CALCULATION OF RATE COEFFICIENTS FOR SOME ELEMENTARY REACTIONS. HYDROGEN, DEUTERIUM, AND DEUTERIUM HYDRIDE WITH CHLORINE
Abstract
Rate coefficients were calculated for the reactions of hydrogen, deuterium, and deuterium hydride with chlorine. The potential energy surfaces of the isotopic transition complexes of HCl2 and H2Cl were constructed by the Sato method to match experimental activation energies in accordance with absolute rate theory. The rate coefficients calculated using absolute rate theory are then used to evaluate the relative rates of reaction of H2/HD, H2/ D2 with chlorine atoms, and the relative rates of the fast reaction step HCl2 compared to the back reaction HHCl. The results agree very well with the few experime-l values reported in the literature. Theoretical calculations show that prior experimental values of the preexponential factors in the Arrhenius type expression for rate constants are not required in order to obtain better information on the structure and vibrational frequencies of the transition states. Agreement of the activated complex theory with experiment was satisfactory.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 15, 1963
- Accession Number
- AD0407555
Entities
People
- Roger L. Wilkins
Organizations
- The Aerospace Corporation