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The rates of unimolecular reactions in gases

Published online by Cambridge University Press:  24 October 2008

N. B. Slater
N. B. Slater
Affiliation:
Gonville and Caius CollegeCambridge
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Extract

The molecule of a dissociating gas is treated as a dynamical system with n normal modes of vibration with incommensurable frequencies. The assumption that the molecule dissociates when one coordinate attains a critical high value leads to a unimolecular velocity constant expressed as an integral; analytical expressions are derived for bounds to its value. Calculations in a simple case indicate that the velocity constant is approximately of the form

This is in general agreement with experiment if the constant W is identified with the corresponding empirical energy constant.

Type
Research Article
Information
Mathematical Proceedings of the Cambridge Philosophical Society , Volume 35 , Issue 1 , January 1939 , pp. 56 - 69
Copyright
Copyright © Cambridge Philosophical Society 1939

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References

* Trans. Faraday Soc. 17 (1922), 599.Google Scholar

* Z. Elektrochem. 42 (1936), 94.Google Scholar

* Proc. Cambridge Phil. Soc. 31 (1935), 455.Google Scholar

* This theorem is an extension of one stated for n − 1 = 2 by Hardy, and Littlewood, , Acta Math. 37 (1914), 164Google Scholar; cf. Weyl, , Math. Annalen, 77 (1916), 319CrossRefGoogle Scholar. The surface H must lie within the unit “cube”; this is true of our H if h 2 is small.