Ph. Taylor et al., DETAILED MODELING OF THE PYROLYSIS OF TRICHLOROETHENE - FORMATION OF CHLORINATED AROMATIC SPECIES, Combustion science and technology, 101(1-6), 1994, pp. 75-102
Comprehensive product yield determinations from the high-temperature,
gas-phase pyrolysis of trichloroethene (C2HCl2) using two fused silica
tubular how reactors coupled to in-line gas chromatographic-mass spec
trometric analyses are reported. Initial decomposition was observed at
1000 K with formation of HCl and C2Cl2. Pronounced molecular growth w
as observed at higher temperatures as evidenced by the formation of C2
Cl4, C4Cl4, and C6Cl6 (cy) as major (greater than or equal to 5 mole %
) products and C4Cl2, C4Cl6, C6HCl5 (cy), C8Cl6 (cy), C8Cl8 (cy), C10C
l8 (cy), and C12Cl8 (cy) as minor (less than or equal to 5 mole %) pro
ducts. 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 the higher S/V ratio, C2HCl3 decompositio
n was increased by an order of magnitude and product distributions sug
gested that radical-radical and radical-atom recombination rates were
enhanced. Product yields under reduced S/V ratio indicated that yields
of perchlorinated aromatic and perchlorinated PAH species were a fact
or of 10 larger than observed for higher S/V ratios. A detailed reacti
on mechanism is presented for the 1 cm i.d. reactor data describing mo
lecular growth up to the formation of C8Cl6 (cy) and C8Cl8 (cy). Compa
rison of predicted versus experimental major and minor species profile
s are presented, with generally good agreement. Important radical-mole
cule addition reactions leading to molecular growth are identified usi
ng sensitivity analysis and production rate calculations.