Development and validation of a detailed reaction mechanism for the condensed phase decomposition of ammonium perchlorate

IF 5.8 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2025-02-13 DOI:10.1016/j.combustflame.2025.114045

Jay Patel, Arindrajit Chowdhury, Neeraj Kumbhakarna

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引用次数: 0

Abstract

The primary objective of the current research is to develop and validate a detailed reaction mechanism for the condensed-phase decomposition of ammonium perchlorate (AP), which is crucial for understanding the combustion behavior of AP-based propellants that are extensively used in solid rocket propulsion systems. Quantum mechanics calculations were performed at the B3LYP/6–311++G(d,p) level of theory to investigate the elementary reactions in the condensed phase, utilizing the Integral Equation Formalism of the Polarizable Continuum Model (IEFPCM) to simulate these reactions. Transition state theory was employed to determine the kinetic parameters, while the CBS-QB3 method was used to calculate the thermodynamic properties of the reactions. Experimental validation was achieved by comparing the computational results with data from laser pyrolysis and Fourier-transform infrared spectroscopy (FTIR) experiments, conducted at four isothermal conditions (410 °C, 430 °C, 450 °C, and 470 °C) in terms of mass loss and gas-phase mole fraction profiles. The computational model, incorporating a detailed reaction mechanism and product evaporation, closely matched experimental observations, with minor deviations attributed to experimental uncertainties. The model assumes that 40 % of AP undergoes sublimation, forming NH₃ and HClO₄ in the gas phase, while the remaining 60 % reacts in the condensed phase, producing species such as H₂O, HCl, NO₂, N₂O, ClO₂, HNO₃, and Cl₂, which evaporate into the gas phase. This validated reaction mechanism represents a significant advancement in modeling AP decomposition, providing valuable insights for safety and performance assessments in industrial applications.

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来源期刊

Combustion and Flame 工程技术-工程：化工

CiteScore

9.50

自引率

20.50%

发文量

631

审稿时长

3.8 months

期刊介绍： The mission of the journal is to publish high quality work from experimental, theoretical, and computational investigations on the fundamentals of combustion phenomena and closely allied matters. While submissions in all pertinent areas are welcomed, past and recent focus of the journal has been on: Development and validation of reaction kinetics, reduction of reaction mechanisms and modeling of combustion systems, including: Conventional, alternative and surrogate fuels; Pollutants; Particulate and aerosol formation and abatement; Heterogeneous processes. Experimental, theoretical, and computational studies of laminar and turbulent combustion phenomena, including: Premixed and non-premixed flames; Ignition and extinction phenomena; Flame propagation; Flame structure; Instabilities and swirl; Flame spread; Multi-phase reactants. Advances in diagnostic and computational methods in combustion, including: Measurement and simulation of scalar and vector properties; Novel techniques; State-of-the art applications. Fundamental investigations of combustion technologies and systems, including: Internal combustion engines; Gas turbines; Small- and large-scale stationary combustion and power generation; Catalytic combustion; Combustion synthesis; Combustion under extreme conditions; New concepts.