Accession Number : AD0699953

Title :   COMPETITIVE UNIMOLECULAR DECOMPOSITION OF ALKYL RADICALS. TERTIARY BUTYL RUPTURE.

Descriptive Note : Technical rept.,

Corporate Author : WASHINGTON UNIV SEATTLE DEPT OF CHEMISTRY

Personal Author(s) : Larson,C. W. ; Rabinovitch,B. S.

Report Date : 15 JAN 1970

Pagination or Media Count : 14

Abstract : The competitive unimolecular decomposition of vibrationally excited 3,4,4-trimethylpentyl-2 radical was investigated. Relative and absolute rate of decomposition by tert-butyl (tBu) and methyl (Me) radical rupture were measured. Results were interpreted in terms of the Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular rate theory and lead to a value for the dissociation energy of (tBu-H) as 89.0 kcal/mole. Activation energies at 0K for tBu and Me radical addition to olefins are discussed; some disproportionation-recombination ratios involving tBu radical were obtained. (Author)

Descriptors :   (*FREE RADICALS, *DISSOCIATION), (*ALKENES, *ADDITION REACTIONS), REACTION KINETICS, VIBRATION, EXCITATION, HEAT OF ACTIVATION

Subject Categories : Physical Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE