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Predictive thermodynamics for ionic solids and liquids.

Leslie Glasser1, H Donald Brooke Jenkins2

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New thermodynamic tools simplify estimating properties for ionic materials. Volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR) provide accessible methods for researchers without advanced computational expertise.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Thermodynamic parameter estimation for ionic materials is often challenging.
  • Existing methods may require significant computational resources or expertise.
  • Accurate thermodynamic data is crucial for predicting material behavior and feasibility of reactions.

Purpose of the Study:

  • To introduce and demonstrate accessible tools for estimating thermodynamic parameters of ionic materials.
  • To provide a simplified approach to calculating key thermodynamic and thermomechanical properties.
  • To extend these methods to various ionic systems, including liquids and novel materials.

Main Methods:

  • Volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR).
  • Supplemented by the simple salt approximation (SSA) and single-ion values.
  • Application to calculate properties like enthalpy, entropy, heat capacity, and Gibbs energy.

Main Results:

  • Successful estimation of elusive thermodynamic parameter values for solid and liquid ionic materials, hydrates, and solvates.
  • Methods are largely independent of crystal structure, enabling application to ionic liquids and new materials.
  • Validation through application to K2SnCl6, showing good agreement with experimental results.

Conclusions:

  • VBT and TDR offer powerful yet simple methods for thermodynamic analysis.
  • These techniques do not require high-level computational expertise or expensive tools.
  • The established connection between formula unit volume and thermodynamic parameters is a key advance.