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Enthalpy-entropy compensation: a phantom phenomenon.

Athel Cornish-Bowden1

  • 1Bioénergétique et Ingénierie des Protéines, Institut Fédératif "Biologie Structurale et Microbiologie", Centre National de la Recherche Scientifique, 31 chemin Joseph-Aiguier, B.P. 71, 13402 Marseille Cedex 20, France. athel@ibsm.cnrs-mrs.fr

Journal of Biosciences
|April 9, 2002
PubMed
Summary
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Enthalpy-entropy compensation, a correlation between reaction enthalpy and entropy, is often an artifact. This phenomenon arises because these two variables are frequently measured as different aspects of the same underlying factor.

Area of Science:

  • Thermodynamics and Physical Chemistry
  • Chemical Kinetics

Background:

  • Enthalpy-entropy compensation describes correlations between reaction enthalpy and entropy estimates from temperature-dependence data.
  • The artefactual nature of this correlation is well-established but the phenomenon periodically resurfaces due to its perceived excellence.

Purpose of the Study:

  • To explain the persistent observation of enthalpy-entropy compensation.
  • To clarify the underlying reasons for the strong correlation between enthalpy and entropy in reaction data.

Main Methods:

  • Analysis of temperature-dependence data for chemical reactions.
  • Statistical examination of correlations between thermodynamic variables.

Main Results:

  • The observed enthalpy-entropy compensation is largely an artifact of the measurement process.

Related Experiment Videos

  • What appear as two independent variables (enthalpy and entropy) are often different perspectives of a single underlying variable.

    • Conclusions:

    • Enthalpy-entropy compensation is an artifactual correlation, not a fundamental thermodynamic principle.
    • Understanding this artifact is crucial for accurate interpretation of reaction data and thermodynamic studies.