EN

DTA; ab initio DFT B3LYP/6-31G**; thermal decomposition; polynitro arenes

• Wydawca: Sieć Badawcza Łukasiewicz - Instytut Przemysłu Organicznego
• Czasopismo: Central European Journal of Energetic Materials
• Rocznik: 2004
• Tom: Vol. 1, nr 1
• Strony: 3--21
• Opis fizyczny: Bibliogr. 27 poz.

Twórcy

autor

Zeman S.

• Department of Theory & Technology of Explosives, University of Pardubice, CZ-532 10 Pardubice, Czech Republic

autor

Friedl Z.

• Faculty od Chemistry, Brno University of Technology

Bibliografia

• [1] Zeman S., A Study of Chemical Micromechanisms of Initiation of Organic Polynitro Compounds, in Politzer P. & Murray J. S. (Eds.), Energetic Materials, Part II,Elsevier B. V., Amsterdam 2003,25-52.
• [2] Zeman S., The Relationship between the Arrhenius Parameters of the Low-Temperature Thermolysis and the 13C and 15N Chemical Shifts of the Nitramines, Thermochim. Acta, 1992, 202,191.
• [3] Zeman S., Analysis and Prediction of the Arrhenius Parameters of Low-Temperature Thermolysis of Nitramines by Means of the I5N NMR Spectroscopy, ibid., 1999, 355,121.
• [4] Zeman S., New Aspects of the Impact Reactivity of Nitramines, Propellants, Explos., Pyrotech.,2QW,25,66.
• [5] Zeman S., Zeman V., Kamensky Z., Relationships between the Electric Spark Sensitivity and the NMR Chemical Shifts of some Organic Polynitro Compounds, in Proc. 28th Int. Annual Conf. ICT, Karlsruhe 1997, 66/1
• [6] Zeman S., Relationship between Detonation Characteristics and 15N NMR Chemical Shifts of Nitramines, J. Energ. Mater., 1999,17, 305.
• [7] Zeman S., Friedl Z., Relationship between Electronic Charges at Nitrogen Atoms of Nitro Groups and Thermal Reactivity of Nitramines, J. Thermal Anal. Calorim., 2004,77,217.
• [8] Zeman S., Thermal Stabilities of Polynitroaromatic Compounds and their Derivatives, Thermochim. Acta, 1979, 31, 269.
• [9] Zeman S., The Relationship between Differential Thermal Analysis Data and the Detonation Characteristics of Polynitroaromatic Compounds, ibid., 1980, 41, 199.
• [10] Zeman S., Possibilities of Applying the Piloyan Method of Determination of Decomposition Activation Energies in the Differential Thermal Analysis of Polynitroaromatic Compounds and of their Derivatives. Part I., J. Thermal Anal. 1979,77,19.
• [11] TITAN v.LO.8. [CPU Intel P4/3.2 GHz (800 MHz) 512 kBL2HT, 1 GBRAM, 36GB SCISIHDJ. Wavefunction, Schrodinger, Inc., USA, 2001.
• [12] Zeman S., Huczala R,, Friedl Z., The Study of Chemical Micromechanism Governing Detonation Initiation of some m-Dinitrobenzopolyazaarenes, J. Energ. Mater., 2002, 20, 53.
• [13] Matveev V. G., Dubikhin V. V, Nazin G. M., Soglasovanyi mekhanism razlozheniya aromaticheskikh nitrosoedinii v gazovoy faze (Thermolysis Mechanism of the Aromatic Nitrocompounds in the Gas Phase), Izv. Akad. Nauk SSSR, Ser. Khim., 1978,474.
• [14] Bulusu S., Axenrod T., Electron Impact Fragmentation Mechanisms of 2,4,6-TNT Derived from Metastable Transitions and Isotopic Labeling, Org. Mass Spectrom.,1979,14, 585.
• [15] Wang J., Lang H.-Y., Mechanistic Study of Polynitro Compounds by XPS:Mechanism of the Thermal Decomposition of Polynitro Phenols, Science in China, Ser. B, 1990, 33, 257.
• [16] Nazin G. M., Manelis G. B., Thermal Decomposition of Aliphatic Nitrocompounds, Russ. Chem. Revs., 1994, 63,313.
• [17] Bulusu S. et al., Deuterium Kinetic Isotope Effect., Proc. 8lh Int. Symp.on Detonation, Albuquerque, NM, July 1985.
• [18] Zeman S., Kinetic Data of Low-Temperature Thermolysis in the Study of the Microscopic Initiation Mechanism of the Detonation of Organic Polynitro Compounds, Thermochim. Acta, 1981, 49, 219.
• [19] Zeman S., Krupka M., New Aspects of Impact Reactivity of Polynitro Compounds, Part II. Impact Sensitivity as "the First Reaction" of Polynitro Arenes, Propellants, Explos., Pyrotech., 2003, 28, 249.
• [20] Maksimov Yu. Ya., Polyakov N. V, Sapranovich V. R, Nitromethylbenzenes Thermal Decomposition, Trudy MCHTim. Mendeleeva, 1974, 83, 55.
• [21] Andreev K. K., Termicheskoe razlozhenie i goreniye vzryvchatykh veschestv (Thermal Decomposition and Combustion of Explosives), Izdat. Nauka, Moscow 1966.
• [22] Exner O., Friedl Z., Transmission of Substituent Effects: The Through-Space and Through-Bond Models and Their Experimental Verification, Progr. Phys. Org. Chem.,1993,19,259.
• [23] Galwey A. K., Brown M. E., Thermal Decomposition of Ionic Solids, Elsevier, Amsterdam 1999, 22.
• [24] Zeman S., Compensation Effect and Thermolysis Mechanisms of Organic Polynitroso and Polynitro Compounds, Thermochim. Acta, 1997, 290, 199.
• [25] Mathieu D., Becker J.-P., Theerlynek E., Beyond the Group Contribution Approach to Fluid Properties: New Models forthe Density and Thermal Stability of Energetic Compounds, in Vagenknecht J. (Ed.), Proceedings of the 7 Int. Seminar "New Trends in Reserach of Energetic Materials", Univ. of Pardubice, April 2004, p. 184.
• [26] Hoffsommer J. C., Feifer J. S., Thermal Stabilities of Hexanitroazobenzene and Hexanitrobiphenyl, Res. Rep. NOLTR 67-74, U. S. Naval Ordnance Lab., White Oak, Silver Spring 1967.
• [27] Zeman S., Thermostable Polynitro Aromatic Compounds, Ph. D. Dissertation, Univ. of Pardubice, June 1973.