| Abstract
| - In kinetic models, gas-phase reactions involving large molecules (of more than about a dozen atoms) areoften assumed to be in the high-pressure limit, that is, to not exhibit significant falloff or chemical activationeffects. However, cases are known where rather large molecules are indeed involved in chemically activated,pressure-dependent reactions particularly at high temperatures. Here, we present simple formulas givingguidance for deciding whether a particular reaction's rate can be accurately approximated using the high-pressure limit rate constant k∞(T). We find that under practical combustion conditions for liquid and gaseousfuels, few reactions are truly in the high-pressure limit, regardless of the size of the molecules involved.
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