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Solubility and interaction parameters as references for solution properties. I. Exceptional mixing and excess

Jarl B Rosenholm1

  • 1Center of Excellence for Functional Materials, Finland. Jarl.Rosenholm@abo.fi

Advances in Colloid and Interface Science
|November 15, 2008
PubMed
Summary

This study critically compares two reference thermodynamic networks used in molecular behavior analysis. It highlights how variations in definitions, particularly for Gibbs free energy, impact results and introduces new models for complex systems.

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Area of Science:

  • Physical Chemistry
  • Thermodynamics
  • Materials Science

Background:

  • Reference parameter networks are crucial for analyzing molecular behavior by subtracting ideal properties from experimental data.
  • Traditional thermodynamic networks rely on defined thermodynamic variables, but increasing complexity introduces system-specific corrections.
  • Existing reference models, like standard Gibbs free energy functions and van der Waals models, face challenges with varying definitions.

Purpose of the Study:

  • To critically compare the conceptual constraints of two primary reference thermodynamic networks.
  • To analyze the impact of differing definitions of mixing and excess functions on thermodynamic property analysis.
  • To introduce novel functions for systems exceeding standard van der Waals behavior.

Main Methods:

  • Comparative analysis of conceptual constraints in standard Gibbs free energy functions and tailored models (e.g., van der Waals liquids, polymer solutions).
  • Examination of how variations in the definition of mixing and excess functions influence the analysis of divergence from reference functions.
  • Development of new functions based on multiple solubility parameters for systems beyond standard van der Waals behavior.

Main Results:

  • Significant variations in the definition of formally similar mixing and excess functions across different reference models.
  • Demonstrated consequences of these definitional differences on the analysis of entropy and enthalpy derived from temperature dependency.
  • Successful development of new functions utilizing multiple solubility parameters, leveraging accessible reference data.

Conclusions:

  • The choice and definition of reference thermodynamic networks critically influence the interpretation of experimental molecular behavior data.
  • Discrepancies in function definitions can lead to serious errors in thermodynamic property calculations, especially with temperature dependence.
  • New multi-parameter models offer a more adaptable framework for analyzing complex systems where standard models fall short.