The modifications in our earlier paper by the above title, necessitated by recent work on the absolute rate of chemical reactions, are considered, and it is shown that the assumption that the fragments resulting from a unimolecular decomposition must be ``exactly oriented'' (in the sense of the preceding article) in order to be able to recombine is equivalent to the assumptions made by Kassel in his quantum theory of unimolecular reactions. The relation between the observed activation energy and the energy necessary to break the bond is discussed.
REFERENCES
1.
Parker Traveling Fellow of Harvard University.
2.
3.
Tolman, Statistical Mechanics (Chemical Catalog Co., 1927), pp. 261–2. See also footnote 11 of Ref. 2.
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8.
Essentially this assumes the rate is not determined by the entropy of a “normal” (see preceding article, §1) activation complex, for at the top of the saddle point no energy is available from the bond to be formed.
9.
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© 1935 American Institute of Physics.
1935
American Institute of Physics
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