The thermal decomposition of 2,5-dipicryl-1,3,4-oxadiazole, near its ignition temperature: An isothermal DSC study

Abstract 2,5-Dipicryl-1,3,4-oxadiazole (DPO) is a thermally stable, high impulse shock sensitive explosive, which decomposes in the solid state at a rate easily followed by isothermal differential scanning calorimetry between 575 K (302°C) and 598 K (325°C). The α-t plots follow a typical sigmoidal profile and the kinetic data has been analysed in terms of the two standard rate laws which characterise many sigmoidal nucleation, growth and decomposition reactions, viz. the Prout-Tompkins rate law and the Avrami-Erofe'ev rate law. Both give an excellent description of the reaction kinetics over the approximate range 0.08 < α <0.80, but the apparent reaction order associated with Avrami-Erofe'ev kinetics is temperature dependent. An Arrhenius plot based on Prout-Tompkins kinetics suggests that the thermal decomposition of DPO proceeds with an activation energy of 218 kJ mol−1 and a pre-exponential, In A(s−1), of 39.83, while that based on Avrami-Erofe'ev kinetic data yields an activation energy of 184 kJ mol...

[1]  B. Achar,et al.  Numerical Data for Some Commonly Used Solid State Reaction Equations , 1966 .

[2]  L. G. Harrison.  The Theory of Solid Phase Kinetics , 1969 .

[3]  J. Sharp,et al.  Method of Comparing Solid‐State Kinetic Data and Its Application to the Decomposition of Kaolinite, Brucite, and BaCO3 , 1972 .

[4]  A. Galwey,et al.  The low temperature thermal decomposition of ammonium perchlorate: nitryl perchlorate as the reaction intermediate , 1984, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[5]  C. D. Hutchinson,et al.  Aminotetryls: Synthesis, spectral characterization, thermal decomposition and explosive properties , 1984 .

[6]  The kinetics and mechanism of the thermal decomposition of copper(II) malonate , 1986, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[7]  M. Maciejewski,et al.  Method of the selection of the g(α) function based on the reduced-time plot , 1987 .

[8]  V. Melbourne.  MATERIALS RESEARCH LABORATORY , 1988 .

[9]  M. E. Sitzmann.  2,5-dipicryl-1,3,4-oxadiazole: a shock-sensitive explosive with high thermal stability (thermally-stable substitute for petn) , 1988 .

[10]  D. Whelan,et al.  Kinetics and thermochemistry of the boron-fuelled pyrotechnic compositions BLC 190 and BLC 181 at their ignition temperatures , 1988 .

[11]  The thermal decomposition of basic lead styphnate RD 1349 at its ignition temperature , 1989 .

[12]  C. Macosko,et al.  DSC sample temperature control while measuring reaction kinetics , 1991 .

[13]  Deuterium isotope effects on the rates of thermal decomposition of 2,2',4,4',6,6'-hexanitrostilbene in the condensed phase , 1992 .

[14]  A. Galwey,et al.  The thermal decomposition of dehydrated d-lithium potassium tartrate monohydrate: molecular modification by a homogeneous melt mechanism , 1993, Proceedings of the Royal Society of London. Series A: Mathematical and Physical Sciences.