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How to Get Kinetic Parameters

  • A. P. J. Jansen
Part of the Lecture Notes in Physics book series (LNP, volume 856)

Abstract

This chapter shows how rate constants can either be calculated or be derived from experimental results. Calculating rate constants involves determining the initial and the transition state of a process, the energies of these states, and their partition functions. We show that the general expression for the partition functions can often be simplified when a degree of freedom is a vibration, a rotation, or a free translation. Recipes can be given for how to combine partition functions to get rate constants for processes like Langmuir–Hinshelwood and Eley–Rideal reactions, adsorption and desorption, and diffusion. The phenomenological or macroscopic equation is the essential equation to get rate constants from experiments. It is shown how to use it for simple desorption, simple and dissociative adsorption, uni- and bimolecular reactions, and diffusion. Lateral interactions can affect rate constants substantially, but because they are relatively weak, special attention needs to be given to the reliability of calculations of these interactions. Cross validation and Bayesian model selection are discussed in relation to the cluster expansion for these interactions.

Keywords

Partition Function Adsorption Energy Lateral Interaction Cluster Expansion Sticking Coefficient 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  1. 1.ST/SKAEindhoven University of TechnologyEindhovenNetherlands

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