Accession Number : AD0715899

Title :   Role of Active Modes in Unimolecular Reactions. Volume I. Thermal Decomposition of Sulfur Tetrafluoride and Sulfur Hexafluoride.

Descriptive Note : Rept. for Jun 69-Jul 70,

Corporate Author : AEROSPACE CORP EL SEGUNDO CALIF LAB OPERATIONS

Personal Author(s) : Wilkins,Roger L. ; Bott,Jerry F. ; Jacobs,Theodore A.

Report Date : 15 DEC 1970

Pagination or Media Count : 31

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)

Descriptors :   (*SULFUR COMPOUNDS, *DECOMPOSITION), REACTION KINETICS, SHOCK WAVES, FLUORIDES, VIBRATION, MOLECULAR ENERGY LEVELS, EMISSIVITY, INFRARED RADIATION, FLUORESCENCE, PYROLYSIS, THERMOCHEMISTRY

Subject Categories : Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE