Plasma-based global pathway analysis to understand the chemical kinetics of plasma-assisted combustion and fuel reforming

The Global Pathway Analysis (GPA) algorithm helps analyze the chemical kinetics of complex combustion systems by identifying important global reaction pathways connecting a source species to a sink species through various important intermediate species (i.e., hub species). The present work aims to extend GPA algorithm to plasma-assisted combustion and fuel reforming systems to identify the dominant global pathways in such systems at various conditions. In addition, the present study extends the ability of GPA algorithm to identify reaction cycles involving the excitation of high-concentration species (e.g., O₂, N₂, and fuel) to their vibrational and electronic states and the subsequent de-excitation to their ground state, based on their significance on the reactivity of plasma-assisted systems in terms of gas heating and radical production. Provisions are made in the GPA algorithm to evaluate the reactivity of identified reaction pathways and cycles based on the element-flux transfer (i.e., dominance), heat release, and radical production rate. The newly developed Plasma-based Global Pathway Analysis (PGPA) algorithm is then used to analyze the plasma-assisted combustion of ammonia and reforming of methane. The PGPA analyses elucidated the significance of vibrational-translational cycles on the reactivity of NH₃/air mixtures. Further, analyses on the production of NO ascribed the early reforming of NH₃ to N₂ and H₂ in impeding the production of NO during plasma-assisted NH₃ ignition. Lastly, the enhanced reforming of CH₄/N₂ mixtures using plasma has been attributed to electron impact dissociation of CH₄ when compared to thermal reforming. In contrast, conventional path-Flux analysis (PFA) was found to require significant manual effort and pre-analysis intuitions from expert knowledge, making it arduous to provide valuable insights into plasma chemistry. The user-friendly and automated nature of PGPA thus provides a valuable tool for assessing the kinetics of plasma-assisted systems helpful in analyzing and, further, a foundation in reducing plasma-assisted chemistry, without the needs of expert knowledge.