Role of Active Modes in Unimolecular Reactions. Volume I. Thermal Decomposition of Sulfur Tetrafluoride and Sulfur Hexafluoride.
Abstract
A new modification is introduced in the theory of unimolecular reactions. This modification assumes that not all normal vibrations of the active molecule are active modes. The modified theory has been used to investigate the thermal decomposition of sulfur tetrafluoride and sulfur hexafluoride in a background of inert atoms. Unlike previous failures to determine the pressure dependence for the thermal decomposition of these highly symmetrical molecules by means of the quantum statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory of unimolecular reactions, the new model correlates available experimental data for sulfur tetrafluoride and sulfur hexafluoride. The success of this modification is due to: (1) the assumption in the modified theory that not all normal vibrations of the active molecule are equally available to transfer energy to the bond to be broken, and (2) the simple rule used for an a priori selection of the active modes of the active molecule. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Dec 15, 1970
- Accession Number
- AD0715899
Entities
People
- Jerry F. Bott
- Roger L. Wilkins
- Theodore A. Jacobs
Organizations
- The Aerospace Corporation