The Rate-Determining Step is Dead. Long Live the Rate-Determining State

The concept of a rate‐determining step (RD‐Step) is central to the kinetics community, and it is basic knowledge even for the undergraduate chemical student. In spite of this, too many different definitions of the RD‐Step appear in the literature, all of them with drawbacks. This dilemma has been th...

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Bibliographic Details
Published in:Chemphyschem 2011-06, Vol.12 (8), p.1413-1418
Main Authors: Kozuch, Sebastian, Martin, Jan M. L.
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Exact sciences and technology
General and physical chemistry
kinetics
rate-determining step
reaction mechanisms
Theory of reactions, general kinetics
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
transition-state theory
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Summary:The concept of a rate‐determining step (RD‐Step) is central to the kinetics community, and it is basic knowledge even for the undergraduate chemical student. In spite of this, too many different definitions of the RD‐Step appear in the literature, all of them with drawbacks. This dilemma has been thoroughly studied by several authors in the attempt to “patch” the drawbacks and bring the RD‐Step to a correct physical meaning. Herein we review with simple models the most notable definitions and some challengers of the RD‐Step concept, to conclude with the deduction that there are no rate‐determining steps, only rate‐determining states. A roller‐coaster ride: The rate‐determining step concept is revised, since the difficulties on its definition are evidence of its inconsistency. In view of this, a physically correct kinetic concept is proposed: the rate‐determining state.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.201100137