Mj. Thomson et al., AN EXPERIMENTAL AND NUMERICAL STUDY OF THE HIGH-TEMPERATURE OXIDATIONOF 1,1,1-C2H3CL3, Combustion and flame, 98(1-2), 1994, pp. 155-169
Gaseous 1,1,1-trichloroethane (1,1,1-C2H3Cl3) is injected into the pos
tflame region of a turbulent combustor with equivalence ratios, reside
nce times and temperatures in the range of those encountered in the po
stflame regions of hazardous waste incinerators. Measured concentratio
ns are compared with a detailed chemical kinetic mechanism, which is p
resented with the sources of the reaction rate constants. Each rate is
based on literature evaluation of experimental data, or if it is esti
mated, on fundamental principles of thermochemical kinetics and molecu
lar thermodynamic properties. By basing the mechanism on fundamental p
rinciples, its applicability should extend beyond the experimental con
ditions for which it was developed. The model and the experimental dat
a show reasonable agreement for all temperatures. A study of the impor
tant destruction pathways indicates that 1,1,1-C2H3Cl3 undergoes unimo
lecular decomposition to form 1,1-C2H2Cl2. Reacting with either Cl or
OH, the 1,1-C2H2Cl2 forms the 1,1-dichlorinated vinyl radical CCl2CH.
This radical reacts via competing routes CCl2CH = C2HCl + Cl, CCl2CH O2 = COCl2 + HCO, to form chloroacetylene (C2HCl) or phosgene (COCl2)
.