Autocatalytic decomposition of energetic materials: interplay of theory and thermal analysis in the study of 5-amino-3,4-dinitropyrazole thermolysis

Abstract

A reliable kinetic description of the thermal stability of energetic materials (EM) is very important for safety and storage-related problems. Among other related issues, autocatalysis very often complicates the decomposition...

Physico-geometrical Kinetic Aspects of the Thermal Dehydration of Trehalose Dihydrate

“…Reaction kinetics with progressive liquefication under isothermal conditions may be characterized by a conjunction of two kinetic models for the process until complete liquefication and the subsequent process in the liquid state, as has been formalized by Bawn . The similar kinetic procedure may be applicable to the reaction under linearly increasing temperature conditions by combining two empirical kinetic models, such as the extended Prout–Tompkins (ePT) model, , as recently reported by the present authors. ,, Further complex kinetic behaviors are expected when reactions in the solid and liquid states occur successively, because of the special distributions of the solid product and the solid reactant to be liquefied during the reaction.…”

“…The physicochemical features of the thermal dehydration of TH-DH accompanied by liquefaction is fundamentally different from the previously studied reactions, that is, thermal decompositions of 3,4,5-trinitropyrazole ammonium salt , and monosodium l -glutamate . Notably, the previously studied reactions accompanied by liquefaction were controlled by the chemical process of the intermolecular decomposition and product gas formation, followed by the diffusional removal of the product gas.…”

“…The basic kinetic modeling for such process under isothermal conditions is originated from Bawn’s approach, which describes the overall process by a conjunction of individual kinetic expressions for each stage that switch at a specific α value ( α *). The similar can be applied to the reactions under any temperature conditions based on the experimental master plot. normald α normald θ = A 1 f 1 ( α ) + A 2 f 2 ( α ) Previously, we derived the formal kinetic description of the thermal decomposition/dehydration of solids accompanied by liquefaction under linearly increasing temperature conditions using an ePT( m , n , q ) model for both reaction stages. ,, normale normalP normalT ( m , n , q ): f ( α ) = false[ 1 − q ( 1 − α ) false] m false( 1 − α false) n The acceleration and deceleration stages with a rate behavior depicted by upswept peak shape and sharp peak top were well described by ePT(1, 0, q ) and ePT(0, 1, q ), respectively. ,, However, the present reaction exhibited the rate behavior at a constant temperature with a bell-like peak shape and a dull peak top different from previously studied thermal decomposition processes accompanied by liquefaction (Figure b). Therefore, the previous approach based on Bawn’s model was not particularly successful in an application to the present reaction (Figure S15).…”

“…Previously, we derived the formal kinetic description of the thermal decomposition/dehydration of solids accompanied by liquefaction under linearly increasing temperature conditions using an ePT(m, n, q) model for both reaction stages. 25,26,30 = [ ] m n q f q ePT( , , ):…”

“…27 The similar kinetic procedure may be applicable to the reaction under linearly increasing temperature conditions by combining two empirical kinetic models, such as the extended Prout−Tompkins (ePT) model, 28,29 as recently reported by the present authors. 25,26,30 Further complex kinetic behaviors are expected when reactions in the solid and liquid states occur successively, because of the special distributions of the solid product and the solid reactant to be liquefied during the reaction.…”