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On Enthalpy-Entropy Compensation Characterizing Processes in Aqueous Solution.

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  • 1Dipartimento di Scienze e Tecnologie, Università del Sannio, Via Francesco de Sanctis snc, 82100 Benevento, Italy.

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|July 29, 2025
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Summary
This summary is machine-generated.

Enthalpy-entropy compensation is common in water, especially for biomolecules. A general hydration theory explains this occurs when solute-water attraction is weaker than water-water hydrogen bonds.

Keywords:
Gibbs free energycavity creationconformational stability of proteinsenthalpy–entropy compensationhydrationsolute–water interactionswater–water H-bonds

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Area of Science:

  • Physical Chemistry
  • Biophysical Chemistry
  • Thermodynamics

Background:

  • Enthalpy-entropy compensation is a widespread phenomenon in aqueous solutions.
  • It is particularly prevalent in processes involving biological macromolecules.
  • Existing explanations for this compensation are diverse and numerous.

Purpose of the Study:

  • To present a general theory of hydration.
  • To focus on a specific physical condition for enthalpy-entropy compensation.
  • To apply this theory to understanding aqueous processes.

Main Methods:

  • Focus on a general theory of hydration.
  • Analysis of solute-water and water-water interactions.
  • Application of physical chemistry principles.

Main Results:

  • A physical condition for enthalpy-entropy compensation is proposed: weak solute-water attraction relative to water-water hydrogen bonds.
  • This condition is generally met in water due to its cooperative H-bonded network.
  • The theory provides a unified framework for understanding hydration effects.

Conclusions:

  • The proposed hydration theory offers a fundamental explanation for enthalpy-entropy compensation.
  • The cooperative nature of water's hydrogen bond network is key to this phenomenon.
  • This work advances the understanding of molecular interactions in aqueous systems.