1. Collisional Transition Probabilities for Vibrational Deactivation of Chemically Activated sec-Butyl Radicals. Diatomic and Polyatomic Molecules 2. Large Statistical Secondary Isotope Effects in Non-Equilibrium Reaction Systems. Unimolecular Decomposition of a Chemically Activated Ethyl-d1 and Ethyl-d3 Radicals.

摘要

The study of coalitional transitional probabilities for the de-excitation by inert gases or chemically activated sea-butyl Radicals, excited to Internal energies in excess of 40 kcal mole has been extended to H2, D2, H2, C02, CH4, CD3F, CH3C1 and SF6 the diatomic gases display behavior similar to the rare gases and. on a preferred exponential model of coalitional transition probabilities the average amount of energy transferred per collision is kcal/mole. On step-ladder model the corresponding amount is AE 2.5 kcal mole From higher pressure data, the efficiency (assumed AE) for CD3F, CR3Cl and SF6 is deduced to be comparable with that for butane and on a preferred step-ladder model, AE > 9 Kael. For CO2 and CH4 the behavior is intermediate. The possible importance of the role .of internal rotation of butyl in facilitating energy transfer is noted;some uncertainty concerning the role of overall rotations and vibration modes of the deactivator in the relaxation processed.