njit-etd2003-111 - New Jersey Institute of Technology

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the energized adduct makes chemical activation reactions much more important in these
systems. A treatment for the rate of conversion, which includes decomposition of
energized adduct to product(s) (including back to reactant) and the competing rate of its
collision stabilization, is needed.
An example of a chemically activated reaction system is CH 3C.O with 02. As is
discussed by Lee et al., 3° CH3C.0 radical reacts with 02 to form a chemically activated,
energized adduct [CH 3C03•*], this process of forming adduct is much more efficient
than that by thermal molecular collision, and adduct contains excess energy from the new
bond formed in this chemical (addition) reaction. The energized adduct [CH 3C03
could go back to reactant
intramolecular H shift. The QRRK analysis (A + BC —> ABC*) shows that the chemical
activation process is more important than thermal dissociation process.