Abstract
IN the Arrhenius equation , C is the collision frequency and P the steric factor. For gas reactions the kinetic theory gives C 1011. Bimolecular reactions in solution can be divided into two main types1: (a) reactions involving simple ions where Z 1011; (b) reactions involving molecules with many internal degrees of freedom, where Z 1011 (slow reactions). For reactions (a) a statistical mechanical treatment shows2 that P should be of order unity and here it can be concluded that C is of order 1011. For reactions (b) a statistical mechanical calculation of P is difficult and thus it is possible a priori that C falls below the gas value by several powers of ten.
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References
Moelwyn-Hughes and Hinshelwood, J. Chem. Soc., 230 (1932); Moelwyn-Hughes, Chem. Rev., 10, 241 (1932); ” Kinetics of Reaction in Solution”, Oxford (1933).
Cf. papers mentioned in the footnote of the preceding letter.
Wassermann, Ber., 66, 1392 (1933); NATURE, 134, 101 (1934); J. Chem. Soc., 828, 1511 (1935); Trans. Farad. Soc., 62, 69 (1936) and preceding letter.
Kistiakowsky and Lacher, J. Amer. Chem. Soc., 58, 123 (1936).
These figures have been calculated from measurements over a larger temperature interval than those in Ber. and J. Chem. Soc., loc. cit.
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WASSERMANN, A. Collision Frequency in Solution; Kinetics of Diene Syntheses in Solution and in the Gaseous State. Nature 137, 497 (1936). https://doi.org/10.1038/137497a0
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DOI: https://doi.org/10.1038/137497a0
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