A detailed kinetic model of the high-temperature pyrolysis of tetrachloroethene

✍ Scribed by Philip H. Taylor; Debra A. Tirey; Barry Dellinger

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 903 KB
• Volume: 104
• Category: Article
• ISSN: 0010-2180
• DOI: 10.1016/0010-2180(95)00117-4

✦ Synopsis

Comprehensive product yield determinations from the high-temperature, gas-phase pyrolysis of tetrachloroethene (C2C14) using two fused-silica tubular flow reactors are reported. The effects of reactor surface area to volume (S/V) ratio were evaluated by conducting detailed product analyses with 0.1-cm i.d. and 1.0-cm i.d. reactors. Under low S/V ratio, initial decomposition was observed at 1123 K with formation of dichloroacetylene (C2C12) and hexachlorobenzene (C6C16(cY)). Molecular chlorine was also observed as a product at higher temperatures. Under high S/V ratio, C2C14 decomposition was initiated at 973 IC Reaction products included CI 2, carbon tetrachloride (CC14), hexachlorobutadiene (C4C16), and CrC16(cY). Product yields under low S//V ratio indicated that yields of CrClr(cy) were a factor of 4 larger than observed for high S//V ratios. A previously published detailed pyrolysis mechanism for trichloroethene (C2HCI 3) was incorporated into a C2C14 pyrolysis model to provide predictions of the high-temperature reaction behavior of C2C14. The model predictions are in much better agreement with product distributions obtained using the 1 cm i.d. reactor versus the 0.1 cm i.d. reactor. Minor revisions of the C2HCI 3 model significantly improved comparisons with the observed C2C14 product distributions without compromising previous agreement with C2HC13 product distributions. Important radical-molecule addition reactions leading to CrC16(cy) are identified using sensitivity analysis and production rate calculations.