Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate

doi:10.6023/A23020056

Abstract

The thermal decomposition characteristics of ammonium perchlorate (AP) have a great influence on the performance of solid propellant. Although a large number of mechanistic studies have been published over the past few decades, there is no unified understanding of the decomposition yet, and the overall mechanism pathway is still unclear. In the present work, the thermal decomposition pathways of AP were studied systematically using broken-symmetry density functional theory method (BS-UB3LYP/6-311＋G(d,p). This method can describe the homo-cleavage process of covalent bond well, and locate the transition state with singlet-diradical characteristics. Compared with typical multireference method, broken- symmetry density functional theory (BS-UDFT) can give good results and is much faster, and therefore is highly convenient for practical application. The results show that, the overall thermal decomposition pathway under the experimental conditions is initiated by the proton transfer between NH₄⁺ cation and ClO₄⁻ anion, leading to neutral NH₃ and HClO₄ molecules, which are absorbed on the AP surface and then escape to the gas phase. The second important step is the homolytic cleavage of the Cl—OH bond in HClO₄. The energy barrier is 67.5 kJ/mol under 620 K. Then, •OH radical and •ClO₃ radical react with NH₃ molecule, yielding •NH₂ radical. Then the •NH₂ radical react with HClO₄, leading to •ClO₄ radical, which reacts with NH₃, leading to the oxidized species H₂NO. The radical species, such as •OH, •NH₂, •ClO and so on, abstract the H atom of H₂NO, yielding NO. NO reacts with •OH radical, leading to NO₂; NO reacts with •NH₂ radical and •OH radical, leading to N₂O. These products are consistent well with the experimental observations. Due to the complexity of the mechanisms, some strategies are used in this study: firstly, we concentrate on the reaction pathways of active species and the NH₃ and HClO₄ molecules, which exist in large amount; secondly, more reaction pathways involving the newly formed active species are considered.

Key words: ammonium perchlorate, thermal decomposition mechanism, broken-symmetry density functional theory (BS-UDFT), open-shell singlet diradical, solid propellant

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Jie Yang, Lin Ling, Yuxue Li, Long Lu. Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate[J]. Acta Chimica Sinica, 2023, 81(4): 328-337.

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Fig. & Tab. 18

Figure 1. The possible thermal decomposition mechanisms of ammonium perchlorate (AP). a: adsorption state; g: gaseous state

Figure 2. The possible thermal decomposition mechanisms of ammonium perchlorate (AP)

Figure 3. Path-b: the electron transfer mechanism of AP

Figure 4. Path-b: the proton transfer process of ammonium perchlorate. Energies are in kJ/mol, and selected bond lengths are in nanometer (nm)

Figure 5. Some optimized geometry structures on Path-b. The selected bond lengths are in nanometer (nm)

Figure 6. Path-c: the thermal decomposition pathways of perchloric acid. Energies are in kJ/mol, and selected bond lengths are in nanometer (nm)

Figure 7. The optimized structure of the transition states of Path-c and their spin density distribution

Figure 8. Path-d and Path-e: the pathway of dehydration mechanism. The selected bond lengths are in nanometer (nm)

Figure 9. Path-f: the reaction pathway of ?OH and NH3. The selected bond lengths are in nanometer (nm)

Figure 10. Path-h: the reaction pathway of ?OH and HClO4. The selected bond lengths are in nanometer (nm)

Figure 11. Path-g and Path-g': the reaction pathways of ?ClO3 and NH3. The selected bond lengths are in nanometer (nm)

Figure 12. Path-i: the reaction pathway of ?ClO3 and HClO4. The selected bond lengths are in nanometer (nm)

Figure 13. Path-j: the reaction pathway of ?NH2 and HClO4. The selected bond lengths are in nanometer (nm)

Figure 14. Path-k~Path-m: possible reaction pathways of ?NO formation. The selected bond lengths are in nanometer (nm)

Figure 15. Path-n: possible reaction pathways of ?NO2 formation. The selected bond lengths are in nanometer (nm)

Figure 16. Path-n and Path-p: possible reaction pathways of N2O formation. The selected bond lengths are in nanometer (nm)

Figure 17. Path-q~Path-s: possible reaction pathways of N2 formation. The selected bond lengths are in nanometer (nm)

Figure 18. The overall thermal decomposition mechanisms of ammonium perchlorate

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