Abstract
The importance of the values of parameters occurring in a rate equation is usually secondary compared to the functional from of the rate equation itself. However, the values sometimes carry important information and the values can be used to validate theoretical ideas. This chapter derives maximum rate constants for diffusion controlled reactions, then introduces the concept of activation and the activation parameters. The Arrhenius and Eyring equations are given special emphasis in interpreting the temperature dependence of rate constants. Slight systematic changes in the chemical structure of a reagent can often give rise to insight into how a process works. The usual forms and validity range of the linear free energy relationship is also discussed.
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Notes
- 1.
This author believes that an experiment cannot be wrong, but its information content can be seriously misinterpreted.
- 2.
The notations Δ ‡ G, Δ ‡ H, and Δ ‡ S follow IUPAC recommendations. In actual use, the forms Δ G ‡, Δ H ‡, and Δ S ‡ are a lot more common in the literature.
- 3.
It is much more common to use e to denote the charge of an electron. Yet this text uses e t very often for the exponential function, so it seemed necessary to avoid possible confusions by selecting the notation Q e instead of the usual one.
- 4.
The reader should not confuse the dipole moment used here with the reduced mass defined in Eq. (4.2) despite the fact that, following well-established conventions, the Greek letter μ is used to denote both of these different physical quantities.
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Lente, G. (2015). Information from Parameter Values. In: Deterministic Kinetics in Chemistry and Systems Biology. SpringerBriefs in Molecular Science. Springer, Cham. https://doi.org/10.1007/978-3-319-15482-4_4
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