Application of scanning calorimetry to the study of chemical kinetics

Rogers, R. N.; Smith, L. C.

doi:10.1016/0040-6031(70)85023-7

Cited by 71 publications

(7 citation statements)

References 10 publications

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“…The results from both models are in good agreement with the experimental value of 28.6 kcal mol −1 using the Kissinger method. 42 The above discussion confirms that the NNP accurately describes the kinetics of RDX decomposition. In the following section, we discuss the detailed decomposition mechanism of RDX crystals from the condensed phase to the gas-phase species.…”

Section: Resultssupporting

confidence: 65%

Revealing the thermal decomposition mechanism of RDX crystals by a neural network potential

Chu¹,

Chang²,

et al. 2022

Phys. Chem. Chem. Phys.

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Section: Resultssupporting

confidence: 65%

Revealing the thermal decomposition mechanism of RDX crystals by a neural network potential

Chu¹,

Chang²,

et al. 2022

Phys. Chem. Chem. Phys.

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“…The activation energies predicted by NNP and ReaxFF are 25.24 and 26.01 kcal/mol, respectively. The results from both models are in good agreement with the experimental value of 28.6 kcal/mol using the Kissinger method 38 . The above discussion confirms that the NNP accurately describes the kinetics of RDX decomposition.…”

Section: Species Evolution During Rdx Decompositionsupporting

confidence: 82%

Revealing the thermal decomposition mechanism of RDX crystal by a neural network potential

Chu

Chang

Ma³

et al. 2022

Preprint

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A neural network potential (NNP) is developed to investigate the complex reaction dynamics of RDX thermal decomposition. Our NNP model is proven to possess good computational efficiency and retain the ab initio accuracy, which allows the investigation of the entire decomposition process of bulk RDX crystal from an atomic perspective. A series of molecular dynamics (MD) simulations are performed on the NNP to calculate the physical and chemical properties of the RDX crystal. The results show that the NNP can accurately describe the physical properties of RDX crystal, like cell parameters and equation of state. The simulations of RDX thermal decomposition reveal that the NNP could capture the evolution of species at the ab initio accuracy. The complex reaction network was established, and a reaction mechanism of RDX decomposition was provided. The N-N homolysis is the dominant channel, which cannot be observed in previous DFT studies of gas RDX. In addition, the H abstraction reaction by NO2 is found to be the critical pathway for NO and H2O formation, while the HONO elimination is relatively weak. The NNP gives an atomic insight into the complex reaction dynamics of RDX and can be extended to investigate the reaction mechanism of novel energetic materials.

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“…Figure 10 also shows the kinetics of LX-17 decomposition is slightly slower than that of TATB. The slower gas release from LX-17 decomposition could be due to the polymeric binder, Kel-F. Kel-F is known to exhibit endothermic thermal decomposition behavior with an activation energy of 271 kJ/mol [48], which is slightly higher than those reported for TATB thermal decomposition (210 kJ/ mol) [5][6][7][8][9][10][11]. Although Kel-F melts before TATB decomposes, it decomposes nearly 100°C higher than TATB [48].…”

Section: The Comparison Of Thermal Decomposition Kinetics For Tatb Lx-17 and Deuterated Tatbmentioning

confidence: 89%

“…An overall insight into the decomposition chemistry of TATB is gained through the temperature dependent i) heatrelease rates measured using differential scanning calorimetry (DSC) [5][6][7][8] and ii) weight loss monitored using thermogravimetric analysis (TGA) [9][10][11]. The results suggest that TATB decomposition involves two consecutive autocatalytic-type reactions.…”

Section: Introductionmentioning

confidence: 99%

Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

Köroğlu

Crowhurst

Kahl

et al. 2021

Propellants Explo Pyrotec

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Real-time measurements of the product gases arising from the thermal decomposition of triamino-trinitro benzene (TATB), its deuterated analogue, and plastically bonded TATB (LX-17) are presented in this study. Gas-phase decomposition products are identified by IR absorption spectroscopy. The frequency shifts in rovibrational spectra due to isotopic substitution and the change in rate of formation of decomposition products due to the kinetic-isotope-effect (KIE) help elucidate the decomposition pathways. The formation of H 2 O precedes other molecules (e. g., HCN, HNCO) during decomposition. After the concentrations of HCN and HNCO molecules reach a peak, their amounts gradually decrease. The concentrations of the other decomposition products (e. g., NH 3 and CO 2 ) rapidly rise after an induction period, which is attributed to the presence of autocatalytic reactions. The trends of chemical evo-lution are similar for all the samples, but their kinetic behaviors are different. This indicates the rates of consistent pathways are changed during thermal decomposition. The kinetics of deuterated TATB decomposition is slower than that of unsubstituted TATB due to the KIE (k H /k D~1 .41). The rate of LX-17 decomposition is slightly lower than unsubstituted TATB (k TATB /k LX-17~1 .15). The KIE is more pronounced during the early stage of decomposition, which is attributed to the first steps of TATB decomposition involving water formation (i. e., H vs D transfer). The KIE slows down the formation of all gases, including those lacking hydrogen (e. g., CO 2 ). These results suggest the TATB thermal decomposition mechanism might involve a series of pathways rather than a set of independent and parallel reactions.

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Application of scanning calorimetry to the study of chemical kinetics

Cited by 71 publications

References 10 publications

Revealing the thermal decomposition mechanism of RDX crystals by a neural network potential

Revealing the thermal decomposition mechanism of RDX crystals by a neural network potential

Revealing the thermal decomposition mechanism of RDX crystal by a neural network potential

Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

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