Document Type


Date of Award


Degree Name

Master of Science in Environmental Science - (M.S.)


Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Deran Hanesian

Third Advisor

Paul H. Kydd


Thermal decomposition experiments on dichloromethane in absence and presence of added O2 and/or 4 and in argon bath gas were conducted in a tubular flow reactor. The thermal reactions were studied at 1 atmosphere pressure with residence times of 0.3 - 2.0 seconds in the temperature range from 680 to 840 °C.

The degradation of dichloromethane and the decomposition product distributions were studied in both oxidative and pyrolytic reaction environments. The slowest decay of dichloromethane occurred when CH4 was present and 02 was absent. The concentration of all products, (except HCl, CO, and CO2 in the oxidation), are below 10% in the reaction environments. The chlorinated products, such as C2HCl3, CH3Cl, CHClCHCl, are shown to be more stable in the pyrolysis than in the oxidation. When oxygen is present, the concentration of chlorinated products decreases more rapidly above 780 °C than when no oxygen is present. Carbon mass balance in the CH2Cl2/Ar reaction environment was less than 60% at temperatures above 780 °C, and less than 20% at temperatures above 820 °C. This implies that the formation of high molecular species and soot are occur at higher temperatures in the absence of oxygen.

The overall (global) rate constants of CH2Cl2 decay in this study were found as:

  1. CH2Cl2 : CH4 : O2 : Ar = 1 : 1 : 4 : 94 k = 6.74 x 1015 x EXP(-75.84/RT) (1/sec)
  2. CH2Cl2 : O2 : Ar = 1 : 4 : 95 k = 1.56 x 1024 x EXP(-114.68/RT) (1/sec)
  3. CH2 C:l CH4 : Ar = 1 : 1 : 98 k = 6.46 x 1013 x EXP(-67.85/RT) (1/sec)
  4. CH2Cl2 : Ar = 1 : 99 k = 1.21 x 1018 x EXP(-86.92/RT) (1/sec)

A detailed kinetic reaction mechanism consisting of 94 species and 382 elementary reactions based on thermo-chemical principles and Transition State Theory, was modified and used to model results obtained from the experimental system. The results of model prediction for dichloromethane decay were slower than experimental results. Major products (CH3Cl and C2HCl3) distribution below 780 °C match the experimental results well.



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