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Experimental research on multistep decomposition kinetics of ammonium perchlorate in the space-confined environment

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Abstract

The decomposition kinetic analysis of ammonium perchlorate (AP) has long been the research focus for involving various physicochemical phenomena. In this article, differential scanning calorimetry (DSC) measurements with specially made glass crucible were carried out to study the decomposition process of AP in the space-confined environment for the first time. It discovers that the peak temperature (Tp2) of high-temperature decomposition (HTD) and the final reaction temperature (Tend,D) shift to a lower temperature as the sample mass increased. It also indicates that such decomposition process can be deconvoluted into three reaction steps: endothermic, low-temperature decomposition, and HTD. Moreover, kinetic parameters of the reaction process were calculated via isoconversional and model fitting methods. The correctness of the fitted kinetic parameters was verified by the reconstruction of the primitive experimental curves. The obtained reaction model contributes to an improved understanding of AP’s thermal decomposition in the space-confined environment.

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Abbreviations

A(α):

Pre-exponential factor, s−1

A 1 :

Pre-exponential factor of endothermic reaction stage, s−1

A 2 :

Pre-exponential factor of LTD reaction stage, s−1

A 3 :

Pre-exponential factor of the HTD, s−1

E α :

Apparent activation energy, kJ mol−1

E 1 :

Apparent activation energy of endothermic reaction stage, kJ mol−1

E 2 :

Apparent activation energy of LTD reaction stage, kJ mol−1

E 3 :

Apparent activation energy of HTD reaction stage, kJ mol−1

F i(t):

The mathematical peak function

N :

The total number of peaks

Q :

Specific decomposition heat, J g−1

R :

Universal gas constant, 8.314 J mol−1 K−1

T :

Temperature, K

T 0 :

The temperature at which the DSC curve begins to deviate from the baseline, °C

T p1 :

The LTD exothermic peak temperature, °C

T p2 :

The HTD exothermic peak temperature, °C

T end, D :

The end reaction temperature of decomposition, °C

T onset :

Onset temperature of phase transition, °C

T end :

The end reaction temperature of phase transition, °C

T p :

Peak temperature of phase transition, °C

Δ H :

The average heat production, J g−1

a 0 :

The amplitude, mW

a 1 :

The position, °C

a 2 :

The half width, °C

a 3 :

The asymmetry

f(α) :

Reaction model

n 1 :

Reaction order of endothermic reaction stage

n 21 , n 22 :

Reaction order of LTD reaction stage

n 3 :

Reaction order of HTD reaction stage

r i :

Reaction rate of the stage i, stage

t :

Time, s

x :

Arbitrary independent variable

α :

Reaction progress, the extent of conversion

β :

Heating rate, K s−1

i :

Reaction number

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Acknowledgements

The authors gratefully acknowledge the National key R&D Program of China (2017YFC0804701-4) and the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2020L0660) for their financial support.

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  1. Hua-Bo Li and Xiao-Qiao Zhao contribute equally to the article.

Authors and Affiliations

  1. Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, Jiangsu, China

    Hua-Bo Li, Xiao-Qiao Zhao, Wen-Qian Wu, Li-Ping Chen & Wang-Hua Chen

  2. Wanhua Chemical Group Co., Ltd, Yantai, 264002, Shandong, China

    Shi-Ran Li

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Li, HB., Zhao, XQ., Wu, WQ. et al. Experimental research on multistep decomposition kinetics of ammonium perchlorate in the space-confined environment. J Therm Anal Calorim 147, 11535–11547 (2022). https://doi.org/10.1007/s10973-022-11310-x

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