Abstract
Halogen loss from iodoethane, 1-bromopropane, 2-bromopropane, 1-iodopropane, and 2-iodopropane has been studied by means of electron-ion coincidence techniques and by observation of metastable transition. Analysis of the breakdown curves and the study of residence times gave the zero-kelvin thresholds for halogen loss and indicated the size of the kinetic shift. The fragmentation onset for iodoethane was located in a Franck-Condon gap. The zero-kelvin thresholds for the propyl halides were found to lie at or just above the upper spin-orbit level of the parent ion. All of the propyl halides exhibited a unimolecular metastable transition. At fragmentation onset the 2-halopropane ions have negligible fragment kinetic energy while the 1-halopropane produce secondary propyl ions wih 100-200 meV of kinetic energy. It was established that a potential barrier must be surmounted in this fragmentation-isomerization process and analysis suggests a dynamic mechanism other than conventional QET, for example, weak couplings of vibrational modes. Analysis of the 2-halopropane fragmentation thresholds leads to an accurate, absolute value for the proton affinity of propylene, 751.4 +/- 2.9 kJ/mol at room temperature. This value reconciles some differences inherent in the proton affinity scale based on various relative measurements.
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