The Journal of Physical Chemistry B · 2000 · 70 citations · 31 references
Natural SciencesChemistryMaterials SciencePhysical ChemistryThermal AnalysisThermodynamicsCalorimetryChemical ThermodynamicsEvaporation ProcessesGas-phase Reaction KineticsThermogravimetric AnalysisActivation EnergyDecomposition MechanismsPrimary DecompositionThermal DecompositionThermal Decomposition ReactionsThermogravimetric CurvesThermogravimetric Data AnalysisVaporization
The thermal decomposition of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Activation energies as a function of the extent of conversion, α, have been determined by model-free isoconversional analysis of these data. In open pans, evaporation is a prevalent process with an activation energy of ∼100 kJ mol -1 . Confining the system in either a pierced pan or a closed pan promotes liquid state decomposition of RDX that occurs with an activation energy of ∼200 kJ mol -1, which suggests scission of an N−N bond as the primary decomposition step. In such a confined environment, gas phase decomposition is a competing channel with an activation energy estimated to be ∼140 kJ mol -1 . In a closed pan, RDX generates a heat release of ∼500 kJ mol -1 that is independent of both the heating rate, β, and the mass.
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Reaction Kinetics in Differential Thermal Analysis
H.E. Kissinger · Analytical Chemistry · 1957 · 13K citations
Sergey Vyazovkin, Charles A. Wight · Annual Review of Physical Chemistry · 1997 · 532 citations
Natural Sciences, Chemistry, Physics +17