Evaluating the thermal stability of chemicals and systems: A review

Abstract

In the realm of chemical processing, particularly at the industrial scale, safety is of utmost importance. A predominant factor causing accidents within the chemical industry is runaway phenomena, primarily initiated by uncontrolled exothermic reactions. This review critically examines the often-overlooked decomposition mechanisms as a significant contributor to thermal energy release, necessitating a comprehensive revision and understanding of both experimental and theoretical strategies for assessing thermal degradation. Key to this discourse is the explication of calorimetry as the principal experimental technique, alongside ab initio quantum chemistry simulations as a robust theoretical framework for quantifying the most relevant properties. However, more than mere cognisance of these methodologies is required for a meticulous thermal stability assessment. The review emphasizes identifying and quantifying fundamental parameters through experimental and theoretical investigations. Only upon acquiring these parameters, including kinetic, thermodynamic, onset, and peak characteristics of the exothermic decomposition reactions, can one effectively mitigate risks and hazards in designing and optimizing chemical processes and apparatus. Furthermore, this review delineates qualitative and quantitative methodologies for hazard assessment, proffering strategies for estimating safe operational conditions and sizing relief devices. The paper culminates in exploring future trajectories in thermal stability assessments, focusing on emerging applications in lithium-ion batteries, electrolyzers, electrified reactors, ionic liquids, artificial intelligence and machine learning approaches. Thus, the paper underlines the evolving landscape of thermal risk management in contemporary and future chemical industries.