Fall‐off Curves of Unimolecular Reactions

Author:
  • JTJ. Troe
    J. Troe
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Abstract
Fall‐off curves of thermal unimolecular reactions in the strong collision limit and in the general weak collision case are discussed. The fall‐off curves are represented in (k0, k∞)‐reduced form interpolating between both the limiting low pressure and the limiting high pressure rate constants k0 and k∞. In this reduced form fall‐off curves are very insensitive to details of the theory and simplified models can be used. Reduced fall‐off curves are represented in terms of tabulated Kassel integrals; the two Kassel parameters Sk and Bk are expressed in terms of experimental observables like the apparent activation energies in the low and high pressure limit and the collision efficiency. By this procedure some uncertain parts of the theory of unimolecular reactions can be eliminated from the calculation of fall‐off curves.

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