Model identification and classification of autocatalytic decomposition kinetics

• Published in: Journal of thermal analysis and calorimetry 2023-06, Vol.148 (12), p.5455-5470
• Main Authors: Wu, Wenqian, Zhao, Xiaoqiao, Meng, Fuqing, Chen, Liping, Guo, Zichao, Chen, Wanghua
• Format: Article
• Language: English
• Subjects: Analysis; Analytical Chemistry; Autocatalysis; Chemistry; Chemistry and Materials Science; Decomposition; Heating rate; Inorganic Chemistry; Kinetics; Mathematical models; Measurement Science and Instrumentation; Numerical analysis; Physical Chemistry; Polymer Sciences; Risk management; Simulation methods; Venting systems
• ISSN: 1388-6150; 1588-2926
• DOI: 10.1007/s10973-023-12072-w

Decomposition of most hazardous chemicals is accompanied by autocatalytic characteristics. Strength of autocatalytic decomposition sheds light on the development of risk control measures and identification of the most dangerous scenes in emergency venting systems. In this paper, autocatalytic factor Z ( T ) which was deduced based on the Perez–Benito model can be considered as the characterization of autocatalysis. And the value of autocatalytic factor can be calculated by the formula Z ( T ) = ( k 1 / k 2 )exp [− ( E 1  −  E 2 )/ RT ] under known kinetics. By deriving the relationship between autocatalytic factor and intersection conversion of different heating rate curves, the calculation value of autocatalytic factor can be simplified by formula Z ( T * ) = 1 − ( α βi  +  α βni ) under unknown kinetics. Through the numerical simulation under different kinetic parameters, autocatalytic strength can be divided into five intervals based on the value of Z ( T ). Reliability of the method was verified by application and comparison of five substances with the known autocatalytic strength. Graphical abstract