Influence of Molecular Parameters on Rate Constants of Thermal Dissociation/Recombination Reactions: The Reaction System CF ⇄ CF + F.

The possibilities to extract incompletely characterized molecular parameters from experimental thermal rate constants for dissociation and recombination reactions are explored. The reaction system CF (+M) ⇄ CF + F (+M) is chosen as a representative example. A set of falloff curves is constructed and compared with the available experimental database.

The Thermal Dissociation-Recombination Reactions of SiF, SiF, and SiF: A Shock Wave and Theoretical Modeling Study.

Monitoring UV absorption signals of SiF and SiF, the thermal dissociation reactions of SiF and SiF were studied in shock waves. Rationalizing the experimental observations by standard unimolecular rate theory in combination with quantum-chemical calculations of the reaction potentials, rate constants for the thermal dissociation reactions of SiF, SiF, and SiF and their reverse recombination reactions were determined over broad temperature and pressure ranges. A comparison of fluorosilicon and fluorocarbon chemistry was finally made.