Determination of unimolecular rate data from reaction mid-point temperatures derived from EPR Spectra

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Abstract

The activation energies of unimolecular homolytic reactions (E-r) are predicted to correlate linearly with the mid-point temperatures (T-mild) defined as the temperature at which the rearranged and unrearranged species are of equal concentration, for photochemically initiated processes under EPR conditions. A linear relationship (E-r/kcal mol(-1) = 0.044T(mid) + 0.22) has been demonstrated from experimental data and shown to hold for a range of solvents and instrumental configurations. The relationship will facilitate the determination of kinetic parameters, particularly for processes where the spectra of the intermediates are of low intensity.

Original languageEnglish
Pages (from-to)603-605
Number of pages3
JournalJournal of Chemical Society, Perkin Transactions 2
Issue number3
DOIs
Publication statusPublished - Mar 1998

Keywords

  • ELECTRON-PARAMAGNETIC RESONANCE
  • RING-OPENING REACTIONS
  • SPIN RESONANCE
  • RADICALS
  • SPECTROSCOPY
  • CYCLOBUTYLMETHYL
  • STABILIZATION

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