Document Type
Thesis
Date of Award
9-30-1981
Degree Name
Master of Science in Chemical Engineering - (M.S.)
Department
Chemical Engineering and Chemistry
First Advisor
Joseph W. Bozzelli
Second Advisor
Richard Clyde Parker
Third Advisor
James M. Grow
Abstract
The kinetics of the reactions of atomic hydrogen with methylene chloride and carbon tetrachloride were studied spectroscopically and chromatographically using a 4 cm i.d. discharge flow reactor at pressures of 1 to 8 mm Hg absolute and room temperature. Hydrogen atom concentrations were measured by chemiluminescence titration with nitrogen dioxide. Evidence was found for the formation of atomic carbon intermediate in the reaction with carbon tetrachloride, but methane and HCl were the chief products in both reactions for reaction times of 150 ms and higher, showing that secondary reactions were so fast that almost all halomethane consumed went toward the production of methane.
Studies were done on the thermodynamic properties and the kinetic parameters of the secondary reactions in order to propose a complete mechanism for the reaction processes. Through computer modelling of the reaction scheme and comparison with experimental data, the rate constants for the primary reactions of H + CH2Cl2 -> CH2Cl + HCl and H + CCl4 -> CCl3 + HCl were determined to be 3.0 x 10-16 and 6.0 x 10-14 cm3/mol sec respectively. These values were of the same order of magnitude as those determined in earlier studies.
Recommended Citation
Chari, Sriram, "Reactions of atomic hydrogen with selected halomethane" (1981). Theses. 3616.
https://digitalcommons.njit.edu/theses/3616
