Modeling the Organic Nitrate Yields in the Reaction of Alkyl Peroxy Radicals with Nitric Oxide. 2. Reaction Simulations
journal contributionposted on 20.08.2003, 00:00 by John R. Barker, Lawrence L. Lohr, Robert M. Shroll, Susan Reading
Master equation calculations are used to model gas-phase literature experimental data for alkyl nitrate formation via the following reaction system of reversible reactions: (1) RO2 + NO ↔ ROONO, (2) ROONO ↔ RO + NO2, (3) ROONO ↔ RONO2, and (4) RONO2 ↔ RO + NO2 for R = CH3, i-C3H7, and 2-C5H11. The structures and thermochemistry of the stable species are based on electronic structure calculations described in the preceding companion paper in this issue (Lohr et al. J. Phys. Chem. A 2003, 107, xxx−xxx). Literature data for recombination rate constants are used to constrain the model calculations. Several transition state models and a range of energy transfer parameters are investigated. The results for R = CH3 show that a wide variety of plausible transition state models for k-4 gives good agreement with experiment for reaction (−4), because changes in assumed energy transfer parameters can compensate for differences between the transition state models. It is concluded that recombination reactions are good sources of absolute energy transfer parameters only when transition state properties are known with great accuracy. Although satisfactory models are obtained for the individual systems, the parameters cannot be transferred reliably from one system to another. Master equation models can be made to reproduce the experimental 2-pentyl nitrate yields from the title reaction as long as 〈ΔE〉down, the average energy transferred in deactivating collisions, is assumed to be surprisingly, and perhaps unphysically, small (∼25 cm-1), regardless of assumptions about the barrier to isomerization reaction 3. Several critical assumptions in the master equation models are examined, but none of them accounts for the small value of 〈ΔE〉down. It is concluded that new experiments should be carried out to verify or possibly revise the pressure-dependent alkyl nitrate yield data currently available in the literature.
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recombination reactionsisomerization reaction 3.ROONOROrecombination rate constantscompanion papermaster equation modelsstructure calculationstransition state propertiestitle reactionalkyl nitrate formationmodel calculationsreaction systemenergy transfer parametersAlkyl Peroxy RadicalsCH 3C 3 H 7Organic Nitrate YieldsCH 3 showNitric OxideRONOdeactivating collisions2. Reaction Simulations Master equation calculationsSeveral transition state modelsdatatransition state models