Document Type


Date of Award


Degree Name

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


Chemical Engineering, Chemistry and Environmental Science

First Advisor

Joseph W. Bozzelli

Second Advisor

Wing T. Wong

Third Advisor

James M. Grow


The reactions of atomic hydrogen with chloroform were studied in a tubular flow reactor both in a 4 cm i.d. and 2.6 i.d. discharge flow reactor at pressure of 2.22 to 2.82 mmHg and room temperature using GC and GC/MS for analysis of the reaction. The hydrogen atom concentration at the reaction flame was measured by Chemiluminescence titration with nitrogen dioxide. The hydrogen concentrations are in the 2.48 x 10+14 to 4.83 x 10+14 atoms/cc range at six different hydrogen flow rates. Evidence was found for the formation of atomic carbon intermediate in the reaction, but methane was the primary final product in both reactions for reaction times of 0.024 sec to 0.072 sec.

We propose a mechanism for the secondary reactions that almost all chloroform consumed went toward the production of methane. Thermochamical data were calculated for this purpose and energy studies were done along with analysis of many references. The Kinetics were computer-simulated by solving the simultaneous first-order differential equations describing the time dependence of the concentrations of the various chemical species, using both Runge-Kutta method for integration and Rosenbrock method for optimization of the system. Through this computer modelling of a reaction scheme and comparison with experimental data the rate constants for the primary reaction of hydrogen atom with chloroform at 298° K,

H + CHCl3 ---> HCl + CHCl2,

was determined to be 4.2 x 10-14 cc/molecule sec. This value was larger than that determined in the only earlier study unpublished (23).

Included in

Chemistry Commons



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