Gas Phase Formation of Chlorinated Aromatic Compounds from the Pyrolysis of Tetrachloroethylene

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Abstract
The thermal degradation of tetrachloroethylene (C2C14.,) has been compared to that of ethylene (C2H2) using a high-temperature flow reactor system. Kinetic studies were conducted in an oxygen-Tree helium carrier for reaction times of 2,0 s. Exposure temperatures for this reaction time were varied from 300-1050° C. Significant yields of perchlorinatcd olcfinic and aromatic species were observed from C2C14 with similar yields of non-chlorinated aromatic species from C2H4. Acetylene (C2H4) was the major organic product from C2H4 while hexachlorobenzene (C6Cl6) was the major organic product from C2Cl4. Dichloroacetylene (C2C14) was not observed from C2C14, which is attributed to a rapid polymerization pathway. Chlorine atom displacement reactions involving perchlorinated olefinic radical attack on per-chlorinated olefins and acetylenes are proposed as key steps in molecular growth pathways.