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Dimensionless thermodynamics: a new paradigm for liquid state properties.

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The corresponding states principle (CSP) applies to dimensionless thermodynamic properties of saturated liquids at the same reduced density. This principle consolidates liquid properties, validated by an improved van der Waals model.

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Area of Science:

  • Thermodynamics
  • Physical Chemistry
  • Fluid Dynamics

Background:

  • Van der Waals-type equations of state predict a corresponding states principle (CSP) for saturated liquids.
  • The CSP posits that dimensionless thermodynamic properties are comparable at equal reduced densities (ρR = ρ/ρc).

Purpose of the Study:

  • To investigate the applicability of the CSP to various dimensionless thermodynamic properties of saturated liquids.
  • To develop and validate an improved van der Waals model using scaled particle theory.

Main Methods:

  • Evaluating the CSP across multiple dimensionless thermodynamic properties, including entropy of vaporization, cohesive energy density, and surface tension.
  • Developing an enhanced van der Waals model based on scaled particle theory.
  • Comparing the model's predictions with experimental data in dimensionless form.

Main Results:

  • The CSP was confirmed for a range of thermodynamic properties, demonstrating superposition onto master curves for two liquid classes.
  • Dimensionless property expressions effectively consolidate and harmonize liquid state data.
  • The improved van der Waals model showed good agreement with experimental data.

Conclusions:

  • The corresponding states principle is a robust framework for understanding and correlating thermodynamic properties of saturated liquids.
  • Dimensionless thermodynamic property analysis provides a unified approach to liquid state behavior.
  • Scaled particle theory offers a valuable tool for refining equations of state.