Quantum chemical pathways for the formation of 2,3,7,8-tetrachloro dibenzo-p-dioxin (TCDD) from 2,4,5-trichlorophenol: a mechanistic and thermo-kinetic study

• Published in: Journal of molecular modeling 2024-07, Vol.30 (7), p.199, Article 199
• Main Authors: Hussain, Raghibul, Ali, Sk. Musharaf, Pugazhenthi, Gopal, Banerjee, Tamal
• Format: Article
• Language: English
• Subjects: Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Condensates; Density functional theory; Dioxins; Molecular Medicine; Original Paper; Quantum chemistry; Radicals; Rate constants; Reaction mechanisms; Theoretical and Computational Chemistry; Trichlorophenols; Vapor phases
• ISSN: 1610-2940; 0948-5023; 0948-5023
• DOI: 10.1007/s00894-024-05999-w

Context Dioxins, specifically 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD), are highly toxic dioxins known for their severe health impacts and persistent environmental pollutants. This study focuses on understanding the formation pathways of TCDD from its precursor molecule 2,4,5-trichlorophenol (2,4,5-TCP). In our exploration of reaction pathways from 2,4,5-trichlorophenol (TCP), we delve into three reaction mechanisms: free-radical, direct condensation, and anionic. Our findings highlight the significance of the radical mechanism, particularly propagated by H radicals, with a notable increase in dioxin formation around 900 K. These results are consistent with experimental observations indicating an increase in the conversion of trichlorophenol from 600 to 900 K in the non-catalytic gas phase reaction. Thermodynamic parameters (∆ H , ∆ S , and ∆ G ), reaction barriers, and rate constants (k) were calculated across a temperature range of 300–1200 K to support the findings and provide insights into the optimal temperature range for controlling dioxins during the incineration process. Method In this study, quantum chemical calculations were conducted using density functional theory (DFT) with the B3LYP functional and the 6–311 +  + G(d,p) basis set in Gaussian 16 software. Stationary points, including transition states (TS), were confirmed with frequency calculations. Intrinsic reaction coordinate (IRC) calculations ensured minimum energy paths between TS and products, visualized in GaussView 6.0 Program. Single-point energy calculations utilized a more precise basis set, 6–311 +  + G(3df,2p), for enhanced energy accuracy, incorporating zero-point vibrational energy (ZPE) and other energy corrections. These calculations were repeated over a temperature range of 298.15–1200 K at 1 atm pressure. Finally, rate constant (k) expressions associated with TCDD formation were determined using transition state theory (TST).