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Related Experiment Videos

Win some, lose some: enthalpy-entropy compensation in weak intermolecular interactions

J D Dunitz1

  • 1Organic Chemistry Laboratory, Swiss Federal Institute of Technology, Zürich, Switzerland.

Chemistry & Biology
|November 1, 1995
PubMed
Summary

Enthalpy-entropy compensation, common in biological processes, arises from weak intermolecular interactions. This thermodynamic principle explains how enthalpy and entropy nearly balance for hydrogen bonds at physiological temperatures.

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Area of Science:

  • Thermodynamics
  • Biophysical Chemistry
  • Molecular Interactions

Background:

  • Enthalpy-entropy compensation is frequently observed in chemical reactions and biological systems.
  • The underlying reasons for this phenomenon remain largely unexplained.
  • Understanding this compensation is crucial for deciphering molecular interactions and biological processes.

Purpose of the Study:

  • To elucidate the origin of enthalpy-entropy compensation.
  • To investigate the role of weak intermolecular interactions in this phenomenon.
  • To provide a thermodynamic basis for the balance between enthalpy and entropy in molecular systems.

Main Methods:

  • Development of a simple thermodynamic argument.
  • Analysis of the contributions of enthalpy and entropy to free energy.

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  • Focus on hydrogen bonds as a model system.

    • Main Results:

    • A simple thermodynamic argument suggests enthalpy-entropy compensation is a general property of weak intermolecular interactions.
    • The enthalpy and entropy contributions to free energy are shown to nearly balance.
    • This balance is particularly evident for hydrogen bonds at approximately 300 K.

    Conclusions:

    • Enthalpy-entropy compensation is a predictable outcome of weak intermolecular forces.
    • The near-cancellation of enthalpy and entropy terms is a fundamental aspect of hydrogen bonding at physiological temperatures.
    • This finding offers a fundamental explanation for a widespread thermodynamic observation in chemistry and biology.