Chloroform Pyrolysis: Experiment and Detailed Reaction Model

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Abstract
Chloroform was used as a model chlorocarbon system with high Cl/H ratio to investigate the thermal decomposition processes of chlorocarbons in pyrolytic reaction environments. The thermal decomposition of 1.0% chloroform in argon bath gas was studied to determine important chlorocarbon reaction pathways in pyrolysis. The reactions were studied in tubular flow reactors at a total pressure of 1 atm with residence times of 0.3-2.0 sec in the temperature range 535-800°C. A detailed kinetic reaction mechanism to describe the important features of products and reagent loss was developed. The mechanism is based on thermochemical principles and accurately describes the overall reaction process. We determine that the primary decomposition reaction pathway for chloroform is: CHCl3 → HCl +: CCl2 in the above temperature regime by combined experiment and modeling studies. High pressure limit rate constants obtained in this work for initially important decomposition of chloroform were determined as: A(1/sec.) Ea (Kcal/mol) We also show that combination and insertion reactions of :CCl2 form the C2Cl4, which is observed to be relatively stable and that CCl4 is formed by combination of Cl with CCl3.