A THEORETICAL ANALYSIS OF THE REACTION BETWEEN ETHYL AND MOLECULAR OXYGEN

Using a combination of electronic-structure theory, variational transition-state theory, and solutions to the time-dependent master equation, the authors have studied the kinetics of the title reaction theoretically over wide ranges of temperature and pressure. The agreement between theory and experiment is quite good. By comparing the theoretical and experimental results describing the kinetic behavior, they have been able to deduce a value for the C{sub 2}H{sub 5}-O{sub 2} bond energy of {approximately}34 kcal/mole and a value for the exit-channel transition-state energy of {minus}4.3 kcal/mole (measured from reactants). These numbers compare favorably with the electronic-structure theory predictions of 33.9 kcal/mole and {minus}3.0 kcal/mole, respectively. The master-equation solutions show three distinct temperature regimes for the reaction, discussed extensively in the paper. Above T {approx} 700 K, the reaction can be written as an elementary step, C{sub 2}H{sub 5} + O{sub 2} {leftrightarrow} C{sub 2}H{sub 4} + HO{sub 2}, with the rate coefficient, k(T) = 3.19 x 10{sup {minus}17} T{sup 1.02} exp(2035/RT) cm{sup 3}/molec.-sec., independent of pressure even though the intermediate collision complex may suffer a large number of collisions.

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