Journal of Biological Physics

, Volume 5, Issue 3–4, pp 167–183 | Cite as

On the reality of transition state dissociation constants

  • George H. Czerlinski


Transition state dissociation constants are currently considered, utilizing stopped flow equipment. The underlying theory is briefly reviewed, relating the ideas to steady state kinetics of enzyme systems. The ideas are further analyzed under the consideration of chemical relaxation. Test conditions are described which would allow an investigation of the concepts of transition state dissociation constants by chemical relaxation techniques. A discussion concerning the way in which the concepts of transition state dissociation constants relate to other theories which assume short-lived, but real, dissociation constants is included. The theory is rigorously analyzed (in a second part), revealing the nature of the assumption of a transition state dissociation constant: While they may be written in a formal manner, they are not based on reality—on kinetic grounds direct interconversions between transition states are practically impossible. This applies also to transition state dissociation constants involving protons.


Enzyme Polymer Steady State Statistical Physic Transition State 
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Copyright information

© Physical Biological Sciences Ltd 1978

Authors and Affiliations

  • George H. Czerlinski
    • 1
  1. 1.Department of BiochemistryNorthwestern UniversityChicago

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