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

Taylor, PH; Tirey, DA; Dellinger, B

HERO ID

1444392

Reference Type

Journal Article

Year

1996

HERO ID 1444392
In Press No
Year 1996
Title A detailed kinetic model of the high-temperature pyrolysis of tetrachloroethene
Authors Taylor, PH; Tirey, DA; Dellinger, B
Journal Combustion and Flame
Volume 104
Issue 3
Page Numbers 260-271
Abstract Comprehensive product yield determinations from the high-temperature, gas-phase pyrolysis of tetrachloroethene (C2Cl4) 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 (C2Cl2) and hexachlorobenzene (C6Cl6(cy)). Molecular chlorine was also observed as a product at higher temperatures. Under high S/V ratio, C2Cl4 decomposition was initiated at 973 K. Reaction products included Cl-2, carbon tetrachloride (CCl4), hexachlorobutadiene (C4Cl6), and C6Cl6(cy). Product yields under low S/V ratio indicated that yields of C6Cl6(cy) were a factor of 4 larger than observed for high S/V ratios. A previously published detailed pyrolysis mechanism for trichloroethene (C2HCl3) was incorporated into a C2Cl4 pyrolysis model to provide predictions of the high-temperature reaction behavior of C2Cl4. 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 C2HCl3 model significantly improved comparisons with the observed C2Cl4 product distributions without compromising previous agreement with C2HCl3 product distributions. Important radical-molecule addition reactions leading to C6Cl6(cy) are identified using sensitivity analysis and production rate calculations.
Doi 10.1016/0010-2180(95)00117-4
Wosid WOS:A1996TZ13800003
Is Certified Translation No
Dupe Override No
Comments Source: Web of Science WOS:A1996TZ13800003
Is Public Yes